Professional Documents
Culture Documents
Adsorption Science
and Technology
Adsorption Science
and Technology
May 25-29,2003
Kyongju, Korea
Editor
Chang-Ha lee
Yonsei University, Korea
r heWorld Scientific
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Preface
The Third Pacific Basin Conference on Adsorption Science and Technology was held
fiom May 25 to May 29, 2003 in Kyongju, Korea. The theme for this conference was
thinking about adsorption at a splendid, enjoyable, and sound conference.
It was the first time that an international conference on adsorption was ever held in
Korea. Since the previous conferences organized by Professor K. Kaneko (1997) and
Professor D. D. Do (2000) were very successful, I was very excited as well as very
nervous when I was asked to organize this conference for I wanted to make this one as
successful as the previous ones.
The main purpose of this conference was to encourage the development of new
adsorption science and technology as well as to reflect the growth of this area. The
conference covered a variety of adsorption-related fields from fundamentals to
applications. The conference consisted of plenary and invited sessions, oral sessions and
poster sessions. And the conference areas were as follows: Fundamentals of Adsorption
and lon Exchange, New Materials, Adsorption Characterization, Novel Processes, Energy
and Environmental Processes.
I was very happy to see many contributions from 16 countries, with more than 120
papers. The plenary lectures of Professors D. D. Do (Univ. of Queensland, Australia), K.
E. Gubbins (North Carolina State Univ., USA), K. Kaneko (Chiba Univ., Japan), M.
Morbidelli (ETH Ziirich, Switzerland), A. L. Myers (Univ. of Pennsylvania, USA), D. M.
Ruthven (Univ. of Maine, USA), R. Ryoo (KAIST, Korea), S. Sircar (Leigh Univ. USA),
M. Suzuki (United Nations Univ., Japan), and R. T. Yang (Univ. of Michigan, USA) set
the tone for the theme of the conference. Also, I would like to thank Professors G.Baron,
A. Neimark, and L. Zhou for their contribution as invited speakers. Plenary speakers
presented an in-depth overview of key research areas: Materials, Characterization,
Molecular Simulations, Equilibria, Kinetics, and Processes. Furthermore, many
contributed papers were of high standard. 1 hope that this conference was a worthwhile
and memorable one for all the participants.
I would like to thank all the participants for all the contributions to the conference. I
would like to take this opportunity to thank all the reviewers for their efforts to review
papers within a very short period of time. Thanks should also go to the members of the
organizing committee and secretary, the advisory and scientific committee and session
chairs for their input and assistance. Also, special thanks goes to Professor J. Ritter (Univ.
of South Carolina, USA) for the organization of the US side. And I would like to express
my gratitude to Yeong-Joo Park, my wife, for all of her support and I thank my graduate
students for all of their hard work to make this conference work.
The conference would not have been possible without the generous financial support
from many organizations such as the National Science Foundation, Yonsei University,
Korean Institute of Chemical Engineers, KOSEF, KRF, Daesung Sanso Co., Research
Institute of New Energy and Environmental Systems at Yonsei Univ., Yonsei Center for
Clean Technology, Chonnam National University, Chungnam National University, NRL
for Themophysical Properties, ERC for the Advanced Bioseparation Technology, NRL
for Separation Process, NRL for Environmental Materials & Process.
Professor Chang-Ha Lee
Chairman of the Third Pacific Basin Conference on Adsorption Science and Technology
Department of Chemical Engineering, Yonsei University, Korea
Sponsors
Yonsei University
Korean Institute of Chemical Engineers
The Korean Federation of Science and Technology Societies
Korea Science and Engineering Foundation
Korea Research Foundation
Daesung Sanso Co.
National Science Foundation (USA)
Co-Sponsors
Research Institute of New Energy and Environmental Systems
at Yonsei University
Yonsei Center for Clean Technology
Chonnam National University
Chungnam National University
ERC for the Advanced Bioseparation Technology
NRL for Themophysical Properties
NRL for Separation Process
NRL for Environmental Materials & Process
vi
Conference Chair
Chang-Ha Lee
(Hanyang Univ.)
(Yonsei Univ.)
(Seoul National Univ.)
Organizing Committee
S. H. Cho
D. K. Choi
S. H. Hyun
J. W. Jang
H. Kim
Y. M. Koo
C. S. Lee
H. Moon
D. S. Park
S. K. Ryu
Y. G. Shul
J. E. Sohn
J. Yi
(KIER)
(KIST)
(Yonsei Univ.)
(SK Eng. & Construction)
(Seoul National Univ.)
(Inha Univ.)
(Korea Univ.)
(Chonnam Univ.)
(Daesung Sanso Co.)
(Chungnam Univ.)
(Yonsei Univ.)
(Dong-A Univ.)
(Seoul National Univ.)
Vii
J. U. Keller
J. M. Lee
K. H. Lee
N. Lemcoff
M. D. LeVan
M. Mazzotti
G. McKay
F. Meunier
J. K. Moon
A. Neimark
Y. D. Park
A. E. Rodrigues
W. Rudzinski
R. Ryoo
A. Sakoda
N. Seaton
S. Sircar
W. A. Steele
M. Suzuki
0. Talu
Y. Teraoka
Y. Xie
Organizing Secretary
C. H. Cho
S. S. Han
K. T. Lee
J. Y. Yang
(Youngdong Univ.)
(KIER)
(Yonsei Univ.)
(SK Eng. & Construction)
...
Vlll
Contents
Preface
Plenary Papers
Adsorption Equilibria of Sub-critical and Super-critical Fluids in
Carbonaceous Materials
D. D. Do and H. D. Do
17
27
35
44
51
64
72
79
Invited Papers
iX
87
91
Contributed Papers
99
104
109
114
121
126
131
136
141
147
152
157
162
167
172
177
182
189
194
199
204
209
214
219
224
229
234
xi
239
244
249
254
259
264
270
276
28 1
286
29 1
296
xii
30 1
306
313
318
324
329
334
339
344
349
354
359
xiii
365
370
375
38 1
387
392
398
403
408
413
417
422
427
xiv
432
437
442
447
452
458
463
468
474
479
484
489
xv
494
499
504
509
514
519
524
529
534
539
544
549
554
559
xvi
564
569
574
579
584
589
595
600
605
610
615
620
625
xvii
630
635
640
645
xviii
Plenary Papers
Introduction
Adsorption equilibria and kinetics are important for the proper design of adsorption
processes. The equilibria information of adsorption isotherm. is clearly the first hand
information that one needs to approximately size the adsorber. Since the adsorption
affinity can vary by many orders of magnitude. Ranging from very low for weakly
adsorbing gases to very high for strongly-adsorbing hydrocarbon vapours, it is very
important that we know the value of this adsorption affinity. Experimentally this
information can be obtained from careful experimentation of adsorption isotherm
measured from very low pressure (where adsorption affinity can be calculated) to very
high pressure where saturation capacity can be determined. Alternatively, the adsorption
affinity can be determined from some appropriate theories or computer simulation. With
the advances of high speed computer and the development of modem tools to deal with
inhomogeneous fluids in confined space such as micropores, the second approach is
gaining ground and new theories are constantly developed allowing engineers and
scientists to calculate adsorption isotherm from minimum amount of information.
Nevertheless, that does not mean to say that we can make do without experimental data.
We still have some ground to cover before that stage can be reached. At the present time,
careful and reliable experimental data are still required for validation of theories and even
confirmation of molecular simulations.
In this paper we will discuss some modem tools for studying adsorption equilibria of
super and sub-critical fluids on non-porous surface and in porous carbons. In particular,
the tools of grand canonical Monte Carlo (GCMC) simulation [l, 21, Density Functional
Theory [3], Molecular Layer Structyre Theory (MLST) [4, 51, and the enhanced
molecular layering and pore filling of Do, first developed in 1998 [6]and later applied in
a number of practical systems [7-101, will be discussed. Their applications to
experimental systems are illustrated to highlight the advantages and disadvantages of
these modem tools of equilibria characterization.
2. I
Tools of characterisation
Grand canonical Monte Carlo simulation
2.2
The DFT method was popularized in the sixty and was increasingly modified and applied
to many problems involving inhomogeneousfluids in the 80s. Among the many versions
of DFT, the one proposed by Tarazona and co-workers [3] remains the popular one in
solving adsorption of confined fluid in pores. Their method is the non-local DFT and is
applied on a grand canonical ensemble. The starting point of the method is the grand
potential of the system
(la)
= F(p(l)) + jP@)ucxtcr)dx
- jP@>P&
where p(rJ is the singlet particle density. The first term on the RHS of the above equation
is the Helmholtz free energy of the system. The Helmholtz free energy is expressed as a
sum of two terms. The first term is that obtained from a reference system (hard sphere
fluid is chosen as one) and the other is the perturbed component (which is due to the
attractive component of the intermolecular fluid-fluid interaction), that is
F(PCr)) = FH(P@N+ FA-( P O
The Helmholtz free energy of the reference hard sphere system, in turn,can be expressed
as two terms. One is due to the ideal gas contribution (accounting for the momenta of all
particles) while the other term is the repulsive interaction among the hard spheres. It is
jP@
FH(P(E)) =
[In(A3P(IN - 11dr + j P ( 0 f m G(INdI
where the smoothed density is given by
P(I) = I P W w(x-il;p(l))dzI
Assuming a mean field approximation, the perturbed component of the Helmholtz free
energy due to the attractive force is
FA-(P(I))
=?j j P 0 P W %(I-d)dd
dx
(1b)
The equilibrium density profile can then be obtained by finding minimum of the grand
potential as defined in eq.(la). Tarazona used the Carnahan-Starling equation to derive
the excess function f(p(I)) as (here, d is the hard sphere diameter)
f(&)) = (4y - 3 ~ )/(I
2.3
- y) ;
The Molecular Layer Structure Theory (MLST) was first developed [4, 51 to study the
vapour liquid equilibrium and surface tension of many substances over a wide range of
temperature. In this method, the fluid is considered as parallel molecular layers, whose
surface densities are different for inhomogeneous
fluids. Similar to the DFT method, we
define the following grand potential:
R=
+urf - jl]
cp;k(p;)+cpj
where py is the surface density, Ask)is the intrinsic Helmholtz free energy of the layer
i
j,
pj
is the interaction energy between one molecule on the layerj and all surrounding
layers, and u; is the external potential exerted on the layerj. In this method of MLST,
the intrinsic Helmholtz free energy is calculated from the equation of state of
homogeneous fluid, and pi is calculated from the integration of 12-6 Lennard-Jones
potential energy. The equilibrium density is calculated by minimizing the grand potential
with respect to density as well as distances between layers [4,5].
2.4
The Do-Method
Recently, Do and co-workers [6-101 have proposed a very simple method but it does
reveal the mechanistic pictures of what are occurring in pores of different size. The
process of adsorption in
pore is viewed as follows. Molecules in pore are constantly
in motion but statistically there is a spatial distribution of these molecules due to the
interactive forces between them and the surface atoms. We treat this spatial distribution
as a step function; uniformly high density near the surface and uniformly low density in
the inner core of the pore. Due to the long range interaction of the surface, the pressure
of the fluid in the inner core is not the same as that in the bulk phase. Assuming a
Boltzmann distribution, the pressure of the inner core is related to the bulk fluid as
Pp = P.exp(- a E/ kT)
(2)
where E is the average potential of the inner core, which is a function of pore width and
the layer thickness. The adsorption process is basically treated as a molecular layering
process, and it can be described by a layering equation, for example an equation taking
the same
the form of the BET equation. The affinity parameter C, of this equation
as the C-parameter for a flat surface. Rather they are related through the following
relation
c,(H) = c.~xP[(Q,(H)-Q)/RT~
(3)
where Q is the heat of adsorption of the flat surface and Qp is the correspondingvalue for
a pore. These values may be taken as the minimum value of the potential energy between
a molecule and a flat surface and that between a molecule and a pore. The layering
equation can be written as
(4)
t / t, = f(P, (HI, c, (HI)
where ,t is the thickness of a monolayer. This layering process is followed by a pore
filling process. Here the term pore filling is used in its most general sense, that is pore
is filled with molecules by either two-dimensional condensation in small pores or three
dimensional condensation in large pores. We argue that this general pore filling process
is governed by the equation
H / 2 - t - ~ , =)*
where ~0 is the position at which the solid-fluid potential energy is zero. Although this
form is similar to that of the Kelvin equation, the significant difference rests on the use of
the pore pressure P, in the above equation. If we substitute the pore pressure of eq.(2)
into the above equation, we get
P M
(H/2 - t - 2,)
For small pores, E(H) dominates the RHS of the above equation and hence the pore
filling pressure in small pores is dominated by the strength of the potential field created
by the overlapping of the fields of the two walls. On the other hand, for larger pores
where &H) = 0 , the RHS is dominated by surface tension and this equation reduces to
the well known modified Kelvin equation.
10
20
30
Pore Width (A)
40
50
Having presented briefly the working procedures of the various methods, we now would
like to illustrate their applications to adsorption of super and sub-critical fluids on nonporous carbon surface and in porous carbonaceous solids having slit pores. But first it is
worthwhile to compare the time scales of computation of these methods:
Do-method < MLST <4 DFT < GCMC
(seconds)
3.1.1
(hours)
(minutes)
(day)
Non-porous surfaces
10
Resslm,(MPa)
15
10
15
WPa)
The continuous lines in these plots are fiom the results of MLST theory and GCMC. We
see that the agreement between the MLST theory and the data [131 is excellent (Figure
2a). In patticular, the temperature dependence of the isotherms is well described by the
MLST model. The results obtained from GCMC are shown in Figure 2b, and it is
surprising that the GCMC results are not as good as the MLST results. It describes the
data well at low pressure but it consistently over-predicts the amount adsorbed at higher
pressures. One probable explanation for this might be the possibility of temperature and
density dependence of the molecular parameters in GCMC simulation for high pressures.
This reason needs some justification because the MLST also uses molecular parameters,
and they are kept constant in the calculations. This illustrates that the molecular
simulation, despite its great potential, is less effective than the MLST for this problem of
high pressure adsorption of super-critical fluids on non-porous surfaces. The MLST is
very effective in the study of the effects of parameters and operating conditions, such as
surface carbon density and solid-fluid interaction energy, on the behaviour of surface
excess at extremely high pressures. This will be discussed in details at the conference.
What we observed for argon are also repeated with Kr, methane, ethylene, propane
and sulphur hexafluoride. Figures 3 show the comparison between GCMC and MLST
for ethylene at 283 JC, which is just greater than the critical temperature.
We see that at this temperature, the surface
excess versus pressure shows a distinct
spike at a pressure very close to the critical
pressure of 5.036 MPa Beyond this
pressure, the surface excess decreases very
sharply and this is due to the large change
in density in the bulk fluid for a small
change in the pressure. It is remarkable
that the MLST describes the data [14] very
0.1
1
10
100
well. The GCMC, on the other hand,
Pmssurs (MPa)
Figure 3: Comparison between GCMC & MI.ST for describes well at low pressures but badly
predicts at higher pressures.
ethylene adsorption at 283 K
3.1.2
Slit pores
For slit pores, we compare the results of DFT and GCMC for slit pores having width 8
and 14 A in Figures 4 for argon adsorption at a super-critical temperature of 298K.
1.o
0.8
0.8
0.8
-&
0.4
B
0.2
0.2
0.0
104
104
10=
10'
lo-'
0.0
100
10'
lW
10'
103
101
10'
16
10'
102
AdMty, zd
Activity. z d
We fmt note the gradual behaviour of the adsorption isotherms, and this is typical for
super-critical fluid adsorption in pores of all sizes. For sub-critical adsorption which we
will consider later, there is a possibility of phase transition for certain pore widths.
We see that the agreement between the DFT and GCMC results is very good for
large micropores of 14 A, while there is a distinct deviation in small micropore of 8 A.
This is due to the mean field approximation of the DFT method (eq. lb). In terms of
computation time, the DFT method is modestly faster than the GCMC (depending on the
error criteria as well as the grid points used in the determination of singlet density
distribution) but not substantially fast enough to warrant it in its use in routine process
applications.
3.2
3.2.1
Sub-criticalfluid
Non-porous surface
Sub-critical fluids are widely applied for surface and pore characterization. Figure 5
shows the surface excess adsorption of argon at 87.3K on graphitized thermal carbon
black. The results are obtained fiom the GCMC and DFT. The subtle difference in the
formation of second and higher layers is observed and this is due to the mean field
approximation. As an illustration of the MLST method, we show in Figure 6 the results
in the prediction of argon adsorption isotherm on graphitised carbon black at 87.3 K [IS].
The theory exhibits a kink formation of the second layer and this deviation from the data
could probably be due to the heterogeneity of the graphene surface. It is interesting to
note that that kink exists in the DFT as well as GCMC simulation (see arrow in Figure 5).
10
Gas Density. po
pigpre 5: GCMC v
3.2.2
1b
18
-M
1@
101
(Pa)
Slit pores:
Here we would like to show the difference between the three methods used in pore
characterization: GCMC, DFT and Dos method. Figures 7 show the average pore
density versus pressure for argon adsorption in slit pores having width of 8 and 30A.
Here we see that the difference between the DFT and GCMC for 8 A pore is quite
significant, and not only in terms of the pore filling pressure but also on the behaviour of
the adsorption isotherm curves. The local isotherms obtained from the Do-method for
these pores, although not completely in agreement with the GCMC results, qualitatively
match these results rather well over the complete range of pressure. The fast computation
of the Do-method can be the greatest advantage among the various methods, and it can be
effectively used in process optimizationor in routine pore characterisation.
*r-K!f,Pb
Figure 7a: GCMC versus DFT for slit pore H = 8 A
Qaa Den*,
Figwe
Fa?
Conclusions
We have presented in this paper an overall but brief summary of various tools commonly
used in the adsorption equilibria calculations in carbon. These tools rage fmm simple
methods such as the Do-metho& the MLST of Ustinov and Do to advanced methods such
as the DFT and the GCMC simulation. Although the DFT is modestly faster than the
GCMC, they are both computer time-hungry and unsuitable in any applications that
require routine computation of isotherms, especially when parameters are varied. The
simple methods,in particular the Do-method,might provide an answer to this.
5
Acknowledgements
A&,
1.
Introduction
the liquid and solid phases in the pore. "Contact layer" phases of various kinds often
occur, in which the layer of adsorbed molecules adjacent to the pore wall has a different
structure fi-om that of the adsorbate molecules in the interior of the pore. These contact
layer phases have been predicted theoretically, and confirmed experimentally for several
systems [4*91. In addition, for some systems in which strong layering of the adsorbate
occurs (e.g. activated carbon fibers), hexatic phases can occur; such phases have quasilong-ranged orientational order, but positional disorder, and for quasi-two-dimensional
systems occur over a temperature range between those for the crystal and liquid phases.
These are clearly seen in molecular simulations, and recent experiments provide
convincing evidence for these phases [14]. It has been shown that this apparently complex
phase behavior results ftom a competition between the fluid-wall and fluid-fluid
intermolecular interactions. For a given pore geometry and width, the phase diagrams for
a wide range of adsorbates and porous solids can be classified in terms of a parameter a
that is the ratio of the fluid-wall to fluid-fluid attractive interaction t1,97131.
In this paper we report molecular simulation studies of fteezing in slit-shaped pores and
in multi-walled carbon nanotubes. Simulations make use of the Landau-Ginzburg
formalism for the free energy[I3] and parallel tempering"']. Experimental results from
dielectric relaxation spectroscopy are reported for several fluids in these materials.
2.
Methods
2.1. Simulation
10
where the fmt sum is over the adsorbed molecular layers and
plane in which molecules in layerj are most likely to lie on. We expect @(r)=l for twodimensional hexagonal crystals and @(r)=O for two-dimensional liquids. YGJ(p)measures
the hexagonal bond order at position p = x ex + y ey within each two-dimensional layer j.
is the number of nearest neighbors of a molecule at position and Bk is the orientation
of each nearest neighbor bond with respect to an arbitrary axis E31. For slit-shaped pores,
these two-dimensional layers lie in the xy plane. For cylindrical pores, a quasi-two
dimensional configuration of each molecular layer can be obtained by cutting each one of
the concentric layers along the axial direction and unrolling it flat. The grand fiee energy
of a particular phase is then related to the Landau fkee energy by [13]:
Nb
The probability distribution fhction P[@(r)] was determined during the simulations
using umbrella sampling in pores of slit-like geometry [13], and parallel tempering [I5] for
pores of cylindrical geometry I19]. The method of parallel tempering is a Monte Carlo
scheme that has been derived to achieve good sampling of systems that have a fiee energy
landscape with many local minima [*'I. Yan and de Pablo [''I implemented this scheme in
the grand canonical ensemble, performing an MC simulation in n-systems which differ in
both temperature and chemical potential. In addition to the standard MC trial moves, they
proposed configuration swaps in this method. A swap attempt between configurations i
a n d j is accepted with probability given by
empty capacitance Co.The capacitance C and the tangent loss, tan(b) of the capacitor
filled with the sample were measured at different frequencies and temperatures, using a
Solartron 1260 Gain Analyzer. For the case of CC4 in multi-walled carbon nanotubes, the
sample was introduced between the capacitor plates as a suspension of the adsorbent
(multi-walled nanotubes with average internal diameter of 5 nm, average external
diameter of 10 nm)in the pure adsorbate (CC14). The relative permittivity is related to the
measured quantities by K,=C/C~,~ = t a n ( S y Kwhere
,
6 is the angle by which current leads
the voltage. Further details of the experimental methods are described elsewhere
3.
Results
6 .
TJK
@)
Figure 1. (a) Landau free energy in the two molecular layers of LJ CCIJ confined in a graphitic, slit-like pore of
width H=3ojj(1.5 nm),at T=335 K and P290 K. (b) Grand free energy as a function of temperature for liquid,
hexatic and crystalline phases, for the same system. From
A corresponding states a n a l y ~ i s ~ ~
shows
" ~ ] that the shift in the freezing temperature, as
well as the temperature of any other surface-driven phase transitions, should depend on
three reduced variables, namely H*=H/c~fi a = ~ , E ~ O & A /and
E ~o-j&fi here f and w
refer to confined fluid and wall, respectively, avis the atom density of the pore wall, and
A is the spacing between the atomic layers that make up the pore wall. For relatively
12
small fluid molecules the size ratio parameter is found to have little effect on the freezing
behavior, except in the molecular sieving regime. Thus it is possible to plot global
freezing diagrams in terms of a, the ratio of fluid-wall to fluid-fluid attractive forces.
Such a diagram is shown in Figure 2 pores of width H*=3, obtained from both simulations
and experiments [I3. The diagrams from simulations and experiments are in qualitative
agreement, and demonstrate that a parameter determines the qualitative nature of the
fieezing behavior. Large values of a lead to an increase of the freezing temperature of the
confined fluid and to the formation of hexatic phases. As the fluid-wall interactions
become weaker, a decrease on the freezing temperature is observed and the temperature
range where the hexatic phase is stable decreases. Similar diagrams for larger pores, e.g.
H*=7.5, using molecular simulations [I show the presence of contact layer phases, in
which the layer of adsorbed molecules adjacent to the pore wall has a different structure
from that of those molecules in the interior of the pore. These simulations show that for
simple fluids the role of a is to determine the nature of the fkeezing behavior, while that of
H* is primarily to determine the magnitude of shifts in the transition temperatures.
.(a)
(b)
Figure 2. Global phase diagram of a fluid in a slit pore of width H=303 (I .5 nm) from (a) simulations, and (b)
experiments. The experiments are for various adsorbates confined within activated carbon fibers: 1=H20,
2=C&N&
3=c&NH2, kCH@H, 5=CCL, 6 e . From and references therein.
13
an isotropic liquid. At T=252 K, the features observed in both pair correlation functions
are characteristic of a two-dimensional hexagonal crystal "". Similar features were found
for the other layers.
0.8
0.6
0.4
e
02
(a)
(b)
Figure 3. (a) Two-dimensional,bond orientational order parameter average values in the molecular fluid layers
of IJ CCL confined in a multi-walled carbon nanotube of diameter D = 9 . 7 9 (5 nm). Triangles, squares,
diamonds and circles represent the order parameter values for the contact, second, third and fourth layers,
respectively. The dotted line represents the bulk solid-fluid transition temperature. (b) Positional and
orientational pair correlation functions in the unwrapped contact layer of LJ CC4 confined in a multi-walled
carbon nanotube of diameter D = 9 . 7 0 ~ ( run)
5 showing liquid phase at 7'=262 K and crystal phase at T=252 K.
Our results for the D=9.7ufcarbon nanotube did not show any sign of ordering of the
confined LJ CCl, into regular, three-dimensional crystal structures. This finding is in
agreement with previous simulation [lo] and experimental 110*22-241 studies, where it was
shown that for pore diameters below 200- only partial crystallization occurs. The same
studies found that for silica materials, the lower limit below which there are no 3-D
crystal domains in the system was around D=120- 110*22-241. Our simulations for carbon
nanotubes of smaller diameters show that the freezing temperatures increase as the pore
diameter decreases. We are currently performing free energy calculations to determine the
thermodynamic stability of each of the phases, as well as to determine the exact phase
transition temperatures for the confined layers [''I.
14
temperatures found in the experiments are in qualitative agreement with those found in
our simulations.
Figure 4. Dependence of capacity C on T for CCL in multi-walledcahon nanotubes with average pore diameter
of 5 nm (10 nm average external diameter), from dielectric relaxation spectroscopy. Symbols represent results
obtained at different frequencies: circles, 30 kHz; squares, 100 kHz; and triangles, 6OOkHz. The signals are for
both bulk and confined CCL.
4.
Conclusions
Our results in slit pores show that the solid-fluid phase behavior for this case depends on
two main parameters, the reduced pore width H and a parameter measuring the ratio of
the fluid-wall to the fluid-fluid (a)attractive potential. An increase of the freezing
temperature of the confined fluid relative to the bulk is observed for large values of a,
whereas a decrease is observed for small values of a. We found evidence of new surfacedriven confined phases, such as contact layer and hexatic phases. The hexatic phase
was found in slit-shaped pores with larger a values, and it is stable over extended
temperature ranges. Phase diagrams of the transition temperature vs a were depicted for
several LJ fluids confined in activated carbons H*=3. These phase diagrams are in
qualitative agreement with experimental results. For cylindrical pores, our results for a
D=9.7oS multi-walled carbon nanotube show no formation of regular 3D crystalline
structures, in agreement with experimental results. Our results also suggest that the outer
layers experience an increase in the freezing temperature, while the inner layers
experience a depression in the freezing temperature with respect to the bulk freezing
point. Simulations for carbon nanotubes of smaller diameters show that the freezing
temperatures increase as the pore diameter decreases. Preliminary experimental results
show solid-fluid transition temperatures for CCl, in carbon nanotubes that are in
qualitative agreement with those determined in our simulations.
This work was supported by a grant from the National Science Foundation (Grant No.
CTS-9908535). Supercomputer time was provided under a NSF/NRAC grant
(MCA93S011).
15
For a review to mid-1999 see: L.D. Gelb, K.E. Gubbins, R. Radhakrishnan and M. SliwinskaBartkowiak, Phase Separation in Confined Systems, Rep. Prog. Phys. 62 (1999) pp. 1573-1659
I[' M. Miyahara and K.E. Gubbins, FreezingMelting Phenomena for Lennard-Jones Methane in
Slit Pores: a Monte Carlo Study, J. Chem. Phys. 106 (1997) pp. 2865-2880
r31 R. Radhakrishnan and K.E. Gubbins, Free Energy Studies of Freezing in Slit Pores: An OrderParameter Approach Using Monte Carlo Simulation, Mol. Phys. % (1999) pp. 1249-1267
r41 M. Sliwinska-Bartkowiak, J. Gras, R. Sikorski, R. Radhakrishnan, L.D. Gelb and K.E. Gubbins,
Phase Transitions in Pores: Experimental and Simulation Studies of Melting and Freezing,
Langmuir 15 (1999) pp. 6060-6069
['I H. Dominguez, M.P. Allen and R. Evans, Monte Carlo Studies of the Freezing and Condensation
Transitions of Confined Fluids, Mol. Phys. 96 ( 1998) pp. 209-229
[61 K. Kaneko, A. Watanabe, T. Iiyama, R. Radhakrishnan and K.E. Gubbins, A Remarkable Elevation
of Freezing Temperatureof CCL, in Graphitic Micropores, J. Phys. Chem. B, 103 (1999) pp. 70617063
[71 A. Watanabe and K. Kaneko, Melting Temperature Elevation of Benzene Confined in Graphitic
Micropore", Chem. Phys. Lett. 305 (1999) pp. 71-74
[*I R. Radhakrishnan, K.E. Gubbins, A. Watanabe and K. Kaneko, Freezing of Simple Fluids in
MicroporousActivated Carbon Fibers: Comparison of Simulation and Experiment,J. Chem. Phys.
111 ( 1999) pp. 9058-9067
l9] R. Radhakrishnan, K.E. Gubbins and M. Sliwinska-Bartkowiak, Effect of the Fluid-Wall
Interaction on Freezing of Confined Fluids: Towards the Development of a Global Phase Diagram,
J. Chem. Phys. 112 (2000) pp. 11048-1 1057
['I M. Sliwinska-Bartkowiak,G. Dudziak, R Sikorski, R. Gras,R. Radhakrishnan and K.E. Gubbins,
MeltingRreezing Behavior of a Fluid Confined in Porous Glasses and MCM-41: Dielectric
Spectroscopyand Molecular Simulation, J. Chem.Phys. 114 (2001) pp. 950-962
[ I i 1 M. Sliwinska-Bartkowiak,G. Dudziak, R. Sikorski, R. Gras,K.E. Gubbins and R. Radhakrishnan,
Dielectric Studies of Freezing Behavior in Porous Materials: Water and Methanol in Activated
Carbon Fibers, Phys. Chem. Chem. Phys. 3 (2001) pp. 1 179-1184
[*'] M. Sliwinska-Bartkowiak,R. Radhakrishnan and K.E. Gubbins, Effect of Confinement on Melting
in Slit-Shaped Pores: Experimental and Simulation Study of Aniline in Activated Carbon Fibers,
Mol. Sim. 27 (2001) pp. 323-3337
["I R .Radhakrishnan, K.E. Gubbins and M. Sliwinska-Bartkowiak, Global Phase Diagrams for
Freezing in Porous Media, J. Chem. Phys. 116 (2002) pp. 1147-1155
[14] R. Radhakrishnan, K.E. Gubbins and M. Sliwinska-Bartkowiak, On the Existence of a Hexatic
Phase in Confined Systems, Phys. Rev. Lett. 89 (2002) art. 076101
["I Q. Yan and J.J. de Pablo, Hyper-Parallel Tempering Monte Carlo: Application to the LennardJones Fluid and the Restricted Primitive Model, J. Chem. Phys. 111 (1999) pp. 9509-95 16
[I6] W.A. Steele, Physical Interaction of Gases with Crystalline Solids: 1. Gas-Solid Energies and
Properties of Isolated Adsorbed Atoms, Sut$ Sci. 36 (1973) pp. 3 17-352
[I7] B.K. Peterson, J.P.R.B. Walton and K.E. Gubbins, Fluid Behavior in Narrow Pores, J. Chem.
Soc., Faraday Trans. 2 82 (1986) pp. 1789-1800
[lS1 R.M. Lynden-Bell, J.S. van Duijneveldt and D. Frenkel, Free-Energy Changes on Freezing and
Melting in Ductile Metals, Mol. Phys. 80 (1993) pp. 801-814
[I9] F.R. Hung, M. Sliwinska-Bartkowiakand K.E. Gubbins, in preparation (2002).
I'[ D. Frenkel and B. Smit, Understanding Molecular Simulation: From Algorithms to Applications
2"* Edition (Academic Press, London, 2002)
["I A. Chelkowski, Dielectric Physics (Elsevier, North-Holland, New York 1980)
I'[ D. Morineau, G. Dosseh, C. Alba-Simionesco and P. Llewellyn, Glass Transition, Freezing and
Melting
of
Liquids
Confined
in
the
Mesoporous Silicate
MCM-41,
Philos. Mag. B 79 (1999) pp. 1847-1855
["I G. Dosseh, D. Morineau and C. Alba-Simionesco, Benzene Confined in MCM-41 Below its
Melting Point: A Proton NMR Study, J. Phys. IV 10 (2000)pp. 99-102
[241 D. Morineau, F. Casas, C. Alba-Simionesco, A. Grosman, M.-C. Bellisent-Funel and N.
RatovClomanana, A Neutron Scattering Investigation of the Structural Properties of
Glassforming M-Toluidine Confined in MCM-41, J. Phys. IV 10 (2000) pp. 95-98
[I1
16
E-mail:
druthven!dumche.maine.edu
The experimental methods for measurement of transport and self-diffision in zeolite crystals (and in
other microporous materials) are reviewed. Large discrepancies between different techniques are
commonly observed and appear to be related to the scale of the measurements, suggesting that
structural defects may be more important than is generally believed.
Introduction
Definition of Diffusivities
Molecular transport and tracer diffision in porous solids are conveniently correlated in
terms of difisivities defined in accordance with Ficks first equation:
az
= -D(q). aq
J* = - D * ( q ) . Y l
az
The self-difisivity defined on the basis of the random walk representation of a diffusive
process:
~
2n t
2n r
is identical to the tracer diffbsivity. The relationship between the transport and tracer
diffusivity is more complex.
Considering the chemical potential gradient rather than the concentration gradient as
the fundamental driving force leads to:
17
where
0;
measures the rate of migration to vacant sites, the velocity of which (u,+,) is zero.
For single component diffusion (e,=O, N,=O) this reduces to:
J=--.-.-
DV
(1-8)
dp
RT dz
This formulation suggests that at low loadings ( b 0 ) the corrected and tracer diffisivities
should coincide but at higher loadings D < Do except when D is very large.
These formulations are applicable only to normal systems in which diffusing
molecules can pass each other in the channels. When molecules cannot pass we have
single file or string of pearls diffusion which has entirely different features. This topic
has been well reviewed by Kiirger [9] and will not be considered here.
Experimental Methods
A summary of the major experimental techniques that have been applied to study
diffusion in microporous solids is given in Table 1. These can be classified according to
the nature of the measurement (transient or steady state), the scale of the measurement
(micro, meso or macro) and the type of process (transport or self-diffision). Additional
details with complete references are given in recent reviews [lo-121.
Most of the microscopic techniques are restricted to relatively small and rapidly
diffising species since a measurable mean molecular displacement must be achieved
within a short time. In general the microscopic techniques show reasonable consistency
with other micro techniques but, as the length scale of the measurement increases, the
apparent diffisivities decrease and show increasing discrepancies between different
techniques.
18
TABLE 1
Classification of Experimental Techniques for Diffusion Measurements
Transport Diffusion
Self-Diffusion
Transient
Steady State
Macroscopic
Methods
Membrane
permeation (14, 15)
Effectiveness factor
(18919)
Mesoscopic
Methoa3
Single crystal
membrane (14, 15)
Single crystal
membraneltracer
Microscopic
Methods
Interference microscopy
(24325)
Coherent QENS (26)
The ZLC technique [ 131 depends on measuring the desorption curve for a small sample of
adsorbent pre-equilibrated with sorbate under well defined conditions. The essentials of
the experimental system are shown in figure 1. The column consists of a very small
sample of adsorbent held between two suiter discs in a Swagelock fitting. The
desorption curve is determined by both the adsorption equilibrium and the kinetics but
these two effects can be easily separated by making measurements over a range of flow
rates. In the low flow rate regime intraparticle diffusion is relatively rapid. The
gradient of sorbate concentration through an adsorbent particle is very small and the
desorption rate is determined by convection (the rate of removal of sorbate fiom the
adsorbent surface). In contrast, at high flow rates, the concentration at the external
surface of the particle is always very small and the desorption rate is controlled by
diffusion out of the particle. Thus, by making measurements over a sufficiently wide
range of flow rates both the equilibrium and kinetic parameters may be determined.
This approach is illustrated in fig. 2 which shows a family of ZLC desorption curves
for COz fiom a sample of a carbon monolith, measured over a wide range of flow rates.
The isotherm is linear so at low flow rates (equilibrium control) the response is given by:
19
when plotted against the volume of purge (Ft) the response should be invariant with flow
rate and linear in coordinates of In (c/co) vs Ft. The slope yields the sum V,+KV,. For
strongly adsorbed species the dead volume (V3 is usually negligible but for weakly held
species (as in this example) the correction may be important. V, is conveniently
determined from a blank experiment with no adsorbent present.
The general response (treating the adsorbent as a parallel sided disk of thickness 21)
is given by:
,
-c- co
2 L e x p - P 2I
(9)
and y = VdKV,. The simplification for y + 0 is obvious. Varying the flow rate
changes L and thus provides a simple experimental test for consistency with the
isothermal d i m i o n model. The corresponding expression for spherical particles is also
available [131.
The ZLC method offers advantages of speed and simplicity and requires only a very
small adsorbent sample thus making it useful for characterization of new materials. The
basic experiment using an inert carrier (usually He) measures the limiting transport
diffusivity (Do)at low concentration. A variant of the technique using isotopically
labeled tracers (TZLC) yields the tracer diffisivity and counter diffision in a binary
system may also be studied by this method. To obtain reliable results a number of
preliminary experiments are needed, e.g. varying sample quality, nature of the purge gas,
the flow rate and, if possible, particle size to c o n f m intracrystalline diffiision control.
5
PFG NMR measurements can be applied over a wide range of diffusivities and the scale
of the measurement can be varied from a few unit cells to perhaps half the crystal or
particle diameter. For a number of systems good agreement between ZLC and PFG
NMR measurements has been demonstrated; examples are shown in fig. 3. The data for
methanol-NaX are particularly interesting as the unusual concentration trend is revealed
by both sets of data and at low concentrations the tracer diffusivities converge to the
limiting value of Do as is to be expected. Unfortunately such agreement is far 6om
universal. Figure 4 shows data for some systems for which large discrepancies are
found, both in absolute values of the diffusivities and in the concentration trends.
6
20
because of their short relaxation times and relatively low diffisivities. ZLC and
frequency response (FR) diffusivities for benzene are compared in Fig. 5. The data
show reasonable agreement as to the magnitude of the diffisivities but when trends with
loading are examined some striking discrepancies emerge. For both benzene and pxylene the TZLC data show the self-diffisivity to be almost independent of loading
whereas the FR data suggest that Dodecreases quite strongly. For benzene the ZLC data
show that tracer and corrected transport diffisivities are almost the same but for p-xylene
the transport diffisivity is smaller. For both species diffusion in ZSMS (A1 rich) is
slower than in silicalite, presumably as a result of blocking by the strong A1 sites.
The diffusional behavior of p-xylene is complicated. The FR measurements reveal
two different diffusivities corresponding to movement through the straight and sinusoidal
channels. The ZLC method increases only the average diffisivity which is similar to the
value for benzene but it is possible that the difference between the self and transport
diffisivity results from the two channel behavior revealed by the FR data [33].
The extensive diffusivity data for linear alkanes in silicalite have been recently reviewed
by Talu et a]. [151. The values obtained by several different techniques are shown in fig.
6. It is clear that for these species the discrepancies between different measurements
amount to several orders of magnitude. We have measured diffisivities for a series of
linear alkanes in several different zeolites by the ZLC technique. In all cases we see a
continuous but slow decline at higher carbon numbers with no evidence of local maxima
as shown by the membrane data. For offi-etite-erioniteour results agree well with those
of Maghalaes et al. [34] and show no evidence of the window effect originally
suggested by Gorring [35]. It should be noted that the membrane technique measures
diffusion along the long axis of the crystal whereas other methods measure an average
diffisivity. However the long axis diffisivity difisivity is expected to be lower so the
difference between membrane, FR and ZLC data is puzzling.
8
Concluding Remarks
The diffisivities predicted from molecular simulation are generally too high. For small
rapidly diffusing species the values are comparable with the highest experimental values
but for slower (larger) species the simulation values are higher than even the largest of the
experimental values. For example, it is clear from fig. 6 that the simulation results do
not capture the decreasing trend of difiivity with carbon number which is observed by
all experimental techniques.
In general the shorter range measurements yield higher diffisivity values than the
longer range measurements and this difference becomes greater for larger molecules.
The different microscopic methods commonly show fair agreement but differences
between different macroscopic measurements are often very large.
In a recent experimental study of the adsorption of methanol in a large crystal of
CrAPO by interference microscopy, Lehmann et al. [36] observed that, even at
equilibrium, the distribution of sorbate through the crystal is far from uniform. It seems
clear that access is controlled largely by the defect structure and the growth planes of the
crystal. This observation may provide a plausible explanation for the discrepancies
observed between different diffusion measurements. The impact of the defect structure
21
is minimal over short distances (a few unit cells) but becomes important as the length
scale of the measurement is increased. Furthermore, one might expect that the effect of
defects will be more severe for larger sorbates and the defect structure may differ
substantially between different samples, thus explaining the discrepancies between
different microscopic measurements.
Notation
B
c
c,
D
Do
n
intrinsic mobility
concentration (gas or fluid phase)
initial value of c
difisivity (transport)
corrected diffusivity
tracer or self-diffusivity
dimensionality of pore system
q
qs
R
t
T
D'
F
J
K
L
see Eq. 7
purge flow rate
flux (relative to adsorbent framework)
Henry's Law constant (dimensionless)
F12/KV,D - dimensionless parameter
1 half thickness of adsorbed slab
u
velocity in Maxwell Stefan
expression (Eq. 4)
Volume of gas (dead volume),
V,,V,
volume of solid
z
distance
P
parameter in Eq. 8
Y
V&V,
8
q/qs hctional loading
h
step length (random walk)
T
dimensionless time M/l2 Eq. 8;
time between molecular jumps Eq. 2
References
M. Eic and D.M. Ruthven, Zeolites 8,4045 (1988).
D.M. Ruthven and M. Eic, Amer. Chem. SOC.Symp. Ser. 368,361-375 (1988).
L.S.Darken, Trans. A.I.M.E. 175,184(1948).
J.C. Maxwell, Phil. Trans. Roy SOC.m , 4 9 - 7 9 (1866).
J. Stefan, Bet. Akad. Wissen. Wien 65,323-363 (1872).
R. Krishna, Chem. Eng. Sci.
1779 (1990).
R. Krishna, Chem. Eng. Sci. 48,845 (1993).
D. Paschek and R. Krishna, Chem. Phys. Letters, 333,278-284.
J. Ktirger, Single File Diffusion, Ch. 7 in Molecular Sieves: Science and
Technology, H.G. Karge and J. Weitkamp eds., Wiley-VCH (2002).
10. D.M. Ruthven and M. Post, Diffusion in Zeolite Molecular Sieves, Ch 12 in
Introduction to Zeolite Science and Practice, H. van Bekkum, E.M. Flanigen, P.A.
Jacobs and J.C. Jansen eds. Elsevier, Amsterdam (2001).
11. J. Ktirger and D.M. Ruthven, Diffusion and Adsorption in Porous Solids, Ch. 5 in
Molecular Sieves: Science and Technology, H.G. Karge and J. Weitkamp eds.,
Wiley-VCH (2002).
1.
2.
3.
4.
5.
6.
7.
8.
9.
a,
22
12. J. Kager and D.M. Ruthven, Di#&on in Zeolites and other Microporous Solids,
John Wiley, New York (1992).
13. D.M. Ruthven and S. Brandani in Recent A&. In Gas Sep. by Microporous Ceramic
Membranes,N.K. Kanellapoulos ed., p. 187-212 Elsevier, Amsterdam (2000).
14. D.T. Hayhurst and A. Paravar, Proc. Sixth Internat. Zeolite Con$, p. 217-224,Reno
(1 983)D. Olson and A. Bisio eds. Butterworth, Guildford (1 984).
15. O.Talu,M.S.SunandD.B.Shah,A.I.ChEJl.~,681-694(1998).
16. W. Niessen and H.G. Karge, Microporous Materials L, 1-8(1993).
17. R. Schurnacher and H.G. Karge, Microporous Materials 1,1-8(1993).
18. W.O. Haag, R.M. Lago and P.B.Weisz, Faraday Discussions Chem. SOC. 72, 317330 (1982).
19. M.F.M. Post, J. Amstel and H.W. Kouwenhoeven, Proc. Sixrh Internat. Zeolite Con$
p. 5 17-527,Reno, (1983)D. Olsson and A. Bisio eds. Butterworth, Guildford (1 984).
20. L.V.C. Rees and L. Song in Recent Advances in Gas Separationby Microporous
Ceramic Membranes p. 139-186, N.K. Kanellopoulos ed., Elsevier, Amsterdam
(2000).
21. D.D. Do, X. Xu and P.L.J. Mayfield, Gas. Sep. PuriJ 5,35-48(1991).
22. J.R. Ebner and J.T. Gleaves, U.S. Patent 4,626,412(1986).
23. J.T. Gleaves, J. R. Ebner and T.C. Kuechler, Catol. Revs. Sci. Engg. 30, 49-116
(1988).
24. U. Schemmert, J. Kiirger, C. Krause, R.A. Rakoczy and J. Weitkarnp, Europhys.
Letters 46,204-210 (1 999).
25. U. Schernrnert, J. K&ger, J. Weitkarnp, Microporous and Mesoporous Materials 32,
101-110 (1999).
26. H. Jobic in Recent Advances in Gas Separation by Microporous CeramicMembranes
p. 109-137 N.K. Kanellopoulos ed. Elsevier, Amsterdam (2000).
27. D.M. Ruthven, Zeolites 13,594(1993).
28. S. Brandani, D.M. Ruthven and J. Karger, Zeolites l5,494-496(1995).
29. S.Brandani, J.R. Hufion and D.M.Ruthven, Zeolites l5,624-631 (1995).
30. S. Brandani, Z. Xu and D.M. Ruthven, Microporous Materials 3, 2791-2798
(1 998).
3 1. S.Brandani, M. Jama and D.M. Ruthven, Microporous and Mesoporous Mats. 35-36
283-300(2000).
32. D.M. Ruthven, M. Eic and E. Richard, Zeolites ll,647-653(1991).
33. L. Song and L.V.C. Rees, Microporous and Mesoporous Materials 35-36 301-314
(2000).
34. F.D. Magalhaes, R.L. Lawrence and C.W. Conner, AIChE Jl. a,68-86(1996).
35. R.L. Gorring, J. C a t a l s , 13 (1973).
36. E. Lehmann, C. Chmelik, H. Scheidt, S. Vasenkov, B. Staudte, J. Kgrger, F. Kuemer,
G. Zadvozna and J. Kornatowski, J. Am. Chem. SOC.- in press.
23
Fig. 1.
0.1
0
0
0.01
10
12
t (9
Fig. 2.
24
:eIr
2I.,
1i
m
Y.
Fig. 4 (a) Comparisonof PFG hMR data (325K)and mcer ZLC &fa
(358IQ for propane and propene inNaX oeoiite crystals [29].
(b) Cmpakon of PFG W R , FR and mer ZLC difbivities for
bepane-wax at 468K (201.
25
1 E-07
Benzene
u)
*-
l.E-08 .
0-
+-
F R a . 1 1331
D = S . 2 6 ~lo- c--~
1.E-09
.
0 NZLCTrmsD.
0 TZLCTracera
A NZLC Richud De(1991)
1.E-10
1.9
25
2.3
2.1
2.7
2.9
3.1
33
4ooofr
Fig. 5
D or o0 i m s-
10%
109
1o-O
lo-
1010-3
10
12
14
16
18
(+)
26
INTRODUCTION
The microporous (pore diameters less than 2 nm) and mesoporous (2-50 nm) carbons are
widely used in many areas of modem science and technology, including water and air
purification, gas separation, catalysts preparation, chromatography, fuel storage, and
manufacturing of electrochemical devices [ 1,2]. The wide-spread use results from their
high specific surface areas, large pore volumes, ability for hosting catalytic components
(e.g., metal particles), chemical inertness, good mechanical stability, high electrical
conductivity, and excellent affinity with organic species. The technological importance
has led to many scientific researches on the adsorption of guest species, their diffusion
into the pore systems, and the interaction with the carbon frameworks. Many works on
experimental measurements and theoretical modeling are still being actively performed in
order to characterize accurately the adsorption phenomena as a function of the pore
diameters, shapes and pore-wall structures.
For the accurate characterization of the adsorption phenomena, it is necessary to
obtain accurate information on pore structures. However, most of ordinary microporous
carbons and mesoporous carbons are obtained with amorphous structures that are
characterized by irregular arrangements of non-uniform pores. X-ray (or electron)
diffraction (XRD) techniques are not useful for such carbons because there are no welldefined structural factors to correlate with the adsorption behavior. Moreover, porous
carbons exhibit wide varieties of the surface functional groups and the thickness of the
pore walls, depending on the details of the synthesis conditions. The lack of distinct XRD
lines makes it difficult to distinguish structural differences between samples which causes
many works to depend empiricaIly on specific samples.
27
SYNTHESIS METHOD
The principle of the carbon synthesis is shown in Fig. 1. Suitable carbon sources such as
sucrose, furfuryl alcohol, phenol-resin monomers and acetylene gas are converted to
carbon frameworks inside mesoporous silica template by pyrolysis. An effective method
for the restriction of carbonization to inside the template is to incorporate a suitable
catalyst such as Al, Sn and Fe onto the silica pore walls prior to the use as template. The
template after the carbonization is removed using ethanol-water solution of HF or NaOH.
As shown in Fig. 1, rod- or tube-type carbons are obtained depending on the synthesis
conditions. Rod-type carbons are prepared if cross-linkable carbon precursors such as
sucrose and phenol resin are carbonized after the template pores are filled with the carbon
sources [3-51. Carbon deposition outside the template can be prevented under the present
carbonization conditions using catalyst. Moreover, the carbon formation can be controlled
to occur uniformly throughout the entire volume of the template pore system. Normally,
the conversion of the organic compounds leads to a significant decrease in volume, and
this is accommodated by the generation of micropores in the carbon nano-frameworks.
The micropore volume depends on the source of carbon and the details of carbonization
conditions such as vacuum, nitrogen flow and heating rate.
28
Figure 1. Schematic representation of the templated synthesis route using mesoprous silicas.
Tube-type carbons are obtained when organic compounds are carbonized in a thinfilm state on the template pore walls 161. The tube-type carbon can be obtained even after
the entire volume of pores is filled with carbon source, if the excess carbon source is
removed before the carbonization is completed. For example, cylindrical pores are
generated along the center of the carbon frameworks due to the systematic volume
decrease when furfuryl alcohol is pyrolyzed under vacuum after the initial polymerization.
Alternatively, the tube-type carbons can be synthesized as follows: carbonization can be
controlled to occur partially by catalyst at the pore walls at moderate temperatures. The
remaining carbon source is removed by evacuation, and the carbonization is completed by
pyrolysis at high temperature. Chemical vapor deposition on the pore walls can also be
used to produce the tube-type carbon [ 111 as well as the aforementioned rod-type carbons
[12]. The structure of the resultant carbon depends on the thickness of the carbon
deposition.
3
3.1
CMK-1carbon was the first carbon material reported to exhibit well-resolved XRD lines
characteristic of ordered arrays of carbon mesopores [3]. The synthesis of the carbon was
achieved by carbonization of sucrose inside the MCM-48 mesoporous silica. As shown in
Fig. 2, the XRD pattern exhibits a new diffraction line around 1.4. compared with its
MCM-48 template. This change can be explained by the formation of two separate carbon
networks in the bicontinuously mesoporous MCM-48 template. After the separating silica
frameworks are removed, the two carbon networks join together. The joining of the two
carbon networks attributes to the symmetry change from cubic Zu3d to either 14,h or
lower [12]. The new ordered mesoporous structure is indicated by the XRD pattern and
transmission electron microscopic image shown in Fig. 2.
29
XI (deg-1
Figure 2. (a) XRD patterns for MCM-48 silica template and the CMK-1 carbon synthesized using the MCM-48
template. (b) Transmission elechon microscope image of CMK-I . (c) Scanning electron microscope image of
CMK-I .
The synthesis of carbon with MCM-48 was also reported by another research group
using phenol-formaldehyde resin, following the report on CMK-1 [ 131. However, this
carbon exhibited the same XRD pattern as CMK- 1.
As shown in Fig. 3, nitrogen adsorption isotherms of CMK-1 feature well-pronounced
capillary condensation steps similar to those of ordered mesoporous silicas and indicative
of high degree of mesopore size uniformity. The isotherms reveal that the CMK-1 carbon
has high nitrogen BET specific surface area (1500-1800 m2 g-I), and large total pore
volume (0.9-1.2 cm3 g-') [14]. The adsorption capacity is comparable or larger than that of
MCM-48 template. The pore-size analysis (calibrated BJH analysis) shows that typical
CMK-1 has uniform mesopores about 3 nm in size, which is accompanied by a certain
amount of micropores when sucrose is used as the carbon source.
30
0.0
0.2
44
0.6
48
1.0
Relativepressure
Figure 3. Nitrogen adsorption isotherm for CMK-1. (inset) Correspondingpore size distribution obtained from
adsorption branch by calibrated BJH method [14].
3.2
Other rod-type carbons with various structures have been synthesized with the SBA- 1,
SBA-15 and SBA-16 (large cage-type, cubic Im3m) mesoporous silica templates. These
carbons (designated as CMK-2 [4], CMK-3 [5] and CMK-6 [15, 161, respectively) exhibit
very similar XRD patterns to those for their silica templates, as shown in Fig. 4. This
result indicates that the structures are maintained in the same space groups during the
synthesis of the carbons from silicas, unlike the case of the CMK-1 synthesis. It is
therefore reasonable that these silica templates are composed of 3-dimensional (3-D)
mesoporous networks of the same continuity. The carbon synthesis within the mesoporous
networks of the same continuity gives the CMK-2, CMK-3 and CMK-6 mesoporous
carbons corresponding to faithful replication of the template pore systems.
It is also noteworthy that, despite the apparently same 2-D hexagonal structures, the
SBA-15 and MCM-41 silicas are distinguished by their markedly different pore
connectivity in addition to the difference in the pore diameters. The MCM-41 silica has 1D channels that are not interconnected. However, the large 1-D mesoporous channels
(typically, 9 nm in diameter) of the SBA-15 silica are interconnected through the so-called
complementary pores, which are around or less than 3.5 nm in diameters, and randomly
located perpendicular to the 1-D channels. Because of the 3-D channel structure, the
structure of the SBA-15 silica can be converted to the negative carbon replica exhibiting
the same kind of structural symmetry. Accordingly, the structure of the CMK-3 carbon is
composed of a hexagonal arrangement of 1-D carbon rods as shown by the structural
model in Fig. 4(c). On the other hand, replication of the MCM-41 silica with carbon
results in the formation of carbon fibers that do not retain the 2-D hexagonal arrangement
141.
31
Figure 4. XRD patterns for rod-type carbons: (a) CMK-2, (b) CMK-3. (c) Structural model for CMK-3.
3.3
Tube-Type Carbons
CMK-5 is the first example of the ordered tube-type mesoporous carbons that can be
characterized with well-defined Bragg diffractions by ordinary XRD instrument [6]. The
XRD pattern of the CMK-5 carbon is distinguished from that of CMK-3 by the much
lower intensity of the (100) diffraction. The structure of CMK-5 may be described by the
substitution of the carbon nanorods in CMK-3 with nanopipes. The CMK-5 carbon is
synthesized using SBA-15, similar to CMK-3, but the carbon source and synthesis
condition are somewhat different from those for CMK-3. The synthesis method for the
tube-type carbon can be extended to the SBA-16 mesoporous template. The resultant
CMK-7 carbon has a bicontinuous mesoporous structure [ 151.
It is noteworthy that the pore-size distribution curve obtained by the N2 adsorption
has exhibited two sharp peaks with the maxima corresponding to the inside diameter of
the carbon nanopipes (typically, 5.5 nm) and the pores formed between the adjacent pipes
(4.2 nm), respectively [6]. It is reported that the outside diameter of the nanopipes is
tailored by the pore diameter of the template SBA-15, while the wall thickness of the
carbon nanopipes are also controllable to a certain degree. The specific BET surface area
of the CMK-5 varies from 1500 to 2200 m2g-'depending on wall thickness [ 171.
4
PERSPECTIVES
The methods developed for the synthesis of ordered mesoporous carbons are simple and
cost-efficient, and the pore size can be tailored. The synthesis process can be scaled up for
production in bulk quantities. Recent works on the synthesis of mesoporous silicas
brought about much improvement in the cost-efficient and custom-tailored synthesis of the
templates [18]. The discovery of new mesoporous silicas is also expected to provide
additional promising templates for the synthesis of new mesoporous carbons. The
resulting high-surface-area materials with uniform pores promise to be suitable as
32
adsorbents, catalyst supports, sensors, and materials for other advanced applications.
The presence of the distinct XRD patterns provides us new opportunities for precisely
monitoring various physico-chemical phenomena that take place inside the well-defined
carbon pores or at the pore walls such as adsorption, impregnation, framework changes,
formation of metal clusters and grafted functional groups. The materials constructed with
such well defined and controllable pore diameters are suitable as standards or references
for the characterization of porosity of the carbons, similar to the already well-known case
of the MCM-41silica.
In addition to this significance, the carbon frameworks can be grafted with various
organic and organometallic functional groups on the carbon-pore walls [19]. The carbon
can be used to compose systematic nanostructures between organic polymers and carbons
[20]. In addition, there was a recent report on the synthesis of an ordered microporous
carbon using NaY zeolite [21]. This result shows possibilities to extend the templating
route to other zeolite-type carbons with various structures. Furthermore, the template
synthesis methods have been being fully advanced for the synthesis of ordered
mesoporous carbons exhibiting graphite-like atomic orders [22]. These new CMK-nG
carbons will give many new possibilities in the adsorption science and technology, in
addition to the CMK-type mesoporous carbons composed of disordered atomic
arrangement.
References
1. Bansal C. R., Donnet J.-B. and F. Stoeckli, Active carbon, (Marcel Dekker, New
York, 1988).
2. Foley H. C., Microporous Muter. 4 (1995) pp. 407-433.
3. Ryoo R., Joo S. H. and S. Jun, J. Phys. Chem. B 103 (1999) pp. 7743-7746.
4. Ryoo R., Joo S. H., Kruk M. and Jaroniec M., Adv. Muter. 13 (2001) pp. 677-671.
5. Jun S., loo S. H., Ryoo R., Kruk M., Jaroniec M., Liu Z., Ohsuna T. and Terasaki 0..
J. Am. Chem. Soc. 122 (2000) pp. 10712-10713.
6. Joo S. H., Choi S. J., Oh I., Kwak J., Liu Z., Terasaki 0. and Ryoo R., Nature 412
(2001) pp. 169-172.
7. Ryoo R., Joo S. H., Jun S., Tsubakiyama T. and Terasaki O., Stud. Surf: Sci. Cutul.
135 (2001) p. 150.
8. Kresge C. T., Leonowicz M. E., Roth W. J., Vartuli J. C. and Beck J. S., Nature 359
(1992) p. 710-712.
9. Huo Q., Margolese D. I., Ciesla U., Feng P., Gier T. E., Sieger P., Leon R., Petroff P.
M., Schuth F. and Stucky G. D., Nature 368 (1994) pp. 317-321.
10. Zhao D., Huo Q., Feng J., Chmelka B. F. and Stucky G. D., J. Am. Chem. Soc. 120
(1998) pp. 6024-6036.
11. Bang W.-H., Liang C., Sun H., Shen Z., Guan Y., Ying P. and Li C., Adv. Muter. 14
(2002) pp. 1776- 1779.
12. Kaneda M., Tsubakiyama T., Carlsson A., Sakamoto Y., Ohsuna T., Terasaki O., Joo
S. H. and Ryoo R., J. Phys. Chem. B 106 (2002) pp. 1256-1266.
13. Lee J., Yoon S., Hyeon T., Oh S. M. and Kim K. B., Chem. Commun. (1999) pp.
2177-2178.
14. Kruk M., Jaroniec M., Ryoo R. and Joo S. H., J. Phys. Chem. B 104 (2000) pp. 79607967.
15. Ryoo R. et al., manuscript in preparation.
33
34
#)Instituteof Research and Innovation, 1201 Takada, Kashiwa, Chiba 277-0861, Japan
*I Japan Science and Technologv Corporation, c/o NEC Corporation, 34 Miyukigaoka, Tsukuba
305-850 I , Japan.
+) Department of Physics, Meijo Universiv, I501 Shiogamaguchi, Tenpaku7
1. Introduction
35
sieving effect more to establish a more efficient separation technology. At the same time,
a new possibility of the molecular sieving should be challenged.
Recently nanocarbons such as single wall carbon nanotube (SWNT)[16,171 or single
wall carbon nanohorn (SWNH) have offered an important possibility for hydrogen and
methane storage [19-221. Although reliable adsorption data are not available for
previous SWNT samples[23,24], highly pure samples of SWNH is going to provide a
precise understanding of their storage potential [22]. In particular, nano-scale windows
can be donated on the wall of SWNH and thereby micropore filling in internal and
interstitial nanospaces can be clearly separated experimentally. Hence, SWNH leads to a
better understanding of adsorption properties of nanocarbons. Theoretical researches on
hydrogen storage by SWNT predicted the important contribution of quantum effect due to
the small mass of the hydrogen molecule [23-251. At the same time, these studies
suggested that the quantum effect should be taken into account in general nanoporous
systems and some experimental results on zeolites were discussed from the basis of this
quantum effect [26]. According to these theoretical studies, the zero-point vibration
cannot be negligible for a light molecule and the quantum molecule behaves as if it had a
larger size than the classical molecule. Some papers on quantum effect in nanoporous
systems were published before the above studies. Kaneko et a1 applied a simple
rectangular box model for He adsorption in slit-shaped graphitic nanospaces of ACF,
suggesting the presence of quantum excitation of translational motion of He atoms in the
motion perpendicular to the pore-walls [27]. Beenakker et a1 [28] proposed the possibility
of quantum sieving using hard spheres in a square-well cylindrical tube.
As D2 is a quite important gas in the present industry, an efficient separation of D2 fiom
H2 has been requested. If the quantum effect can be applied to the separation, a new
separation technology should be introduced. Tanaka et a1 examined the temperature
dependence of Ne adsorption on well-crystalline A1P04-5, showing the presence of an
explicit quantum effect [29]. Murata et a1 and Tanaka et al studied hydrogen adsorption on
SWNH over the wide temperature range from the boiling temperature to 303 K [30]. This
paper will review the quantum effect in micropore filling of Ne, H2, and D2 on A1P04-5,
nanocarbons, and ACF.
2. Classical DFT calculation, classical GCMC simulation and effective potential for a
quantum molecule
The molecular potential of a quantum molecule in a model SWNT is described here. For
simplicity, we assumed a homogeneous cylindrical pore for a model of open-ended
SWNT. Thus classical solid-fluid interactions can be calculated using the Lennard-Jones
(LJ) potential integrated over an infmitely long cylinder [3 I]:
2
&J4=&,E,fQsf
63 F(-4.5,-4.5,1.0;P2)
32
[R*(l-P2)]'o
-3
36
where F( a,p, y ; x ) is a hypergeometric function, R and pr are the radius of the pore
and the density of solid atoms in the pore wall (38.21m-~).The interaction parameters for
H2, ad and Gp/R are 0.3 18nm and 32.1 K, respectively.
The quantum correction to the classical potential can be calculated by Feynmans
procedure, which employs an effective potential [32,33].
where r is the vector between two particle, 1 = h2/(6mk7)and m is the molecular mass of
hydrogen isotopes. Fig. I shows the effective potentials of hydrogen H2 and deuterium D2
inside the (3,6) nanotube (d = 0.62 nm) at 20 K fiom eq. (3). There is a large difference
in effective potentials for H2 and D2.This suggests that hydrogen is easily excluded from
hydrogen isotopes mixture with the (3,6) nanotube at 20 K. Therefore, such a nanotube
with the small diameter is predicted to exhibit very large seectivity and the other porous
materials that have pores corresponding to the size of the (3,6) nanotube should be
suitable for the hydrogen isotope separation.
The Ne adsorption isotherms on model A1P04-5 micropores were calculated fkom thc
Tarazonas version of the nonlocal density functional theory [34,35] which has beer
actually applied to the study on micropore filling [36,37]. The necessary parameters werc
obtained from the adsorption isotherms of Ne on A1P04-5 at 27K and 30K in a low
pressure range.
0
37
SWNT. GCMC simulation was carried out using the established procedures. We used the
12-6 Lennard-Jones(LJ) potential for the N2-N2 interaction. The used LJ parameters for N2
are E~ I kB= 95.2 K and = 0.375 nm. As to H2, -1 kB= 36.7 K and aff= 0.2959 nm
were used. The classical solid-fluid interactions given by eq. I were used for the
simulation. We used an established technique of the repeated cell determined by the
triangular and square arrays of SWNHs [7,9,38 - 401. The thickness of the graphene wall
was assumed to be 0.34 nm.
A1Po4-5 has one- dimensional pores of wider and narrower parts whose widths are
1.137 and 1.002 nm, respectively. Also well-crystalline samples are available to provide
reliable experimental data. The framework of A1Po4-5 consists of alternate tetrahedral
aluminum and phosphorous atoms bridged by oxygen atoms and thus is electricallyneutral.
The pores of AIP04-5 are not interconnected and form one-dimensional channels parallel
to the crystallographic c -axis [42].
The adsorption isotherms were calculated using DFT based on the classical potential
for narrower pore (radius R of structure = 0.501nm: AP-50) and the average size pore
models (R = 0.5347nm: AP-53). The adsorption increased steeply below P/Po = lo4,
being almost saturated above P/Po =
The higher the measuring temperature, the
larger the rising PIPo. The DFT isotherms for both models are completely different from
each other. AP-53 model gives the two-step isotherm, whereas AP-50 model leads to the
single step isotherm which coincides with the experimental one, as shown in Fig.2.
Although the average pore model of AP-53 is expected to be fit for description of the
experimental result, the narrower pore model of AP-50 is better after the correction of the
pore volume by Ar adsorption.
The most probable cause for this marked discrepancy from the prediction is the
quantum effect. The quantum effects are included by replacing parameters E and 0 in V,,
with temperature and A-dependent parameters E and d (where A = h/a(m&).)).The
parameters E and d can be estimated by Feynmans effective potential method. For
quantum neon pairs, the location of the minimum of the effective potential is shifted to
26d and the value at the minimum to 4,and the quantum contributions are dla=
1.014 and &I& = 0.947 at 27 K, respectively. Therefore, the quantum effect decreases the
fluid-fluid interaction. That is, quantum Ne can behave as if they had a bigger size and the
38
39
lo*
10-10
lo4
106
10-2
lo0
PRO
Fig. 3. Experimental adsorption isotherm of N2 on SWNH at 77 K (0)and simulated isotherms
of N2on three models at 77 K: triangular array (+ symbols); square array (0);
adsorption on
the external surface of an isolated model ( A ) .
04
03
.-
02
c
a.
b
v1
0
U
01
n- 10-17
10-6
lo-*
10-11
10-9
10-7
10
10-3
10-1
P/ Po
20
15
W
.-0
10
71
rl
0.2
0.4
0.6
0.8
7. Acknowledgement
This work was funded by Nanocarbon project from the New Energy and Industrial
Technology Development Organization of Japan.
41
References
(2002).
42
43
A. L. MYERS
Department of'Chemical and Biomolecular Engineering
University of Pennsylvania, Philadelphia PA 19104 USA
E-mail: amyers@seas.upenn.edu
Existing analytical equations for Type I isotherms such as the Langmuir equation and
its modifications fail to describe experimental adsorption isotherms at high pressure.
All of these equations predict that the amount adsorbed increases monotonically with
increasing pressure. Experimental adsorption isotherms attain a maximum value in the
amount adsorbed and then fall to zero. At the critical temperature of the gas, the
maximum in the isotherm occurs at a pressure of about 10 bars and the zero occurs at a
much higher pressure of several hundred bars. For subcritical gases, the maximum occurs
at lower pressure and for supercritical gases the maximum occurs at higher pressure.
The observed behavior of high-pressure adsorption isotherms can be predicted from the
low-pressure (subatmospheric) portion by separating the Type I behavior expected for
absolute adsorption from the experimental behavior observed for excess adsorption.
Introduction
Tabulated data for experimental adsorption isotherms are fitted with analytical equations
for the calculation of thermodynamic properties by integration or differentiation. These
thermodynamic properties expressed as a function of temperature, pressure, and composition
are input to process simulators of adsorption columns. In addition, analytical equations for
isotherms are useful for interpolation and cautious extrapolation. Obviously, it is desirable
that the isotherm equations agree with experiment within the estimated experimental error.
The same points apply to theoretical isotherms obtained by molecular simulation, with the
requirement that the analytical equations should fit the isotherms within the estimated
statistical error of the molecular simulation.
Type I isotherms [3]are characterized by an asymptotic approach to a saturation capacity
with increasing pressure. This class of isotherms is most commonly observed for gases or
vapors (water is an exception) adsorbed in zeolites or activated carbon. A typical set of
Type I adsorption isotherms is shown in Fig. 1. Several questions may be asked about sets
of isotherms like these. How is the saturation capacity measured? Is the saturation capacity
a constant or does it decrease with temperature as suggested by Fig. l?
Variation of the pressure P with respect to temperature T at constant loading n is given
by the equation [l]:
IE
nI-[
-E
where is the differential enthalpy of desorption (isosteric heat). This derivative of the
adsorption isotherms in Fig. 1 along a horizontal line becomes ambiguous at high loading
(n).The differential enthalpy for this system measured by a calorimeter is plotted on Fig. 2.
44
For type I1 isotherms with multilayer adsorption, the differential enthalpy for the second and
higher layers approaches the enthalpy of condensation of the liquid. Does the differential
30 C
20 c
70 C
g3
8
-E2
1
0
0.2
0.6
0.4
0.8
1.o
Pressure (bar)
Fig. 1. Adsorption isotherms of C,& on NaX zeolite. The 2OoC isotherm
was measured experimentally [4]. The other two isotherms were calculated
from Eq. (1) using the differential enthalpies in Fig. 2.
45
35
0
45
Adsorption isotherms
where H is the Henry constant, m is the saturation capacity, and the Ci are virial coefficients
terminated after three or four terms, which are usually sufficient to fit adsorption isotherms
over several decades of pressure. Unlike most adsorption equations, this equation is implicit
in the pressure. This disadvantage is more than offset by the direct connection between the
differential enthalpy and the temperature dependence of the virial coefficients. The main
advantage of this equation is that it can be integrated analytically for the grand potential
(spreading pressure), which is needed for mixture calculations as shown in this mixture
section of this paper.
Experimental measurements yield excess adsorption; molecular simulations calculate absolute adsorption. The relationship between the two variables is given by:
ne = n - V,p
(3)
V, is the specific pore volume of the material; typical values are 200-400 cm3/kg for zeolites
and up to 1000 cm3/kg for activated carbon. n is the actual number of molecules contained
in the micropores; the excess adsorption ne subtracts from n the number of molecules which
would have been present in the micropores at the bulk density in the absence of adsorption.
The (oversimplified) case when absolute adsorption is described by the Langmuir equation
and the gas obeys the perfect gas law ( p = P / R T ) has been worked out in detail for the
isotherms and thermodynamic functions (enthalpy, entropy, etc.) [2].
The key step in this development is the recognition that a Type I adsorption equation like
Eq. (1) applies to absolute adsorption n. Absolute adsorption refers to the actual number
of molecules present in the micropores and increases monotonically with pressure to an
asymptote called the saturation capacity m. Experimental excess adsorption isotherms pass
through a maximum and then decrease with pressure.
The adsorption isotherms in Fig. 1 may be considered absolute adsorption as a function
of gas-phase fugacity f of ethylene. For P < 1 bar, the term V,p in Eq. (3) is negligible
compared to n. Therefore a fit of these isotherms with Eq. (1) using constants reported
previously [4] provides the absolute amount adsorbed n ( f ) . Given an equation for the
absolute isotherm and the pore volume of faujasite (340 cm3/kg), one can calculate the
excess isotherms at high pressure. Taking the fugacity f as an independent variable, the bulk
properties of gaseous ethylene derived from the SRK equation [5] were used to determine
the pressure P and density p = P / ( z R T ) , where z is the bulk compressibility factor of
gaseous ethylene. The excess functions for three temperatures are plotted on Fig. 3. For
subatmospheric pressure, the values of absolute and excess adsorption coincide. At higher
pressure, the absolute adsorption approaches a saturation value (4.534 mol/kg) while the
excess adsorption passes through a maximum and eventually decreases to negative values at
pressures above 100 bar. The isotherm for -30 C terminates at the dew point of ethylene
vapor, 19.4 bar. The maximum excess adsorption decreases with temperature. At the
pressure where the isotherms intersect, the temperature coefficient of adsorption is zero.
Above this pressure, excess adsorption increases with pressure.
The maximum in the excess adsorption isotherm occurs at the point where the densities
in the micropore and the bulk gas are increasing at the same rate with respect to pressure, so
46
that an increase in pressure has no effect upon the amount adsorbed. Zero excess adsorption
occurs at the pressure where the bulk and micropores densities are equal. Since the pore
density at saturation is p = m/% = (4.534/340)= 0.0133 mol/cm3, zero excess adsorption
corresponds to the same value for the bulk density of ethylene. The pressures corresponding
to this bulk density are 175 and 345 bar at 20C and 70"C, respectively. The density of
0.0133 mol/cm3 inside the micropores is 1.7 times the critical density or 0.7 of the liquid
density of ethylene at its normal boiling point (-110C). It is interesting that the micropore
volume may be calculated from the bulk density at which excess adsorption is zero using
V, = m/p.
5
0.1
0 . m 1 o.oO01
0.001
0.01
0.1
.o
10
100
500
Pressure (bar)
Fig. 3. Adsorption isotherms of CzH4 on NaX.The -30C isotherm terminates at the dewpoint of ethylene vapor (19.4 bar)
The absolute adsorption isotherms for -30C and 70C were calculated from the 20C
isotherm using the integrated form of Eq. (1) and the differential enthalpy plotted on Fig. 2.
The reasonable approximation was made that the differential enthalpy is independent of
temperature. No other assumptions were needed to calculate the excess adsorption isotherms
on Fig. 3.
Examination of Fig. 1 answers the questions raised in the introduction about the determination of the saturation capacity. The saturation capacity for absolute adsorption cannot
be extracted from supercritical isotherms measured at sub-atmospheric pressure such as the
70C isotherm. Raising the pressure would bring the isotherm into the region where the difference between absolute and excess adsorption is no longer negligible. The Henry constant
(the slope of the adsorption isotherm at the limit of zero pressure) is difficult to extract from
sub-critical isotherms such as the -30C isotherm because the linear region occurs at very
low pressure. The optimum temperature for the determination of both the Henry constant
and the saturation capacity is near the critical temperature of the gas (9C for ethylene),
which is the 20C isotherm on Fig. 1.
47
3 Gas Mixtures
The principles of phase.equilibrium do not apply to excess adsorption variables at high
pressure where the excess adsorption passes through a maximum. Under these conditions,
the pressure is no longer a singlevalued function of excess adsorption so that ne cannot serve
as an independent variable for the determination of partial molar quantities such as activity
coefficients. Additional complications which arise at high pressure are: (1) the selectivity
for excess adsorption (S1,= (n:/v1)/(n;/~z)) approaches infinity BS $ + 0; and (2) the
differential enthalpy of the ith component has a singularity at the pressure corresponding to
maximum nt. For excess variables, the differential functions are undefined but the integral
functions for enthalpy and entropy are smooth and well-behaved [l].
The principles of solution thermodynamics can be applied to absolute adsorption variables without any of these complications. For absolute variables, which arise naturally in
molecular simulation, the pressure is a singlevalued function of n, the differential functions
exhibit no singularities, and the selectivity approaches a finite value as P ---t 00. Absolute
adsorption may be determined experimentally by measuring excess adsorption in the usual
way (volumetric or gravimetric method) at sub-atmospheric pressure where the difference
between absolute and excess adsorption is negligible.
The fugacity equations are solved using absolute variables. As discussed previously, the
single-gas isotherms at sub-atmospheric pressure provide the absolute isotherm in the form
f;(np). Given the temperature of the isotherms, the independent variables are P and y1 in
the bulk gas. For a binary mixture the fugacity equations are written:
The fugacity fi = Pyi&(P, yi) is determined from an equation of state (EOS) for the pure
bulk gas. The adsorbed-phase activity coefficients are functions of the grand potential (Q)
and composition, where $ = -R/RT. The form of Eq. (2) allows the grand potential to be
calculated analytically [4]:
The standard-state properties are measured at equal values of the grand potential:
$l(n;) = $z(%)
(7)
Given a bulk EOS to determine the fugacity functions and noting that ( q + z z ) = (y1+yz) =
1, the three Eqs. (4), (5), and (7) can be solved for the three unknowns: ni, n:, and 21.
Following methods described previously 141, the absolute total (n)and individual amounts
adsorbed (nl,nz) are calculated from the standard-state values n;l and ni. Finally, using
an EOS to determine the bulk density p(P,yl), the absolute variables are converted to
experimental excess variables by [l]:
nt = ni - V , p y i
(8)
Excess isotherms are shown on Figure 4 for binary mixtures of ethylene and ethane
adsorbed on NaX. Both curves are for 20C and a vapor composition of 10 mole percent ethylene. The individual excess isotherm for ethylene is the difference between two isotherms.
Ethylene is preferentially adsorbed and the individual isotherm for ethane reaches a maximum at a pressure of 3 bar. The individual isotherms show the same behavior as the
singlegas isotherms shown on Figure 3: a maximum value in the amount adsorbed followed
by a steep decline to zero.
5
total
C2H6
0.1
0 .001
0.01
0.1
lo
30
Pressure (bar)
Fig. 4. Adsorption of mixtures of C&
and c2H6 on NaX at 20 C for
10 mole % ethylene in gas phase. The individual isotherm for CzH4 is the
difference between the total and the individual isotherm piotted for C2H6.
The solid lines on Figure 4 take into account the nonideal behavior of adsorbed mixtures
of ethylene and ethane in NaX. This system is highly nonideal because of the interaction of
the quadrupole moment of ethylene with the sodium cations of NaX. Activity coefficients at
iniinite dilution are unity at the limit of zero pressure and 0.27 at high pressure. The dashed
lines on Figure 4 were calculated for an ideal adsorbed solution (IAS) and the resulting error
in the individual isotherm for ethane at 30 bar is 20%.
Discussion
The high pressure adsorption of single gases and mixtures can be predicted from the low
pressure (subatmospheric) data for the same systems. The optimum temperature for measuring the adsorption of single gases is near their critical temperature where both the Henrys
constant and the absolute saturation capacity can be determined accurately.
The absolute adsorption isotherm as a function of gas-phase fugacity is obtained directly
from molecular simulations based on the grand canonical Monte Carlo (GCMC) method.
Since the difference between absolute and excess adsorption is negligible at subatmospheric
pressure, the low-pressure portion of the absolute isotherm can also be determined from
experiment. Eq. (2) is suitable for extrapolating the absolute isotherm from low to high
pressure and Eq. (3) provides the conversion to excess adsorption. Experiments are needed
to test these predictions of adsorption at high pressure.
49
References
[l] Myers, A. L., A.I.Ch.E. J., 2002,48, 145.
[2] Myers, A. L., and Monson, P. A., Adsorption in porous materials at high pressure:
Theory and experiment, Langmuir, 2002,in press.
[3] Ruthven, D.M.,Principles of Adsorption and Adsorption Processes, Wiley Interscience,
New York, 1982.
(41 Siperstein, F.R. and A.L. Myers, A.I.Ch.E. J., 2001,47, 1141.
[5] Smith, J. M., Van Ness, H.C., and Abbott, M.M., Introduction to Chemical Engineering
Themodynamics, 6th Edition, McGraw-Hill, New York, 2001.
Introduction
Removal of sulfur-containing compounds is an important operation in petroleum refining,
and is achieved by catalytic processes at elevated temperatures and pressures [I]. The
hydrodesulhkation (HDS) process is highly efficient in removing thiols and sulfides, but
less effective for thiophenes and thiophene derivatives. New legislation will require
substantial reductions in the sulfur content of transportation fuels. For example, the new
US.EPA s u l k standards require that the sulfur contents in gasoline and diesel fuels for
on-board transportation will be 30 and 15 ppm, respectively, decreased fiom the current
levels of several hundred ppm. Faced with the severely high costs of compliance, a
surprisingnumber of refiners are seriously considering reducing or eliminating production
of on-board fuels [2]. The new challenge is to use adsorption to selectively remove these
sulfur compounds from liquid fuels. Since adsorption would be accomplished at ambient
temperature and pressure, success in this development would lead to a major advance in
petroleum refming. However, success would depend on the development of a highly
selective sorbent with a high sulfur capacity, because the commercial sorbents are not
desirable for this application. First results on sorbents based on n-complexation for
desulfurization have been reported recently by Yang et al. [3,4] which were shown to be
superior to all previously reported sorbents.
During the last decade, there have been several published accounts on using
adsorption for liquid fuel desulfurization. Commercially available sorbents (i.e., zeolites,
activated carbon and activated alumina) were used in all of these studies. Weitkamp et al.
51
[5]reported that thiophene adsorbed more selectively than benzene on ZSM-5 zeolite.
Based on this study, King et al. [6]studied selective adsorption of thiophene, methyl- and
dimethyl-thiophenes (all with one ring) over toluene and pxylene, also using ZSM-5.
They showed that thiophene was more selectively adsorbed, both based on fixed bed
breakthrough experiments. However, the capacities for thiophene were low (only 1-2%
wt. adsorbed at 1% thiophene concentration). Both vapor phase and liquid phase
breakthrough experiments were done in these studies, and the results from two phases
were consistent. The pore dimensions of ZSM-5 are 5.2-5.6A. Hence organic sulfur
compounds with more than one ring will be sterically hindered or excluded. Zeolites with
larger pores, as well as larger pore volumes, will be more desirable than ZSM-5 as the
selective sorbents. Indeed, results of Salem and Hamid [7]indicated that 13X zeolite as
well as activated carbon had much higher sorption capacities for s u l k compounds.
Based on the data of Salem and Hamid [7],the capacity for sulfur compounds by 13X
zeolite was approximately an order of magnitude higher than that of ZSM-5, when
compared with the data of King et al. [6]extrapolated to the same conditions. Modified
activated alumina (Alcoa Selexsorb), which contains proprietary modifier to provide
optimum adsorption of a number of polar organic compounds, has been used in an
adsorption process by Irvine [8].No direct comparison has been made among these
commercial sorbents. Their experiments were mostly done in fixed bed adsorbers, by
measuring the breakthrough capacities. Based on the literature, the large pores zeolites
(NaX or Nay) are about the same as activated carbon and alumina, in terms of adsorption
of thiophene.
Based on the principles of n-complexation, we have already developed a number of
new sorbents for a number of applications. These include sorbents for: (a)
olefdparaffm separations [9- 121,(b) diene/olefm separation or purification (i.e., removal
of trace amounts of dienes fiom olefins) [ 131,and (c) aromatics/aliphatics separation and
purification (i.e., removal of trace amounts of aromatics fiom aliphatics [141.Throughout
this work, we have used molecular orbital calculations to obtain a basic understanding for
the bonding between the sorbates and sorbent surfaces, and further, to develop a
methodology for predicting and designing n-complexation sorbents for targeted molecules
(e.g. Ref. 11).
First results on n-complexation sorbents for desulfurization with Ag-Y and Cu(1)-Y
zeolites have been reported recently [3,4]. In this work, we included the known
commercial sorbents such as Na-Y, Na-ZSM5, H-USY, activated carbon and activated
alumina (Alcoa Selexsorb) and made a direct comparison with Cu(1)-Y and Ag-Y which
were the sorbents with n-complexation capability. Thiophene and benzene vapors were
used as the model system for desulfiuization. Although most of these studies can be
applied directly to liquid phase problems, Cu-Y (auto-reduced) and Ag-Y zeolites were
also used to separate liquid mixtures of thiophenehenzene, thiopheneh-octane, and
thiophenehenzene/n-octane at room temperature and atmospheric pressure using
fixed-bed adsorptiodbreakthrough techniques. These mixtures were chosen to understand
the adsorption behavior of s u l k compounds present in hydrocarbon liquid mixtures and
to study the performance of the adsorbents in the desulfurization of transportation fuels.
Moreover, a technique for regeneration of the adsorbents was developed in this study [4].
52
Experimental
Adsorbent Preparation
Various kinds of sorbents were investigated in this work. Four as-received sorbents:
Na-type Y-zeolite (Si/A1=2.43, Strem Chemical), H-type ultra-stable Y-zeolite (Si/AI=l95,
TOSOH Corporation), activated carbon (Type PCB, Calgon Carbon Corporation) and
modified activated alumina (Selexsorb CDX, Alcoa Industrial Chemical), were used in
this study. According to the product datasheets, Selexsorb CDX is formulated for
adsorption of sulfur-based molecules, nitrogen-based molecules, and oxygenated
hydrocarbon molecules. Na-Y and H-USY were in powder form (binderless). Since
activated carbon was in granular form and activated alumina was in pellet form, they were
crushed into powder form for evaluation.
Cu(1)-Y was prepared by ion exchange of Na-Y zeolites with Cu(NO3)Z followed by
reduction of Cu2' to Cu'. First, as-received Na-Y was exchanged twice using excess
amounts (10-fold cation-exchange-capacity(CEC) assuming that one Cu" compensates
two aluminum sites) of 0.5 M Cu(NO& at room temperature for 24 hours. After the
exchange, the zeolite suspension was filtered and washed with copious amount of
de-ionized water. The product was dried at 100 "C overnight. Several groups have
reported reduction of Cu" to Cu' in zeolite in He (i.e., auto-reduction). In this study,
reduction of Cu2' to Cu' was carried out in He only at 450 "C for periods in the 1 to 18
hours range. Ag' ion-exchange Y-zeolite (Ag-Y) was prepared at room temperature for 24
h in the same manner as Cu" exchange, using 5-fold excess AgN03 (O.1M). 13X
(Si/Al=1.25, Linde) was used for the preparation of Cu-X (10 fold CEC solution of
Cu(NO&, ion-exchanged at 65 "C for 24 hrs, three times) and Ag-X (5-fold CEC solution
of AgN03, ion-exchanged at RT for 24 hrs, twice). Na-type ZSM-5 (Na-ZSM-5) was
prepared at room temperature by Na'-exchange of Nh-ZSM-5 (Si/Al=lO, ALSI-PENTA
Zeolite GmbH).
Vapor Phase Isotherms and Heat of Adsorption
The objective of this study is to compare the strength of adsorptive interaction between
adsorbents and thiophenehenzene. Extremely low partial pressures at less than l o 5 atm
would be necessary to meet this objective if isotherms were measured at ambient
temperature, because the isotherms at ambient temperature are fairly flat and are difficult
to compare. However, it is very difficult to obtain and control such low partial pressures
experimentally. Therefore, single component isotherms for benzene and thiophene were
measured at 90, 120 and 180 "C using standard gravimetric methods. A Shimadzu
TGA-50 automatic recording microbalance was employed. Isosteric heats of adsorption
were calculated using the Clausius-Clapeyron equation from isotherms at different
temperatures.
Fired Bed A&orptiodBreakthrough Experiments
53
sorbent at a rate of 0.5 cm3/min.After wetting the adsorbent for about 30 minutes, the feed
was changed to a mixture of CgHI8(n-octane) and/or c6H6 (benzene) containing different
concentrationsof C4H4S(thiophene) also at a 0.5 cm3/minrate. Samples were collected at
regular intervals until saturation was achieved, which .depended on the adsorption
dynamics and amount of adsorbent.
All the samples collected during the breakthrough experiments were analyzed using a
Shimadzu GC (Gas Chromatography) unit equipped with a polar column, an automatic
multi-sampler, and a FID detector. The minimum thiophene concentration detection was
around 10 ppmw or 4 ppmw on a sulfur basis.
Molecular Orbital Computational Details
Molecular orbital (MO) studies on the n-complexation bonding for benzene and sorbent
surfaces had been investigated recently [3]. In this work, similar MO studies were
extended to thiophene and zeolites. The Gaussian 94 Program [ 151 in Cerius2 molecular
modeling software [161fiom Molecular Simulation, Inc. was used for all calculations. MO
calculations for thiophene and sorbent surfaces were performed at the Hartree-Fock (HF)
and density functional theory (DFT) level using effective core potentials (ECPs) [17-191.
The LanL2DZ basis set [20] is a double-t; basis set containing ECP representations of
electrons near the nuclei for post-third-row atoms. The reliability of this basis set has been
confirmed by the accuracy of calculation results as compared with experimental data.
Therefore, the LanL2DZ basis set was employed for both geometry optimization and
natural bond orbital (NBO) analysis.
The restricted Hartree-Fock (RHF) theory at the LanL2DZ level basis set was used to
determine the geometries and the bonding energies of thiophene on AgCl and CuCI. The
simplest models with only a single metal chloride interacting with a thiophene molecule
were chosen for n-complexation studies. The optimized structures were then used for
bond energy calculations according to the following expression:
Eads = Eadsorbate -k Eadsorbent - Eadsorbent-adsorbate
where
is the total energy of thiophene, Eadsorbent
is the total energy of the bare
adsorbent i.e. the metal chloride and Ea~~t-adsorb.te
is the total energy of the
adsorbate/adsorbentsystem. A higher value of Endscorresponds to a stronger adsorption.
The optimized structures were also used for NBO analysis at the B3LYP/LanL2DZ level.
The B3LYP [21] approach is one of the most useful self-consistent hybrid (SCH)
approaches [22], it is Becks 3-parameter nonlocal exchange functional[23] with nonlocal
correlation functional of Lee, Yang and Parr [24]. The NBO analysis performs population
analysis that pertains to localized wave-function properties. It gives a better description of
the electron distribution in compounds of high ionic character, such as those containing
metal atoms [25]. It is known to be sensitive for calculating localized weak interactions,
such as charge transfer, hydrogen bonding and weak chemisorption. Therefore, the NBO
program [26] was used for studying the electron density distribution of the adsorption
system.
54
The zeolite models selected for this study are similar to the ones used by Chen and Yang
[33], with the molecular formula of (HO)3Si- 0 -A1(OH)3, and the cation Ag' or Cu'
sits 2 - 3 A above the bridging Oxygen between Si and Al. This is a good cluster model
representing the chemistry of a univalent cation bonded on site I1 (SII) of the faujasite
framework (Z). Once the optimized structures of AgZ and CuZ are obtained at the
B3LYPLanL2DZ level, then a molecule of thiophene (C4&S) or benzene (C6&) is
added onto the cation of the zeolite model, and the resulting structure is hrther optimized
at the B3LYPLanL2DZ level.
55
1
1.5
._.-
4.0
3.5
3.0
2.5
2.0
1.o
1.5
1.o
0.5
0.0
1.E45
--
1.E.M
1.E-
1. E m
l.E-01
(-1
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
1.E.05
1.E.M
1.E1.E-02
PuUd Pmsun(um)
1.E-01
l.wE.05
1.wE.M
l.wE.03
1.oQE42
l.wE-01
P N W Raun(am)
Heat of Adsorption
Heats of adsorption were calculated using the Clausius-Clapeyron equation fkom
isotherms at two different temperatures, and are shown in Table 1. All the heats of
thiophenehnzene adsorption had the tendency to decease as the loading increased. This
is a common phenomenon for the sorbents such as ion-exchanged zeolites that have
heterogeneous sites. The heats of adsorption on activated carbon, in particular, ranged
widely fkom 23.9 kcaYmol (at OSmmoVg loading) to 8.0 kcaYmol (at 3mmoVg). Ag-Y
and Cu(1)-Y exhibited the higher heats of adsorption than Na-Y for both benzene and
thiophene because of .rr-complexation. More importantly, the heats of adsorption for
thiophene were higher than that of benzene. These experimental results can be explained
by molecular orbital calculation and NBO analysis, which will be discussed shortly.
At the low loading of 0.5 mmoVg, Na-ZSM-5 showed nearly the same heats of
adsorption as Na-Y for both thiophene and benzene. The different pore dimensions
A for ZSM-5 vs. 7.4 A for Na-Y) apparently had no influence on the heats of
adsorption. It is not clear why the amounts adsorbed on Na-Y decreased sharply at very
low pressures while that on Na-ZSM-5 maintained.
(5.2-5.6
Ag-Y
Cu-Y
BUSY
Na-ZSM5 ActivuedC.rbon
T y ~ PCB
e
Selcxsorb CDX
8.0-23.9
16.1-17.5
Thiophc~c 19.1-19.6
21.3-21.5
20.8-22.4
7.9-11.2
(0.5-2.0)
(1.5-1.7)
(2.0-3.0)
(0.1-0.3) (0.45-0.60)
(0.5-3.0)
(0.2-1.O)
17.0-18.2
19.0-20.1
19.3-21.8
6.6-13.1
16.5-17.9
13.1-16.1
16.8-19.6
(1.5-2.0)
(1.5-1.8)
(1.8-2.5)
(0.1-0.9
(0.45-0.65)
(1.0-3.0)
(0.6-1.0)
Benzea~
18.6-19.2
AaivakdALumi~
57
Table 2. Summary of energies of adsorption for thiophene and benzene in kcaUmol calculated
from molecular orbital theory (Z denotesZeolite anion)
E,,(Thiophene)
E,,(Benzene)
CUCl
13.5
12.4
9.0
8.6
AgCl
21.4
20.5
CUZ
A@
20.0
19.1
Table 3. Summary of NBO analysis* of n-complexationbetween thiophene and MCVMZ
C+M interaction
(adonation)
M+C interaction
(d x'backdonation)
Mx
91
CUCl
AgCl
CUZ
0.037
0.022
0.112
-0.022
-0.014
-0.063
0.101
-0.086
A@
~
~~
Net Change
91+e
0.015
0.008
0.049
0.015
~~
~~
* q I is the amount of electron population change in valence s orbitals of the metal, and e is the
total amount of electron populationdecrease in valence d orbitals of the metal.
Figures 5 and 6 show breakthrough curves obtained for 2000 ppmw thiophene (760
ppmw s u l k basis), for n-octane as solvent (the breakthrough curve for Cu(1)-Y is shown
in a separate figure for clarity since the abscissas are quite different). All adsorbents
showed remarkable selectivity towards C41&S, indicating that CgHIg adsorption is not
competitive. Saturation adsorption capacities calculated from the breakthrough curves
were 1.05 and 0.90 mmoVg for Na-Y and Ag-Y, respectively. However, for Na-Y, the
breakthrough of thiophene molecules occurred earlier, at about 2.84 cm3/g compared to
22.50 cm3/g in Ag-Y. This was evidence of weak adsorbate-adsorbent interactions on
Na-Y, which did not have the ability for n-complexation as in the case of Ag-Y. This
agrees very well with the pure vapor phase adsorption data reported above. The saturation
adsorption amount in Na-Y was higher than that Ag-Y due to pore volume differences and
difference in the densities of zeolites.
For the same feed conditions described above, Cu(1)-Y showed again the highest
selectivity and capacities among the adsorbents studied. The saturation capacity was 2.55
mmoVg, which was more than twice the amount found for the other adsorbents, indicating
superior interaction with the thiophene molecules. For about 2 grams of Cu(I>Y, it took
more than 300 minutes for the thiophene molecules to break through the adsorbent at a
feed rate of 0.5 cm3/min (refer to figure 6). Saturation was reached after 600 minutes,
which was remarkable for such a small amount of adsorbent. A large amount of Cu2+ions
must have been reduced to Cu'. As mentioned earlier, Takahashi et al. and others [14]
have reported 50% auto-reduction of copper under helium/vacuum atmospheres after just
1-2 hours. The adsorbent used in this part of the work was exposed to helium at 450'C for
no less than 18 hours. Possibly longer activation time increased the amount of reduced
copper ions, while the adsorption behavior already indicates that the auto-reduction
process yields promising results.
58
Figure 7 shows breakthrough curves for Cu(1)-Y for an influent containing 500 ppmw
thiophene (190 ppmw sulfur> in n-octane. The saturation capacity was reduced to 1.28
mmoVg, which was about 50% of the amount obtained previously with the 2000 ppmw
thiophene feed. This indicates that the equilibrium adsorption isotherm was not
"rectangular" in shape at low concentrations and rather showed a noticeable decrease in
adsorbed amount as one decreased the concentration. Despite this, the observed saturated
amount was not low, when taking into account that the thiophene concentration was 75%
less than the case discussed previously (i.e., 2000 ppmw).
Figure 7 also shows breakthrough curves after Cu(1)-Y adsorbent regeneration
(second cycles). Under an atmosphere of nitrogen at 350'C, the regenerated adsorbent did
not recover the original capacity. The new capacity for the adsorbent at saturation was
0.80 mmoVg, which was more than a 30% reduction fkom the original capacity. In fact, the
color of the adsorbent remained black, which indicated the presence of copper thiophene
complexes. Meanwhile, regeneration under air at 350'C followed by reactivation under
helium at 450'C recovered almost all of the original capacity. For this case, the observed
saturation capacity was about 1.20 mmoVg, which was only a 5% reduction from the
original capacity.
1
0.8
0"
"
0.2
0
0
10
20
30
40
50
60
70
cmVg (cumdative efauent volumdsorbentweight)
0.4
o
0.2
o
0
50 100 150 200 250 300 350 400
cmVg (cumdative d u e n t vohmdsorben~weight
(a)
o
0
5 0 1 0 0 1 5 0 # ) 0 2 5 0
weight)
For the final part of this study, it was desired to use mixtures with compositions
similar to that of transportation fuels. Gasoline contains about 20-30 wtoh aromatics, many
thiophenic compounds and 70-80% alkanes such as n-hexane and n-octane. The aromatic
contents in diesel and jet fuels are < 20%. Thus, a mixture containing 20 wt% benzene, 80
wt% n-octane, and 200 ppmw sulfiu (ca. 500 ppmw thiophene) was used to simulate
gasoline. Figure 8 shows a breakthrough curve for thiophene in such mixture after
adsorption at room temperature on Cu(1)-Y. The sulfur adsorption capacity was 0.44
mmoVg or about 1.4 wt% sulfur. The results are promising when compared to other
adsorbents used in previous studies. Ma et al. studied fixed-bed adsorption of thiophene
compounds fiom diesel and jet fuels using an undisclosed transition metal compound ( 5
wt% loading) supported in silica gel [28,29]. They obtained a saturation adsorption
capacity of 0.015 g of sulfur per cm3 of adsorbent which can be compared directly to our
results. Assuming that the density of the Cu(1)-Y is close to that of Na-Y (- 1.3 g/cm3),
which is lower than the actual value because sodium is lighter than copper, then the
observed saturation capacity in our case is approximately 0.018 g of sulfur per cm3 of
adsorbent. Ma et al. also showed that breakthrough occurs at about 20 cm3 effluent
volume for about 3.2 cm3 of the metal loaded silica gel compared to 30 cm3 effluent
volume for about 0.75 cm3 volume of Cu(1)-Y. Therefore, our adsorbent is capable of
processing more fuel with very low sulfur streams with less adsorbent material. It should
be mentioned that jet fuel and other fuels contain heavier thiophene compounds such as
benzothiophenes, dimethylthiophenes, and dimethylbenzothiophenes and these should
adsorb strongly in Cu(1)-Y. Breakthrough results on gasoline and other transportation
fuels will be published elsewhere shortly.
Conclusions
In this work, vapor-phase benzene/thiophene adsorption isotherms were investigated to
develop new sorbents for desulfurization. Among the sorbents studied, Cu(I>Y and Ag-Y
exhibited excellent adsorption performance (capacities and separation factors) for
desulfurization. This enhanced performance compared to Na-Y was due to the
x-complexation of thiophene with Cu' and Ag'. Molecular orbital calculations confirmed
the relative strengths of n-complexation: thiophene > benzene and Cu' > Ag'.
This work has also demonstrated that copper (auto-reduced) and silver exchanged
Y-type zeolites are excellent adsorbents for removal of thiophene tiom aromatic and/or
hydrocarbon mixtures, based on fixed-bed adsorption experiments. Both adsorbents were
capable of reducing sulfur content to values < 4 ppmw sulfur for long periods of time.
Cu(I>Y provided the best adsorption capacity both at breakthrough point and at saturation,
surpassing all other adsorbents by more than 50%. Regeneration of the copper based
adsorbents can be accomplished in air at 35072 which recovered almost all of the original
adsorption capacity. More studies will be needed in order to fully understand the effect of
copper loading and to include heavier thiophenes, which are abundant in liquid fuels.
Breakthrough results on gasoline and other transportation fuels will be published
elsewhere shortly.
Acknowledgements
Supports from NSF and DOE are acknowledged. A U.S. Patent is pending filed with U.S.
and foreign Patent Offices.
References
1. Farrauto, R. J.; Bartholomew, C . H.
2.
3.
4.
5.
1991,1133.
6. King, D. L; Faz,C.; Flynn, T. Desulfurization of Gasoline Feedstocks for Application
Patent 5,730,860(1998).
61
62
28. Ma, X.; Sun, L.; Yin, Z.; Song, C. New Approaches to Deep DesulfUrization of
Diesel Fuel, Jet Fuel, and Gasoline by Adsorption for Ultra-Clean Fuels and for Fuel
Cell Applications. Am. Chem. SOC.Div. Fuel. Chem. Prepr. 2001,46,648.
29. Ma, X.; Sprague, M.; Sun, L.; Song, C. Deep Desulfurization of Liquid
Hydrocarbons by Selective Adsorption for Fuel Cell Applications. Am. Chem. Sac.
Div. Pet. Chem. Prepr. 2002,47,48.
63
M.MAZzOTrI
ETH Zurich ,Institut f i r Verfarenstechnik, Sonneggstrasse3, CH-8092 Zurich, Switzerland
E-mail: manotti@ivuk mavt.ethz.ch
Two recent developments of the simulated moving bed chromatographic separation units, i.e. the
Varicol and the PowerFeed processes, are addressed. The performances of these three processes are
compared with reference to two chiral separation systems taken from literature, using a multiple
objective optimization technique based on a genetic algorithm. The performance of each process has
been optimized in a wide range of operating conditions, and from their comparison a good assessment
of their relative potential has been made. The optimization results have been discussed in the frame of
equilibrium theory and the N I ~ S of optimal design of the Varicol and PowerFeed processes have beem
discussed.
Introduction
64
changing within the switching period the flow rates, of the solid and the fluid, respectively.
In this sense, as mentioned above, they do not try to better approximate the TMB unit from
which the SMB is derived.
t ----
SMB
Powdd
sectiw 2, Q
Figure 1. (a) Operating diagram of a four section SMB unit; (b) Fluid flow rates schemes in the SMB and
PowerFeed operations during one switching period, t,
In this paper, we present and compare the optimal performances of the SMB,Varicol
and PowerFeed operations, using a multiobjective optimization technique, on two chiral
separation systems from the literature. The aim is to provide a clear picture, although
inevitably confined to the cases examined, of the relative potentials of these three operation
modes.
2
Optimization of the SMB,Varicol and PowerFeed processes is very complex due to the
large amount of continuous and discrete parameters involved. These parameters include
fluid flow rates, switching time, unit configuration (total number of columns, column
distributionand column dimension), feed conditions, size of the packing particles and so on.
These parameters might have different values in the subintervals of one switching period in
the Varicol and PowerFeed operations. Depending upon the specific application, the best
process performance may be achieved by maximizing the product quality (mostly in terms
of the purity of either extract or raftinate stream or both) under fixed cost and productivity,
or by minimizing the cost and at the same time maximiig the productivity under some
given specification on product quality, or by other combinations of practical interest. Note
that in most cases, two of the objective hctions to be optimized are conflicting, as for
example: productivity increases if the unit operates at higher system fluid flow rates which,
however, imply a decrease in column efficiency, and therefore in the product purities.
Furthermore, various practical constraints on the column or entire unit pressure drop,
switching time, pump flow rates and product quality etc. complicate the optimization
problem.
In our earlier works [6,7],we have developed a new optimizationprocedure based on a
genetic algorithm, i.e. the non-dominated sorting genetic algorithm (NSGA), that allows to
handle these complex optimization problems. A more detailed description of this global
search and Optimizationtechnique is available elsewhere [18, 191.
65
3
3.1
An important aspect in comparing SMB and Varicol processes is the effect of the total
number of columns, Ned.It is in hct expected that as N,, increases, the discretizationof the
movement of the solid in the SMB improves and thereforethe main advantage of Varicol, i.e.
the possibility of better tuning the distribution of the columns in the sections by using non
integer values, becomes less effective. We consider in this work a single objective
optimization problem using as a model system the chiral separation reported by Biressi et al.
[3], aiming at investigating the effect of NW1on the performance of these two processes,
according to the following statement of the optimization problem:
XI
Maximize
Subject to
J = PE[QI,
ml, m2, m4,
P R 2 90% and APdt 5 70 bar
-8
where the extract purity, PE is the objective to be maximized under the following
constraints: minimum 90% raffiate purity, PR,maximum 70 bar pressure drop along the
entire unit, Munit,
given total solid volume, Vlolid,given production rate (i.e. faed feed flow
rate, F and total feed concentration, C,) and given packing particle diameter, d,. Having
fixed also the column cross section a,changes in NCdimply changes in column length. The
optimization variables are the flow rate in section 1, Q1,the flow rate ratios, ml,m2 and m4
[2], and the unit configuration represented by the parameter, x. For the SMB this can be
represented in the form of n1/n2/n3/n4where njrepresents the number of columns in section
j. For the Varicol operation the decision variables are the same, but now x can attain a much
larger number of values, which is in fact determined by the number of subintervals
considered in each switching interval. Thus for example, the complete configuration of a
4-subinterval Varicol unit with NC.l=5 can be described by the configuration sequence
2/1/1/1-1/2/1/1- 1/1/2/1-1/1/1/2 fiom the first subinterval to the last.
The equilibrium stage model reported by Zhang et al. [7], which accounts for the
influence of fluid flow rate on the column efficiency, has been used for the optimization
simulations.
The optimization results for a SMB and a 3-subinterval Varicol unit are compared in
Table 1 for various values of NWI.
Table 1. Optimization results of SMB and Varicol processes for various values ofNml
Process
I
I
I
SMB
varicol
N
,
,L
Qi
rnl
rnz
mc
(crn)
(mumin)
4
5
6
7
8
4
30
24
20
17.14
15
30
30.328
30.747
35.126
34.735
36.595
29.502
1.550
1.567
1.512
1.584
1.643
1.747
0.867
0.843
0.900
0.888
0.900
0.837
0.754
0.738
0.594
0.525
0.444
0.680
24
35.761
1.538
0.895
0.663
011~11-012/111-1111111;** 1/1/2/1-112/111-1/2/1/1
66
m
u
n
t
i
PR
PE
1/1/1/1
1/2/1/1
1/2/2/1
1/3/2/1
1/3/3/1
(barj
52.79
52.14
60.47
57.86
59.86
48.40
%
90.02
90.00
90.07
90.02
90.06
90.01
%
86.49
91.68
96.04
97.13
97.29
91.55
61.81
90.00
94.22
*
**
It is seen that PEincreases with increasing number of columns, particularly at the lower
values of N d . PEincreases in fact by almost 10%from 86.5% for Nc0,=4to 96.0% for NcOl=6.
A further increase in total number of columns has a smaller influence on PE.In addition,
from a practical point of view, it is worth noting that the short switching time values caused
by the short column lengths may lead to difficulties in the operation of the recycle pump.
With respect to column configuration x, the results in Table 1 indicate that all the additional
columns tend to distribute equally between sections 2 and 3. This is because, once the lower
bound on ml and the upper bound on m4 are satisfied, sections 2 and 3 are the most
important in determining PEand PR.The mivalues in Table 1 indicate that indeed in the
cases under examinationboth such constraints are satisfied. In Table 1 the performances of
a 3-subinterval Varicol with 4 and 5 columns are also shown. It is seen that Varicol
For Nco1>5, the
outperforms SMB both for NCoI=4,and to a lower extent, for NeoI=5.
optimization technique has not been able to find a Varicol configuration which improves PE
over the corresponding SMB value. This means that, as expected, for increasing total
number of columns, the Varicol configuration is not worthwhile anymore.
It is worth noting that in the case of N,,=4, the following five possible configurations
have been considered for Varicol: 0/1/2/1, 0/2/1/1, 1/2/1/0, 1/1/2/0 and l/l/l/l. The first
four of such configurationshave only three sections, which actually were not considered in
the cases where NmI>4.The configuration 0/1/2/1~0~/1/1-1/1/1/1
was found to be optimal
for the 3-subinterval Varicol, which improves PEby about 5% over the corresponding SMB
with a 1/1/1/1 configuration. It is interesting to note that in the first two subintervals there is
no column in section 1; the fourth column moves in fact from section 3 in the first
subinterval to section 2 in the second and eventually to section 1 in the last subinterval. This
corresponds to the time averaged configuration 0.33/1.33/1.33/1, which compared to the
configuration 1/1/1/1 ofthe SMB, indicates that in this particular case Varicol improves the
performance of the separation by reducing the length of section I and increasing that of
sections 2 and 3.
3.2
Another situation of interest in applications is one where the product purities are fixed, and
the objectives for optimal process operation are to reduce operating costs and increase
production. Hence, in this case, for a fixed target product purity of both extract and raffiate
streams, we seek the optimal process parameters for a SMB and a 4-subinterval Varicol unit,
which maximize production using minimum amount of eluent, for another chiral separation
system taken fiom literature [6,15]. The optimization problem is represented
mathematically as follows:
Max
Min
Subject to
J I = F CQz, F, D,t XI
Jz = D [Q2, F, D,4, XI
PE= x f 0.002, x = 0.90,0.95,0.99
P R = Xf0.002,~=0.90,0.95,0.99
Q1= 27.5 mYmin, NWI
= 5 , Lcol= 0.1 m, NNTP=80
where Q1,the column flow rate in section 1, is set at 27.5 ml/min to fix the maximum column
pressure drop, and the total solid used is also set by fixing total number of columns, NmIand
column length, L,I. The decision variables are the column flow rate in section 2, Q2, feed
flow rate, F,eluent flow rate, D, switching time, t, and column configuration parameter, x.
Note that the two variables F and D appear also in the objective functions. The Pareto
67
optimal solutionsare shown in Figure 2 for purity requirementsfor both extract and rafiinate
streams of 90%, 95% and 99%.
P. and PI
= M%
PrandPm=SB%
.....................................................
.......................................................
....................................................
...................................................
....
................................
...................
2.3
2.4
2.5
2.8
C. r U m b
2.7
1.5
2.0
1.8
.T
............ ........
.o..............
0
2.2
5.8
1.7
1.8
F, mVhlln
vuisol
5.4
0.4
1.9
0.8
F, mumln
0.8
1.2
Figure 2. Optimal solutions for the SMB and Varicol processes with 9004 95% and 99% purity requirements.
In all cases, using 5 columns, the optimal column configurationsare found to be 1/2/1/1
and 1/1/1/2-1/1/2/1-1/1/2/1-1/2/1/1
for the SMB and 4-subinterval Varicol unit,
respectively. It can be observed that for fixed purity specifications, both the SMB and the
Varicol processes require to increase the eluent consumption in order to increase the feed
flow rate. Secondly, the Varicol process consumes less eluent, D than the SMB process for
the same feed flow rate, F;or equivalentlyfor the same eluent consumption, D,the Varicol
process can treat more feed, F.However, the extent of improvementdepends on the purity
specifications. The more stringent the purity requirement, the larger the improvement
achieved by Varicol over SMB. For example, at D = 5.6 mymin, the improvement in
production rate, F of Varicol over SMB is lo%, 25% and 127% for a purity requirement
both in the extract and in the d m a t e streams of 90%, 95% and 99%, respectively. Finally,
it is seen fkom Figure 3 (for the case of purity requirement of 95%)
42
4.2
VIriCol
4 ..............................................................
SYB
4 .............. ............ 0............ ?..........................
~
3.8 .............................................................
. e
em
3.8 .......................................................
3.6 ............................................................
.......................................................
E 3.4 .............................................................
A
A
A
3 2 ......................................................................
1.5
1.8
3 ............x............
2.8
g............0...........................
........................................................
1.8
F, mllmln
1.0
...... . . ~.....
~L
d ..... ....
3 ................... I......
x.............x .....x ..... x... r ......
1
1.7
*---.
....
32
....
3.4
2.8
A
1.5
1.8
1.7
1.8
F. mllmln
1.9
Figure 3. Flowate ratio parameters ml to nu for the SMB and Varicol processes with 95%purity requirement.
that the optimal values of the flow rate ratios in sections 2 and 3, m2 and m3, in the SMB and
in the Varicol process are very similar (although the corresponding optimal performances
are different) and change very little as the feed flow rate increases. This is consistent with
the triangle theory, which indicates that the optimal operating point in the (mz, m3) plane is
independent of the feed and eluent flow rates [1,2].
68
3.3
The separation problem examined in this case requires the simultaneous maximization of
the rafiate (PR)and the extract purity (PE)for a given feed flow rate, F,eluent flow rate, D
and fixed configuration of the unit, for the same chiral separation considered in section 3.2.
This optimization problem in the case of PowerFeed operation can be represented
mathematically as follows:
Max
MaX
Subject to
Fs-I,DI,*-,b - 1 , t XI
Fs-I,Di,--, Dsi, 4, XI
P E 90%
~
Q1=27.5ml/min, N,I=~ or 6, D,,=6.24 ml/min, Fa,, NNTp
where Q2s, Fi and DI represent the flow rate of section 2, the feed flow rate and the eluent
flow rate in the P subinterval,respectively. The average feed and eluent flowrates (Fave and
Dave respectively) are fixed; therefore the flow rates in the last subinterval are not
independent since they are determined by the corresponding values in the previous
subintervals. Note that in this case it has been assumed that the flowrates Q2, F, D and
consequently Q3, Q4,R and E, change in S subintervals. The problem can be simplified by
changing in time less flow streams, e.g., only F,which implies the change of Q3 and R.It is
to be noted that in the problem above both the SMB and the Varicol operation modes have
three decision variables, i.e. Qz,t,and x. The same stage in series model described by Zhang
et al. [6]has been adopted to simulate SMB, Varicol and PowerFeedprocesses, with a slight
revision, which enables the column flowrates to change in time.
A comparison of the SMB, Varicol and PowerFeed operations has been conducted for
two sets of operatingconditions, one with FBve=1.62ml/min and NNTP=80and the other with
F,,,=2.2 ml/min and Nm=60. Two different PowerFeed configurations, one varying F in 4
subintervals ( S 4 ) and the other varying Q2,F and D in 3 subintervals(S=3), are considered
for the two cases, respectively. In the first configurationthe decision variables reduce to Q2,
, ~ JF1,
, F2, DI, D2, t, and x. The
FlyF2, F3, t,and x, while in the second they are Qz,,, Q ~ J Q
optimization results of a 5-column PowerFeed unit are compared to those of the
corresponding SMB and Varicol units in Figure 4(a) and 4(b) for the two sets of operating
conditions, respectively. It is interesting to observe that firstly, in both cases for the SMB,
Varicol and PowerFeed units,we obtained Pareto solutions. Secondly, each Pareto has at
least one discontinuity due to change in column configuration x. This is due to the fact that
different purity requirement requires different column configuration. Thirdly, the 5-column
Varicol and PowerFeed processes perform better than the corresponding 5-column S M B
process. Finally, as the difficulty of the separation increases, as shown in Figure 4(b), the
PowerFeed performs better than the Varicol, and is even comparable to the 6-column S M B
at the two ends of the Pareto curve.
A better understanding of these results can be achieved by reasoning in terms of the
flowrate ratio parameter, m as shown in Figure 5, taking as an example the separation case
shown in Figure 4(a). It can be observed from Figure 5(a) that m2 and m3for the 5-column
SMB, Varicol and PowerFeed units are almost constant, although they tend to decreases
slightly as PRincreases. This is in agreementwith triangle theory as discussedby Bang et al.
[6].For the 5-column PowerFeed unit, the m3 values changing in time are shown in Figure
5(b). It is interestingto note that the m3of the SMB process, goes very closely to the average
m3 of the PowerFeed process, m3ave and to a slightly less degree to the m3of the Varicol
69
process due to the column configurationchange of the Varicol operation, as shown in Figure
5(a). Therefore, the optimal design of the Varicol and PowerFeed processes can be replaced
by the optimal design of the corresponding SMB process given by the equilibrium theory,
followed by the search of the optimal ports switching and flow rates variation schemes
within the switching period, respectively.
0.99
--"
0.98
-.
0.87
..
OD=-
O O O
0.98
0.96 --
0.96
2" 0.95 -.
0.94 -.
0.83
0.94
-.
0.92 -.
0.92
0.91 -.
0.94
0.9
0.91
0.92
0.93
0.94
;
0.85
,i
0.97
0.88
0.99
0%
0.9
I
1
0.9
0.82
0.94
0.96
0.98
PR
PRI'
Figure 4. Optimal solutionsfor the SMB, Varicol and PowerFeedprocesses (x changes with increasing PR:5-col
SMB and PowerFeed: (a) and (b) 1/2/111-+1/1/2/1; 6-column SMB: (a) 1/212/1+211/2/1, (b) 1/2/2/1; 5-col
Varicol: (a) 111/~1-111/2/1-112/1/1-1/2/111+1/1/211-1/1/2/1-1/1/211-1~/1/1~1/112/1-1/11211-1/11211-2111111,
(b) 1~11211-112/1~1-1/2/111+1/1/2/1-1/1/211-1/2/1/1).
3.8
3.9
3.6
3.5
"
3.7
3.7
'
3.5
E 3.3
E" 3.4
(.3.1
3.3
2.8
3.2
A SMB, m3
2.7
AVarkol n0
Varkol nQ
SMB,nQ
rFvwerFeed.ave tr3
FuwerFeed, nQ
3.1
2.5
0.8
0.91
0.92
0.93
0.94
0.95
0.88
0.97
0.88
0.99
0.9
PR
PR
Figure 5. Comparison of (a) the average m 2 and m3 among the 5-column SMB, the Varicol and the PowerFeed
processes and (b) Values of m3 in the 4 subintervals of the PowerFeed process corresponding to the points in
Figure 4(a).
Conclusions
Our results show that the Varicol and the PowerFeed operations improve the performance of
the SMB process, particularlywhen the total number of columns is small and the separations
are difficult. The optimal design of the Varicol and PowerFeed processes can be replaced by
the optimal design of the corresponding SMB process given by the equilibrium theory,
followed by the search of the optimal ports switching and flow rates variation schemes
within the switching period, respectively.
70
References
1. Storti G., Mazzotti M., Morbidelli M. and Carra S., Robust design of binary
countercurrent adsorption separation processes, AICHE J. 39 (1993) pp. 471-492.
2. Mazzotti M., Storti G. and Morbidelli M., Optimal operation of simulated moving bed
units for nonlinear chromatographic separations, J. Chromafogr. A 769 (1997) pp.
3-24.
3. Biressi G.,Ludemann-HombourgerO., Mazzotti M., Nicoud R.M. and Morbidelli M.,
Design and optimization of a simulated moving bed unit: role of deviations from
equilibrium theory, J. Chromatogr. A 876 (2000)pp. 3-15.
4. Klatt K.U., Hanisch F. and Dunnebier G., Model-based control of a simulated moving
bed chromatographic process for the separation of hctose and glucose, J. Process
Contr. 12 (2002) pp. 203-219.
5. Ruthven D.M. and Ching C.B., Counter-current and simulated counter-current
adsorption separation processes, Chem. Eng. Sci. 44 (1989) pp. 1011 1038.
6. Zhang Z., Hidajat K., Ray A.K. and Morbidelli M., Multiobjective optimization of
simulated moving bed system and Varicol process for chiral separation, AZChE J.
(2002) in press.
7. Zhang Z., Mazzotti M. and Morbidelli M., Multiobjective optimization of SMB and
Varicol processes using genetic algorithm,J. Chromafogr.A (2002) in press.
8. Mazzotti M., Storti G.and Morbidelli M., Supercritical fluid simulated moving bed
chromatography,J. Chromafogr.A 786 (1997) pp. 309-320.
9. Di Giovanni O., Mazzotti M., Morbidelli M., Denet F., Hauck W. and Nicoud, R.M.,
Supercritical fluid simulated moving bed Chromatography 11. Langmuir isotherm, J.
Chromafogr.A 919 (2001) pp. 1-12.
10. Denet F., Hauck W., Nicoud R.M., Di Giovanni O., Mazzotti M., Jaubert J.N. and
Morbidelli M., Enantioseparation through supercritical fluid simulated moving bed
(SF-SMB) chromatography,Ind. Eng. Chem. Res. 40 (2001) pp. 4603-4609.
11. Migliorini C., Wendlinger M., Mazzotti M. and Morbidelli M., Temperature gradient
operation of a simulated moving bed unit, Ind. Eng. Chem. Res. 40 (2001) pp.
2606-2617.
12. Jensen T.B., Reijns T.G.P.,Billiet H.A.H. and van der Wielen L.A.M., Novel
simulated moving-bed method for reduced solvent consumption, J. Chromafogr.A 873
(2000) pp. 149-162.
13. Antos D.and Seidel-MorgensternA., Application of gradients in the simulated moving
bed process, Chem. Eng. Sci. 56 (2001) pp. 6667-6682.
14. Abel S., Mazzotti M. and Morbidelli M., Solvent gradient operation of simulated
moving beds I. Linear isotherm, J. Chromafogr.A 944 (2002) pp. 23-29.
15. Ludemann-Hombourger O., Nicoud RM. and Bailly M., The Varicol process: a new
multicolumn continuous chromatographic process, Sep. Sci. Technol. 35 (2000) pp.
1829-1862.
16. Kloppenburg E. and Gilles E.D., A new concept for operating simulated moving-bed
processes, Chem. Eng. Technol. 22 (1999) pp. 8 13-817.
17. Zang Y. and Wankat P.C., SMB operation strategy-Partial feed, Znd. Eng. Chem. Res.
41 (2002) pp. 2504-25 1 1.
18. Bhaskar V., Gupta S.K. and Ray A.K., Applications of multi-objective optimization in
chemical engineering,Rev. Chem. Eng. 16 (2000) pp. 1-54.
19. Srinivas N. and Deb K., Multiobjective function optimization using nondominated
sorting genetic algorithms, Evol. Compuf.2 (1 995) pp. 22 1-248.
71
'lut R val
Trace Organicand inorganic Impurity Removal
hDrYing
Air PollutionControl
Nuclear Waste Management
Solvent Vapor Recovery
Electronic Gas Purification
Air Separation (4
and NZfrom Air)
Hydrogen and Carbon Dioxide Roduaion from
Steam-Methane Reformer W G a s
Roduction of Ammonia SynthesisGas
Hydrogen Recovery fromRefinery off Gases
Methane-CarbonDioxide w o n from Landfill Gas
Carbon Monoxide-HydrogenSeparation
N o d Isoparaffn Scparahon
Alcohol Dehydration
rn
The interest and growth in the research and development of adsorptive separation
processes have been phenomenal. Table 2 lists the number of U.S. patents cited by the
Derwent Chemical Patent index between the years of 1980 and 2000 under the keywords
given in the table [I]:
Table 2. Results of U.S. Patent Search Between 1980 and 2000
Kevwords
Gas Separation by Adsorption
Adsorption for Air Pollution
Ressun swing Adsorption
Temperature Swing A m t i o n
NumberofP@nts
3050
1164
608
60
m r d s
Air Separation by PSA
Hydrogen Purification by PSA
Gas Drying of PSA
391
185
32
Gas adsorption has become the state-of-the-art technology for (a) trace impurity removal,
(b) small to large scale (1 40,000 SCFH) gas drying, (c) small to medium scale (0.0 1-1 00
TPD) production of O2 (90+%) and N2 (99+%) from air, and (d) small to large scale
72
The points discussed above can be demonstrated by the case of simultaneous production
of O2 and N2 enriched gases from ambient air. Air can be fractionated by selectively
(thermodynamic) adsorbing N2 over O2 and Ar on a zeolite [3], or selectively (kinetic)
adsorbing O2over N2 and Ar on a molecular sieve carbon [4,5].
Furthermore, many different process schemes for air separation can be developed using
different zeolites and molecular sieve carbons having different adsorptive properties.
For example, a zeolite like Na-mordenite having a moderate N2 selectivity of -4 over O2
at ambient conditions can be used in a four-step PSA process [3]. The cyclic steps
would include (a) adsorption of N2at near ambient conditions by flowing air through a
packed bed of the zeolite, while producing the O2enriched product gas at feed air pressure
(PA),(b) rinsing the adsorber cocurrently with a stream of essentially pure N2 and venting
the air-like effluent, (c) evacuating the adsorber counter-currently to pressure PD and
withdrawing a N2 rich product gas, a part of which is used in step (b), and finally (d)
counter-currently pressurizing the adsorber from PD to PA with a part of product gas
generated by step (a).
The N2 rinse step is needed to displace the co-adsorbed and the void 0 2 remaining in the
column at the end of step (a) so that the desorbed gas in step (c) is essentially pure N2.
This step can be eliminated if the N2 selectivity over O2by the zeolite is high (say >8) as
in the case of CaX zeolite. The desorbed gas, in this case, can be hctionated in order to
73
reject the N2lean earlier part, and collect the N2rich latter part as the N2product gas [3].
Higher Nz selectivity of an adsorbent allows the desorbed gas fractionation concept to be
practical, which leads to a simpler three-step process scheme, while meeting the product
specificationsof the former four-step cycle.
The cyclic steps of one of the PSA processes using the molecular sieve carbon as the
adsorbent consist of (a) flowing compressed air through a packed bed of the carbon so that
0 2 can diffuse and adsorb into the carbon pores faster than N2and Ar and produce a N2
rich product gas at feed air pressure (PA), (b) pressure equalizing the adsorber with a
companion adsorber, (c) counter-currently depressuring the adsorber to near ambient
pressure to produce the O2 enriched gas, (d) pressure equalizing with another adsorber,
and finally (e) repressurizingthe adsorber to PAwith feed air [4].
Table 3 shows an example of the comparative performances of these three processes. All
of them can produce a 99+%N2enriched product gas. The two zeolite processes also
produce a 85-90% O2 enriched product gas. The O2 product purity of the carbon sieve
process is, however, low. This shows that different adsorbents can be married with
different process schemes to obtain similar product purities but different process
performances (recovery, productivity, product pressure, etc.).
Table 3. ComparativePerformancesof Various Air Fractionation Processes
Process
(a)
(b)
(c)
Process
(a)
(b)
(c)
Adsorbent
Na-Mordenite
Ca-X
Carbon Molecular Sieve
Adsorbent
Na-Mordenite
Ca-X
Carbon Molecular Sieve
Purity
(%)
84. I
90.0
33.8
Purity
99.0
99.0
99.0
Productivity
(SCfh/P)
31
20
144
Productivity
122
83
92
Recovery
(W
Pressure
(Psi@
63.0
24.0
98.1
2
2
0
Recovery
Pressure
65.0
30.0
49.4
0
0
104
Two areas of development have attracted considerable attention in recent years. They are:
(a) Rapid PSA cycles for bulk gas separation
(b) Novel adsorbet designs
RaDid PSA
The concept is to use faster cycle times (seconds) than those used by the conventional
PSA cycles (minutes) in order to obtain a step change in the productivity of the process
(volume of productholume of adsorbenthour). Some of these designs use a
conventional PSA cycle but they are operated faster by appropriate changes in the
mechanical designs [6]. Others, propose novel process schemes in order to
accommodate fast cycle times [7-91. An example of the second case is a RPSA process
for air separation where a single adsorber vessel is packed with two or more (even
numbers) shallow layers of small zeolite particles (-0.5 mm). The layers are separated
74
by screens which act as pressure drop devices. The cycle steps consist of (a)
simultaneouslypressurizing and adsorbing N2from air on one layer of the adsorbent while
producing an O2 enriched product gas, and then (b) simultaneously depressurizing and
back purging the layer with a part of the O2 enriched product gas produced by a
companion layer [9].
Using a 5A zeolite as adsorbent and a total cycle time of 10 seconds (compared to
conventional PSA cycles of 60-240 seconds), the RPSA process could produce a 27.5%
O2enriched gas stream with an O2recovery of -64.1% from feed air at a pressure of 2.22
atm [3]. The 0
2 productivity rate was -2300 sfi?/ft3/hrwhich was an order of magnitude
higher than that of a conventional PSA. The process was found to be suitable for
producing 2340% 02 from air for enhanced combustion applications in cupolas,
metallurgical furnaces, etc. [lo].
Novel Designs
Conventional adsorber designs include vertical (length/diameter >1) or horizontal
(lengtlddiarneter 4)packed beds. The maximum permissible gas flow rates through
these vessels is governed by pressure drop and the possibility of local fluidization and
channeling [ 1 13. Some of these problems are solved by novel designs such as (a) radial
bed and (b) rotary bed adsorbers.
Radial Bed Adsorbers (PSA and TSA)
The adsorbent is placed in an annular section between two co-axial cylinders. The walls
of the cylinders are perforated for gas flow in a radial direction. The entire assembly is
enclosed inside the adsorber vessel with gas inlet and outlet conduits. Many different
designs are patented [ll-131. The adsorbers allow faster cycle times, lower pressure
drops, and higher gas throughputs without fluidization. However, the equipment design
is more complex and costly.
75
Gas Components
C3H8
c3H6
CZH6
c
2
H
4
CH4
Hz
Commnent Reiections
SSF
PTMSP
98.2
86.0
98.8
86.0
94.1
76.0
93.3
72.0
52.0
46.0
40.0
40.0
76
Feed
1-
Press. (psia)
Feed
Purge Steam
Hydrogen Product
26.2
0.60
1.88
0.25
H2 (9'0
cH4 (YO
94.4
5.6
40
Methane Conv.
CO m
Not detected
77
-125 Psia, (b) co-current C02 rinse at that pressure with recycle of effluent gas as feed,
(c) counter-current evacuation to 2.5 Psia with simultaneous steam purge, and (d)
counter-current pressurization with a part of C02depleted product gas from step (a). The
effluent gas from step (c) is partly used as the purge gas in step (b) after recompression,
and the balance is withdrawn as the recovered C02 product gas. The inert gas and COZ
recoveries from the feed gas are, respectively, 100 and 78% [21]. This application may
be attractive for green house gas emission control (C02sequestration from a hot flue gas
or C02 removal fkom combustion gases for power generation).
REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
78
Introduction
In the past few decades, membrane technologies have emerged as an important means of
separation in a variety of industries. Membrane separation technology offers the
advantages of, at least, high selectivity, low energy consumption, moderate cost to
performance ratio, and compact and modular design in comparison with other separation
processes. In addition, inorganic membranes such as ceramic and carbon membranes
possess characteristics of high thermal stability, chemical compatibility, and good
mechanical strength over membranes made of organic polymers. It is therefore that
inorganic membranes have come into wide use in the water/ wastewater treatment
industries. However, fouling/cake generation problem is one of the challenges for the
membrane separation technology.
The particles, colloids, macromolecules or
bio-materials in the water permeation process will deposit on the membrane surface and
79
generated secondary film. As a result, membrane will be blocked and permeate flux will
diminish with time [l-31.
We report two types of membrane namely, carbon whisker membrane (CWM) and
carbon-coated ceramic membrane. The CVD method and iron catalysts were used to
fabricate a layer of carbon whiskers grown on the surface of the tubular ceramic
membrane. This novel membrane is called carbon whisker membrane (CWM). We
demonstrate the formation of the CWMs with various whisker sizes and membrane pore
size as well as their performance on the filtration process using PMMA particles. A
comparison of cleaning process with conventional membranes will also be discussed.
Carbon coated ceramic membrane were also fabricated by CVD method. By controlling
experimental factors such as concentration of carbon source, pyrolysis temperature or
deposition time, we demonstrate that it is possible to adjust the thickness of the carbon
thin film so that the pore size of the membrane can be regulated. It is therefore that the
membranes can be used for microfiltration, ultrafiltration or even nanofiltration. Figure
1 shows the cross-section of the different type of the membrane. Figure 1(A) is ceramic
membrane made by sintered granular ceramics. We used this ceramic membrane as a
substrate for fabrication of C W M or carbon-coated ceramic membrane. Figure 1(B) is
activated carbon membrane. The membrane is made by spin dipping & coating of a
layer of carbon source on the surface of the ceramic membrane. By thermal activation
process, a layer of porous and activation carbon thin film can be formed. Figure 1(C) is
carbon-coated ceramic membrane fabricated by CVD method. Clearly, the membrane is
80
different fiom activated carbon membrane. Figure 1(D) is the carbon whisker membrane
(CWM).
(C) Carbon-Coated
Ceramic Membrane
Cerami; Substrate/
Membrane
CarbonFilm
Ceramic
Substrate
Carbon Whisker
Carbon L,ayer
CeramidSubstrate
Carbon
Film
Ceramic
Substrate
Figure 1 Cross-sections of (A) Ceramic Substrate, (B) Activated Carbon Membrane, (C) Carbon-Coated
ceramic Membrane, and (D) Carbon Whisker Membrane
Experimental
To grow carbon whiskers on the membranes, we employed our recipes fkom the previous
studies [5, 6]. We used methane as carbon source to make carbon whiskers and nitrogen
as carrier and diluting gases. Femc sulhte was employed as catalyst precursor to make
Fe catalysts. The recipes offer a cost-effective production and safe process. The
experiments were carried out with a tubular quartz reactor and a furnace. A porous
ceramic tube from Kubota Co., Japan was firstly coated with aqueous ferric sulfate
solution using dipping & coating technique and then dried at room temperature overnight
prior to be suspended in the center of the reactor. A designed pipe line allowed to reverse
feed flow in the tubular reactor was employed for the fabrication. The temperature was
then ramp up to 1000C with nitrogen as a purging gas to form Fe catalyst particles fiom
the precursor. After the temperature reaches the steady state, methane was then introduced
into the reactor and started to pyrolysis and deposition. In order to ensure a consistent
carbon deposition profile for a uniform layer of carbon whiskers, the direction of the feed
flow was reversed periodically after a desired deposition time. The CWM can be
therefore fabricated.
Filtrations for CWM were carried out with a cross flow membrane separation system. It
consists of a cross flow membrane module, a feed pump, a recirculation pump and process
pipes. The feed steam contained 1000 ppm PMMA with a mean particle size of 0.8
81
3
3.I
Figure 2 shows the top-view and side-view of the CWMs under the observation of SEM.
As can be seen, the whiskers were grown on the substrate randomly to form a network
structure on the surface of the membrane. The results show that the diameter of carbon
whisker is about 100 nanometers and the thickness of the carbon whisker film is about 2
micrometers. However, the diameter, density and layer thickness of carbon whiskers is
strongly dependant of experimental conditions such as deposition time, deposition
temperature, concentration of methane, feed flow rate and catalyst concentration.
Different experimental or operational conditions will change the characters of CWMs.
Figure 3 shows the CWMs with different size of carbon whiskers. In three CWMs, the
one on the top has a thickest and longest carbon whisker layer but smallest pore size of
membrane. The diameter of visible carbon whiskers is about a few minimeters while the
length is about 1-2 centimeter. It was known that, if the size of carbon whiskers
increases, the pore size of the membrane decrease. This is because that, while the CVD
of methane is in process, carbon species not only deposited on the catalyst particle to grow
carbon whiskers but also deposited on the surface of the substrate to form a carbon film on
the substrate. As the deposition time increased, diameter and length of carbon whisker
increase and the carbon film thicken, which causes the decrease of the pore size of the
membrane. The middle CWMs has carbon whiskers which vaguely can be seen. The
diameter of whiskers is in micrometer scale while the length can reach to a few minimeters.
The last CWM has to be characterizedby SEM observationjust like Figure 1 showed.
82
Figure 3 Carbon whisker membranes with different size of carbon whiskers. The one on the top has a thicker
and longer carbon whisker layer but smaller pore size of membrane compare to the rest of the two CWMs.
Figure 4 shows the filtration performance between carbon whisker membrane (CWM) and
carbon membrane (CM). The results clearly reveal that the permeant flux of CWM is
higher than that of CM even after a few cycles of filtration. Because of the large amount
and network structure of carbon whiskers, particles will be trapped in the carbon whisker
layer before contacting porous membrane substrates during filtration processes. As a
result, the pores of substrate will not be blocked, which will not cause the fouling
phenomenon and not reduce the life-time of the membrane. In addition, if we used pulse
flow for the feedings or changed the direction of the feedings, the flexible whiskers might
remove the attacheaadsorbed particles away as a self-cleaning function. Figure 5 shows
the result of backflushing cleaning process for the membrane after the filtration. We
found that particles attached on the CWM can be easier to remove than that of the CM.
Within the same cleaning time, particles (white color) were still attached on the CM while
no obvious particle was found on the CWM. These results lead to suggest that the CWM
possess a higher flux permeability, a self-cleaning character and a easier regeneration
process of the membrane.
.
0.013
0.012
o.oll
0.010
t
0
'
10
20
30 40 50
Time Wn.01
60
70
80
Figure 4 Flux versus time for crossflow membrane filtration with backflushing cleaning
83
3.2
Carbon-coatedceramic membranes
Carbon-coated ceramic membranes were made by the CVD of methane without the
presence of the catalysts. Figure 6 shows the ceramic membrane and carbon-coated
ceramic membranes with different pore size. We simply controlled the deposition time
so that the thickness of the carbon film is different resulting the different pore size in each
membrane. As can been seen, the top membrane has a brighter color and, under the
observation of the surface by SEM, it was found to be a dense membrane. The pore size
can be reduced to nano-scale. The second membrane &om the top has submicro pores
which can be used as an ultrafilter. It is no doubt that the deposition time to fabricate
ultrafilter is less than that of the nanofilter. If only a little carbon deposited on the
ceramic membrane, the pore size of the membrane might just change slightly. However,
the properties of the membrane altered dramatically such as hydrophobicity, electrical
conductivity and thermal conductivity because of the nature of carbon. These changes
create a new research field for a better separation process by membrane technology such
as membrane filtration with assistance of electrically conductivity, hydrophobicity or
magnetic field separation [8]. Gas permeability can also be used for examining the pore
size of the membrane. Figure 7 shows nitrogen flux against transmembrane pressure
through Membranes A, B, and C. It is clear that a higher pressure drop increase the
nitrogen flux for all the membranes. Under the same condition of the pressure drop, the
nitrogen flux through Membrane A is the highest. This result suggests Membrane A has
a bigger pore size so that more nitrogen can flow through. Therefore, the pore size of the
membrane A is biggest followed by Membrane B and then Membrane C.
4
Conclusions
We reported our recent developed membranes called carbon whisker membrane (CWM)
and carbon-coated ceramic membrane. The CWM performed a better permeant flux in
the filtration process in comparison with the membrane without whiskers. Also, C W s
have a self-cleaning function which can increase the separation efficiency during the
filtration and increase the lift-time of the membrane. The carbon-coated ceramic
membranes with various pore sizes can be made for the purpose of nanofiltration,
84
5 0.4
r
B
'
E
0.3
2 0.2
0.1
0
0
25
50
75
100
125
150
175
200
P w u n drop (mmHg)
References
85
4. Bemhard, S., Edwin, N., Markus, O., 2002, Geometyrical shaping of surfaces with a
lotus effect, Patent US2002164443, EP1238717, DElOllO589, JP2002321224.
5. Li, Y.Y.,Bae, S.D., Sakoda, A. and Suzuki, M., 2001, Formation of vapor grown
carbon fibers with sulfuric catalyst precursors and nitrogen as carrier gas, Carbon,
39(1), 91-100.
6. Li, Y.Y., Bae, S.D., Sakoda, A. and Suzuki, M., 2000, Fabrication and
characterization of carbon whisker, The 2nd Pacific Basin Conference on Adsorption
Science and Technology, May 14-18,Queensland, Australia, p376-380.
7. Li, Y.Y.,Nomura, T.,Sakoda, A. and Suzuki, M., 2002, Fabrication of carbon coated
ceramic membranes by pyrolysis of methane using a modified chemical vapor
deposition apparatus, Journal of Membrane Science, 197 (1-2), 23-35
8. Li, Y.Y.,Sakoda, A. and Suzuki, M., 2001, A review of fabrication methods of
carbon membranes and applications related to their hydrophobic and electrically
conductive properties, Journal of Institute of Industrial Science, University of Tokyo,
53(3), 70-74.
86
Invited Papers
Introduction
Physisorption is often included in gas phase reaction models, and its importance well
recognized, but the parameters are often estimated from reaction data, leading to poor fits
and biased parameters, often leading to erroneous mechanisms. Independent measurement
of reactant and product adsorption in near reaction conditions allows for elegant modeling
of complex reaction systems. For a variety of heterogeneously catalysed gas and liquid
phase reaction systems, we have systematically determinedthe adsorption properties of the
catalyst in close to reaction conditions. Given the high temperatures, high pressure,
multi-phase conditions, only a few of the usual techniques are really applicable. These are
mainly gas or liquid chromatography, both in tracer and perturbation mode and batch
adsorption experiments which we currently run in a robotic system as these measurements
are very labor intensive. These data are then used to model quantitatively the reaction
system, and allowing to extract intrinsic rates of reaction, or used to analyse the behaviour of
the reaction when changing zeolite composition, type, pore size or solvent used. Two
examples from our work are briefly described next as an illustration of the methodology.
2
87
methanol. This preference has been explained by a model in which methanol coordinateson
the active Ti sites [1,2]. The possible link between physisorption and solvent effects in
olefin epoxidation, however, has not extensively been studied. In the case of alkene
oxidation with TS-I ,the slower reaction of larger alkenes has been attributed to diffusion
limitation of these molecules. These measurements were however performed at high
conversion where deactivation was dominating.
Tracer liquid chromatographic methods were used to study liquid phase adsorption on
TS-1, Ti-Beta and Ti-MCM-41 and completely elucidate the reaction properties [3].
Partition coefficients for alkenes, alkanes, epoxides, and other, polar products are strongly
dependent on the carrier solvent. Linear a-olefins are concentrated inside the TS-1
micropores, particularly when methanol is the solvent. This agrees well with the superior
initial rates of olefin epoxidation with TS-1 in methanol. Sorption also governs the relative
reactivities of olefin substrates, especially in competitive experiments. Thus, in truly initial
conditions, I-hexene is less reactive than I-octene or I-nonene. For the latter substrates,
however, deactivation is fast, especially in methanol. This process is related to the strong
adsorption of higher 1,2-epoxyalkanes in TS-1 in methanol. Deactivation due to
competitive epoxide adsorption is slower in acetone, making this a more suitable solvent
than methanol for 1-nonene epoxidation with TS-1. Physisorption effects play a dominant
role in the small pore TS-1 catalyst, due to the close interaction of substrates such as alkenes
with the pore wall. Wider-pore catalystssuch as Ti-Beta and especially Ti-MCM-41, do not
adsorb olefins as selectively and hence intraporous olefin concentrations and reaction rates
are much lower.
Hydroeonversion of n-alkanes
Bifhctional zeolite catalysts such as platinum loaded acid zeolite catalysts are applied
in several petroleum refinery operations, designated as hydroconversion processes:
isomerisation of light naphtha, iso-dewaxingand hydrocrackingof heavy fractions [4]. Most
experimental investigations in academic laboratories are typically performed with pure
model components or simple mixtures thereof as feedstock, and using reaction conditions
under which the hydrocarbon compoundsare in the vapor phase. Industrialhydroconversion
processes are mostly run under three phase, or even in some cases under liquid phase
conditions and with feedstocks that are extremely complex mixtures of large numbers of
different hydrocarbon compounds [4].
In earlier work, adsorption equilibria of a broad range of hydrocarbon components
were determined on ultrastable Y (USY)zeolites under catalytic conditions. It was found
that Henry adsorptionconstants increase exponentiallywith the alkane carbon number [5,6].
This adsorptive discrimination of long alkanes in favor of shorter ones is most pronounced
in the Henry regime and decreases when the pores are more filled up with hydrocarbon
molecules at increasing vapor pressures [7]. USY type zeolite contacted with liquid alkanes
does not show any differences in affinity towards alkanes of different molecular weight [8].
These investigations showed that on USY type zeolite, adsorption selectivity depends
strongly on the loading of the micropores and on the aggregation state of the alkane
contacted with the zeolite.
The conversions of n-alkanes, cyclo-alkanes and their mixtures over WUSY zeolites
under vapor phase reaction were successhlly modeled using independently determined
adsorption equilibria and fundamental reaction networks based on alkylcarbenium ion
chemistry [9-121. In these models, the intrinsic reaction rate of an individual reaction step
88
0.7
;
P
g
o.s
OS
0.4
0.3
0.2
0. t
0
0.0
0.1
02
0.8
0.0
1.0
Figure 2 shows the selectivity for the longer alkane is strongly reduced in liquid phase
and that a non-competitive model for adsorption is needed in that case to represent the
results. Using a Langmuir type model based on gas phase data rather approximates the gas
phase results and is completely in error for the prediction of liquid phase conversion.
Both in vapor and in liquid phase reaction conditions, nonane is more reactive than
heptane. The reactivity difference is however much more pronounced in the vapor phase. In
USY zeolite micropores exposed to the vapor of the two n-alkanes, the heaviest alkane
molecule is preferentially adsorbed, resulting in a higher apparent reaction rate. When the
alkane mixture is fed in the liquid phase, the competing alkanes are adsorbed in a
non-selective manner in the micro- and mesopores of USY.Consequently, in liquid phase
conditions the relative reactivity of the n-alkanes corresponds to the relative intrinsic
reactivities.
89
Conclusion
These two examples show that adsorption effects can be dominant over the other
phenomena in a spectacular way and need to be taken into account directly through
independent measurement. Understandingthese phenomena can help in selecting, designing
or optimizing catalysts or reaction conditions.
5
Acknowledgements
References
1. Bellussi, G., Carati, A., Clerici, M.G., Maddinelli, G., and Millini, R., J. Cuful. 133,
220 ( 1992).
1.
1.I
I .2
The adsorption below and above the critical temperature looks different as shown by
experimental isotherms. There are five types of isotherms below the critical temperature
depending on the porous structure of adsorbents [6],however, there is only one type of
isotherms at above-critical temperatures no matter what kind of adsorbents was tested.
The supercritical isotherm shows type-I feature for its initial part, but there must be a
maximum followed by a negative increment as long as pressure is high enough or
temperature is low enough. Each type of isotherm reflects a definite mechanism o f
adsorption, therefore, supercritical adsorption must have just one mechanism. All
adsorption isotherm equations available, for example, the Langmuir or the BET equation,
were derived at from a prescribed mechanism and explained the experimental isotherms
satisfactorily. Therefore, clarification of the unique mechanism of adsorption at above
critical temperatures is necessary for setting up a pertinent model of supercritical
adsorption.
91
I .3
phase, pa,and the pressure corresponding to f i in the integral is, however, not known.
Therefore, there is not a way to spec!& the adsorption potential at above-critical
temperatures and, hence, the knowledge of potential theory available cannot directly solve
the problems encountered at above-critical temperature.
1.4
92
was omitted, and a continuous density profile in the normal direction of solid surface was
assumed in the computations basing on minimizing the grand potential energy. Rome is
there, and many ways lead to Rome. The results obtained by different methods may
contribute to better understanding supercritical adsorption, therefore, microscopic or
macroscopic way of study should not expel each other.
1.5
The Gibbs definition of adsorption is valid not only for subcritical adsorption, but
also for supercritical one:
n = n, - Vapg
(1)
The experimentally measured amount adsorbed, n, is an excess quantity concentrated in
the so-called adsorption space over the bulk gas phase, and the so-called absolute
adsorption, n , corresponds to the total quantity of adsorbate in the mentioned space.
According to Gibbs, there is a thermodynamically distinct interface between the bulk gas
and the equilibrium adsorbed phase, the density of which (pa)is remarkably higher than
that of the bulk gas phase @B). V, is the volume of the adsorbed phase, and the product
V& accounts for the difference between n and nt.
All isotherm equations were derived at for absolute adsorption. Therefore, there are
more choices for the expression of nt. However, the initial part of supercritical isotherms
looks like Type-I, and a simple model proposed for this kind of adsorption on
heterogeneous surface [151 was applied
n = n$ - exp(- bp4)l- rapg
(2)
Such a model bears prominent merits: 1. It keeps the formal continuity of isotherm
93
equations available to date; 2. It keeps the simplicity of isotherm equation because there
are only three parameters to be determined experimentally: &', b and q. This equation is
similar to the Langmuir-Freundlich equation and so does the parameters. Parameter np is
a saturation quantity of n, since
n,' if p=m. Parameter b is related to the energy
change of adsorbate after adsorption, and parameter q is an index of surface heterogeneity.
There are two unknowns in Eq.(l): n, and V,. Either one is determined, the other could be
evaluated from the equation. Previous efforts were to determine n, basing on an assumed
V, [161 or the density of the adsorbed phase (pb) [171. However, a value of nt determined
basing on experimental data would be preferable.
3
Because n, is the totai mass confined in the adsorbed phase, it must vary with the
experimental condition, therefore, should be determined as a function of temperature and
pressure. A straightforward method was proposed by the author [ 18-19]. It is known from
Eq.1 that n = n, if Vs, can be neglected comparing to n. Therefore, we can use the
experimental values of n that comply with the constraint to formulate the model of
absolute adrorption. The experimental data experienced twice transformations to reach a
linear plot as was usually done for the establishment of a model for a set of data. The
experimental data were utilized to the utmost in the transformation processes, and the data
that do not comply with the constraint were sifted out. A plot of In[ln(dk)] versus lllnp 0,
in kPa) was thus constructed. Parameter Swas used to adjust the magnitude of n in order
to avoid evaluating the logarithm of negative numbers. Its value could be set at 1, 10 or
100. A model with two parameters were obtained from the linear plots for the absolute
adsorption isotherms:
[(
Eq.(2) together with Eq.(3) describe isotherms not only for supercritical, but also for
subcritical if the isotherms show type-Ifeature. It was shown recently [22] that this model
works well for the isotherms distributed densely around the critical temperature as shown
94
in Fig.3. Although 298 K is lower than the critical temperature (304.2 K), maximum is
shown on the isotherm. Therefore, the difference between the excess and the absolute
adsorption cannot always be neglected for subcritical region. The evaluation of absolute
adsorption is especially important for the characterization of adsorbents basing on the
adsorption isotherm of C02at 273 K [23] and the isotherm shows type-I feature. Shown in
Figd is a calibration isotherm of COz at 273 K for a sample of activated carbon, where
dots are the data measured, and the solid line is the absolute adsorption isotherm
generated by Eq.(3). Since 273 K is below the critical temperature (304 K), the density of
COz gas is so low that the product Vfig is much less than the value of n for most
conditions. As consequence, most experimental points locate on the absolute adsorption
isotherm. More points would also locate on the linear plot shown in Fig.5, which renders
the formulation of absolute isotherms more reliable. However, the difference between the
absolute and the excess isotherm becomes considerable as pressure approaches saturation.
This difference is important because both pore volume and the specific surface area are
determined by the highest amount adsorbed. The volume of micropores was usually
estimated by dividing the amount adsorbed at relative pressure of pips = 0.95 by the
density of saturated liquid if the isotherm is type4 [24]. The assumption underlined is the
full-filled pore space with liquid adsorbate. However, the amount of adsorbate determined
as such does not correspond to the total mass fillkd in the space, but only a part of it,
although the major part. It is the absolute adsorption that corresponds to the total mass in
the adsorbed phase, therefore, the volume of pores should be determined basing on it. As
is seen in Fig.4, the absolute isotherm intersects the condensation line when pressure
reaches saturation, which proves a convention that the adsorbed phase has the same state
as saturation liquid. It is thus concluded,pore volume should be evaluated by dividing the
saturated absolute amount by liquid density. For example, the pore volume of the sample
shown in FigA would be 1.52 cm3/g basing on the absolute isotherm compared to 1.27
cm3/g basing on the excess isotherm. The relative difference is as large as 20%. The
surface area was usually determined by the DRK plot if the calibration isotherm is type-I
[24]. The difference in the DRK plot between the excess and the absolute adsorption is
also considerable as shown in Fig.6 for the same sample. The intercept of the two plots is
1.43 and 1.49 respectively yielding a relative difference of 15% in the surface area.
5
It is well known that the saturation pressure, ps, is the border of subcritical
adsorption, beyond which another phenomenon, condensation, happens. It seems there is
not a similar border for supercritical adsorption because no matter how high the pressure
is, adsorption isotherms could always be recorded. However, such border must exist
considering the cause of adsorption. It is the interaction between gas and solid that causes
the density difference between gas phase and adsorbed phase. The strength of the
intermolecular (atomic) attraction force is limited, therefore, the density difference
resulted must be limited, and the pressure difference corresponds to the density difference
must be limited. So, there is no reason to think of supercritical adsorption (or
high-pressure adsorption as synonym)as borderless.
A proof for the existence of the border can be found in a parameter of the
above-mentioned model of supercritical adsorption isotherms. Parameter np in Eq.(2)
indicates a saturated amount of absolute adsorption, which is the maximum adsorbate
95
contained in the adsorbed phase, therefore, presents the border of adsorption. The linear
plots of isotherms provide another proof. Shown in Fig.7 is such a plot for the adsorption
of hydrogen on activated carbon AX-2 1 for 77- 298 K [181. All plots intersect at one point,
which defmes a limit state of supercritical adsorption. The representation of isotherm in a
system of n versus pgprovides h t h e r proof of existing border of supercritical adsorption.
As Menon [25] pointed out, such isotherm has a linear section after the maximum. This
was proven by the adsorption of C02 on activated carbon for the near-critical region [22]
as shown in Fig.8. Applying Eq.(l) to the linear section of the isotherm, one would
conclude that both V. and n, must be constant if isotherm is linear. It means the value of 4,
V,, and does not change although pressure keeps increase for the region of linearity.
However, such state of the adsorbed phase is not thermodynamically stable. The density
of bulk gas & keeps increase while the density of the adsorbed phase pa keeps constant.
The metastable state would be broken if pgbecomes larger enough than A.As a symbol of
the breakage of the metastable state, the recorded "isotherm" begins to deviate from
linear.
Determination of the border of supercriticaladsorption is very important for the study
of supercritical adsorption. For example, the fugacity at the border can be used to replace
pr to define adsorption potential or used to draw the 4 plot. In fact, most theories
available for subcritical adsorption would be possible to apply for supercritical adsorption
if the border could be properly defined.
Acknowledgements
This work is subsidized by the Special Funds of Major State Basic Research Projects
(G2000026404) and supported by the National Natural Science Foundation of China
(#I29936100).
References
1. Matranga K. R., Mayers A. L. and Glandt E. D. Storage of Natural Gas by
Adsorption on Activated Carbon. Chem. Eng. Sci. 47 (1992) pp. 1569-1579.
2. Noh J. S., Agarwal R. K. and Schwarz J. A. Hydrogen Storage Systems Using
Activated Carbon. lnt. J. Hydrogen Energy 12 (1987) pp. 693-700.
3. Yang R.T. Gas Separation ly Adsorption Processes (Butterworths, London, 1987).
4. Ruthven D. M., Farooq S. and Knaebel K. S. Pressure Swing Adsorption (VCH
96
97
p.-,
.. ,,
PYR
the
Fig3 M,,,.J~~~
adsorption of co2on
activated carbon for the
near-critical region. points:
experimental; Curves:
model predicted.
ti1::
I
P#=+rn*
98
Contributed Papers
Introduction
Organic aerogels (RF aerogels) are prepared by the sol-gel polycondensation of resorcinol
(1,3-dihydroxybemene) (C6H4(OH)2) (R) with formaldehyde (HCHO) (F) and
supercritical drying with carbon dioxide ( C 0 3 [3]. Carbon aerogels are also obtained by
pyrolyzing RF aerogels in an inert atmosphere at 1323 K [4]. RF and carbon aerogels
have high porosity (> 80 %), and high surface areas (400 - 900 m2/g). The authors have
experimentally elucidated the influence of the amounts of resorcinol, water, and basic
catalyst used in the sol-gel polycondensation on porous structures of EW and carbon
aerogels [5, 61. Carbon cryogels are also prepared via sol-gel polycondensation of
resorcinol with formaldehyde, freeze drying, and pyrolysis [7-101.
The cryogels are unique materials with high surface areas and large mesopore
volumes, and they are expected to be used as catalysts, adsorbents, electric double layer
capacitors, and materials for chromatographic separation. The drying time of freeze
drying is, however, extremely long. Hence, the objective of the present work is to study
the applicability of microwave drying to the preparation of mesoporous carbons.
2
Experimental
99
length: 4 cm), and gelled by curing them at 298 K for 1 day, at 323 K for lday and at 363
K for 3 days to obtain RF hydrogels. The synthesis conditions are listed in Table 1.
Table 1.
carbon cryogel
674
0.73
7.0
496
1.14
6.2
RF cryogel
696
carbon cryogel
1.29
6.2
200
1.45
554
0.375
0.5
RF cryogel
5.5
662
carbon cryogel
0.94
5.5
200
RF cryogel
472
0.500
0.5
4.2
1.05
carbon cryogel
609
2.5
0.56
I00
492
0.I25
0.5
RF cryogel
1.17
7.0
carbon cryogel
754
0.78
6.2
100
0.250
RF cryogel
542
0.5
6.2
1.06
625
carbon cryogel
0.82
3.6
100
0.375
558
0.5
RF cryogel
2.4
0.79
577
carbon cryogel
1.9
0.35
100
548
0.500
0.5
RF cryogel
0.72
2.1
carbon cryogel- .0.31
599
1.6
-___
200
RF xerogel
1.8
0.125
0.5
I52
0.27
1.8
49
carbon xerogel
0.07
200
0.5
RF xerogel
1.8
255
0.375
0.31
carbon xerogel - 1.6
121
0.06
200
0.125
0.5
RF MW gel
2.1
361
0.58
626
carbon MW gel
0.47
1.6
323
200
0.250
0.5
RF MW gel
2.2
0.47
582
carbon MW gel
2.I
0.48
422
200
0.375
0.5
RF MW gel
2.4
0.56
549
carbon MW gel
1.8
0.48
465
2.6
0.68
200
0.500
0.5
RF MW gel
608
2.0
0.47
carbon MW gel
407
1.8
0.42
100
0.250
0.5
RF MW gel
carbon MW gel
1.5
407
0.14
WC:mole ratio of resorcinol to basic catalyst, R/W: ratio of resorcinol to water,
WF: mole ratio of resorcinol to formaldehyde, ND: not detected.
200
0.250
0.5
0.16
ND
0.14
ND
0.14
ND
0.13
ND
0.15
ND
0.11
ND
0.15
ND
0.13
ND
ND
ND
0.03
0.I4
0.I4
0.21
0.41
0.33
0.09
0.25
0.14
ND
0.15
100
adsorption apparatus (BEL Japan, Inc.; BELSORP28). BET surface area, SBET,
mesopore
size distribution, and kcroporosity were evaluated. The pore size distribution and the
mesopore volume, V-, were determined by applying the Dollimore-Heal method [ 11 to
the desorption isotherm, and the micropore volume, V,,,i,, was evaluated by the t-plot
method [2]. The cross sections of RF drygels and carbon gels were observed using a
scanning electron microscope (JEOL, Ltd.; JSM-6340FS).
3
3. I
Figure 1 shows the pore size distributions of RF drygels, and Table 1 also shows the
porous properties of RF @gels. r w denotes the peak value of pore size distribution. One
can see the development of mesoporosity in RF cryogels, and the values of rw and V,,
of RF cryogel decrease as decreasing WC or as increasing WW. On the other hand, SBET
shows no obvious dependence on R/C and WW. The above dependencies are considered
to reflect the structure of RF hydrogels. This is because solvent inside the pores is
removed retaining the porous structure of RF hydrogels. From Fig. 1 (b) and Table 1, it
can be seen that pore size distributions of RF xerogels have sharp peaks at around 2 nm,
and SBET and Vmes are much smaller than those of RF cryogels. Figure 1 (c) and Table 1
also show the mesoporosity of RF MW gels. The pore size distributions of RF MW gels
have sharp peaks at around 2 nm.Although it is difficult to detect obvious depencence of
the porous properties on the value of WW,the values of S ~ E Tand V,,, are respectively
estimated to be 65 - 85 % and 38 - 67 % of those of RF cryogels.
R/W=OJ25
---D--
R/W=O350
____
&-..
R/W=O375
- - V - .
R / W = m
Figure 1. Pore size distributions of (a) RF cryogels, (b) RF xerogels and (c) RF MW gels synthesized under
the condition of WC = 200.
From the above results, it can be concluded that freeze drying is strongly
recommended to obtain mesoporous RF drygels among the drying methods examined in
this work. It is also possible to prepare mesoporous RF drygels by microwave drying.
However, it is difficult to prepare mesoporous RF drygels by hot air drying.
RF aerogels have previously been prepared over wide ranges of WC (12.5 IWC I
800) and R/W (0.125 I R/W I0.500) [6]. By comparing the drying methods from the
viewpoint of the ranges of R/C and R/W to obtain mesoporous RF drygels, supercritical
101
drying is considered to cover the widest ranges, followed by freeze drying, microwave
drying and hot air dtyiig.
3.2
From Figure 2 (a) and Table 1, one can see that the values of V,, of carbon cryogels are
slightly smaller than those of RF cryogels and also see that micropores are formed on
carbon cryogels, which is caused by the shrinkage of mesopores during pyrolysis.
Interestingly, SeErincreases to some extent because of micropore formation during
pyrolysis. Figure 2 (b) and Table 1 show that carbon xerogels scarcely have mesopores
because mesopores of RF xerogels have been collapsed by pyrolysis. Figure 2 (c) and
Table 1 also indicate that the mesopores of RF MW gels have shrunk by pyrolysis. It
should be noted that carbon MW gels prepared under the condition of R/C = 200 also
show mesoporosity although rpcd and V,,, are smaller than those of carbon cryogels.
These results suggest that appropriate values of R/C and R/W should be selected to obtain
mesoporous carbon MW gels. The values of& and V,,, of carbon MW gels synthesized
under the condition of R/C = 200 are confirmed to be 83 - 99 % and 37 - 84 % of those of
carbon cryogels respectively.
The cross sections of RF drygels and carbon gels were observed by SEM and the
following results were obtained. Carbon cryogels are also composed of primary particles.
On the other hand, primary particles composing RF xerogels and RF MW gels are melted
by pyrolysis. Carbon xerogels have smooth surface and no mesopores, which fact supports
the results of nitrogen adsorption. Although the porous structure of carbon MW gels are
partially melted, the cross-linked structure is partially maintained and retaining
mesoporosity.
From the above results, freeze drying and microwave drying are recommended to
prepare mesoporous carbon gels. It is confirmed that freeze drying is available to prepare
mesoporous carbon cryogels over wide ranges of R/C (50 I R/C I 200) and R/W (0.125 I
R/W I0.500).When microwave drying is used, the value of R/C should be kept close on
200 to obtain mesoporous carbon MW gels.
5
3- 4
8
n'
;1'
4
b
M
Q
>
3a
a 0
1
10
Q
>
10
0
1
10
Figure 2. Pore size distributions of (a) carbon cryogels, (b) carbon xerogels and (c) carbon MW gels
synthesized under the condition of WC = 200.
102
Conclusion
Acknowledgements
This research was partially supported by Japan Society for the Promotion of Science,
Grant-in-Aid for Scientific Research (B), No. 14350416 (2002), Industrial Technology
Research Grant Program in '01 from New Energy and Industrial Technology
Development Organization (NEDO) of Japan, and Hosokawa Powder Technology
Foundation (2000).
References
1. Dollimore, D. and Heal, G.R., An improved method for the calculation of pore-size
distribution fiom adsorption data, J. Appl. Chem., 14 ( 1964) pp. 109- 1 14.
2. Lippens, B.C. and de Boer, J.H., Pore system in catalyst V. The t- method, J. Cutul.,
4 (1965) pp. 3 19-323.
3. Pekala, R.W., Alviso, C.T., Kong, F.M. and Hulsey, S.S., Aerogels derived fkom
multifunctional organic monomers, J. Non-Crysr. Solids,145 (1992) pp. 90-98.
4. Pekala, R.W. and Alviso, C.T., Carbon aerogels and xerogels, Muter. Res. SOC.Proc.,
270 (1992) pp. 3-14.
5. Tamon, H., Ishizaka, H., Mikami, M. and Okazaki, M.,Porous structure of organic
6.
7.
8.
9.
10.
103
Introduction
The simulations conducted model the flow of Lennard-Jones (LJ) methane at 150 K and
170 K in a cylindrical silica pore of radius 1.919 nm, having infinitely thick pore walls
comprising spherical LJ sites. For methane we use the established LJ parameter values
104
&jkB= 148.2 K,q =0.381 m. For the solid W parameters we use 4 k B = 290 K, a, =
0.29 nm, obtained by fitting argon isotherms at 87 K in MCM-41 of various pore
diameters [15], using grand canonical Monte Carlo (GCMC) simulation. The
Loren&-Berthelot d e s are used to estimate solid-fluid LJ interaction parameters. A
cut-off separation of 1.5 nm corresponding to about 3.94q is used in computing
fluid-fluid potentials.
In the molecular dynamics calculations the trajectories of methane molecules in the
pore are followed using the equation of motion with appropriate temperature control. A
diffuse reflection condition is applied at the pore wall. For the EMD simulations a
collective transport coefficient obtained from autocorrelation of the fluctuating axial
streaming velocity via a Green-Kubo relation [5]
Dm = N lirnC<
u,(O)u,(t) > dt
r-hw
where udt) = C&id. For the NEMD simulations a constant axial acceleration is applied
to the particles, and a transport coefficient computed from the measured flux as
D, = k,Tg&nr, where 1 is the axial number flux and
is the methane density in the
pore. For the DCV-GCMD simulations a three-zone method is used [5,16], with the two
end wnes maintained at different chemical potentials. An effective Fickian transport
coefficient is then computed h m the measured flux through D,,a = -jUAp where I!
is the length of the central gradient zone and Apthe applied density difference.
3
Comparison of Methods
A A
A%
105
'O0
Our results clearly indicate that the EMD
transport coefficient does include the viscous
.
N<
640
part, despite the absence of imposed bulk flow,
contradicting earlier assertions [5,11] discussed 0
2e 480
above. This is rationalised if cross-sectional
equilibrium of the streaming velocity and density
320
profiles is attained. Evidence of the latter is g
provided in the inset in Figure 2 for a pore $ 160
E
density of 5.95 nm-3at 150 K.
A large number of DCV-GCMC runs were
0
also conducted at 150 K, for various pair of
0
160 320 480 640
800
predicted
D,
x
l
Og
(m2/s)
density values in the two end sections, and the
effective Fickian transport Coefficient, D,,,
obtained. A similar coefficient is also estimated Figure 2. Comparison of measured
C O e f i c i e n ~obtained using
from h e EMD and NEMD values of Dm,that
correspond to a chemical potential gradient DCV-GCMD, with those predicted
based on coefficients obtained using
driving force, following
Rn
a hf
Dt,g-= --4 = 4 ~ ~ D ~ ~' l( npp) (T dp
- ) (2)
jt
which matches that from DCV-GCMD, as seen in Figure 2 [ 131, over the wide range of
densities covered. Herefis the bulk hgacity of methane in equilibrium with adsorbed
density p, and the associated derivative is estimated from isotherms obtained by GCMC
simulation. Thus, it is clear that neither NEMD nor DCV-GCMD probes any new
mechanism beyond that captured by EMD simulations, even for mesopores.
4
Transport Model
Here R, represents the pore radius measured from the center of the surface atoms, and
is the mean pore density. The radial density profile p(r) is obtained from simulations,
while the local viscosity is evaluated using the method of Chung et al. [ 171, at a density
locally averaged over a sphere of radius of/2 [ 181. The radius r, in eq. (4) represents
the position of the minimum of the fluid-solid potential, which is essentially the location
106
duL
dr
at r = r,
where po is the local density at the potential minimum, u, is the slip velocity and k a
friction coefficient. Solution of eq. (4) with the above boundary condition yields the
transport coefficient
in place of eq. (4), which has the important feature that it predicts an asymptotic
non-vanishing transport coefficient in the low-density
region. The variation of the ffiction coefficient k
with local density p, at the surface of friction (the
location of the potential minimum) can be obtained by
substituting the values of D,,and density profile p(r)
obtained from GCMC simulation at density
into
eq. (6). Figure 3 [13] depicts the results, showing a
relatively constant value of the friction constant k of
about 1.2- 1.6 N.sec.mole-' at I50 K and 1.3- 1.7
N.sec.mole-' at 177 K, for local density ,q, below a
0
20
40
80
80
100
critical value (about 85 m-3at 150 K, and 70 run3 at
density at potential minimum (nm?
177 K). Subsequently it increases steeply to very
Figure 3. Variation of friction
large values, approaching the no-slip condition at high
factor with density at potential
densities.
minimum, obtained at temperatures
The constancy of the friction coefficient is a
of I50 K and 177 K. Inset depicts strong indicator of the importance of slip flow at the
predicted and measured streaming
pore wall in rnicropores. Further, calculations
velocity profile at adsorbed density
showed
that the above values of the friction constant
of 5.95 nm-3 and temperature of
are
closely
consistent with momentum transfer
150 K.
arguments. For this we consider the frictional force
as arising from the momentum loss ondiffise reflection at the wall leading to
kp,u, = mu ,
Z
(7)
107
imposed acceleration of 0.07 nm/ps*, showing excellent agreement except for some
deviation in the inner low density region where the flux is negligible.
The abrupt increase of the wall fiction coefficient to very large values leading to the
no-slip condition at a critical density is most likely due to the high frequency of
interparticle collisions in this region. Diffuse wall reflection then dissipates the collective
axial momentum in this region, and the no-slip condition is approached as seen in figure 3.
5
Conclusion
It is clear from the above results that all three simulation techniques yield identical
results for the transport coefficient in pores with diffusely reflecting walls. Further, a
combination of momentum transfer at the wall and viscous transport in the fluid suffices to
explain the transport behavior of pure component fluids in mesopores.
6
Acknowledgements
This research has been supported by a grant from the Australian Research Council under
the Large Grants Scheme.
7
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
References
M.E. Davis, Nature 417,813 (2002).
S . Ijima, Nature 354,56 (1991).
S.K. Bhatia, Proc. R SOC.Lond A446,15-37 (1994).
S.K. Bhatia, in Advances in Transport Processes LY,edited by AS. Mujumdar and
R.A. Mashelkar (Elsevier, Amsterdam, 1993).
D. Nicholson and K. Travis, in Recent Advances in Gas Separation by
Microporous Membranes, edited by N. Kanellopoulos (Elsevier, Amsterdam,
2000).
E.A. Mason, A.P. Malinauskas and R.B.Evans, J. Chem.Phys. 46,3 199 (1967).
R. Jackson, Transport in Porous Catalysts (Elsevier, Amsterdam, 1977).
J. Ktirger, and D.M. Ruthven, Dimion in zeolites and other Microporous solids
(John Wiley, New York,1992).
D. Nicholson, JMemb Sci. 129,209-219 (1997).
J.H. Petropoulos, and G.K. Papadopoulos, J. Memb. Sci 101,127 (1995).
K. D. Travis and K.E. Gubbins, Molecular simulation 25,209 (2000).
G. Arya, H-C. Chang. And E. Maginn, J. Chem. Phys. 115,8112 (2001).
S.K.Bhatia and D. Nicholson, Phys.Rev. Lett., accepted (2002).
S.K.Bhatia and D. Nicholson, J. Chem. Phys., submitted (2002).
M. Kruk. and M. Jaroniec, Chem. Muter. 12,222 (2000).
R.F. Cracknell, D. Nicholson and N. Quirke, Pbs. Rev. Lett. 74,2463 (1995).
T.H. Chug, M. Ajlan, L.L. Lee and K.E. Starling, Ind Eng. Chem. Res. 27,671
(1988).
1. Bitsanis, T.K. Vanderlick, M. Tirrell and H.T. Davis, J. Chem. Phys. 89, 3152
(1 988).
108
Introduction
Methods
A multicomponent HSDM for acid dyelcarbon adsorption has been developed based on
the ideal adsorbed solution theory (IAST) and the homogeneous surface diffision model (H
SDM)to predict the concentration versus time decay curves. The IAST with the Redlich-P
eterson equation is used to determine the pair of liquid phase concentrations, Cs,land C.s,2,
fiom the corresponding pair of solid phase concentrations,q5.1and qs.2,at the surface of the
carbon particle in the binary component.
The concentration of solute inside the typical particle at distance r from
the centre and at time t is defined by qi (ri, t) and the variation of 9 with distance and time
is governed by the diffusion equation for each componentj:
= Xfli,
D t and ,y = L in
=s
R2
equation (1) to form equation (2) with following boundary condition (3) and (4).
109
do,r )= 0 = ul(x,o)(31,
The material balance equation for the multicomponentsystem and the rate of change of
solid phase concentrationof each componentj are:
' 1
- ( $ ) 9 J- (5)y
=',.I
E('J)=
3fpJ(xJ9rJ)xja
(6)
By considering a short time interval, ro.rl, r2 rn,in the integration of equation (8) forj
component and it is assumed that the time intervals (rI- T , - ~ ) are sufficiently short that
f(?) is effectively constant in each interval to solve equation (8) by a numerical method.
,
The IAS theory dictates that the spreading pressure should be constant for each
component in a given system (v,= vZ= ...= y,,)[2].
For a given pair of qe,,and qe,2,the values of sI,s2 amd qT cam be calculated.
-=l++
1
s (12)
9r
'
9z.1 4r.2
For a given (guess values) pair of qe,1 and qe,2,the values of S1,S2 and qTcan be calculated.
By applying the Redlich-Peterson equation (14) (Redlich & Peterson, 1959) in the equation
(12), it gives equation (15).
S.
S,
Since 'y, = 'y, ,a numerical computer program is used to optimize the ct1value until
the spreadingpressures of component 1 and 2 are equal. Hence, the value of C,, and Ce,2can
and
be calculated from the c;., and c,q2by equations (16) and (17) while q I= c:,~
c8,*= c;,,.Consequently:
110
3
3. I
The equilibrium isotherms were measured for Acid Blue 80 (AB80) and Acid Yellow
1 17 (AY 1 17) on Activated Carbon F400.The Redlich-Peterson isotherm (equation 14) is
used to relate equilibrium concentrationsbetween liquid phase and solid phase loading. The
values of KR, aR andpare 28.32dm3/g, 103.6 (dm3/mmole)0.965,
0.965 for AB8O on activated
carbon and 55.40dm3/g, 200.2 (dm3/mmole)0.910, 0.910 for AY117 on activated carbon.
Those isotherm parameters have been used in the multicomponent HSDM to correlate the
concentration decay curve.
3.2
The effects of initial solute concentration and adsorbent mass have been studied on the
diffusion processes for the multicomponentHSDM. The HSDM was used to correlate two
acid dyes (AB80 & AY 117) in the single component system in order to determine the
relation between the single component and multicomponent systems. A comparison of the
theoretical and experimental data for the AY 1 17 in ABSO+AY 1 17 binary systems with
different carbon masses is illustrated in Figure 1. The correlated results are good for all
adsorbent mass variations for the AB80+AY 1 17 system. There is some deviation in the first
30 minutes for the three binary component systems. This is due to the single component
external mass transfer coefficient, k j l and kJ2, (see Tables 1&2) which are used in the
multicomponent HSDM model; indicating that the values of the external mass transfer
coefficient in the multicomponent system are slightly different to those of the single
component system. The Ds,iand SSE values for AB80+AY I I7 binary system with different
carbon masses are shown in Table 1. It was found that parameters D.,I and Ds,2are almost
constant for different carbon mass systems. These results are consistent with the findings in
the single component HSDM and the values of the surface diffusion coefficient in the binary
system of the acid dyes are different to those values in the single component systems (shown
in Table 2).
Figure 1: Effect of Activated
Carbon Masses on the Adsorption
of AY117 in AB8WAY117 using
MulticomponentHSDM (IASRP).
0.5
4
0
200
400
600
800
Time (min)
eO.6 WO.88 A I . 2 g 0 1 . 7 g X2.2g
111
.oo
0.90
uo 0.80
3 0.70
0.60
0.50
For the AB80+AY 1 17 system, the D, values of AB80 in the single component system are
smaller than the Ds,fvalues of AB80 in the AB8O+AY 1 17 binary system while the D, values
of AY 117 produce an opposite trend, the D, values of AY 1 17 in the single component
system are greater than the Ds,2values of AY 1I7 in the AB80+AY 1I7 binary system. The
D, values of AB80 (DS,Jare greater than the D,,values of AY 117(Ds,2)in the AB8O+AY 1 17
system. This may be because the AB80 dye has a higher molecular mobility in the
AB80+AY 1 17 mixture. This implies a higher adsorption affinity towards the surface of the
activated carbon than the AY 117 dye.
The effect of different initial dye concentrations is shown in Figures 2 for a wide range of
initial dye concentrations for AB80 in ABSO+AY1 17 binary system. A good correlation
between experimental and theoretical results is also obtained in the binary systems. The
fitted parameters, kl,
k2,D , , and Ds,2are given in Table 1. According to the table, the
surface diffusion coefficient is dependent on the initial dye concentration of each system, as
in the single component system, parameters Ds,, and Ds,2are strongly dependent on the
initial dye concentration. The Higashi expression [3] has been used to correlate the
relationship between the multicomponent surface diffisivities, 0,.I and Ds,2, and the
fractional coverage, 0" and BB, of the acid dyes in the binary adsorption system.
4.OE-I0
3.OE-I0
- 2.OdlO
a*
I.OE-10
112
where D,and 0
2 are the self-diffiivities
for the component 1 and 2 in the mixture. It
was found that the surface diffusivitiesare
lineirly proportion to the M o n a 1
coverage expressions and are similar in
trend with the
findings in the single component HDSM
(see Table 3).
Table 1: Extend Masa T r a d e r and Solid-phuc Diffusion
Coeffidentafor the Adaorplioa of ABM)cAY117 011 Aetiv.
ted Carboa using tbe Multieomment HSDM (IASRP).
SOP
i.
1.7
1.7
f
100
I00
1.7
100
I :::: I
7.36xlC"
934x10'"
1.69xIO-~~
2.26~10-'~
9.11~10'
9.35xIQ"
9.34~10'"
9.34x10'"
6.002
7.749
3.363
3.070
6.471 '
3.512
some
AdBhK80
MYdlow
117
ABW (sin&)
2.646~10'
, ABW+AY117
BW+AY117
1.449xI1T'~
1.449~IO.'~
AYll7(riagk)
ABW+AYI17
2.525~10~
2.702~10'
y-intcmpt
2.686~10'
1.524~10"~
1.524~10"~
2.8%x109
2.566xlO9
113
References.
[l] McKay, G., Application of Surface
Diffusion Model to the Adsorption of
Dyes on Bagasse Pith, Adsorption 4
(1998) pp. 361-372.
[2]
Radke, C.J., Prausnitz, J.M.,
Thermodynamics of multi-solute
adsorption from dilute liquid solutions.
AlChE Journal 18(4) (1972) pp.
76 1-768.
[3] Higashi, K. Ito, H. and Oishi, J. Surface
Diffusion Phenomena in Gaseous
Diffusion: I, Suflace Di@iuion of Pure
GUS5 (1963) pp. 846-853.
CQ,RpoltedearliaforthesameNaLSXsorbent.
Introduction
The Sorption Isosteric Method (SIM)was used to determine thermodynamic data of N2O
sorption by zeolites NaLSX and CaLSX. This technique and its utilization for an
investigation of sorption-thermodynamic properties of COz on identical NaLSX beads
were described in detail in refs. [4-81.
Sorbentsused representbeads of NaLSX (98.99% Na) and CaLSX (97.29 % 0,
both of
(8 x 12) mesh. CaLSX is prepared by Na vs. Ca2+exchange of NaLSX beads with c. 12 %
attapulgite binder. Ihe appamt XRD crystallinity ofNaLSX beads amounts to c. (78+5)% as
amparedto arefenmce sample without binder. Dry weights ofNaLSX and CaLSX beads utilized
by SIM amount to 92727 g (bulk densii of NaLSX: 0.67
and 8.7033 g, respectively. Prior
to
the z e o b rlre a c t i care~v
~
in ti^ S I M - ~ ~ ~ sample
~ W Wc e at
~ <1 0 - ~ t o ~
and 673K, during 4 8 h m ibr NaLSX (beads wm nearly dry at loading), and over 7days for
CaLSX (fully hydrated beads).
114
'
'
'
'
'
'
'
'
'
rn
0.0592 7
0.1167
0.2200
0.4599
0.7225
x 1.0304
1'
.cI
i ' l
n. mom:
1.3083
1.7314
2.1365
:
.
:
-
A 2 . 7 ~
D
3.0571
3 . m
4.2140
4.7400
5.2701
-:
6.20M
.
I 5.5905
0
6.9337
I 7.7254
E 8.6133 Y
'.
'
i
'
'
'
'
'
'
'
'
'
'
1 0 1 1 1 2 1 3 1 4
1000/(T, K)
Figure 1. Sorption isosteres for NzO on NaLSX zeolite (clay-bound beads).
of these isosteres change with n if the sorption heat depends on concentration. Except for
a few isosteres for concentrations close to saturation capacity, the isosteres determined at
actual experimental conditions appear to be liiear, indicating that no sorption-phase transition
takes place. Therefore, they are characteristicof well-defined sorption-equilibriumprocesses
of N20on NaLSX and CaLSX zeolites. They are attributed to the correspon-ding sorptionphase concentrations set via dosing procedures. Since the boiling point, 184.67 K, and the
triple point, 182.33 K, of an N20-bulkphase at 1 at, are close to each other, the related phase
transitions can be. observed h m isosteres as N20 concentmtion approaches and exceeds the
sorbent-samation capacity. This feature is obvious h m r.ks. isosteres in Figs. 1 and 2. From
particular slopes of two segments of the isostere for highest n, 8.6133 molikg, shown in Fig.
1, the latent heats of vaporization, 16.55 kl/mol at 184.67 K, and fusion, 6.54 kJ/mol at
182.33 K, are obtained. These quantities agree well with handbook data [9].
Values of isosteric sorption enthalpy, -AH,standard sorption entropy, AS3 and
standard Gibbs fiee sorption energy, AGO, are calculated as dependences on n, c j , [4-81.
To calculate AGO, the boiling-point temperature of N20 is chosen as reference state. This
choice provides a check for thermodynamic consistency of experimental data since AGO
115
1000/(T,K)
Figure 2. Sorption isosteresfor N20on CaLSX zeolite (clay-bound beads).
116
=i
Y
i
?
lo
n, mollkg
60
-a-
N,O I CaLSX
-0- CO,
I NaLSX
e--o
-120
-1401
0
n, moMkg
Figure 4. Standard sorptionentropies of N20 and C02on CaLSX and NaLSX
Dependences dG" vs. n of N20 and C02 for NaLSX, as r e f e d to both the boiling
ternperatwe of each gas and the gas pressure, p o = 760 ton; as standard state are shown
in Fig. 5, together with related data for the N20-caLSX system. Values Mi0 for all
systems change k n negative ones to zefo as n increases, approaches and exceeds the
micropore-saturation capacities.This proves thennodynamic consistency and correctness of
the SIM data,
117
-5
-2 5
-30
- 3 5 : .
0
. , .
I
9
n , mol/kg
Figure 5. Standard Gibbs free sorption energies of NzO and Cot on CaLSX and NaLSX,
referred to the boiling temperatures as standard.
A large difference in AGO values exists between the two gases for n c c. 2 molkg on
NaLSX, which disappears as n increases. This proves that COz is sorbed preferentially over
NzO. Asp and, thus, n increase, this selectivity disappears. If the quantities AGO for NzOand
COZare referred to one and the same temperature, e.g., 298 K, sorption isotherms can be
obtained directly and compared to each other at this temperature.
Sorption thermodynamics for NzO-CaLSX is characterized by quantities -AH,AS" and
AGO as functions of n, which are shown in Figs. 3-5 for comparison with those for the
NaLSX systems. Fig. 3 proves that CaLSX compared to NaLSX, provides sorption sites
for NzO, which exhibit stronger sorption interaction at n < 1.5 mol/kg. This indicates
that NzO-Caz' interactions are considerably stronger than the NzO-Na+ ones, in LSX
supercages. As n increases fiom ca. 1 to 5 molkg, the isosteric sorption heats of NzO
on NaLSX and CaLSX zeolites become close to each other. Most probably, nonspecific van der Wads-type interactions between N 2 0 and the lattices prevail, and they
are nearly the same for NaLSX and CaLSX. Fig. 4 shows AS" vs. n dependences for NzO
on CaLSX and NaLSX. Interestingly, these curves differ significantly for the two cationic
modifications of LSX. For NaLSX, NzOprobes at least two different (cationic) sorption sites.
For CaLSX, the curve shape expresses a more smooth distribution of energetically
heterogeneous sorption sites, which reminds qualitatively that for the Nz-CaA system [6,7]. The
shape of the B" vs. n dependence for COz on NaLSX is reminiscent of that for the NzONaLSX system and witnesses preferred sorption of Cot. Standard Gibbs free sorption
energies as basic sorption-equilibrium quantities of NzO and COZ, are referred to
184.67 K and 194.65 K, respectively. The "more negative" values for NzO on CaLSX if
compared to those for NaLSX at n<2molkg, indicate that CaLSX attracts N 2 0
significantly stronger. At n > 2 molkg, values -AGO of N20 for the two zeolites become
close to each other because non-specific sorption interaction between NzO and the LSX
lattice is similar in the two materials. This situation is reflected by the isotherm courses for
NzO on the two sorbents, cJ,Fig. 6, which were derived from SIM data.
Figs. 3-6 elucidate differences in sorption thermodynamics of systems, NzCX~LSX,NzO-
118
NaLSXand CQ-NaLSX. Generally, the -AH data obey a sequence, C&NaLSX >N2G
CaLSX >N2o-NaLsx, over almost the entire ranges of n. However, the cormponding -0
sequence varies withe which can be seen fiom Fig. 5. At n o 1.5 molkg,the absolute values
.......
. .......,
-0-
CO, I NaLSX
-0-
N,O I NaLSX
m
0
4-
3-
.........
....................
...............
n
10'
lo3
10'
105
p, torr
Figure 6. Sorption isotherms of N 2 0 and C02 on CaLSX and NaLSX at 298.15 K.
10"
10'
loo
,,.,..I
10'
of dG" obey the order N20aLSX > CGNaLSX > N20-NaLSX. This indicates that sorption of
N20 by CaLSX is stronger than that of C Q by NaLSX, in that @on. In the mge(2 o n
4.5) m o m the ditkmces for the three systems dkqmr, but they reoccur in a partly r e v 4
order at n o 4.5 m o b : N20aLSX > N20-NaLSX > COTNaLSX.
From these dependences A G O vs. n, sorption isotherms can be obtained for any tempemure
and pressure values that are meaningM physically, as exemplified in Fig. 6. Isotherms therein do
not only illustrate differences in sorption properties for the thm systems, NzO-C~LSX,N20NaLSX and CQ-NUX, but make it obvious that - at low equilibrium pressure - the sorption
capacity of N20 on CaLSX is comparable with that of C02on NaLSX. These capacity values are
much higher than those for N20on NaLSX. Moreover, at very low equilibrium pressure, < 0.5 torr,
the sorption capacity of CaLSX for N20 is higher than that of NaLSX for C02. This particular
feature makes the CaLSX mIite a preferred N20-selective sorbent for the removal of trace
amounts of N@ h m air in h n t of ASU [lo]. For none of the systems investigated at cryogenic
tema Henry region could be identified h m the sorption isostereS, which is due to strong
sorption interactions and m&odical reasonsas well.
A quantitative comparison of sorption-thermodynamicproperties h r N20 as described here
with l i t e m data for a CaA-tYpe zeolite [2] meets difficulties since no such thermodynamic data
could be derived reliably h m the latter source. Prefmntial interaction of e m - h e w o r k Ca"
cations with C@ compared to that with N20as identified in [2] agrees qualitatively with the results
of this investigation.
4
Conclusions
Equilibrium sorption thermodynamic properties of N20 sorbed by NaLSX and CaLSX are
119
investigatedby SIM. These are the first comprehensive data sets ever measured for N20. They
are compared with those for the C&NaLSX system. Soption of N20 on NaLSX is much
weaker than that of CQ on the same zeolite. At low pressures, < lotorr, NaLSX has a very
high sorption capcity for CQ, but has a low capacity for N@. CaLSX has a higher sorption
capacity for N20at pressure less than 0.5 torr, compared with that of NaLSX for CQ, and it has
nearly the same sorption capacity at high pressures. Highly exchanged CaLSX zeolites are
recommended for use as N20-SeleCtive sorbents. By combining NaLSX and CaLSX in certain
adsorber-bed layer anangements for TSA PPU proceses, CQ and N20 could be removed
subsequently and completely h m air streams.
5
Acknowledgements
The authors are grateful to Drs. F.R. Fitch and A.F. Ojo, Murray Hill, for helpful
discussions. They thank the BOC Group for the permission to publish this work.
6
References
[l] Golden T.C., Taylor, F.W., Johnson, L.M., Malik, N.H., and Raiswell, C.J.,
Purification of Air, US Patent No. 6,106,593; August, 22,2000.
[2] Mayinger, F., and Egg&-Steger, R, J Energy. Heat & Mars Traqfiw, 15 (1993) 165.
[3] Ojo, A.F., Fitch, F.R., and Biilow, M., Removal of Carbon Dioxidefiom Gas Streams,
US Patent No. 5,531,808; July 02, 1996.
[4] Biilow, M., and Shen, D., in Fundamentals of Adsorption-6 (Ed.: F. Meunier),
Elsevier, Paris, 1998, p. 87.
[5] Shen, D., and Biilow, M., Micropor. Mesopor, Materials, 22 (1998) 237.
[6] Shen, D., Engelhard, M., Siperstein, F.,Myers, A.L., and BUlow, M., in Adsorption
Science h Technology (Ed.: D.D. Do), Proc. 2d Pacific Bash C o d Adsorption Science
Technol., World Scientific, Singapore, 2000, p. 106.
[7] Shen, D., BUlow, M., Jale, S.R., Fitch, F.R., and Ojo, A.F., Micropor. Mesopor.
Materials, 48 (2001) 2 1 1.
[8] Biilow, M., Shen, D., and Jale, S.R., Appl. Surf Sci., 196 (2002) 157.
[9] The Mathewn Company, Matheson Gar Data Book 4* Edn., East Rutherford, 1%6, p. 83
(CW; P. 387 ( N 2 0 ) .
Eyring, H., Henderson, D., and Jost, W., Physical Chemistry: An Advanced Treatise,
Vol. 1V:Molecular Properties, Academic Press New York, 1970, p. 381.
Shen, D., Huggahalli, M., Biilow, M., Jale, S.R., and Kumar R., TSA Process for the
Removal of Dinitrogen Oxide, Hydrocarbons and Other Trace Impuritiesfrom Air,
US Patent No. 6,391,092; May 21,2002.
120
E-mail: sakoda@iis.u-tokyo.ac.jp
A novel composite membrane (an activated carbon membrane with carbon whiskers) applicable to water
treatment was fabricated by a combination of conventional carbonization and thermal deposition methods. The
carbonization was performed at 1050-1100 c using poly-vinylydenchloride (PVdc) and ply-vinylchloride
(PVC) microsphens, and the thermal deposition was accomplished after femc sulfate (Fe2(S04)j nH20) was
applied as a coat on and within a ceramic support. The membrane consists of three parts, each with a different
function for water treatments: a carbon whisker layer, a carbon layer, and an activated carbon layer. Those
structural characteristics were confirmed with a scanning electron microscope (SEM) and by measuring
electrical resistance and water and gas permeability. Water treatment experiments, using phenol and
polyethylmethacrylate(PMMA) as model pollutants, indicated that this membrane was able to remove dissolved
organics with low molecular weights and suspended solids simultaneously. Also, the carbon whisker layer
prevented the fouling of fine particles on the membrane effectively with performing the frequent back washing.
These results indicate that the novel composite membranes can clarify the water within a relatively short time,
and are usefbl for small scale distributed drinking watedwaste water treatments.
1. INTRODUCTION
Watedwastewater treatment usually consists of several component operations such as
biological treatment, coagulation, sand filtration, membrane filtration, and activated
carbon adsorption. Raw water usually contains solid particles ranging in size from
nanometer to millimeter, as well as dissolved pollutants. This means that any single unit
operation cannot remove all pollutants in one stage. On the other hand, simultaneous
removal of particulate and dissolved pollutants can be achieved if we can combine the
physical filtration and adsorption processes. From this standpoint, we first developed an
activated carbon membrane (Sakoda er ul., 1996, 1998). However, during the membrane
filtration operation, we cannot prevent the deposition and accumulation of fine particles
on and within the membrane, resulting in a cake layer. As a promising method to solve
this fouling problem, we then developed a novel membrane called the carbon whisker
membrane (Li er ul., 200 1a, 200 1b, 2002a), which basically contains vapor-grown carbon
fibers (whiskers) on the external surface of a carbon-coated ceramic support. The
filtration experiments using polyethylmethacrylate (PMMA) as model particles indicated
that the carbon whiskers can prevent direct contact between the membrane body and
PMMA particles, and that fouling would occur with greater dificulty than on as
membranes without carbon whiskers (Li,submitted). Unfortunately, however, the water
flux of this carbon whisker membrane was not large enough for practical use, for the
following reason. To solve this fatal problem, we propose a new methodology for
preparing a new activated carbon membrane with carbon whiskers, as shown in Figure I.
We also characterizethe membrane and the water treatments that can employ it.
For further details of this preceding, see this paper. (Bae ef ul., 2002)
2.EXPERIMENTAL
Ceramic tubing (inner diameter = 9 mm, outer diameter = 13 mm, pore size = 2.3
pm) was kindly provided by Kubota Co., Ltd., Japan, and used as the membrane support.
The polymer latex containingpoly-vinylydenchloride(PVdC) and poly-vinylchloride
121
PerRntatioa
(PVC) microspheres of 0.10-0.15 pm in diameter (Asahi Kasei Co. Ltd., Japan) was used
as a pre-coat reagent and precursor of the activated carbon (Sakoda et ul., 1996).
Preliminary experiments revealed that thermal decomposition occurs around 300 c, and
that a temperature above 700 C is needed for the complete carbonization of the polymer
latex employed. The ferric sulfate (Fe2(S04), nH20) was used as the catalytic
precursor in order to make the carbon whiskers (Li et ul. 2001a, b).
A ceramic tube, with one end plugged by a polymer paste, was slowly dipped into
polymer latex and taken out while being rotated at 600 rpm. By this dipping method, an
aggregate of the polymer micro spheres was formed at the surface and subsurface parts of
the ceramic tube (Sakoda et ul., 1996). The sample was dried at room temperature for
30 minutes. The dried sample was slowly dipped into 0.5 M ferric sulfate solution and
dried at room temperature for 8 hours (Li et ul., 2001 a, b).
A 15-cm-long ceramic sample was put in a quartz tube with an i.d. diameter of 25cm,
placed in an electric oven, then dried at 300 c for 10 c Smin- and kept at 300 c for
30 minutes. The temperature was then raised again to 1000-1100 C at a rate of
10 C-min-. The temperature was reach at 1000-1100 c, we started to input the
nitrogedmethane = (80/20) volume % mixture gas at 500 ml*min-,25C in flow rate, in
order to form carbon whiskers on the activated carbon layer. The hydrocarbon
deposition time and temperature were set at 20 minutes and 1050 or 1100 C,respectively.
Mem.
Component of
polymer
la tex(w t%1
PVdC : PVC
45 : 55
70 : 30
7 0 : 30
Dipping time
in polymer
latexkec.)
CVD time
(min.)
20
20
10
-
20
20
20
20
CVD
temperature
(c 1
1100
1050
1050
1100
122
In this study, we made three novel membranes, labeled Membrane A, B, and C, with
different formation conditions. Table 1 lists the preparation conditions of the
membranes. Membrane D is a carbon whisker reported in Li et al. (2001), and is used
for comparison.
The morphology of each membrane surface was observed using a scanning electron
microscope (SEM).
Pure water flux (PWF) measurements were carried out using a 15-cm-long
membrane in a cross-flow apparatus consisting of a feed reservoir, a membrane module, a
back washing reservoir, and a regeneration reservoir, at 25 'c . Seven gases (hydrogen,
helium, methane, nitrogen, oxygen, argon, and carbon dioxide) were used for the gas
permeability measurements. Gas was introduced to the module, and permeation flux
was measured under a 100 mmHg pressure drop by a bubble flow meter at room
temperature.
Filtration experiments were carried out using this prepared membrane in a cross-flow
apparatus, which was the same as the PWF measurement apparatus. PMMA particles
(1000 mg-l-', 0.8 pm in diameter) were used as model particle pollutants. When the
PMMA solution was introduced by the feed magnet gear pump, the flux of the same
object declined to a certain level. In this time, membranes needed regeneration, we used
the technique of back washing. To carry out the back washing, we changed the flow
direction by niddle valve and used pure water at a pressure of 2 kg*cm'*for 1 minute.
The membrane developed in this work and a commercial activated carbon F-400
(Calgon), which is widely used in various water treatments, were used for adsorption
experiments. The adsorption isotherms of phenol were measured according to the
following batch adsorption method. The sealed vial was placed in a constanttemperature water bath kept at 25 "c. The samples were well stirred, using a magnetic
stirrer overnight (Sakoda er ul., 1991).
3. RESULTS AND DISCUSSION
123
2um
124
4. CONCLUSION
Acknowledgements Ceramic tubing and polymer latexes used in this work were kindly
provided by Kubota Co. Ltd. and Asahi Kasei Co. Ltd., respectively.
REFERENCES
Bae, S.D.,Masaki, S., Sakoda, A. and Suzuki, M. (2002), Activated Carbon Membran
e with Carbon Wiskers and its Application to Water Treatments, Water Research
(submitted)
Endo M., Takeuchi K., Kobori K., Takahashi K., Kroto H.W. and Sarkar A. (1995),
Pyrolytic carbon nanotubes from vapor-grown carbon fibers, Carbon, 33,873-88 I.
Hagg May-Britt (1998), MEMBRANES IN CHEMICAL PROCESSMCj A Review of
Applications and Novel Developments, SEPARATION AND PURIFICATION
METHODS, 27(1), 51-168.
Iijima S. (1991), Helical microtubules of graphitic carbon, Nature, 354, pp 56-58.
Li, Y.Y.,Bae, S.D., Sakoda, A., Suzuki,- M. (2001a), Formation of vapor grow carbon
fibers with sulfuric catalyst precursors and nitrogen as carrier gas, Carbon, 39,9 1- 100.
Li, Y.Y.,Bae, S.D., Nomura, T., Sakoda, A. and Suzuki, M. (2001b), Preparation of
Custom-Tailored Carbon Whisker Membrane by Chemical Vapor Deposition, in: K.
Kaneko (Ed.), Fundamentals of Adsorption, 7,279-286.
Li, Y.Y., Bae, S.D, Nomura, T., Sakoda, A., Suzuki, M (2002a), Carbon Whisker
Membrane, Adsorption (Submitted) .
Li, Y.Y.,Nomura, T., Sakoda, A., Suzuki, M. (2002b), Fabrication of carbon coated
ceramic membranes by pyrolysis of methane using a modified chemical vapor
deposition apparatus; Journal of Membrane Science, 197,23-35.
Pierson Hugh O., HANDBOOK OF CHEMICAL VAPOR DEPOSITION (1992);
Principles, Technology and Application, Noyes Publications, New Jersey.
Sakoda, A., Suzuki M., Hirai R.,and Kawazoe K. (1991), Trihalomethane adsorption on
the activated carbon fibers, Water Research, 25(2), 2 19-225.
Sakoda, A., Nomura T. and Suzuki M. (1996), Application of Activated Carbon
Membrane to Water Treatments: Decolorization of Coke Furnace Wastewater,
Ahorption, 3(1), 93-98.
V. Kuberkar, P. Czekaj, R.Davis (1998), Flux Enhancement for Membrane Filtration of
Bacterial Suspensions Using High-Frequency Back washing, Biothchnology and
Bioengineering, 60,77-87.
125
however, is that it showed short-range MFI zeolite crystallinity as demonstrated by FTIR and XRD
analysis, and hydrophobicity as demonstrated by water and n-hexane adsorption.
Introduction
When the MCM-41s type ordered mesoporous materials were first introduced,'' .*. it was
anticipated that they could function as catalysts for bulky molecules. Subsequent studies
however revealed that their mild acidity and inferior hydrothermal stability could not
filfill such promises. The stability and acidity of these materials may be improved if
zeolite-like order, such as the MFI zeolite structure of ZSMJ and silicalite, could be
introduced into the mesopore walls by using simultaneously the large surfactant as
template for mesopores and the small organic templates as that for zeolitic micropores.
This dual template strategy has been tested'. ' 4. and shown to exhibit enhanced acidity
and steam stability compared to the corresponding MCM-41. However, a composite
material of MCM/MFI instead of a homogeneous one was obtained. Other approaches
include the post-treat with structure directing cations under dry condition for creation of
zeolitic micro ores: *a or the hydrothermal treatment of zeolite seeds after adding
surfactants?
In most case, better hydrothermal stability and stronger acidity could be
achieved.
However, in the post-treatment approach, the surface area decreases quickly with the
formation of zeolite phase. The mesoporous material eventually becomes an aggregate of
zeolite nanocrystals. The zeolite seed hydrothermal ap roach, on the other hand, produces
materials with only indirect hints of zeolitic nature!
Neither the FTIR nor the XRD
spectrum showed strong evidence for the formation of zeolite structure.
From our earlier experiences: we have learned that the zeolite seed hydrothermal
approach is rather difficult to reproduce. Consequently, a three-step-synthesis procedure
involving the preparation of zeolite nanoprecursors (NPs) by a short hydrothermal step,
the flocculation of these NPs using a surfactant, and the steaming of the NPs/surfactant
composite to produce the final material was developed. We have recently"' demonstrated
that aggregates of less than 30 nm silicalite nanocrystals can be prepared from this
procedure. We further discovered that the nature of the as-collected NPs was very much
dependent on the stirring time of NPsKTAMeBr flocculants. Under identical steaming
condition, the 3 h-stirred NPs were converted into nanocrystals of silicalite-1, whereas,
-'
126
*.
11%
Experimentals
47%
-80
-90
-190
-110
-1u)
-130
-140
-'*
Showed in Figure 1 are the NMR spectra of the surfactant-collected precursor before and
after 150C steaming. For both samples, there was approximately an equal distribution of
Q3 and Q4 silicon environment. The steaming produced only a small increase of Q2
species, suggesting the hydration of surface silica species. The NMR spectra are very
similar to that obtained by Kremer et al.'" recently.
As showed in Figures 2, the as-collected NPs and the directly calcined one showed
only a XRD band in the 20-25" 20 range. This band is consistent with the XRD pattern of
nanometer-sized MFI crystallites recently simulated by Schlenker and Peterson,14' where
a broad band was predicted to result from the broadening of the 12 distinct peaks in this
range. The steamed sample, on the other hand, showed distinct MFI XRD peaks.
127
128
accommodate more than 350 mg/g of n-hexane at -0.3P0, which is high even compared to
activated carbon.
PR.
PRO
Figure 5 Room tempenbre adsorption*otbcrms of water
(filkdsymbols)and beune ( o w symbols).
4 Conclusions
We have successfully synthesized a zeolitic material having high surface area, a narrow
mesopore size distribution, and XRD crystallinity of the MFI structure. The size of the
mesopore was -1 nm larger than that of MCM41 materials synthesized from the same
surfactant. This excluded the suspicion of a heterogeneous MCM4l/MFI mixture. We
have further found that the stirring time after the addition of surfactant and the humidity
under which the steaming is carried out have profound effect on the final product. By
indirect proof, it was proposed that the material obtained might be similar to the
delaminated zeolite obtained in other zeolite systems. In any case, the three-step
procedure seemed to give better control over the process of forming this material.
5 References
K.D. Schmitt,
C.T-W Chu, D.H. Olson, E.W.Sheppard, S.B. McCullen, J.B. Higgins, J.L.
Schlenker, J. Am. Chem. SOC.114 (1992) 10834.
1. J.S. Beck, J.C. Vartuli, W.H. Roth, M.E. Leonowicz, C.T. Kresge,
129
130
Adsorption is a widely used separation process in the chemical process industry. Selectivity is a key
property that determines the ease and efficiency of any separation. Although, selectivity is a function
of both composition and pressure, most of the design calculations are carried out using a Langmuirian
approach with constant selectivity, using only pure component data The conventional techniques to
characterizethe selectivitybehavior by measuring mixture equilibrium data require a large investment
of time and elaborate experimental setup. Moreover selectivity is very sensitive to experimentalerrors.
In this article we present an experimental method to measure the selectivity in binary gas
adsorption under infinite dilution conditions over a range of pressures and thereby characterize its
behavior with respect to both pressure and composition. The method is f k t , efficient and robust. We
use the methane-ethane binary gas mixture on silicalite as a demonstration. The experimental results
obtained using this method are compared with the predictions from two models to check their validity.
Introduction
131
6
0
01
01
03
04
RS
01
07
08
08
Yol
as the composition approaches either of the ends. In the combined volumetric- gravimetric
technique an additional error source is introduced if the molecular weights of the gases are
132
close to one another. Both these techniques are cumbersome, time-consuming and require
very specialized equipment and expertise.
There are several reports in the literature that measure binary adsorption equilibria using gas
chromatography [4,5,6]. In GC techniques the adsorbent is equilibrated with a continuous
flow of carrier gas (gas 1). Then a pulse of gas 2 is injected at the column inlet. A peak of the
gas 2 is eluted at the exit of the column after some time. Net retention time (or volume) is
calculated from the first moment of the peak after correcting for void volume (by measuring
the retention time of a non-adsorbing species). If the canier gas is inert (i.e. helium) the net
retention time is related to the pure component Henry's constant. Typical binary
measurements reported so far use a mixture of the two gases as carrier and introduce a small
perturbation in composition. The net retention volume is related to the thermodynamic
properties by [4]
V D
dn
dn
In the above equation PIand p2 are the partial pressures of the gases, nl and n2 are partial
amounts adsorbed and m is mass of the adsorbent. Thus, the experiments yield the
derivative information of the partial isotherms at various conditions. Some mathematical
technique is needed to integrate the experimentaldata and obtain the partial isotherm [5,6].
Although GC techniques are very fast compared to the conventionalmethods, any error
in the experimental data is magnified and propagated in the calculationsdue to integration.
There are also problems associatedwith polynomial fitting for the retention volume in terms
of composition in order to obtain binary isotherms [5,7].
4
Experimental
We used a typical GC setup and a mass spectroscopic detector. The only modification
involves controllingcolumn pressure between 20 - 1000 kPa. The following table lists the
main features of the experimental system used. All previous attempts to use the GC
technique for binary measurementswere conducted at constant (atmospheric)pressure. The
pure component isotherms are obtained form a conventionalvolumetric technique.
Table 1. Experimental system and conditions used
~
Column
Adsorbent
Adsorbent activation temperature
Experimental temperature
Exaerimental aressure
133
Results
When the adsorbent is equilibrated with gas 1 and an infinitely small pulse of gas 2 is
injected into the carrier gas stream, Eq.( 1) can be written as [7]
The selectivity of 2 ( 2,1) at these conditions is given by Eq.(3). The quantity n l ( P } in the
above equation is the pure componentamount adsorbed for gas 1 at total column pressure P.
Experimentalmeasurementsare required for V ,(obtained fiom the infinite dilution system)
and data for pure component isotherm (obtained independently using a volumetric
technique) to calculate selectivity (LHS of Eq.3). A similar equation can be written for the
infinite dilution of gas 1.
Figure 3 shows the variation of selectivity with pressure at infinite dilution conditions
for both the gases. The broken horizontal line is the result from the Langmuir model which
is same at infinite dilution of either gas. The selectivitiespredicted by IAST are different for
the two gases as shown by the solid lines. The points are experimental data.
In contrast to the previous attempts, our GC technique does not involve polynomial fits
and integrations. It is especially developed to measure selectivity at infinite dilution of one
of the components as a h c t i o n of pressure.
This data is also shown in figure 2 as filled circles. As already stated, the solid line AB
is obtained fiom the pure Component data only. After measuring the pure component data,
instead of going through cumbersome measurements of binary selectivity at finite
composition using existing techniques, we characterized it by measuring selectivity at
infinite dilution conditions in a fast and efficient way using the proposed method. Given the
line AB and the infinite dilution curves as the limits, most models will be able to estimate the
3D mesh with reasonable accuracy.
We needed less than two days to measure the data shown. This is much shorter
compared to any conventional technique, which requires almost a day per point for finite
binary compositions. Moreover, the infinite dilution extremes can not be measured using the
conventional techniques.
6
Conclusions
We proposed a novel method which can be used to for fast measurements of infmite dilution
selectivity in binary gas adsorption. This experimental system can handle a wide range of
pressure variation. Using the data obtained one can perform a quick characterization for
selectivity. From the design point of view this method can be effectively employed to check
validity of the model being used.
The major limitation of this technique is that it may not be suitable to use it for highly
selective systems like methane-butane mixture on silicalite. For these systems the retention
times may be long and a significant dispersion in the peak might occur.
134
15
14
0
50
I DO
150
100
I50
P (kPa)
Acknowledgements
We thank the Cleveland State Universitys Doctoral Dissertation Research Expense Award
Program (DDREAP) for partial support of this work.
References
1. Talu,O., Needs,status,techniques and problems with binary gas adsorption
experiments, Advances in Colloid and Interface Science 76-77 (1998) pp.227-269
2. Innes, W.B. and Rowley,H.H. Journal of Physical Chemistry, 51( 1947), pp. 1 154
3. Myers,A.L. and Prausnitz,J.M., Thermodynamics of Mixed Gas Adsorption, AIChE
J , 11 (1965), pp. 121-127
4. Van Der Vlist, E. and Van Der Meijden, J., Determinationof adsorption isotherms of
the components of binary gas mixtures by gas chromatography, Journal of
Chromatography,79( 1973), pp. 1 13
5. Hyun,S.H. and Danner, R.P., Determination of gas adsorption equilibria by the
concentration pulse technique, AIChE Symp. Ser., 34( 1982),pp. 1861-1877
6. Tezel, F.H., Tezel, H.O. and Ruthven,D.M., Determination of Pure and Binary
Isotherms for Nitrogen and Krypton, Journal of Colloid and Interface Science, 149
(1992), pp. 197-207
7. Harlick, P.J.E. and Tezel, F.H., A Novel Solution Method for Interpreting Binary
Adsorption Isotherms from Concentration Pulse ChromatographyData, Adsorption, 6
(2000), pp.293-309
8. Kohl,S., Measurement of the effect of pressure on infinite dilution adsorbed phase
activity coe%cients by gas chromatographic techniques, Diplomarbeit, University of
Seigen (1996)
135
Introduction
Since the discovery of the supramolecular self-assembly of silica and surfactant species [11,
an impressive progress has been achieved in the area of novel mesoporous materials, their
synthesis, characterization and applications [2-4]. The supramolecular self-assembly of
various inorganic and organic species into ordered mesostructures became a powerful
method for the synthesis of mesoporousmolecular sieves of tailored -work
composition,
pore structure, pore size and desired surface functionality for advanced applications in such
areas as separations, adsorption, catalysis, environmental cleanup and nanotechnology.
While the self-assemblyprocess can be successfully used to obtain various organic-inorganic
nanocomposites such as ordered silica-surfactant nanostructures, it is inherently unsuitable
for the synthesis of ordered mesoporous carbons and carbon composites. Although porous
carbons have a very long history and have become adsorbents of great industrial importance,
some attempts to obtain ordered carbon mesostructures have appeared just recently [5-14).
One of such attempts explored by Ryoo and co-workers employs the ordered mesoporous
silicas (OMS),e.g., MCM-48 and SBA-15, as templates [9,11-141. The templating method
involves the filling of the ordered porous structure of a silica material with a carbon
precursor followed by carbonization and silica dissolution, and affords ordered carbons of
pore sizes below 6-7 nm. Another templating method, which is more appropriate for
preparation of macroporous carbons, employs siliceous colloidal crystals [5-81. The colloidal
crystal templating, which affords carbons with ordered macropores of size greater than 50
nm, involves the formation of colloidal crystals, infiltration of the crystal's interstitial space
with a fluid-type carbon precursor-and its solidificationfollowed by removal of the template.
Although the both templating methods are attractive and worthy of further
exploration, they do not allow for the synthesis of carbons with uniform and tailored pore
sizes in the range from 7 to 50 nm. Recently, a new approach to the synthesis of
mesoporous carbons, which employs the idea of colloidal imprinting, was proposed [ 151.
This approach seems to be very promising for the synthesis of mesoporous carbons with
uniform spherical pores, high pore volume and relatively high surface area. The current
work refers to the recently reported synthesis and adsorption properties of colloidimprinted carbons (CIC) [15,16] and focuses on the preparation and adsorption properties
of the CIC samples with bimodal pore size distribution. It is shown that the carbons with
spherical mesopores of two different sizes can be synthesized by using a suitable binary
mixture of colloidal silicas.
136
Experimental
Heating and
imprinting
Mixture of silica
colloids and pitch
particles
Silica
dissolution
_____,
Carbonization
Figure 1. Scheme illustrating the synthesis of mesopomus carbons by colloid imprinting process.
One of the advantages of the colloidal imprinting method is the ease of controlling the pore
size as well as pore size distributionsby choosing proper colloids [HI.
As shown in [I61 the
137
0.0
0.2
0.4
0.6
0.8
1.0
Relative Pressure
Figure 2. Nitrogen adsorption isotherm for the CIC sample synthesized by using 1 I and 24 nm silica colloids.
As can be seen from Figure 2 the adsorption branch of this isotherm exhibits two
distinct steps that reflect the capillary condensation inside smaller or larger mesopores at
relative pressures about 0.79 and 0.9, respectively. The condensation in the relative pressure
range of 0.95-0.995 reflects condensation in secondary mesopores or small macropores,
which resulted fiom the imprintingof agglomeratesof colloidal particles. To our knowledge,
this kind of isotherm has not been reported for porous carbon materials. The pore size
distribution for this mesoporous carbon shown in Figure 3 exhibits two distinct peaks
located about 1 1 nm and 24 nm, which correspond to the particle size of Bindzil30/360 and
Ludox AS40 colloidal silicas, respectively.
It should be noted that the t-plot analysis shows a very small amount of micropores in
the sample studied, which is due to the use of the mesophase pitch as the carbon precursor.
It is known that many precursors, e.g., sucrose and polyfurfiuyl alcohol, infiltrate well
siliceous templates but after Carbonization give meso- or macroporous carbons with
complementarymicroporosity. This is not the case for the mesophase pitch, which is used to
synthesize carbon fibers that are nonporous materials.
138
0.06
0.04
0.02
0.00
10
20
30
40
50
60
Our previous papers [15,16] and the current work show that the imprinting of
mesophase pitch particles with colloidal silica is an efficient technique to prepare
mesoporous carbons with uniform spherical pores as well as carbons with bimodal pore size
distributions. These carbons exhibit negligible amount of micropores, which can be further
eliminated during graphitization process. If micropores are need, they can be created by
controlled oxidation analogous to that used in the preparation of activated carbon fibers.
The possibility of tailoring the size of uniform spherical mesopores is of great importance
for catalysis, adsorption and other advanced applications such as the manufacture of
high-quality electrochemical double-layer capacitors, fuel cells and lithium batteries.
Acknowledgements
The authors gratefully acknowledge the donors of the Petroleum Research Fund
administered by the American Chemical Society for the partial support of this research.
References
1. Kresge C. T., Leonowicz M. E., Roth
2.
3.
4.
5.
139
140
Introduction
The amount of methyl mercaptan (MM) adsorbed (and converted to dimethyl disulfides
(DMDS)) depends on the surface pH [1,2], and the presence of various impregnants, such
as potassium iodide, potassium iodite, potassium carbonate or ammonia [3, 41. It has also
been pointed out in the literature that different functional groups on the carbon surface
or/and metal ions such as iron can catalyze oxidation of mercaptans to disulfides [3-61. As
we have found recently, there is an indication of a competition for high-energy adsorption
sites between dimethyl disulfide and water molecules when adsorption occurs in the
presence of moisture [l, 21. This happens as a result of big differences between water and
DMDS in the strength of adsorption forces and their incompatibility (DMDS has very low
solubility in water) [7].
An objective of this paper it to describe the results of our further investigation of the
competition for adsorption sites between water and dimethyl disulfide molecules during
methyl mercaptan adsorption on activated carbons. Moreover, we attempt to indicate the
apparent borderlines between the conditions of adsorption processes leading to different
adsorptiodoxidation paths. Those working conditions have a significant effect on the
feasibility of methyl mercaptan removal.
Methods
Materials: Adsorption of methyl mercaptan was performed on numerous samples of
activated carbons of various origins. Among the carbons studied were BAX-I500 (wood
based -Westvaco), S208 (coconut shell - Waterlink Bamabey and Sutcliffe), Centaur
(catalytic carbon Calgon), BPL (bituminous coal Calgon), PCB (coconut shell-Calgon),
Maxsorb (mesophase pitch-Kansai), and polymeric based synthetic carbon, SCN [8]. To
broaden the spectrum of pH and surface properties, carbons were oxidized, acidified with
HCl, impregnated with NaOH, and modified with urea [9]. We do not refer to any specific
sample because our objective here is to show the general behavior of the system under
141
study.
CHSH aborption: The carbons were studied as adsorbents of methyl mercaptan in the
dynamic tests described elsewhere [l]. Briefly, 6 cm3 of adsorbent samples were ground
(1-2 mm particle size) and packed into a glass column (bed depth 80 mm, diameter 9 nun)
and prehumidified with moist air (relative humidity 80 % at 25 "C) for one hour. Dry or
moist air (relative humidity 80 % at 25 "C) containing 0.3 % (3,000 ppm) CH3SH was
then passed through the adsorbent bed at 0.5 L/min. The breakthrough of CH3SH was
monitored using a Micromax monitoring system (Lumidor) with an electrochemical sensor,
previously calibrated for MM. The test was stopped at the breakthrough concentration of
50 ppm. The adsorption capacities of each adsorbent in terms of mg of CH3SH per g of
carbon were calculated by integration of the area above the breakthrough curves, and from
the CH3SH concentration in the inlet gas, flow rate, breakthrough time, and mass of
adsorbent. For each sample the breakthrough test was repeated at least twice. The
determined capacities agreed within 4 %.
p H of carbon surface: 0.4 g of carbon powder was placed in 20 mL of water and
equilibrated during night. Then the pH of suspension was measured.
Sorption of nitrogen: Nitrogen isotherms were measured using a ASAP 2010
(Micromeritics) at -196 OC. Before the experiment the samples were heated at 120 "C
and then outgassed overnight at this temperature under a vacuum of l o 5 Torr to constant
pressure. The isotherms were used to calculate the surface area and pore (DFT [lo]) and
characteristic energy of adsorption, (Eo) (Dubinin-Radushkevichmethod [ 1 I]).
Thermal analysis:Thermai analysis was carried out using TA Instruments Thermal
Analyzer. The instrument settings were: heating rate 10 deg/min in nitrogen atmosphere
with 100 mL/min flow rate.
Discussion
0.8
B
g 0.6
.-
3RI 0.4
P
g 0.2
v)
0
2
6
8 1 0
pH of carbon surface
142
microporous carbons the volume of micropores is used whereas for carbons with a large
contribution of mesopores the volume in pores smaller than 50 A was chosen. It was done
assuming that only those pores are active in the adsorption process. This choice was
justified knowing that: 1) at a small concentration of adsorbate in a gas mixture it is likely
that only micropores and small mesopores are active in the adsorption process [12]; 2)
molecular simulation studies of water adsorption suggested that at 80% humidity (our
conditions) 50 A and smaller pores are filled with water molecules [13]; 3) if the
normalization is done using only the volume of micropores the density of adsorbed
species is higher than liquid density of DMDS. Moreover, a certain pore volume has to
be a limiting factor for the adsorption capacity since the products of adsorptiodoxidation
should be stored there [ 1,2, 141. Although the data is scattered due to the complexity of
the system the maximum boundary of the adsorption capacity can be noticed. Moreover,
when experiments were done at dry air the capacity was almost constant. Similar
phenomenon was described for adsorption of hydrogen sulfide on activated carbons 1141.
In the case of MM adsorption on activated carbon the presence of water facilitates its
oxidation to DMDS owing to adsorption and oxidation of thiolate ions [9]. It was found
that for the process to be efficient the pH of the carbon surface should be greater than 7.5.
1.o
@T
-.-s
0.8
c)
F 0.6
$
n
m
.S2 0.4
Q.
1: 0.2
0
ZI
0 . O l - L L F b Y
0.0 0.2
0.4
0.6
0.8
1.0
143
conditions, for instance for adsorption of water, are not fblfilled the amount of DMDS is
usually small and the point "moves" from the established dependence line.
How the adsorption occurs can be evaluated based on Dubin-Radushkevich approach
[ 1 11. The amount of vapor, A, adsorbed at pressure P and temperature T can be calculated
from DR equation [ 1 I]:
0.8
0.e
B 0.4
02
02
0.4
0.e
0.8
Figure 3. The predicted isotherms (with relative pressure units) for MM, DMS and HzO
144
The results presented in this paper indicate the dual role of water in the process of
methyl mercaptan removal on activated carbons. It is demonstrated that DMDS,formed
during surface oxidation of MM, has to compete with water for adsorption sites. However,
the competition exists, DMDS is always the "winner" owing to its strong adsorption on
carbons. On the other hand, the formation of significant amount of DMDS would not be
possible without the presence of water in the system. Water facilitates dissociation of
methyl mercaptan Ieading to its oxidation by oxygen, mainly from air. Since dissociation
is an important step, the pH of the carbon surface has to be greater than the estimated
threshold (about 7.5).
Acknowledgements
Acknowledgement is made to the donors of the Petroleum Research Fund, administered
by the ACS, for support of this research (Grant # ACS-PRF#35449-AC5). The authors are
gratefbl to Ms. Thiri 00for her experimental help.
References
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
145
14.
15.
51.
16. Lodewyckx, P. and Vansant, E.F., Water isotherms of activated carbons with small
amounts of surface oxygen. Carbon 37 (1999) 1647.
146
Introduction
Oxygen is an important gas in industry. It has numerous application such as steel and
nonferrous metallurgy industry, chemical industry, pulp and paper industry, glass melting
furnace, welding, wastewater treatment and city garbage burn out etc.. The traditionally
method of oxygen production is by cryogenic distillation of air. This method needs low
temperature and high pressure equipments which is complicate and high cost. The
cryogenic equipment starts up and shuts down very slowly (several days). Pressure Swing
Adsorption (PSA) as an alternative source of oxygen production first became a viable
option in the early 1970's. Now PSA is more economic and convenient for small and
middle size oxygen production, especially when high purity oxygen is not required [ 11.
Synthetic zeolites 5A and faujasite X (13X
or CaX)have been typically used as adsorbents,
which adsorb NZ more strongly than 0 2 . The
extraframework cations in the zeolites play a
major role in the adsorption selectivity. Because
the quadruple moment of NZ is about 3 times
more than that of Oz,the interaction between the
extraframework cations and nitrogen is much
stronger.
In 1989, Chao [2] reported that LiLSX
(lithium ion-exchanged low silica X zeolite,
having a Si/Al ratio close to 1.0) showed an
unexpected high capacitiy and selectivity for
nitrogen over oxygen. He found a Li' exchange
threshold value in LiNaLSX at about 2/3. Below
that threshold value, the adsorption capacity of
Figure 1. Structure of faujasite zeolite and
the distribution of cation sites
147
Experimental
Sodium, potassium LSX (NaKLSX) was synthesized following the procedure reported by
Kuhl [8]. On the basis of Kuhl's work, the synthesis conditions such as the ageing
temperature, reactants composition etc. were optimized further so that it was easy to
repeatedly prepare NaKLSX with crystallinity near 100% in our lab [9]. The product was
characterized by XRD and elemental analysis. XRD pattern indicated that the synthesized
NaKLSX was pure faujasite-type zeolite without detectable crystalline impurities or
amorphous materials. Elemental analysis showed that the synthesized NaKLSX had SUAl
molar ratio close to 1.O.
LiLSX was prepared by five static ion exchange of the synthesized NaKLSX at 100
C with a 5.6-fold equivalent excess of 2.0 M LiCl [lo]. After ion exchange, LiLSX with
Li/Al greater than 98% was obtained.
The adsorption isotherms of N2 and O2were measured by constant volume method at
ambient temperature. The adsorption properties deduced from the isotherms further
confirmed the high crystallinityand Li' exchange degree of LiLSX prepared in our lab.
148
3. I
Influence of residual water on the adsorption properties of LiLSX has been reported by
RT.Yang et.al. [6]. We repeated the experiment in our lab. Fig.2 (a) shows the N2
capacity versus the residual water in LiLSX. At first, as the water content goes up, the N2
capacity drops sharply from 30mYg to 3.8mVg, then it descends much more slowly. The
curve reveals a turn-point at about 32 H20per unit cell. This result is in good agreement
with that of R.T.Yang.
In the industrial application, dehydrated LiLSX is loaded in the beds of PSA
equipment and water in the air can be adsorbed gradually on LiLSX, resulting in the
decrease of its adsorption performance. The adsorbed water may exert different
influence on the adsorption properties of LiLSX fiom the residual water. So we
introduced water into fully dried LiLSX at ambient temperature step by step and measure
the change of Nz adsorption capacity. Seen fiom Fig2 (b), when water content was below
about 7 molecules per unit cell, the nitrogen capacities were almost the same for the two
kinds of samples. Yet above that water content, the nitrogen capacity was always higher
for the samples with adsorbed water. After heating the samples with adsorbed water
in sealed tube, the nitrogen capacity dropped again to almost the same amount as that of
the samples with residual water, as shown in Fig2 (c).
40
60
80
im
izo
140
160
y\glsrcalent(mdeduC)
This can be explained by the heterogeneity of adsorption sites and the migration of
the adsorbed water in LiLSX. As mentioned above, Li+ at SIII sites are the strongest
adsorption sites in LiLSX, but there are many other site which can adsorb water also.
TPD results obtained by B. Hunger et.al. [I I] showed four desorption peaks for water
adsorbed on L U X , the desorption energy of which were 50, 58, 69, 85 KJ/mol,
respectively. The water content corresponding to the maximum desorption energy (85
KJ/mol) peak was about 29 moIecules/u.c., quite near 32 molecu1edu.c.. Though the
authors didnt make designation to this peak, according to the above results, we
149
tentatively attribute it to water adsorbed on Lit at SIII site inside the supercages. When
water molecules were introduced into a dehydrated LiLSX particle, from the view of
thermodynamics, it was most favorable for them to be adsorbed on the strongest
adsorption sites, namely Li at SIII sites, thus caused the sharp decrease of nitrogen
capacity. But from the view of kinetics, part of the water molecules might adsorb on the
weaker sites before they could diffuse into the inner part of the particle. Therefore, some
Li at SIT1 sites located in the inner part of a LiLSX paricle remained intact, leading to the
higher nitrogen capacity. Heating the samples with adsorbed water caused the
migration of water molecules from the weaker adsorption sites to Li at SIII sites, so that
the nitrogen capacity decreased again to that of the samples with residual water. The
adsorbed water introduced from outside influences nitrogen adsorption not so seriously as
the residual water does. This point provides for us a round understanding of the water
effect in the 4 PSA industrial application.
3.2
(b)
..
j 31
o!
0
,
P
.i/ ,
40
eQ
,
80
,
im
Exchangeoeg- (%I
Figure 3. Comparison of threshold value between LiNaLSX and CaNaLSX.
Acknowledgement
References
1. Kumar R., VSA process for oxygen production-a historical perspective. Separation
Science and Technology31 (1996) pp. 877-893.
2. Chao C. C.,Process for separating nitrogen from mixtures thereof with less polar
substances. US Pat. 48592 17 (1 989)
3. Feuerstein M., Engelhardt G., McDaniel P. L., MacDougall J. E. and Gaffney T. R.,
Solid state nuclear magnetic resonance investigation of cation siting in LiNaLSX
zeolites. Microporous and Mesoporous Materials 26 (1998) pp. 27-35
4. Plevert J., Di R e m F., Fajuia F. and Chiari G., Structure of dehydrated zeolite LiLSX by neutron diffiction: Evidence for a low-temperature orthorhombic faujasite.
J. Phys. Chem. B 101 (1997) pp. 10340-10346
5. Feuerstein M. and Lob0 R. F., Characterization of Li cations in zeolite LiX by solidstate NMR spectroscopy and neutron diffraction. Chem. Muter. 10 (1 998) pp, 21972204
6. Hutson N. D., Zajic S. C. and Yang R. T., Influence of residual water on the
adsorption of atmospheric gases in LiX zeolite: experiment and simulation. Ind Eng.
Chern. Res. 39 (2000) pp. 1775- 1780
7. Coe C. G., Kirner J. F., Pierantozzi R. and White T. R., Nitrogen adsorption with a
Ca andor Sr exchanged LiX zeolite. US Pat. 5 152813 (1992)
8. Kuhl G. H., Crystallizationof low silica faujasite. Zeolites 7 (1987) pp. 451-457
9. Jiang H., Tang W.,Zhao B. Y. and Xie Y. C., Studies on synthesis of Maximun
Aluminum X zeolite. ChemicalJ of Chinese Universities 23 (2002) pp. 772-776
10. Kirner J. F., Nitrogen adsorption with highly Li exchanged X zeolites with low Si/AI
ratio. U S Pat. 5268023 (1993)
11. Hunger B., Klepel O., Kirschhock C., Heuchel M., Toufar H. and Fuess H.,
Interaction of water with alkali-metal cation-exchanged X type zeolites: TPD and
XRD study. Langmur, 15 (1999) pp. 5937-5941
12. Vitale G., Bull L. M., Moms R. E. and Cheetham A. K., Combined neutron and Xray powder diffraction study of zeolite CaLSX and a *H NMR study of its complex
with benzene. J. Phys. Chem. 99 (1995) pp. 16087-16092
151
E-mail: yoshida@chemeng.osakfi-u.acJp
Various organic wastes, such as waste wood chip, sake lees, used tealeaves and so on, were
carbonized with the super-heated water vapor at 623 K. B y the 30 90 minutes treatment, the
organic wastes lost about 50 - 90 % of their original weight. The capability of gas adsorption has
been evaluated. The surface areas determined by nitrogen adsorption for the carbonized materials
were much smaller than that of the activated carbon Granular Shirasagi. The surface area
determined by carbon dioxide adsorption, on the other hand, of the carbonated materials were almost
the same order of magnitude to that of the activated carbons. These results show that the
carbonized materials have micro-pores whose diameter is less than 50 nm.
We have found that the waste wood and used tealeaves showed high adsorption capabilities for
ammonia gas in low equilibrium pressure (< 13.3 kPa). The amount of the adsorbed ammonia for
these carbonized materials were much higher that of the activated carbon Granular Shirasagi GS3 x
4/6. These results suggest that the carbonized materials from organic wastes could be utilized as
adsorbents for ammonia
Introduction
Conversion of organic wastes to usehl resources is a challenging task for the
engineers to contribute to the realization of the sustainable development in the 2 1st century.
The Japanese government, for example, plans to reduce the amount of the wastes
processed by landfill to 370,000,000 todyear in the year of 2010 [ 13. Since about 80%
of the wastes are organic wastes such as sludge, paper, wood chip, fiber, and excreta of
animals and so on, the conversion of the organic wastes to the useful resources is a key
factor to achieve the government plan. Production of methane and compost from the
waste foods and the animal excreta has been studied by the many researchers. Charcoal
production fiom the waste wood chips has also studied to utilized the organic wastes [2].
Super-heated water vapor has been widely used in many industrial processes such as
heat-exchange process and drying, and has also been used in the activation process for
activated carbon production. Recently, the super-heated water vapor has been utilized in
food industry for production of instant food and drying of vegetables and tea leafs. The
characteristics of the super-heated water vapor [3] are (1) it can heat the materials without
oxidation because it does not contain oxygen and carbon dioxide, (2) drying speed
becomes much faster than super-heated air due to heat emission of water molecules, and
(3) waste gas is easily recovered by condensing.
In this work, the various organic wastes were carbonized with the super-heated water
vapor at 623 K. The specific surface areas and adsorption characteristics of the
carbonized materials have been studied.
152
Methods
I Garbage
3
10.0
1.O
90
Results
153
Figure 1 shows a logarithmic plot of the amount of adsorbed ammonia against the
equilibrium pressure. The adsorption isotherms were well correlated by Freundlich
equation. The waste wood and used tealeaves showed high adsorption capabilities in
low equilibrium pressure (< 13.3 Wa). The amount of the adsorbed ammonia for these
carbonized materials were much higher than that of the activated carbon Granular
Shirasagi GS3 x 416. In the case of the activated carbon GAH 4-8, specialized for
alkaline gas adsorption, the straight line bent at the equilibrium pressure 13.3 kPa. This
result suggests that ammonia adsorbed on the mesopores of the activated carbon GAH 4-8
under low equilibrium pressure and then adsorbed on the macro-pores under high
equilibrium pressure. In the cases of the carbonized materials, ammonia gas adsorbed on
the mesopores, because the surface areas measured by nitrogen gas adsorption were very
small. in order to confirm these points, the adsorption data were analyzed by
Dubinin-Radushkevichequation [4]:
W=W&xp[-(RT/E)( In(PdP))]
(1)
where W, Wo,E, PO, P, R, T are adsorption volume [cm3/g-adsorbent], saturated
adsorption volume [cm3/g-adsorbent], characteristic energy for adsorption FJ/mol],
saturated pressure Fpa], equilibrium pressure [kPa], gas constant, and temperature [K].
Figure 2 shows a plot of logW against (log(Pdp)) for the activated carbons. The
experimental data deviated from the straight line in the high-pressure range. These
results suggest that the ammonia adsorbed mainly on the macro pore in the high-pressure
range, and adsorbed on the mesopores in the low-pressure range. The similar plots for
various carbonized materials are shown in Figure 3. All the experimental data were well
correlated by straight lines, suggesting that ammonia adsorbed on the mesopores. The
micro-surface areas determined from ammonia adsorption are also listed in Table 2.
Elementary analysis would be useful to characterize unique carbons developed in this
work.
154
Pressure [ma]
Figure 1.Ammonia adsorption on various carbonized waste materials
0 : Used tealeaves :
0:Scrapwood
'I:
-1
-1
0
M
-1.5
8
-2
-1.5
Discussion
Various organic wastes could be successfully carbonized by the super-heated water vapor
at 623 K. As summarized in Table 1, the organic wastes lost 50 90 'YOof their original
155
not shown) revealed that the macroscopic structures of the carbonized materials strongly
depend on the original structures. The measurements of specific surface area showed
that the diameters of the mesopores of the carbonized materials are smaller than nitrogen
molecule (about 50 nm), and are probably about 20-30 nm.
It should be noted that the adsorption capacities of the waste wood and the used tealeaves
for ammonium gas in the low equilibrium pressure are much higher than that of Granular
Shirasagi, and are compatible to that of GAH 8-4 which is specialized for alkaline gas
adsorption. These carbonized materials probably can be used as the substituted materials
for the activated carbon.
The carbonization of the organic wastes by the super-heated water vapor is an inexpensive
method to convert the organic wastes to useful resources. Effects of carbonization
temperature, heating rate, and other conditions on the characteristics of the carbonized
materials are extensively studying in our laboratory.
Acknowledgement
A part of this research was financially supported by 21" Century COE Program (24403,
E-1) from Ministry of Education, Culture, Sports, Science and Technology of Japan.
References
1. Notification No. 34 of the ministry of the Environment (2001)
2. Nakazaki K., Recycle of organic sludge by conversion into industrial raw materials,
In SOC.Chem. Eng. Japan (ed.), Processing of Wastes (in Japanese) (2001), pp.
65-74.
3. Iyota H., Nishimura N., and Nomura T., Reverse process of super heated steam
drying from condensation to evaporation, Nihon Kikai Gakkai Ronbunshu Part B (in
Japanese) 66 (2000) pp. 2681-2688.
4. Dubunin M. M., Adsorption in micropores, J. Colloid Interjhce Sci. 23 (1967) pp.
489-499
5. Medek J., Possibility of micropore analysis of coal and coke from the carbon dioxide
isotherm, Fuel 56 (1977) pp. 13 1-133
6. Yoshida H., Oehlenschraeger, Water vapor adsorption on basic anion exchangers, Ind.
Eng. Chem. Res., 40 (2001) pp. 4850-4856.
156
TOMASZ PANCZYK
Groupfor Theoretical Problems of Adsorption, Institute of Catalysis and Surjiace Chemistry,
Polish Academy of Sciences, ul. Niezapominajek8, 30-239 Krakow, POUND
It is shown how the new approach to adsorptioddesorption kinetics based on the Statistical Rate
Theory can be successfully applied to describe the kinetics of dissociative gas chemisorption on
solids.
Introduction
Since I9 16 when Langmuir published his fundamental paper on adsorption, the Theory of
Activated AdsorptiodDesorption Kinetics (TAAD) has, almost exclusively, been used for
the interpretation of adsorptioddesorption kinetics. However, contrary to the success of
Langmuir equation to represent the adsorption equilibria, a dramatic failure of TAAD was
observed to represent by the Langmuir kinetic equation and its further modifications, [131 the monitored adsorptioddesorptionkinetics.
So, it became more and more obvious that the theoretical hndamentals of
adsorptioddesorptionkinetics must be reconsidered.
The breakthrough came at the beginning of the eighties of the 20 century with
the new theoretical approach called the Statistical Rate Theory (SRT), linking the rate of
adsorptioddesorptionkinetics to the chemical potentials of the molecules in the bulk and
the adsorbed phases. [4]
The Statistical Rate Theory (SRT) is based on considering the quantum-mechanical
transition probability in an isolated many particle system. Assuming that the transport of
molecules between the phases at the thermal equilibrium results primarily fiom single
molecular events, the expression for the rate of molecular transport between the two
phases I and 2, RI2,was developed by using the first-order perturbation analysis of
the Schrodinger equation and the Boltzmann definition of entropy.
In eq. (I), p1 and p2 are the chemical potentials of the molecules in the phases I
and 2, respectively, and R, is the exchange rate at equilibrium.
The SRT approach was applied first to describe the kinetics of adsorption in the
systems with well-defined solid surfaces. [5-91 However, in spite of the demonstrated
impressive success, that new SRT approach did not meet a general easy acceptance. This
was probably due to some inertia caused by using the classical TAAD approach during
the previous 70 years.
157
Recently the new SRT approach has been generalized fiuther to take into
account the energetic heterogeneity of the actual adsorption systems and the possible role
of the interactions between the adsorbed molecules. 110-20) Most recently, the authors
have shown, that the SRT approach can be successfully applied to describe the multi-siteoccupancy adsorption of molecules which do not dissociate after being adsorbed. [14]
Compact simple analytical expressions were developed, and next used successfully to
correlate experimental data for adsorptioddesorption kinetics in various gadsolid systems.
The purpose of this presentation is to show, that the new SRT approach can be also
applied to represent the kinetics of dissociative gas adsorption on solids. That kinetics is
of a crucial importance in a variety of catalytic reactions occurring on solid surfaces.
Theory
While assuming the Langmuir model for adsorption of atoms, and the ideal gas
expression for pg,from eq. (2), we obtain,
r
1
0, eq. (3)
&
1+ ( ~ p ( ~ ) ) s e k T
state. By a fast surface diffusion, the adsorbed molecules may migrate to another state
158
- p"'
following expression,
K', = K,p(e)(l-6g))"
as the
(5)
where (1 - 6:)
is the fixtion of the adsorption sites available for molecular adsorption
in the' first adsorbed state, and n is the number of these adsorption sites occupied by the
adsorbing molecule consisting of s atoms. To solve the differential eq. (3), el,")has to be
related to 6. That relation will depend on the particular nature of chemisorption system
under consideration. For the purpose of illustration we will take into consideration the
dissociative adsorption of hydrogen molecules on the Fe(100) crystal face. For this
particular system, Christmann e t d . [21J reported kinetic data measured at different nonequilibrium pressures, whereas the related quantum mechanical calculations can be found
in the recent paper by Kresse. [22] These calculations show that the most favorable
reaction path is when the center of hydrogen molecule approaching the surface is located
over the top site, and the molecule is oriented in such a way that after dissociation the
atoms go into two neighboring bridge sites. Thus 6, can be identified with the occupancy
of the top sites, because one adsorbed atom makes (eliminates) adsorption over one
neighboringtop site impossible. Thus 6, can be identified with 6 under the condition that
n=l.
So, we put n=l in eq. (5). Equation ( 5 ) can be then integrated analytically to yield,
1 E_l
_
-I -&
"I
2E
+C(6)
ln[[Kpeg - 1 b 2 -ZKpekT6+KpekT
t(0) =
Using eq. (6) we have been able to fit successfully the kinetic isotherms reported by
Christmann, e t d . [21]. The results are shown in the Figure 1.
So far we have not considered yet the more complicated problem of the kinetics of
dissociative adsorption of asymmetric molecules like CO. The new level of complexity
here lies in the necessity of considering of the mutual blocking of the adsorption centers
for different atoms after dissociation of adsorbed molecule. Nevertheless we continue our
efforts along these lines, and we hope to publish some solution for that problem in our
future publications.
- 0.4
-
CD
CI
0.01
0.1
1
time, min
10
100
figure 1. The bat-fit of the experimental hetic isotherms of hydrogen adsorption on Ni(100). measud by
christmann et.al. at p~7.10-'~
Ton, 2.5 .lo4 Tom and 7.5 .lo* Tom by applying the SRT eq. (6). and the
following best-fit parameters: K"exp(&") = 7.52.103Todn. &=2.58.10' Ton-'min". and N,= 16.02a.u.
where a.u. axe the arbitrary units used by christmanner.al. [21]to represent the adsorbed amount.
References
1. Rudzinski W. and Panczyk T., The langmuirian adsorption kinetics revised: A
160
161
Y.TERAOKA
Department of Molecular and Material Sciences, InterdisciplinaryGraduate School
of EngineeringSciences, Kyushu University,Kasuga, Fukuoka 816-8580, Japan
E-mail: teraoka@mm.kyushu-u.ac.jp
Introduction
The air pollution by vehicle emissions especially in urban area is a serious problem to be
urgently solved, and regulation of the emission has been becoming more and more
tightened with respect particularly to NOx and non-methane hydrocarbons (NMHC). As
for the NMHC emission control, it is well known that the so-called cold-start hydrocarbon
emission, which contributes about 80% of the total emission, should be reduced. Just
after the ignition of an engine, the exhaust gas is too cold for the three-way catalyst
(TWC) to be active for removing CO, NOx and HC. The HC emission before the exhaust
gas heats up to the working temperature of the TWC is called as the cold-start HC
emission. One, and probably the most promising, countermeasure to reduce the cold-start
HC is to install the cold-stat HC trap on the upper stream to or on the same honeycomb
as TWC [I-51. Some of important requirements for trap materials (adsorbents) are as
follows:
0
They should have high adsorption capacity of HC during the cold condition.
0
They should store the adsorbed HC until the exhaust temperature becomes high
enough for TWC to work (200 C or higher).
0
They should not be deteriorated even under the hydrothermal condition in humid gas
stream at elevated temperatures like 850 C.
This paper reports adsorption property for C2-C3hydrocarbons and characterization
of Ag- and Cu-loaded zeolites to explore excellent materials for the cold-start HC trap.
162
Experimental
Three kinds of zeolites, which were kindly supplied by Tosoh Corporation, were used in
this study: W-ferrierite (FER) with SiOdA1203 molar ratio of 60.2, W - M F I with
SiOz/&o3=39.5 and NH4-b (BEA) with Si02/A1203=37. Ag- and Cu-loaded zeolites
were prepared by an impregnation method or an ion-exchange method using aqueous
solutions of metal nitrates, followed by the calcination in an open air at 500 "C for 1 h
(fresh sample). The hydrothermal treatment was carried out by exposing fresh samples to
moist air (10% HzO)at 850 "Cfor 5 h (aged sample). The metal loadings were expressed
on the basis of wt%; for example, 2.0wt% Ag-loaded FER(60.2) is expressed as Ag(2.0)FER(60.2).
The adsorption property was measured by a static method at 30 "C with a
conventional volumetric apparatus as well as by the temperature programmed desorption
(TPD) method. The details of the pretreatment and adsorption procedures were shown in
Results and Discussion section. Metal-loaded zeolite samples were characterized by
XRD, diffuse reflectance UV-Vis spectroscopy @RS) and electron spin resonance (ESR).
3.1
Figure 1 shows adsorption isotherms of CzH.,. C2& and C& on the fresh Ag(2.0)FJZR(60.2). The sample was pre-evacuated at 500 "C for 0.5 h, and after cooling down to
30 "C,the first adsorption isotherm was obtained. After evacuation at the same
5 2.0
E
1
L
1.5
'$
1.0
0.5
0.0
0
-in
-
2.0
1.5
0.6
-b 2.0
-
E
.
E 1.5
c)
e
8
-0
a
0.0
0.1
0.2
0.3
0.4
0.5
0.6
1.0
0.5
0.0
0.3 0.4 0.5
Relative pressure, p/po
0.0 0.1
0.2
0.6
Figure 1. Adsorption isotherms of (a) CZ& (b) Cz& and (c) C3& on fresh Ag(2.0)-FER(60.2)preevacuated
at 500 "C for 0.5 h. Open and closed circles cormpond to the Ist and 2nd adsorption measurements (see text
for the details).
163
temperature for 0.5 h, the second adsorption measurement was carried out. The adsorbed
amount in the second isotherm corresponds to the amount desorbed during the evacuation
at 30 "C or that of weakly (reversibly) adsorbed species (V,,,),and the difference between
the first and second isotherms does to the amount of strongly adsorbed species (V,) which
did not desorb by the evacuation at 30 "C; the amount in the first isotherm thus
corresponds to the total amount adsorbed (V,=V,+V,). The first and second isotherms of
C2Hs completely overlapped each other. This indicates that parafiic C2& reversibly
adsorbs at 30 "C and no strong adsorbed species is formed. For C2& and C&, on the
other hand, the discrepancy between the 1st and 2nd isotherms was observed, showing
that strongly adsorbed species is formed in addition to weakly adsorbed species. These
result clearly show that Ag(2.0)-FER(60.2) is an olefin-selective adsorbent.
0.1
0.2
0.3
Ag loading I mmol g-1
Figure 2. The amount of C2H4 adsorbed on fresh Ag-FER(60.2) (at p/p0=0.15) as a function of Ag loading.
The Ag loading is shown in unit of mmol g-'.
0.0
100
200
300
400
500
Temperature I "C
Figure
TPD chromatograms of C2I% from Ag- and H-FER(60.2). The aged sample was subje :d to the
hydrothermal treatment by exposing to moist air (1 0%HzO)at 850 "C for 5 h.
I64
with increasing the Ag loading, and the values of V, were in the same order of the Ag
loading: the ratios of VJAg ranged between 0.68 and 0.86 except for the Ag-FER(60.2)
with the lowest Ag loading (VJAg d.43). It can thus be concluded that Ag loaded idon
the FER zeolite is responsible for the formation of strongly adsorbed CZ& species.
Desorption of C2& as a function of temperature was measured by means of TPD
technique (Figure 3). A sample was preevacuated at 500 "C for 0.5 h, cooled down to
room temperature in vacuo, and exposed to C2& (100 torr) for 0.5 h. After evacuation
for 0.5 h and replacing the atmosphere with a helium flow, the sample was heated at a rate
of 10 "C min-' and the desorbed CZ& was monitored by TCD. The static adsorption
experiment showed that H-FER(60.2) adsorbed a substantial amount of C2& strongly at
30 "C, but a majority of them desorbed below 250 "C as shown in Figure 3. As for fresh
Ag(2.0)-FER(60.2), on the other hand, a majority of the strongly adsorbed C2& desorbed
above 200 "C.
Another characteristic feature of Ag-FER as a C2& adsorbent is that the adsorption
property depends only slightly on the pretreatments and the existing state of Ag. The
amount (Table 1) and temperature behavior (TPD, not shown) of strongly adsorbed C2&
is roughly the same after the evacuation (fresh) and oxidation at 500 "C;combined use of
DRS and ESR indicated that Ag idon the FER zeolite was present as cluster ions (Ag,,,?
[6] and metallic silver (Ag? after the evacuation and Ag,* and Ag2O after the oxidation.
More importantly, it has tuned out that Ag-FER is tolerant against the hydrothermal
treatment at 850 "C. Although the amount of the strongly adsorbed species somewhat
decreased, the desorption behavior did not so much change as can be seen from Figure 3
and Table 1.
Table 1. Adsorbed amounts of Czfi on various metal-loaded zeolite adsorbents (30 "C, p/@.15)')
Sample
Pretreatment
[metal content I mmol g-'I
Ag(2.0)-FER(60-2)
[0:185]
Cu(0.6)-FER(60.2)
[0.090]
Ag(5.4)-MFI(39.5)
[0.499]
Ag( 1.8)-BEA(37.0)
[O. 1641
Fresh
Ox-5002)
Aging3'
Fresh
Aging"
Fresh
Aging3'
Fresh
Aging3'
Adsorbed amount I
mmol g-'
V.
V..
0.16
0.15
0.13
0.10
0.01
0.35
0.16
0.15
0.81
0.79
0.73
0.91
0.06
0.82
1.10
0.54
1.21
0.20
V,per
0.86
S:)l
m2 g-'
252
0.81
----
0.70
1.10
0.1 1
0.70
0.32
0.9 1
0.37
256
------347
216
487
98
1) All the samdes were evacuated at 500 "C for 0.5 h before. the adsorption measurements.
2) Exposure to 0,(100 torr) at 500 "C for 0.5 h. 3) Hydrothermal treatment by exposing fresh samples
to moist air (10% HzO) at 850 "C for 5 h. 4) VJmetal content. 5) Specific surface area.
3.2
165
There results clearly indicate that Ag is superior to Cu as the active metal species for C2H4
adsorption with respect to the hydrothermal stability.
3.3
The results reported in this paper clearly show that Ag-FER(60.2) is the promising
material for cold-HC trap with the following characteristics.
(1) superior selectivity to olefins (C2H4, C3H6)over a parafin (C2H6)
(2) high adsorption capacity with the VJAg ratio in the range of roughly 0.7-0.9
(at p/po=O.15)
(3) desirable storage ability desorbing the strongly adsorbed species above 200 "C
(4) high hydrothermal stability
Selectivity (l), capacity (2) and storage ability (3) originate from the characteristics
of Ag itself, while the stability (4) of Ag-FER(60.2) is contributed by the structure
stability of the FER(60.2) and insensitivity of the adsorption property of Ag to its existing
states. The higher SiO2/AI2O3ratio of FER(60.2) is the most probable reason for the
zeolite-structure stability. The insensitivity of Ag is a favorable property as -a stable HC
trap material, and its origin will be elucidated by a future study.
References
1.
2.
3.
4.
5.
6.
Burk P. L., Hockmuth J. K., Anderson, D. R., Sung, S, Punke, A, Dahle, U, Tauster
S. J., et al., Stud. S u Sci.
~ Catal., 96 (1995) pp.9 13-939.
Nishizawa K., J. of Soc. of Automotive Engineers of Jpn. (Japanese), 50 (1996) pp.
61-65.
Ballinger, T. H., Manning W. A., Lafyatis, D. S., SAE Paper (1997) pp.27-31
(970741).
Lyfyatis, D. S., Ansell, G. P., Bennett, S. C.,Frost, J.C., Millington P. J., Rajaram, R.
R., Walker A. P., Ballinger, T.H., Appl. Catal. B, 18 (1998) pp.123-135.
Czaplewski, K. F., Reits T. L., Kim, Y. J., Snurr, R. Q., Microporous and
Mesoporuos Materials, 56 (2002) pp.55-64.
Bogdanchikova, N. E., Dulin, M. N., Toktarev, A. V., Shevnia, G. B., Kolomiichuk,
V. N., Zailovskii V. I., Petranovskii, V. P.,Stud Surf: Sci. Catal., 84 (1994) pp. 10671074.
166
An adsorption kinetic model was developed to evaluate the adsorption rates of five pure gases (Nz,
02, Ar, CO, and Ch) on a Takeda-3A CMS over a wide range of pressures up to 15atm. The kinetic
characteristics of adsorptionon the CMS were studied by using the adsorption equilibrium of five pure
gases measured at three different temperatures and their physical properties. Since the diffisional time
constants of all the components showed much stronger dependence of pressure than those expected by
the traditional Darken relation, a structural diffusion model was applied to predict the strong pressure
dependence. The proposed model successfully predicted the diffisional time constant up to high
pressure on the CMS.
Introduction
Carbon molecular sieve (CMS) is useful in air separation processes because of its
ability to selectively discriminate on the basis of molecular size and hence adsorb the
smaller oxygen molecule over nitrogen. The difference in the adsorption kinetics of
various gases aIlows the separation of gas mixtures into pure components using pressure
swing adsorption (PSA).
Generally, the kinetic rate constants on adsorbents increase with increasing surface
coverage. The reason is probably related to surface diffusion (Reid and Thomas, 1999).
Ruthven (1992) pointed out that the diffisivity of oxygen increased with adsorbate
loading on CMS more or less in terms of Darken's equation. The pressure-dependencesof
D/? are generally predicted by Darken-relation, but in some cases the pressuredependeces are so strong that it cannot be predicted by traditional Darken-relation. Hence,
in these cases, the model that can predict these strong pressure-dependencesis needed.
In this paper, the isotherms and diffisivities of five pure gases @I2, 02,Ar, CO, and
CH4)in CMS were studied in the range of 293-313K, 0-15atm.
2
Experimentals
The volumetric method was used to obtain the data of the adsorption equilibrium and
the adsorption kinetics. The adsorbent used in this study was Carbon Molecular Sieve
(Takeda Co.) and has an average pore size of 3A. The adsorbates were 99.99%-purity
gases. Prior to the measurements, the adsorbent was regenerated by evacuation at 423K
during 12hr. The CMS is loaded with an adsorbate in a stepwise procedure; equilibrium
and kinetic data are obtained in each step. In determining the size of each step, we
considered the pressure range in which linear isotherm can be applied.
167
Mathematical Models
3. I
Equilibrium Models
Langmuir isotherm:
L F isotherm:
Toth isotherm:
D-R isotherm:
bP
l+bP
c, = c,
b PI'"
1 + b P""
bP
c, = c,
(1 + (bP)" ) I / "
c, = c,
(4)
If above Darken-relation (Eq.(5)) is combined with the Langmuir, L-F, Toth, and D-R
isotherms, the resulted models are as follows:
t
Darken-Langmuir:
D, = D,, ( 1 + bP )
(6)
Darken-LF:
Darken-Toth:
Da rken-DR.
D, = Dfl
168
ln(4 / P)
(7)
4.1
ResultsandDiscussion
Adsorption Equilibrium
Adsorption isotherms of five gases at 293K for C M S determined from the volumetric
experiments are shown in Fig. 1. Adsorption capacities of each gas are as follows: Nz,4,
Ar < co << CH4.
8E
--- Langmuir
CH,
E3
01
c
0
3
5 2
D
i
$ 1
0
0
10
12
14
16
18
Pressure [atm]
Figure 1. Adsorplion isotherms of five pun, gases at 293K
and h e lib of the Langmuir, LF. and Tom lsomenns
4.2
Adsorprion Kinetics
3:L
0.2
Dodng d l P. (Simu1fi.d)
0.1
0.0
0
400
em sm lorn
[-I
1200 14m 1-
169
In the adsorption rates of all the components on the CMS,the diffusional time constants
showed strong dependence of pressure. Reid and Thomas (1 999) suggest that the reason
for these increases in the adsorption rate with surface coverage is probably related to the
surface diffusion. These exponential increases of the effective diffusional time constant
might be explained by above Darken-based models.
As shown in Figures 3 and 4, the large deviations between experimental and predicted
results by Darken-based models (Eqs. (6)-(9)) were observed in the experimental range of
pressure. At each case, the experimental diffusional time constant showed much stronger
pressure dependence than the results predicted by the Darken-based models.
0.008
c1
0.004 .
0.003-
0.0025
N2
Darkenlangmuir
Darken-LF
Darken-Toth
Darken-DR
-'2
Ar
Darken-Langmuir
DarkEn-LF
Darken-Toth
0.0020
0.0015
a 0.0010
a O.wO5
10
O.oo00
p 11-
10
P 1aMI
Do (1 996) proposed a structural diffusion model, and derived the following relation for
the surface diffusivity on the assumption that the gradient of the isotherm is large in the
initial stage.
A
dC, i d P
D, =
Do-rela tion :
Here, A is a constant.
Above four isotherms were applied to Do-relation (Eq. (lo)), and the following
relations were derived.
Do-Langmuir:
D, = D,, ( 1 + bP )'
DO-LF:
Djl = Djlo
(1 + b P y
I -n
~
P"
Do-Toth:
Do-DR
I+n
* (-P).expEa'(InP)'-2dInP-lnP,]
*
In(P/P,)
170
(1 4)
In Figures 5 and 6, the prediction results by Do-based models (Eqs. (1 1)-(14)) were
shown for N2 and Ar. The similar prediction results were obtained at the other gas
adsorptions. From these results, it is concluded that Do-based models shows better
prediction results than Darken-based models.
0.006
y
L
r
0.005
0.0025
N,
0.004
0.003
b 0.0015
303K-expt
Ar
Do-Langmuir
--- Do-LF
_ - OO-TOth
Do-DR
0.002
0.0020
% 0.0010
a O.OOO5
0.001
0
oooo
0.000
0.OoM)
10
P [am1
10
Conclusions
Acknowledgements
References
1. Ruthven, D.M., Diffusion of Oxygen and Nitrogen in Carbon Molecular Sieve, Chem.
Eng. Sci., 47,4305 (1992).
2. Brandani, S., Analysis of the Piezometric Method for the Study of Diffusion in
Microporous Solids: Isothermal Case, Adsorption, 4, 17 (1998).
3. Bae, Y.S.,* Kim K.I., and Lee C.H., Sorption Equilibrium and Kinetics in CMS by
Piezometric Method, Theory and Applications of Chemical Engineering, 7( l), 2422
(2001).
4. Do, D.D, A model for Surface Diffusion of Ethane and Propane in Activated Carbon,
Chem. Eng. Sci., 51,4145, (1996).
5 . Reid, C.R., and Thomas K.M., Adsorption of Gases on a Carbon Molecular Sieve
Used for Air Separation: Linear Adsorptives as Probes for Kinetic Selectivity, Langmuir,
15,3206 (1999).
171
1 Introduction
172
2 Experimental
2.1 Introduction of
Q new
CSP
2.2 Chemicals
The eluent used was methanol and buffer (40:60). The concentration of triethylamine
acetate in buffer is 2% and the pH of buffer is 5.0 adjusted by addition of glacial acetic
acid. The feed was prepared by dissolving racemic fluoxetine in the mobile phase.
Fluoxetine was extracted from Prozace capsule, providbd by Lilly Company.
2.3 Instrument
The SMB system consists of 8 columns (250mmx1Omm) packed by the new CSP. The
columns are fed with either the feed or the eluent (inlet and outlet) via 5 or 8 port rotary
valves (VICI). The configuration tested is 2222 (two columns per zone. The
concentrations of the extract and the raffinate streams were analyzed for each stage using
a standard analytical chromatographic system. An analytical column (250mmx4.6mm)
packed by 5pm CSP was used to analyze the concentration of these samples. The
adsorbance wavelength was set at 225nm.
2.4 Adsorption Isotherm
In the study, Langmuir model was assumed to fit the adsorption equilibrium relationship
of fluoxetine on the column packed by the new CSP and the following approximated
extended Langmuir model was used to describe the adsorption behavior:
5.94cA
- 1 + 0 . 7 1 5 ~+ ~0 . 2 1 4 ~ ~
5.18~~
qB = 1 + 0 . 7 1 5 ~+~0 . 2 1 4 ~ ~
where A is (S)-fluoxetine and B is (R)-fluoxetine.
Now, let us design the operating conditions following the above process. Several runs
were carried out and the position of every operating point on the m2-1~13plane was shown
in Figure 1. Every sample was collected after the system was stable.
Operating point S is the theoretical optimal operating condition derived from
triangle method [5]. The purity of the extract and the rafinate at this experimental point is
83.4% and 99.8%, respectively. Experimental results show that the theoretical optimal
operation condition is not robust or distorts from actual complete separation region;
Points A and C are close to the actual complete separation region and point B is in the
actual complete separation region, When PACand PBAare extended to intersect at WO,a
triangle W ~ A PisB formed. This is assumed to be actual complete separation region. It
must be mentioned that A and C could be in the theoretical complete separation region
after considering the operational disturbance [6].
4)
41
6.6
6d
mt
174
To improve the robustness of the operation, the difference between m 3 and m2 for
point B is decreased to point H.Due to the increase in eluent flow-rate, the pressure of the
system is increased to an extent that the system cannot tolerate. Thus, the stability of the
operation is damaged, and good separation results are not achieved. This means that
although decreasing the difference between m3 and mz could improve the robustness of
the operation, the operation performance parameters will be sacrificed, sometimes even
the SMB system cannot be run smoothly. Unstable operation should be avoided in real
applications. Runs I, J and K are carried out to find the possible optimal operating
condition by increasing the difference between m3 and m2. At point K, the robustness of
the operation cannot hinder the disturbance of the operation, so the purity of the extract
and the raffinate are all decreased. Enrichment of the extract and the raffinate is increased
when the difference between m3 and m2 is increased. In other words, the solvent
consumption is decreased. Because of the decreasing of the robustness, these three
operation parameters all decreased slightly. With reference to the operation parameters of
B, I, J, K, operating point J can be considered to be the possible optimal operation point.
4 Conclusions
In this work, a new CSP was developed to separate a chiral drug using the
chromatographic technique, and a pragmatic method was developed to establish the
operating conditions of the SMB system based on the theoretical triangle method. A
triangle region determined from the experimental results was assumed to be an actual
complete separation region. In this region, possible an optimal operating condition of the
SMB was found. Good separation results can be obtained. It is shown that this method is
available to establish operating conditions and reduces the experimental efforts
effectively. It can be concluded that the new CSP is efficient for enantioseparation of
chiral drugs.
5 Acknowledgements
175
References
1.
2.
3.
4.
5.
6.
176
G. ERDEM AND M. M O W
ETH Zurich, Automatic Control Laboratory, Physikstrasse 3, 8092 Zurich, Switzerland
E-mail: erdem@aut.ee.ethz.ch; morariamt.ee.ethz.ch
M.MORBIDELLI
ETH Zurich, Laboratory of Chemical Engineering and Industrial Chemistry,8093 Zurich,
Switzerland
E-mail: morbidelli@.tech.chem.etk.ch
In the recent years Simulated Moving Bed (SMB) technology has become more and more attractive for
complex separation tasks. To ensure the compliance with product specifications, a robust control is
required. In this work a new optimization based adaptive control strategy for the SMB is proposed: A
linearized reduced order model, which accounts for the periodic nature of the SMB process is used for
online optimization and control purposes. Concentration measurements at the raffinate and extract
outlets are used as the feedback information together with a periodic Kalman filter to remove model
emors and to handle disturbances. The state estimate from the periodic Kalman filter is then used for
the prediction of the outlet concentrations over a predefined time horizon. Predicted outlet
concentrations constitute the basis for the calculation of the optimal input adjustments, which
maximize the productivity and minimize the desorbent consumption subject to constraints on product
purities.
Introduction
177
control of SMB by adopting different strategies [3,4]. In this work we will follow a new
model-based predictive control method that was introduced by Lee and Natarjan [5,6]. This
is called Repetitive Model Predictive Control (RMPC), and combines the concepts of both
MPC and Repetitive Control (RC).
2
Control concept
The suggested control strategy uses a simplified SMB model in order to optimize the
operating conditions of the plant on-line. The basic concept of the adopted approach is
illustrated in figure 1.
Objective FuncUon
+ Product Specifications
SMB Plant
Internal Flowrates
puw,
Productivity,
_____*
Solvent
Consumption
~
I
I
I
Concentration
Measurements
The controller receives the on-line composition measurementof the product outlets (extract
and rafinate) as feedback data from the plant. These measurements are filtered through a
periodic Kalman filter and used together with the simplified SMB model results to estimate
the state of the system and to remove the possible model errors. The formulation of RMPC
is based on the assumption that possible errors or disturbances are likely to repeat and will
have a periodic effect on the output, which is the most likely correlation between
disturbances and output in a SMB unit. The estimated future concentration profile in the
SMB is used to optimize the future behaviour of the plant over a predefined prediction
horizon. The controller implements the calculated optimal plant input by changing the
external flow rates in order to control the internal flow rates, which are the manipulated
variables. Time lags, e.g. between online concentration measurements and optimizer or
between optimizer and SMB plant, are insignificant relative to the process dynamics and
sampling time for the planned scheme.
2. I
It is not possible to apply a detailed SMB model for on-line use together with the controller
without facing severe computational problems. Hence a simplified model is needed, which
178
is simple enough for efficient computation, but still captures the characteristic process
dynamics of an SMB. This model is then used, according to the control scheme shown
above, to estimate the internal concentration profiles and to calculate optimal operating
conditions as input for the plant. To obtain the simplified model from the equilibrium
dispersive SMB model, the model equations are linearized around a compositionprofile (in
space) calculated at cyclic steady state. Since at cyclic steady state concentration fronts
propagate along the columns and the composition profile (in space) also changes, different
composition profiles are used to linearize the model equations at different points in time
during one SMB cycle. It is worth noting here that one cycle corresponds to a number of
time periods between inlet-outlet switches equal to the number of columns in the SMB unit.
Finally the model order is reduced by using balanced model reduction as proposed by Lee
161. The obtained simplified model is then used to predict and to optimize the future
behaviour of the SMB plant.
2.2
Optimizationproblem
The idea of the control concept introduced in this work is to optimize the process over a
predefined prediction horizon, which has been chosen as 2 cycles. The control horizon in
which possible flow rate changes are calculated, is 1 cycle, though. The optimization
problem of a SMB unit with a constant switch time can be formulated as maximizing the
feed flow rate and minimizing the desorbent consumption (cost function). In practice,
economical considerations or others will guide the choice of the relative importance
attributed to these two optimization goals. Of course, this problem is subjected to certain
constraints. First of all the purity requirements in the extract and rafkinate stream has to be
fulfilled. In addition to this the system has a number of physical limitations such as
non-negative flow rates. The cost function together with the defmed constraints constitute a
Linear Program (LP) to be solved at each time step based on the new measurements
available. Calculated optimal internal flow rates, which fi~lfillthe constraints and optimize
the performance of the SMB unit, are implemented on the unit via changes of the external
flow rates.
3
In order to evaluate the performance of the controller, various scenarios have been
simulated on a virtual platform. This means that instead of a real plant a SMB model based
on the equilibrium dispersive model is used [7]. In the following an example is given to
show the flexibility and performance of the controller.
3. I
VirtualSMB system
179
controls e.g. the recycle flow. The switch time is kept constant during the process.
3.2
Simulation result
To assess the performance of the developed controller the evolution of the purity over time,
in comparison to the uncontrolled case, is monitored. A minimum product purity of 99% is
given as product specifications. The controller is switched on after the plant has reached the
cyclic steady-state at the chosen start-up operating point, which is the operating point used
for linearization (ml=4.0, m2=2.1, m3=3.9,m4=2.1; see [7]for the definitions) and leads to
poor product purities. The chosen example shows the case of a sudden, rather large step
change in Henry constants. The controller is switchedon at cycle 20. Then it brings the plant
to fulfill specificationsand the plant is run at its optimal operatingconditions. A step change
in the characteristicadsorption parameters occurs at cycle 60, when HAand HBincrease by
10% and 15%, respectively. It can be observed, that the purity of both extract and raffmate
outlet decreases down to 85% for the uncontrolled plant. On the contrary the controller
reacts and recovers the purities within 5 to 8 cycles, then driving the plant to the new
optimum operating conditions.
0.91
0.86
O.8ZL
---
extract
10
20
30
40
50
60
70
80
90
100
I
110
Cycles
Figure 2. Comparison of the SMB outlet purities in the controlled and uncontrolled case. The controller is
switched on after reaching steady state and a step disturbance in Henry's constants takes place at cycle 60.
(AHA+~OYO,A Hs=+15%).
Conclusion
An optimizing adaptive control strategy for the automatic control of the SMB process has
180
been proposed. It enables to operate the SMB unit at its optimal conditions. The developed
controller has been tested on a virtual platform where a linear adsorption isotherm was used.
It has been shown that the designed controller fulfills the process specificationsand at the
same time it optimizes the productivity and solvent consumption. It can adapt the operating
conditions to the changes caused by disturbances (e.g. caused by temperature changes),
operate under extreme model mismatch conditions and cope with irregularities andor aging
of the chromatographic system. One of the most important features of the controller is its
ability to find the real optimum of the process and adapt the operating conditions if
necessary.
5
Acknowledgements
The authors are gratefiil to Prof. Jay H. Lee and Prof. Hyun-Kun Rhee for helphl
discussions. The support of ETH Zurich through grant TH-23YOO-1 is gratefully
acknowledged.
References
1. Garcia C.E., Prett D.M. and Morari M., Model Predictive Contol - Theory and Practice
- A survey, Automatica 25 (1989) pp. 335-348.
2. Bemporad A. and Morari M., Model Predictive Contol: A survey, Lecture Notes in
Control and Information Sciences 245 (1999) pp. 207-226.
3. Kloppenburg E. and Gilles E.D., Automatic control of the simulated moving bed
process for C8 aromatics separation using asymptotically exact
input/output-linearization.A of Process Control 9 (2000) pp. 4 1-50.
4. Klatt K.U., Hanisch F. and Dlinnebier G., Model-based control of a simulated moving
bed chromatographicprocess for the separation of fructose and glucose. J. of Process
Control 12 (2002) pp. 203-219.
5. Natarajan S. and Lee J.H., Repetitive model predictive control applied to a simulated
moving bed chromatography system, Computers and Chem. Eng. 24 (2000) pp.
1127-1133.
6. Lee J.H., Natarajan S. and Lee K.S., A model-based predictive control approach to
repetitive control of continuous processes with periodic operations. Journal of Process
Control 11 (2001) pp. 195-207.
7. Migliorini C., Gentilini A., Mazzotti M. and Morbidelli M., Design of simulated
moving bed units under non-ideal conditions, Ind. Eng. Chem. Res. 38 (1999) pp.
2400-24 10.
181
1.
Introduction
Surfactants are the most critical part of a detergent formulation. Surfactants with enhanced
water solubility relative to existing commercial surfactants are highly desirable for the
formulation of improved household detergents and cleaning products. Many existing
commercial detergents are composed of anionic surfactants derived from linear alkyl
benzene. It has been demonstrated that surfactants that are formulated from benzene
alkylated with mono-methyl parafin intermediates have a greater water solubility than
those formulated fiom benzene alkylated n-paraffin intermediates. To create these
enhanced water-soluble surfactants in commercially significant quantities, a raw material
source for Clo to CI3 mono-methyl parafin is required. This range of mono-methyl
paraffm is typically found in kerosene and n-paraffin depleted kerosene. N-Paraffin
depleted kerosene (Molex Raffinate) is a by-product obtained fiom the UOP Molex
process and is typically used in Jet Fuel Pool blending. Both kerosene and n-paraffin
depleted kerosene are composed of a mixture of n-paraffin, mono-methyl parafin,
di-/tri-branched paraffin, naphthenes, and aromatics. Previously, no commercial process
was available to separate mono-methyl paraffin from kerosene or n-paraffin depleted
kerosene. UOP has developed an adsorptive separation process for mono-methyl
parafin. This process utilizes the simulated moving bed system and is called MMP
SorbexTM.
2.
2. I Silicalite Adsorbent
Early in the development of the process, we determined that silicalite, a MFI structure
type adsorbent, is suitable for the process. Silicalite is crystalline silica, which has a
novel topologic type of tetrahedral h e w o r k similar to aluminosilicate molecular sieves.
182
Oxygen rings containing 10-members define the straight channels along the b-axis with an
elliptical cross session of 5.7-5.8 Angstrom by 5.1-5.2Angstrom. These channels are
interconnected by zigzag channels along the a-axis defined also by 10-membered oxygen
rings with a nearly circular cross section of 5.4 Angstrom. Based on the pore openings
above, one would expect n-paraffin, mono-methyl paraffi, and low molecular weight
aromatics and naphthenes enter into the channels of silicalite.
1-butyl-3-propylcyclopentane
2,ddimethyloctane
n-hexylcyclohexane
3,3,5-trimethylheptane
1,2,3-trimethybenzene
2-ethyl-1,3-dimethylbenzene
trans-l,2-di~ro~ylcvclohexane
14
15
27
-13
-17
-15
slow
slow
very slow
45
80
80
125
150
+35
+50
+50
excluded
excluded
excluded
excluded
excluded
+loo
+I07
The simulated diffusion model involves advancing an probe molecule through the
zeolites main channel and using molecular mechanics methods to calculate the energy of
the probe molecule at regular intervals as it interacts with the atoms in the sieve wall.
The energy difference between the low and high energy positions of the probe molecule in
the channel is defined as the energy barrier which can be used to predict the diffusion ease
of the probe molecule in the zeolite channel - the larger the barrier, the more restrictive
the diffusion. Another parameter that assists in predicting diffisivity is the sign and
magnitude of the maximum energy (Emax),which is a measure of how much the probe
molecule is stabilized (negative values) or destabilized (positive values) at the bottleneck
positions in the zeolite channel.
.The modeling results fiom simulating the diffision of pertinent molecules in silicalite
are summarized in Table 1. Note that the predicted diffusivity of the molecules, based
on the magnitude of the energy barrier, agrees with experimental data (see pulse test
session). The n-decane and 2-methylnonane, with energy barriers less than 10 kcal, have
good diffisivity whereas 2,ddimethyloctane and small naphthenes, with energy barriers
183
and 2. Figure 1 shows a plot of the relative concentrations of the components versus
volume of effluent. The improved separation using the pre-pulse is also shows
graphically in Figure 2. A comparison of the two plots shows that use of a pre-pulse
resulted in a much better separation of mono-methyl paraffin (2-methyl nonane) from the
balance of feed components.
184
30
20
10
n
"20
30
40
50-
60
70
80
90
100
110
120
80
_r.
70
3,3,5-TM-C,
6050
2 ,QDM-C,
A third pulse test with pre-pulse of iso-octane was carried out using a feed representative
185
similar the test 2 above. The highly branched paraffins, naphthenes, and aromatics were
rejected and the desired mono-methyl paraffins were extracted. The gas chromatogram mass spectrophotometry of the extracted mono-methyl paraffins is shown in Figure 5.
As expected from the diffusion simulations, trace quantities of naphthenes and other small
molecular compounds are present in the extracted product along with the desired product,
normal and mono-methyl paraffins.
I
Time
I_,
Retention Volume
186
27
29
31
33
Time
35
37
39
41
Figure 5. Gas Chromatogram Mass Spectrophotometryof extract product from Pulse Test
Conclusion
Two adsorption techniques have been developed for the separation of mono-methyl
paraffins from kerosene or n-paraffin depleted kerosene using silicalite adsorbent. The
first one is using a mixture of C5and/or C6 n-paraffin and cyclo- and or iso-paraffin
desorbent. The second one is an enhanced mono-methyl parafin recovering process using
the pre-pulse technique in combination with the previous one.
Pulse tests
(chromatographic separation) with both techniques showed good performance in the
laboratory. The process was demonstrated successfully in a simulated continuous
counter-current chromatographic separation pilot plant using commercial n-parafin
depieted kerosene feedstock. Better than 90% mono-methyl and normal paraffin purity
with greater than 70% recovery of mono-methyl paraffins was achieved from the pilot
187
plant. The simulated diffusion model involves advancing an organic molecule through
the zeolites main channel was investigated. Results confirmed the experimental
findings.
References:
1. R.W.Neuzil, U.S. Patent 5,382,747, 1995
2. Santi Kulprathipanja,Monomethyl paraffin adsorptive separation process, U.S.A.
Patent 6,222,088 B 1,200 1
3. Santi Kulprathipanja, Process for monomethyl acyclic hydrocarbon adsorptive
separation, U.S.A. Patent 6,252,127 B1,2001
4. Santi Kulprathipanja and James Johnson Liquid Separation,Handbook of Porous
Solids, Edited by F. Schuth, K. Sing, J. Weitkamp, To be Published by Wiley-VCH,
Germany in 2002
188
Introduction
Chromium compounds are widely used in many industries: metal finishing and
electroplating, leather tanning, pigments manufacturing, photography and catalysts
production [I]. The presence of chromium species in wastewater of all of these industries
is a problem because of the affect onto the human physiology. Chromium removal from
wastewaters by adsorption onto activated charcoals is an important process in the
environmental protection [2]. On the other hand the chromium species adsorption from
aqueous solution is one of the processes for chromium catalysts supported on activated
carbons production [3].
Usually the activated carbon granules are employed for chromium removal or for
catalysts preparation. However in some previous reports the perspectives and advantages
of activated carbon fibers (ACF) utilization for the same employment have been
documented [2,4]. It seems from the analysis of the articles that the use of ACF or
activated carbon cloth has a great potential.
In the present work the adsorption of Cr(V1) and Cr(II1) on ACF with different pore
structure as well as on the oxidized form of ACF was studied.
2
189
For adsorption 0.1 g of ACF (previously washed up to pH 7.0 and dried) were
added to 100 ml of solution. The experimental variables were: time of contact between
ACF and solutions, initial concentration of chromium ions, pH, and temperature.
Table 1. Preparation conditions and some properties of ACF
3.1
To obtain the experimental data the suspensions of ACF in the solutions of chromium(V1)
with the initial concentrations 200 mg/l were shaken at 22-25C. As the reduction of
Cr(V1) to Cr(II1) was shown in some papers [6] in our investigation the variation of both
chromium ions concentration during adsorption was determined.
Table 2 presents the abatement of Cr(V1) concentration and the rate of all
chromium species adsorptions to wit - the adsorption capacity (AC) of different ACF,
when fig.l show the growth of Cr(II1) concentration. In all cases the initial pH was 4.7,
the final - 6.4. The experiment carried out showed that for ACF- 1, ACF-2, ACF-3 pore
structure and the value of surface area has no great importance.
On the other hand in the case of ACF-4 when the total pore volume is around 0.3
cm3/gand Sh,=500 - 600 m2/g during the initial phase of adsorption (time less then 2 h)
the AC decreases twice. At the same time for all non oxidized ACF the final (reached
after 48 h) amounts of chromium species adsorbed and Cr (VI) reduced to Cr(l11) are very
close. Oxidized sample ACF-~OX,
possessing the similar texture as ACF-3, has notably
lower adsorption and reduction capacity in respect to non-oxidized sorbents.
It is important to mention that at the beginning phase of ACF contact with
solutions the latent period of Cr(IV) to Cr(1II) reduction can be distinguished (fig. I).
This phenomena becomes more visible in the range ACF-4>ACF-3 >ACF-2 >ACF-1 and
can be attributed to the self-catalicale reduction-oxidation reactions between carbon and
Cr(V1) species and/or oxygen-containing groups on carbon (-OH, -COH) and Cr(V1) ions.
The similar effect was described in our previous paper for the platinum and gold species
adsorption on ACF [7].
The data presented in table 3 and fig2 show the abatement of Cr(V1) concentration,
AC of ACF and the growth of Cr(II1) concentration at pH 2.5-2.9. A large increase in the
amount of Cr(V1) transformed to Cr(II1) and in the amount of chromium removed is
produced as the pH decreases. Furthermore the amount of Cr(1ll) (fig.2) rises up to
190
maximum in the initial phase of ACF/solution contact (time up to 2 h) and than falls to
the minimum (time up to 48 h). It indicates that the Cr(II1) species could be adsorbed onto
ACF when the ACF are oxidized during the adsorptiodreduction of Cr(V1) ions. The
presence of oxidized form of ACF is expected to facilitate the Cr(1II) elimination but they
are not effective for Cr(V1) removal.
The ACF-2ox/Cr(VI) solution contact confirm low capacity of oxidized fibers for
chromium (VI) ions adsorption.
Table 2. chromium (vi) species adsorption at initial pH - 4.7 as a function of time.
A.
B.
0,s
1.5
24
48
Figure 1. Chromium (111) concentrationvariation as a function of time. Initial pH 4.7; temperature 20 "C.
A.
B.
Cr (VI).concent&on, mg/l
.
Total mount of chromium (VI) and (Ill) removed - AC, mg/g
0.5
1.5
81me. h
ax
24
48
Figure 2. Chromium (III) concentrationvariation as a function of time. Initial pH 2.5; temperature 20 'C.
191
3.2
As from the previous experiments it was impossible to determine the adsorption capacity
in regard only to Cr(1II) ions theirs adsorption onto different ACF was examined from
Cr@IO3), solution with initial concentration of Cr(II1) - 100 mg/l. Fig.3 shows the
amount of Cr(II1) species removed at pH 3.2 - 3.9 temperature 20-25 "C and at different
ACF/solution contact time.
tACF-4
+ACF-3
t ACF-2
JC-ACF-1
Jlt ACF-ZOX
time, h
According to the experiments carried out the maximum adsorption capacity to Cr(lI1)
ions can be affirmed for oxidized sample ACF-2ox. The Cr(lI1) removal by non-oxidized
ACF is more than twice less. The adsorption equilibrium for all ACF was reached in a
period of time close to 3 h.
3.3
0 # ) 4 0 6 0 8 0
The inverse relationship between the amount of chromium ions removed and the
temperature was found. This fact can be explained in the consideration that the amount of
Cr(V1) reduced to Cr(II1) increases with the increase of the temperature and that the
adsorption of Cr(II1) ions on ACF-1 is relatively low. So, more the Cr(lI1) ions appears in
the solution during ACF and Cr(V1) species contact less the total amount of chromium
removed.
Additionally it can be mentioned that the three states of chromium (Cr20;2, Cr203,
C i 3 ) on surface of ACF were detected by X-ray photoelectron spectroscopy. According
192
to the data obtained the direct adsorption of Cr(V1) and Cr(Il1) species (if they are both in
the solution) as well as Cr(V1) reduction to Cr203 and to Cr (111) ion with the subsequent
adsorption can be supposed.
3.4
The relationship between the initial concentration of Cr (VI) species in the solutions and
adsorption capacity of ACF-1, ACF-2 and ACF-3 at pH 2.5, temperature 20 'C, after 48 h
is presented in figure 5.
400
References
1 . Lalvani S.B., Wiltowsk T., Hubner A., Weston A., Mandich N., Carbon 36 (1998) p.
1219.
2. Morozova A. A., Zh. Prikl. Khimii 68 (1995) p. 770.
3. Brown P.N., Jayson G.G., Thomson G., Wilkinson M.C., Carbon 27 (1989) p. 821.
4. Lyssenko A., Carbon-based media for water purification, The international magazine
for technical textile users 38 N24 (2000) p. 33.
5. Chand S., Agarwal V.K., Kumar P., Indian J., Enviror HLTH 36 Ne3 (1994) p. 15 1.
6. Aggarwal D., Goyal M.,Bansal R.C., Carbon 37 (1 999) p. 1989.
7. Lyssenko A., Simanova S., Abstracts, At 7th International conference of
Fundamentals of Adsorption, Nagasaki, Japan, May (200 1) p. 38.
193
Introduction
Industrial wastewaters are often complex aqueous mixtures containing various pollutants:
heavy metal ions, organic molecules, dyes, etc. and some of them are toxic or undesirable
to many living species.
Previous investigations were mainly focused on the use of low-cost sorbents [ I ] as a
replacement for costly methods of removing heavy metals from solution. Commonly, it
concerns inorganic materials like fly-ash [2] as well as chitosan [3,4], biomass [5,6],
sewage sludges [7], peat [8] ... For these latter of biological origin, the term of
biosorption is used to encompass contaminant uptake via physico-chemical mechanisms
such as adsorption or ion exchange. The low-cost biosorbent used in this paper is a byproduct of the sugar industry: the sugar beet pulp. This material is very cheap (1 00 per
metric tonne) and its production reaches 14.106 tomes of dry matter each year in the
European Community [9]. Sugar beet pulp is a natural polysaccharide and composed of
20 % and more than 40 % of cellulosic and pectic substances respectively. These latter
contain polygalacturonic acids which cany carboxyl functions and consequently exhibit
good capacities to retain metal ions [10,1 I]. Activated carbon, within its different forms,
is commonly used in water treatment for organic pollutant removal [12,13,14].
Nevertheless, some applicationshave showed its ability in metal removal [ 151.
In this work, the treatment of a synthetic wastewater composed by metals ions (Cu2+,
Ni2+ and Pb2+) and organic molecules (benzoic acid, benzaldehyde and phenol) is
investigated with a mixture of two sorbents, sugar beet pulp and granular activated carbon.
In a first step, equilibrium data are determined in a batch reactor for each adsorbent and
mono-component solutions. Then, the pollutants are mixed to treat binary and ternary
systems of metal ions, or a combination of Cu2+with organics. A second part focuses on
an association of the activated carbon with the polysaccharide for the treatment of a
solution containing Cu2 and phenol.
194
The adsorbents
Raw sugar beet pulp was provided by Lyven (France). Its preparation has been previously
2.1
described by GBrente et al. [ 101 and the fixation of several metals have been studied and
published in [11,16]. The granular activated carbon, Pica NC60 from Pica Co. (France),
presents a high specific surface area (1200 mz.g-') coupled with a large microporosity
(94.5% VOI.).
2.2
Sorption experiments
--
............. &!.
alone
......
CuZ'
......................................................
"
-12% - 5 0 % -42%
-10%-40% -43%
% of decrease
Figure 1. Ion competition experiments, conducted at initial equimolar ionic concentrations (8.1O4 mo1.L-I)
In the case of single metal ions adsorption, it has been seen (Fig.1) that the adsorption
capacities order following Pb" > Cu2' > Ni2' [ 161. Smith and Martell [171 and Makridou
et al. [181 have shown that Pb2'presents a higher stability constant with galacturonic acid
than Cu". Moreover, no value are featured for Ni2'and Makridou et al. [ 181 assert that a
complex between this metal and galacturonic acid does not exist. These results confirm
195
the order obtained above. Some experiments are then performed to study the competition
of adsorption of these metallic species. Experiments conducted with two different cations
show that Ni2' ion exhibits the lowest competitive effect: whereas its presence induces
decreases of adsorption capacities of 12 % for Pb" and 10% for Cu", these last two
cations prevent the Ni2'fixation at 47 and 56 % height respectively. Pb" seems to have a
higher effect than Cu". In a mixed solution of copper and lead, the influence of the two
metals is slightly different: Pb2' induces 40 % decrease in Cu2+fixation, and vice-versa
the percentage reaches 50 %. As Pb2' is supposed to have the main preference to the pulp,
this value should be abnormally great, especially as the addition of the third metal induces
a lower decrease (- 42 %). The clear sorption preference for Cu2' and Pb2+is always
marked in the three metal solution: the addition of Ni2' seems to have no effect on the
other metals fixation.
3.2
Preliminary experiments were carried out on each sorbent. As a little part of the organic
content of sugar beet pulp was soluble in water (close to 35 mg.L-' expressed in TOC for a
ratio pulp/water of 2.26 g.L-'), experiments with activated carbon were carried out in a
liquid medium of pulp-water. It was verified that this specific soluble organic matter,
probably composed of great molecules, was not adsorbed on NC60. The results are
presented in Table 1. In a first approach, it was confirmed that phenol was not removed by
sugar beet pulp at this concentration. The removal of copper was efficient with and
without the presence of phenol since the removal percentages reached a value close to
60 % in both cases. This interesting result confirms those obtained above and shows that
copper ions could be treated with pulp, even with a moderate organic charge. As far as
activated carbon is concerned, on one hand the efficiency of this kind of material is
verified towards the organic molecule since NC 60 exhibits a high removal percentage for
phenol (73 %) and low for Cu" ions (14 %). On the other hand, the presence of metal
1%
decreases around 20 % the fixation of phenol and the presence of phenol slightly affects
the copper fixation. The mechanisms of adsorption must be different, favoring a
chemisorption based on an attraction with the surface functions for metal fixation and a
physisorption, highly influenced by steric hindrance when another pollutants, for example
hydrated cations, are present in solution.
0.3
0.25
ECD
3
0.2
20
-ca
0.15
0.1
-ild
0.05
%
Cu alone
Cu + 130 mg.L-1 of benzaldehyde
Cu + 180 mg.L-1 of benzoic acid
Cu + 140 mg.L-I of phenol
0
4
X
Table 1. Removal percentage of copper and phenol, on pulp, NC 60 and a mixture of the two adsorbents
(Initial concentration of copper and/or phenol 50 mg.L-'; pulp ratio 2.26 g.L'; NC 60 ratio 0.5 g.L").
cu2+
Cu2'(with presence of phenol)
Phenol
Phenol (with presence of Cu2+)
Pulp
63
60
0
0
NC60
14
11
73
54
Pulp+NC60
67
66
74
53
When these two different adsorbents are used together, the results show that their
respective properties are conserved. In other terms, the sugar beet pulp exhibits a high
affinity with copper ions (67 YO),
even if phenol is present (66 %), and NC 60 keeps its
efficiency with phenol (74 %) and is greatly influenced by the presence of copper.
To conclude, these preliminary results have shown the important ability of a low-cost
sorbent, the sugar beet pulp, to remove metal ions from aqueous solution. When several
metals are present in solution, a selectivity can be highlighted. The polysaccharide
exhibits high affinities towards Cu" and Pb2+whereas organic molecules are not retained
on it. The influence of organic matter on metal fixation occurs at high concentration or if a
complexation between species is possible. Finally, if the effluent contains organic and
metallic pollutants, the association of two kinds of adsorbent, namely sugar beet pulp and
activated carbon, seems to be efficient since they would keep their respective properties in
197
terms of adsorption. Further investigations would confirm these results in a dynamic pilot
unit and with real industrial wastewaters.
References
,
1.
Bailey S. E., O h T. J., Bricka R. M. and Adrian D. D., A review of potentially lowcost sorbents for heavy metals, Wat. Res. 33 (1999) pp. 2469-2479.
2. Ricou P., Lecuyer I. and Le Clouec P., Removal of heavy metallic cations by fly ash
in aqueous solution, Environ. Technol. 19 (1998) pp. 1005-1016.
3. Guibal E., Milot C. and Tobin J. M., Metal-anion sorption by chitosan beads:
equilibrium and kinetic studies, Ind Eng. Chem. Res. 37 (1 998) pp. 1454-1463.
4. Gerente C., Andres Y. and Le Cloirec P., Uranium removal onto chitosan:
competition with organic substances. Environ. Technol.,20 (1 999) pp. 5 15-521.
5. Volesky B., Advances in biosorption of metals: selection of biomass types. FEMS
Microbiol. Rev., 14 (1994) pp. 291-302.
6. Texier A. C., An&& Y. and Le Cloirec P., Selective biosorption of Lanthanide (La,
Eu, Yb) ions by Pseudomonas aeruginosa. Environ. Sci. Technol. 33 (1999) pp. 489495.
7. Solari P., Zouboulis A. I., Matis K. A. and Stalidis G. A. Removal of toxic metals by
biosorption onto nonliving sewage sludge, Sep. Sci. Technol., 31 (1996) pp. 10751092.
8. Ho Y. S. and McKay G., The sorption of lead(l1) ions on peat, Wat. Rex, 33 (1999)
pp. 578-584.
9. Dronnet V. M., Renard C. M. G. C., Axelos M. A. V. and Thibault J.-F., Binding of
divalent metal cations by sugar-beet pulp, Carbolydr. Polym., 37 (1997) pp. 73-82.
10. Gerente C., Couspel du Mesnil P., Andres Y., Thibault J.-F. and Le Cloirec P.,
Removal of metal ions fiom aqueous solution on low cost natural polyssacharides:
sorption mechanism approach, React. Funct. Polym., 46 (2000) pp. 135-144 .
11. Reddad Z., Gerente C., Andres Y. et Le Cloirec P., Ni(I1) and Cu(I1) binding
properties of native and modified sugar beet pulp, Carbohydrate Polymers, 49 (2002)
pp. 23-3 1.
12. Crittenden B., Thomas WJ., Adsorption technology and design (1998), ButterworthHeinemann, Boston
13. Economy J., Lin R.Y., Adsorption characteristics of activated carbon fibers, Applied
Polym. Symposium, 29 ( 1976) pp. 199-21 1.
14. Faur-Brasquet C., Metivier-Pignon H., Le Cloirec P., Activated carbon cloths in
water and wastewater treatments, Res. A h . in Water Res., 2 (2002) pp. I - 19.
15. Faur-Brasquet C, Reddad Z, Kadirvelu K, Le Cloirec P, Modelling the adsorption of
metal ions (Cu2',Ni2',Pb2+) onto activated carbon cloths using surface complexation
models, Applied Surface Science, 196 (2002) pp. 356-365.
16. Reddad Z., GBrente C., Andres Y. and Le Cloirec P., Adsorption of several metal ions
onto a low-cost biosorbent : kinetic and equilibrium studies, Environ. Sci. h Technol.,
36 (2002) pp. 2067-2073.
17. Smith R. M. and Martell A. E. Critical Stability Constants (Plenum Press, New York,
1989).
18. Makridou C., Cromer-Morin M. and Schatff J.-P., Complexation de quelques ions
metalliques par les acides galacturonique et glucuronique, Bull. Soc. Chim. Fr.,
(1977) pp. 59-63.
198
Introduction
Recently, the recovery and reuse of valuable metal ions such as rare earth metals,
from process waste water of electronic industries and waste electronic devices, is strongly
desired for saving precious resources and for achieving sustainable development. While
synthetic ligands or chelators are widely studied, biosorbents prepared from biomass of
bacteria, fungi, and algae have several advantages over synthetic chemical ligands. The
biosorbents, for example, show high selectivity to various ions depending on their tertiary
structures, and require only relatively mild conditions for adsorption and desorption [ 11.
Peptides and proteins could be efficient metal binding ligands, because they have the
functional groups for metal binding in their amino acid residues, and they can be produced
at low cost by recombinant technologies. While many peptides and proteins are known
to work as metal transport proteins in biological systems, metallothioneins (cysteine rich
proteins with molecular weight of ca. 7 kDa) have attracted researchers attention for
decades because they bind heavy metals in vivo [2]. The metallothioneins are considered
to be involved in detoxication and metabolism of heavy metals.
In this work, a fusion protein has been engineered from maltose binding protein
(pmal) and human metallothionein (MT). The fusion protein (pmal-MT) has been
expressed in E. coli, and purified with an amylose column. The purified fusion protein
was immobilized on a solid matrix, and its characteristics as metal binding ligand have
been studied. We have found that the pmal-MT ligand efficiently binds gallium ion, one
of the valuable rare metals desired to be recovered from aqueous solution [3]. Different
binding mechanisms for two metal ions have been elucidated based on HSAB (hard and
soft acids and bases) theory [4].
199
Methods
Preparation of p-ma1 MT protein, and immobilization of the gmal MT protein on
ChitopearlTMresin were described in detail in the previous work [3]. Chitopearlm resin
inmobilizing p-ma1 MT protein (pmal-MT ChitopearlTM),ChitopearlTMimmobilizing
p-ma1 protein (pmal ChitopearlTM),and ChitopearlTMresins have been prepared. The
latter two resins are prepared as negative controls.
The ChitopearlTMresin was packed in a glass column (inner diameter 1. 4 cm, bed
height 4.3 cm). The column was first equilibrated with a 20 mM MES buffer containing
20 mM NaCl and 10 mM 2-mercaptoethanol. Then 60 ml of the MES buffer containing
metal ion was applied at the flow rate of 0.5 ml/min. Adsorption capabilities of the
ligands were examined for cadmium, gallium, cupric, zinc, or nickel ion. Afier the
column was washed with MES buffer, the adsorbed metal ion was eluted with the MES
buffer (pH of which was adjusted to pH 2.0). In order to examine effects of pH on the
adsorption, pH of the MES buffer was varied from pH 5 to pH 9. The eluted solution
was collected as several fractions of 10 ml each, and the metal concentration of each
fraction was determined with atomic adsorption analysis (SAS 7500A, Seiko Instruments,
Japan). Total amount of the eluted metal ion was defmed as the adsorbed metal ion on
the resin. The total amount of the adsorbed metal ion was divided by the total amount of
immobilized protein to calculate the number of metal molecules bound to one mole of the
protein. The adsorption experiments were carried out multiple times, and the maximum
experimental error was 25%.
Results
Amounts of the protein immobilized on the ChitopearlTMresin were 3.55 (mg/g-wet
resin) for the pmal and 1.51 (mg/g-wet resin) for the pmal-MT. The optimal pH for
cadmium binding was pH 5.2 (data not shown). Figure 1 shows an adsorption isotherm
at 298 K for cadmium adsorption on the pmal-MT ChitopearlTMresin at pH 5.2. Neither
the pmal ChitopearlTMresin nor the ChitopearlTMresin adsorbed cadmium ion under the
employed experimental condition. These results clearly show that cadmium ion binds to
the metallothionein moiety of the pmal-MT ligand. The adsorption equilibrium was
correlated by a Langumuir-type equation. The equilibrium constant K, and adsorption
capacity for cadmium binding Q were 15.74 [mM-'] and 3.76 x 1 0 ' [mol/g-wet resin],
respectively. The maximum amount of adsorbed cadmium ion per metallothionein
molecule is 12.1 (mol cadmium/mol metallothionein), which is relatively close to a
theoretical value 7 confirmed by NMR [ 5 ] . These results strongly suggest that the
methallothionein moiety of the h i o n protein bind cadmium as it works in vivo. Figure 2
shows effect of NaCl concentration in the metal solution applied to the column on the
cadmium adsorption. The amount of adsorbed cadmium ion drastically decreased at
NaCl concentration about 45 mM, suggesting that the tertiary structure of the metal
binding site probably change at this salt concentration, and thus the ligand lose its binding
ability for cadmium ion. The binding ability, however, was easily recovered by washing
the column with the MES buffer (pH5.2).
200
0.2
a4
0.6
QI)
50
100
150
We have found in this work that the pmal-MT ligand also binds a valuable rare metal
gallium ion. Adsorption characteristics of the pmal-MT for gallium ion, however, were
different from those for cadmium ion. An optimal pH for gallium ion adsorption was pH
6.5, which was different fiom that for cadmium ion (pH 5.2). This result suggests that
.the conformation of metallothionein suitable for binding of cadmium ion is not preferable
to gallium ion, and vise versa. An adsorption isotherm for gallium ion at 298 K is shown
in Figure 3. Unlike the case of cadmium ion, the pmal ChitopearlTMresin and the
ChitopearlTMresin adsorbed gallium ion about 4.0 x lom7(mol/g-wet resin) at pH 6.5.
Since these results suggest that gallium ion bind to the proteins non-specifically,
non-specific binding of gallium ion to the proteins was examined by comparing the
adsorption of gallium ion on BSA. The numbers of gallium ions adsorbed on BSA (mol
gallium iodmol BSA) were 0.0335 at pH 5.2 and 0.114 at pH 6.5, while those of
cadmium ions (mol cadmium iodmod BSA) were 0.392 at pH 5.2 and 0.293 at pH 6.5.
These results showed that BSA did not adsorb cadmium ion and gallium ion under the
employed experimental condition, and suggest that both ions do not bind to proteins by
simple ion-exchange effects. In order to evaluate the adsorption on metallothionein
moiety, the amount of gallium ion adsorbed on the base matrix was subtracted from the
resin. The corrected result is shown in
experimental data for the pmal-MT ChitopearlTM
Figure 4, and adsorption equilibrium is correlated by Langmuir-type equation. The
equilibrium constant K, and adsorption capacity for cadmium binding Q were 5.2 1 [mM']
and 9.09 x
[moVg-wet resin], respectively. It should be noted that the maximum
amount of adsorbed gallium ion per metallothionein molecule reached 26.6 (mol gallium
iodmol metallothionein), which is much higher than that of cadmium ion. Effect of
NaCl concentration in the metal solution on the gallium adsorption is shown in Figure 5.
The drastic decrease in metal binding at NaCl45 mM, which was seen for cadmium ion,
was not observed in the case of gallium ion. These results also strongly suggest that the
binding mechanism of gallium ion is different from that of cadmium ion. The amounts of
adsorbed metal ion on the pmal-MT ChitopearlTMfor various ions are summarized in
Table 1. These results show that the metal binding on metallothionein is highly
selective.
201
I,
0.2
0.4
0.6
OS
0.4
0.2
0.6
Gallium C O I I C ~ . [mMl
Cd
0
50
100
150
Adsorbed
amount
26
0.3
0.2
12.1
Ionic radius
[x 1
P m]
62
69
74
91
Hard
Little hard
Little soil
Soil
200
Discussion
We have found that metallothionein, which selectively binds cadmium ion in vivo,
binds gallium ion. The number of the gallium ion bound to one molecule of
metallothionein, 26.6, was about twice as large as that of cadmium ion. The results of
adsorption experiments to BSA, and the adsorption of various metal ions show that
metallothionein selectively binds gallium ion. The specificity is very high because other
metals which as similar ionic radius did not bound to the metallothinein as shown in Table
1.
202
strongly affected by the change in tertiary structure of the metallothinein. Drastic change
of the amount of adsorbed cadmium ion by the increase of NaCl concentration (Figure 2)
suggests that the large conformation change of the cadmium binding sites of
metallothionein. On the other hand, gallium ion should bind to N and 0 atoms of amino
acid residues of the metallothionein molecule. Human methallothionein posses 3 Asp, 1
Glu, 7 Lys, 8 Ser, 2 Thr,1 Gln,1 Asn residues per molecule. Some of these negatively
charged residues are probably located the outer surface of metallothinein might form
binding sites.
As elucidated fiom the adsorption experiment on BSA, adsorption of gallium ion by
simple ion-exchange effect is negligible. The characteristicsof metal ions such as ionic
radius and hardness/sobess, and the conformation of the metallothionein probably affect
the selectivity of metal adsorption. The understanding of the mutual interactions among
those factors would be a key factor in designing the protein-based ligand suitable for a
specific metal ion.
References
1.
Gutnick, D. L., and Bach, H., Engineering bacterial biopolymers for the biosorption
of heavy metals; new products and novel formulations,Appl Microbiol Biotechnol. 54
(2000) pp. 45 1 460
Romero-Isart, N. and Vasak, M., Advances in the structure and chemistry of
metallothioneins,J. Inorg. Biochem. 88 (2002) pp.388-396
Terashima, M., Oka,N., Sei, T. and Yoshida, H., Adsorption of cadmium ion and
gallium ion to immobilized metallothionein fusion protein, Biotechnol. Progress, in
press (2002)
Pearson, R. G., Hard and soft acids and bases, J. Am. Chem. SOC.85 (1963) pp.
3533-3539
Messerle, B. A., Schaffer, A., Vasak, M., Kagi, J. H., and Wuthrich, K.
Three-dimensional structure of human [ 1 13Cd7]metallothionein-2 in solution
determined by nuclear magnetic resonance spectroscopy, J Mol Biol. 214 (1990) pp.
765-779
2.
3.
4.
5.
203
Introduction
204
model, which could be used to simulate the pulse response of a packed column under
supercritical conditions with substantial pressure drop. A dynamic model is especially
useful, since it can be easily extended to simulate the SF-SMB process.
In the present study, experiments have been performed on a preparative column using
pure COz as the mobile phase. Experiments have been performed at four different back
pressure levels. For each back pressure setting, runs were performed both at low flow
rates, i.e. where the pressure drop was negligible and at high flow rates. The main process
aspects, i.e. pressure drop, mass transfer and retention have been experimentally
evaluated and analysed.
Carbon dioxide (99.995% pure, obtained from PanGas, Switzerland) was used as the
mobile phase. Phenathrene @urity>97%) dissolved in Toluene (purity>99.7%, both
100
80
- +- BP =I80 bar
n
L
lu
a
LI
60-
E!
40-
v)
v)
n
20
0 I
0
I
3
4x1Om2
Mass flow [g/s]
2
Figure 1. Pressure drop characteristicsof the SFC column at different back pressure levels.
obtained fiom Fluka, Switzerland) was used as a solute. A Lichrospher 100 RP-18
column (Merck, Darmstadt) 125x4 mm, with an average particle size of 5pm, was used
for the experiments.
The experimental set-up consists of a syringe pump (Isco 260D) capable of
producing a continuous flow of COz which flows through an injection valve (Valco
205
C14W) that has an internal loop volume of 60 nL. The mobile phase then enters the
column at the end of which is a UV detector (Jasco W-1570).The pressure in the system
is determined by a back pressure regulator (Jasco BP1580-81) which is located
downstream of the U V detector. The column and the injection valve are housed in a
temperature controlled water bath. Upstream and downstream pressures are measured
using pressure transducers (Trafag 8891).
The experiments are performed by setting the back pressure regulator at the desired
level and programming the syringe pump to operate at a given flow rate. The system is
then allowed to reach a steady state. Once the pressure profile in the system is established,
a mixture of phenanthrene in toluene (2% w/w) is injected into the column through the
injection valve and the data acquisition is started simultaneously. For each setting, the
experiment is repeated more than three times to ensure reproducibility.
3
Experimental Results
Both high flow rate and low flow rate experiments were performed at 4 different
back pressure levels, namely 130, 150, 180 and 210 bar. Some low flow rate experiments
were also perfomed at intermediate back pressure settings. The operating temperature for
0 BP=150 bar
A B P 4 8 0 bar
V BPe210bar
400
200
600
800
206
all the runs was 64C.The pressures upstream and downstream of the column and the UV
signal were measured.
From the UV detector readings, the retention time and HETP values were calculated.
The HETP was calculated using the formula
N = 5.45(t,/~)~
HETP = L/N
where t R is the retention time, w the width of the peak at half peak height, N the number of
plates and L the length of the column. These equations have been used to describe the
HETP behaviour though they have the limitation that they assume the velocity to be
constant along the column.
The pressure drop characteristicsfor the four different sets of experiments are plotted
against the mass flow-rate in Fig. 1. The mass flow rate is used as the independent
variable since it is the only variable which remains constant throughout the column. At
higher flow rates there is a deviation from linearity. For a given mass flow rate, the runs
at a low back pressure setting show a larger pressure drop.
The measured retention times are plotted against the inverse of mass flow rate in Fig.
2. It can be seen that the points corresponding to a particular back pressure setting fall on
a straight line and the slope of the line depends on the back pressure setting. The line
corresponding to a lower back pressure setting has a larger slope than the one at a higher
back pressure setting. This is in contrast to HPLC where for a given temperature, under
linear conditions, all points, irrespective of the back pressure setting, will fall on one
straight line whose slope is proportional to Hi. This shows that in the case of SFC, Hi,is a
6o
50 -
40 -
E3.
n
F
w
I
3020 -
10 -
10
20
30
207
40
0
50x10"
function of density. Further at high flow rates, there is a velocity gradient and a density
gradient in the system and these affect the retention time. Hence, the observed, or the
apparent, Hi is a combined effect of these two gradients.
The mass transfer characteristics, which are described by the HETP, are shown in
Fig. 3, where the HETP is plotted against the mass flow rates for different back pressure
levels. In general, the HETP curve has the typical shape of the well-known van Deemter
plot. Though plotting the HETP in this fashion (i.e. grouping runs with the same back
pressure setting) does not offer the provision to extract the mass transfer parameters 6om
the van Deemter equation, it nevertheless offers a qualitative picture of the mass transfer
kinetics. In general, at low flow rates, the H E P values fall with increasing flow rates,
reach a minimum, and gradually rise. Let us focus on the part of the curve after the
respective minima. The curve is flat for the runs with a back pressure of 130 bar
compared to those corresponding to 150 and 180 bar. The slopes of the later part of the
curves increase with increasing back pressure. It can also be seen that the curves show
cross over at larger flow rates. For the curve corresponding to 210 bar, it was however,
not possible to perform high flow rate experiments as the upstream pressures rose beyond
the maximum allowable pressure of the syringe pump.
4
Conclusion
Experiments have been performed on a preparative SFC system using pure CO2 as
the mobile phase under significant pressure drop. The retention times, pressure drop
characteristics and the mass transfer behaviour were studied. The trends observed differ
6om the behaviour of HPLC systems. These trends also emphasize the complexity
involved in analyzing the data for SFC measurements, which imply in turn greater
complexity of the SFC model as compared to standard liquid chromatography model.
Reference
1. Denet, F., Hauck, W., Nicoud, R. M., Di Giovanni, O., Mazzotti, M., Jaubert, J. N.
208
Iatroductioa
209
might improve relative to the sorption by distribution with increasing DVB content. The
DVB content not only influences the equilibrium sorption properties of the resin, but also
the sorption kinetics and mechanical properties such as elasticity and attrition resistance.
Published data illustrate the influence of the degree of crosslinking of PS-DVB resins
on the separation of sugar alcohols [6], monosaccharides [7],and malto-OS [8]. Resins
with DVB contents between 3% and 8% are suitable for the separation of two hexoses
[7]. For sugar alcohols the optimal DVB content is 7% DVB for Ca2' form resins [6].
The separation of glucose from maltose improves with increasing DVB content. For
malto-OS and DVB contents between 2% and 6%, the separation improves with
increasing DVB, but is completely lost for a DVB content of 8% due to size exclusion of
the larger 0s by the resin. Resin with 6% DVB was optimal for the separation of malto0s with a degree of polymerisation of 1 to 7.It can be concluded from these literature
data that crosslinking has a large effect on the sorption and separation properties of PSDVB resin and that the effects are dependent on the type of sugar. However, no
information could be found on the separation of FOS or GOS. The goal of the work
presented in this paper was to determine the influence of the crosslinking on sorption
properties of PS-DVB cation exchange resins for FOS and GOS separation. Improved
understanding of the interactions of saccharides with sorbents may lead to the
development of highly selective sorbents for low cost separations.
2
Gel type strong acid PS-DVB cation exchange resin, Dowex 50W (particle diameter 3874 pm), was used with different DVB contents. The resin was ion exchanged into the
desired cation form. Table 1 summarizes the properties of the columns (internal diameter
0.160 m) packed with resin. Porosity was calculated from the retention time of Dextran
T2000 (Pharmacia, Sweden). Dry substance content was measured by air-drying of
filtrated resin at 105C until constant weight. Isotherms and chromatograms were
measured at 60C in a column set-up, as was described earlier [2]. Glucose (0-300 gll),
galactose (0-10
fructose (0-300
sucrose (0-300
lactose (0-200
and
mixtures of FOS (Raftilose@60, Orafti, Belgium), containing fructose, sucrose and 0s
and GOS (Elixor@259, Borculo Domo Food Ingredients, The Netherlands), containing
glucose, galactose, lactose and 0s were used. The isotherms were correlated with
q=uz+bc, with q the saccharide concentration in the resin, a and b fitparamters and c the
concentration in the liquid phase. The chromatograms were plotted as a fimction of
dimensionlesstime, defined as: (r-r,mcer)/r,mce,., with rrmer the retention time of dextran and
r the time. The selectivity of component i relative to component j , was calculated as:
a),
a),
a),
a)
(qh)4@$
Table 1: Properties of columns packed with strong acid PS-DVl3 cation exchange resin (i.e.=ionexchange).
210
3
3. I
Fig. 1 shows the single sugar isotherms for K+ and Ca2' loaded resins with different
degrees of crosslinking. High sugar concentrations were applied, because concentrated
sugar solutions are used in commercial processes. The isotherm data were correlated with
the equations in Table 2. A stronger crosslinked resin, resulted in less sorption of sugars.
This result can be explained by the decreased elasticity and swelling of the resin with an
increased crosslinking. This results in lower water content of the resin (see also Table 1)
and decreasing sorption of saccharides by distribution. Moreover, crosslinking had a
larger effect on sorption than the type of cation [I, 21. For K
' loaded resin, the observed
order of adsorption was galactose2fructose>glucose>lactose>sucrose. The sorption order
of the sugars was for Ca" loaded resin the same as for K" loaded resin, except that
fructose2galactose. Fructose forms a complex with a Cat+ ion [9], which explains that
fructose sorbed better than glucose or galactose in highly crosslinked Ca" loaded resins.
For low crosslinking however, the monosaccharides sorbed almost to the same extent.
The explanation for the loss of selectivity may be that at low crosslinking the resin
contains more water and the amount of cations per volume unit resin is lower.
Consequently, more distribution may occur and the amount of fructose sorbed due to
complexation may decrease relative to the amount sorbed by distribution. In that case, the
sorption of non-complexing monosaccharides such as glucose or galactose is favoured
relative to fructose, as was observed experimentally.
At equal degree of crosslinking, the disacharides lactose and sucrose sorbed less than
the monosaccharides due to their larger size and hence the restricted accessibility to the
resin interstices. The sorption of the disaccharides decreased strongly with increasing
crosslinking. For 8% DVB the sorption was almost vanished. At increasing crosslinking
less water is available in the resin for distribution. In addition, part of the water is
hydration water of the cations [lo]. Apparently, for 8% DVB almost no water was available for distribution of sugar. The effect of crosslinking was stronger for sucrose than for
lactose. Lactose (0-PD-galactopyranosyl-(1,4)-D-gIucopyranose)and sucrose (0-a-Dglucopyranosyl-(1,2)-PD-fructofuranoside)differ in the constituent monosaccharides and
the bond between the monosaccharides. Although sucrose contains a fructose unit, it is
not able to complex with Ca" in the same way as the monosaccharide fructose, because
the glycosidic bond of sucrose occupies the complexation site of the fructose unit. However, the differences in sorption may be the result of differences in the structure of the
molecules. Lactose is able to convert via the open chain form to another anomeric form,
whereas sucrose does not. Sucrose exhibits two interresidue intermolecular hydrogen
bonds in aqueous solution [I 13. These structural differences may result in a larger effective size of sucrose compared to lactose, hence increased size exclusion and less sorption.
Table 2: Isotherm correlations for 2,4 and 8% crosslinking of PS-DVBresin loaded with K' or Ca*' at 60C.
211
1w
200
300
100
300
400
1.1
1.2
3.3
1.3
1.7
1.5
3.8
1.1
1.4
1.3
2.4
2.5
7.0
Chromatograms
212
for 2% DVB were wider than the peaks on the chromatogram for 4% DVB. Especially in
the case of GOS this resulted in poor separation. The long elution times lead to excessive
product dilution, which is for large-scale applications an economical disadvantage.
GOS m 4% DVB
nrinmK+fan
0.0
0.5
1.0
1.5
20
25
dk*nsM...nktbnk.(J
0.0
0.5
1.0
1.5
20
-13
dlnm-
25
1
0.0
GOS m 2% DVB
rcsin m K' fam
0.5
1.0
1.5
20
dkmnimhu-mC)
25
Fig.2: Chromatograms of G O S (K' resins) and FOS (Ca resins) with different DVB content (8?4 4%, and 2%
DVB), injection volume 1 ml, concentration 100 g synrp/l, flow rate 0.545 ml/min, temperature 60C.
*+
Conclusions
The isotherms of sugars on PS-DVB resin showed that increased crosslinking resulted in
more selective sorption of sugars at the cost of sorption capacity. The effect of crosslinking on capacity and selectivity is larger than the effect of cation type [2]. Nonselective sorption of sugars decreases with increasing crosslinking, due to a decrease in
available space in the resin for distribution. Also, with increasing crosslinking, the
relative contribution of complexation to the sorbed mount increases and as a result the
selectivity increases. The chromatogramsof FOS and GOS showed that a DVB content of
8% is better than 4% DVB for monosaccharide removal. A PS-DVB resin with 8% DVB
is best for the removal of fructose from FOS.However, if the goal is to separate the FOS
in several fractions with different degree of crosslinking, then it is better to use 4% DVB.
For separations including molecules with different size, it is recommended to select first
the optimal degree of crosslinkingbefore optimising the cation type.
References
11 J. A. Vente, et al., to be submitted, 2002.
2!I J. A. Vente. et al. in: AIChEAnnual Meeting - Symposium on industria/App[icationsof
I4,dkorption and Ion Exchange. 2001. Reno (NV), USA: AIChE, p. 786.
3 J. Tiihonen, et al., Journal of Applied Polymer Science, 2001.82: p. 1256.
4 S. Adachi, et al., Bioscience Biotechnology and Biochemistry, 1997.61( 10): p. 1626.
5 M.Saska et al., Journal of Chromatography, 1992.590: p. 147.
6 H. Caruel, et al., Journal of Chromatography, 1992.594: p. 125.
7 S. Adachi, et al., Journal of Chemical Engineering of Japan, 1999.32(5): p. 678.
a S. Adachi, et al., Agricultural and Biological Chemistry, 1989.53(12): p. 3193.
J R. W. Goulding, Journal of Chromatography, 1975.103: p- 229.
1 9 R. S. D. Toteja et d.,Langmuir, 1997. 13(11): p. 2980.
1 I] S. Immel and F. W. Lichtenthaler, Liebigs Annalen, 1995(1 I): p. 1925.
1
213
MARC0 MAZZOTTI
Institute of Process Engineering, ETH Zurich, CH-8092 Zurich, Switzerland
E-mail: Mazzotti@ivuk mavt.ethz.ch
Identification technique is applied to a simulated moving bed (SMB)process for chiral separation of
enantiomers of TrOgers base and an advanced predictive controller is designed on the basis of the
identified model. To obtain the identified model, an artificial continuous system is constructed by
keeping the discrete events such as the switching time and the number of columns to be switched
constant. The SMB process is identified as an inputloutput data-based prediction model, which is
then used to design a linear predictive controller. In this study the internal flow rate ratios are chosen
as the input variables whereas the pair of product purities are taken as the controlled outputs. It is
demonstrated by simulation studies that the designed predictive controller performs satisfactorily for
the disturbance rejection as well as for the setpoint tracking in the SMB process.
Introduction
214
In this study, the SMB process is divided into four sections, each of which consists of
2 columns of chromatographyplaying a specific role in the separation. Ethanol solution of
the racemic Troger's base is taken as the feed stream and unsupported microcrystalline
cellulose triacetate(CTA) bead is used as the stationary phase. The separation is carried
out in the two central sections. For the reference conditions of simulation study, one may
refer to the previous work[7].
The principle of operation can be best described with reference to the equivalent true
countercurrently moving bed (TCC) configuration. Since the two configurations are
equivalent, i.e., they achieve the same separation performance provided the geometric and
kinematic conversion rules are fulfilled, the simpler model of the equivalent TCC unit can
be used to predict the steady state separation performances of SMB units, in particular, for
design purposes.
The first principles model of the SMB unit is constructed with reference to the
previous works[4,6] and considered to be the actual plant.
215
"f
216
g .r
t
B
Figure 2. Disturbance rejection performance.
In the second case the setpoints for the average concentrations of A at extract and
that of B at raffiate are changed simultaneously after 20 switching times as shown in
Figure 3. For the control purpose, the prediction and control horizons are set equal to 5
and 2 switching periods, respectively. The weighting matrices are tuned by the trial and
error method. Here it is noticed that the control inputs act predictively to bring the control
output to their new respective setpoints. It is clearly seen that the control performance is
quite satisfactorily.
217
Conclusions
inputloutput data-based prediction model is used to obtain the prediction model. The
identified model exhibits an excellent prediction performance. The inputloutput
data-based predictive controller based on the identified model is designed and applied to
MIMO control problems for the SMB process under the presence of the input and output
constraints. The simulation results demonstrate that the controller proposed in this study
shows an excellent control performance not only for the di'sturbance rejection but also for
the setpoint tracking.
References
1. Wang, C.; Engell, S.; Hanisch. F.;
Triennial World Congress, Barcelona, Spain
2002,1145-1 150.
2. Dunnebier, G.; Fricke, J.; Klatt, Karsten-Ulrich.; Ind. Eng. Chem. Res. 2000,39,
2290-2304.
3. Favoreel, W.;De Moor, B.; Van Overschee, P.; Gevers, M., Proceedings of the
American Control Conference 1999,3372-3381.
4. Kloppenbwg, E.; Gills, E.D. Journal ofProcess Control 1999,9,41-50.
5 . K.-Y. Yoo; H.-K. Rhee, AZChE J. 2002,48(9), 1981-1990.
6. Migliorini, G.; Mazzotti, M.; Morbidelli, M., Journal of Chromatography 1998, A,
827, 161-173.
7. Pedefem, M.; Zenoni, G.; Mazzotti, M.; Morbidelli, M., Chem. Eng. Sci., 1999, 54,
3735-3747.
8. Natarajan, S.; J. H. Lee, Computers and Chemical Engineering 2000,24, I 127-1 133.
9. Song, I.-H.; K.-Y. Yoo; H.-K. Rhee; Ind. Eng. Chem. Res. 2001,40,4292-4301.
10. Verhaegen, M.; Dewilde, P. Inr. J. Control 1992,5, 1187-1210.
218
Introduction
Drinking water resoufrces are inmasingly contmimted with chlorinated pollutants
such as hichloroethene (ICE), etc. ozonation is an oxidation process extensively applied to
water treatments for eliminating such pollutants. However, single omnation isn't always effective
in terms of time required for technical pcess. To enhance the omnation effectiveness, many
studies have focused on AOP ( a d v d oxidation pmcesm) such as omnation combined with
H&[ Beltran et al., 1998 I, etc, in which OH radicals, a much more reactive specie than omne
itself, play a main role. 'Ihe present study performs a new trial aiming at the enhancement of the
omne mction,designing a novel oxidationprocess in which the omne reaction rateis sigruficantly
increased through the use of an omne &orbent. We found in our pvious work [ Fujita et al,
ux)2] that high silica zeolitespcwxseda m n g abiity to adsorb omne. In addition to that,it has
been reposed that dissolved organics were also highly adsorbed onto these zeolites [ Giaya et al.,
20001. The above findings will raise the possibility that a considerable increase of reaction rate can
be achieved due to the adsorptive enrichment of omne and target Organics inside the zeolites. The
objectives of this work are to investigate the effectivenessof the novel omnation process proposed
and to elucidate the fundamental phenonena throughTCE degradation tests using a tubular flow
mtor..
lsMelIligb~zeolitesUsed
Adsorbents
employed are listed in Table
model substance to be
decomposed and its adsorption property was examined by batch and brealahrough tests. In order to
investigate TCE degradation, the experimental appmlus shown in figure 1 was employed. Ozone
solution was produced by bubbling gaseous omne generated by an ozone generator (POX-10,
Fuji
Electric Co., Ltd). A constant concenhation of TCE solution was prepad, miXing hued water
and high comntrationof TCE solution fed by a syringe type microfeeder (KDS-100, Kd Scientific
Inc.,). From different paths, Ozone solution and TCE solution were pumped into the mixing
vessel before the inlet to the fixed bed, using a dual plunger pump without pulsating c m n t
219
(NP-KX-120, Nihon Seinritsu Kagaku Co., Ltd), and this mixed solution was fed into the glass
column. TCE concentrations at the inlet and oudet of die column at a steady state were detected,
and die conversion of TCE, x, at a steady state was
given.
For die determination of TCE, samples
were withdrawn into an aqueous solution phase of
closely
10
0.1
0.01
0.1
OrjP
1
10
220
d[TCE]
=4 ,
[O, 1" [TCElp
dz
(1)
(2)
Intereshgly, this results suggests that n=E conversion, x, was apparently i n f l u e d only by
reaction time r , not by ozone concentration, which differs h m the bulk reaction directly
influenced by ozone concenttation moigne et d, 1983 I. This suggests that there will be
conclusive factors that have a strongly effect on the apparent reaction behavior, independent of the
Charactenstl
' 'csof the adsorbent natu~.
Thus,the effect of other factorssuch as particle size (biier
221
0.2
'
mass-transfer resistance.
Fkhemme,theincrease
of flow rate gave higher
=-k,a,[TCEI
(3)
(4)
?his equation can be transformed kto the following Equation (5). k can be guessed by the
equation proposed by carbery et al[Caheny et aL, lW].and that proposed by W h n W h n et
al., 1%6]., while a,can be given by Fiquation(6).
x = 1-exp(- k,a,T)
(5)
a, =- 3P,
%PP
We assumed that this equation would give the maximumvalue of TCE conversionobserved in the
experimental results when the adsorption performanas for TCE and ozone were high enough.
Close concordances were exjmxsed between the experimental results and the kinetic model. .As a
result, it can be deduced the adsohen& wexe kept almost in a virgin state. Aqueous ozone
mncentration has no effect on TCE conversion under our experimental condition as observed in
the experimental results due to the relatively fast reaction in the pores in comparison to TCE film
diffusion. However,such acase will be very specific. In the case that the substance to be degraded
is more Unreactive or is adwrbed less, or in the case that ozone CoIlCentration is much lower, other
states would occur.
222
CONCLUSION
Remarkable increase in ozone reaction rate toward TCE was observed in the presence
of high silica zeolite in comparison to bulk reaction. TCE conversion increased with the increase in
adsorption of ozone and TCE, which provided the evidence that this significant increase in reaction
rate is likely due to the high enrichment of ozone and TCE inside the adsorbent With further
increase of adsorption, TCE conversion converged to a certain value, which indicated a maximum
limit of reaction improvement exists. The kinetic model provides an accurate description of the
experimental results, which suggested the limit was due to the limitation of mass transfer in film.
This suggested that ZSM-5 (SiO/AlAratio: 3000) were kept almost in virgin state due to the fest
ozone reaction with TCE inside the adsorbent
NOMENCLATURE
w:Linear flow rate[ ms"1 ], L:Column lengthf m], r :Reaction time defined as L/u,[ s ], (TCE]:TCE
Concentration [ molm"3, or mgL"1 ], (TCE]i,:lhfluent TCE Concentration[ molm"3, or mg/L ],
[TCEL^Effluent TCE Concentration[ molm"3, or mg/L ], gLength[ m ], k^: apparent
Reaction rate constant[m3mor1s"1],[O3]:Ozone Concentration [ molm"3, or mg/L ], a,: Surface area
of adsorbent per unit volume[ nfari3 ], kL :Mass transfer coefficient between liquid and solidf ms"1 ],
rah,: Apparent reaction rate[ molL's"1 ], Dm :Difrusion coefficient of TCE in water[ mV ]
Reference
Beltran FJ., Encinar. J. M., Alonso M. A. (1998) A Kinetic Model for Advanced Oxidation
Processes of Aromatic Hydrocarbons in Water Application to Phenanthrene and Nitrobenzene, bid.
Eng. Chem. Res., 37,32-40
Carberry J. J,.(1960) A boundary-layer model of fluid-particle mass transfer in fixed bed. AIChE J.,
6,460-463
Fujita H., Sakoda A., Fujii T., Izumi J., (2002) Adsorption and decomposition of water-dissolved
ozone on high silica zeolite. Wat Res., submitted
Hoigne J., Bader H. Wat Res. (1983) Rate constants of reactions of ozone with organic and
inorganic compounds in water-1 non-dissociating organic compounds. Wat Res. 17,173-183
Wilke C. R., P. Chang. (1955) Correlation of diffusion coefficients in dilute solutioa AIChE J., 1,
264-270
Wilson E. J., Geankoplis CJ. (1966) Liquid mass transfer at very low Reynolds numbers in packed
beds. I&EC Fundamentals, 5(1), 9-14
223
- butane on MFI
- iso-butane on MFI
Pressure Swing Adsorption (PSA) unit is a dynamic separation process. In order to create a precise
model of the process and thus an accurate design, it is necessary to have a good knowledge of the
mixtures adsorption behaviour. Consequently, the diffusion rates in the adsorbent particles and the
mixture isotherms are extremely vital data. This article intends to present a new approach to study
the adsorption behaviour of isomer mixtures on zeolites. In a combined simulation and experimental
project we set out to assess the sorption properties of a series of zeolites. The simulations are based
on the configurational-bias Monte Carlo technique. The sorption data are measured in a volumetric
set-up coupled with an online Near Infta-Red (NIR) spectroscopy, to monitor the bulk composition.
Single component isotherms of butane and iso-butane were measured to validate the equipment, and
transient volumetric up-take experiments were also performed to access the adsorption kinetics.
Introduction
224
for easier handling. Therefore, the experimental systems have to be measured accurately
over a wide range of pressures and temperatures.
Gravimetric or manometric techniques have been used to establish adsorption data of
gases on zeolites. Both techniques present problems, manometric equipment has an
accumulation of the error; and data obtained by the gravimetric method are influenced by
effects associated with flow patterns, bypassing, and buoyancy. In the mixtures
adsorption behaviour, isomers mixtures have the highest degree of difficulty to study.
Isomers can not be differentiated in standard commercial adsorption equipment. This
problem has been solved in this study by coupling a manometric apparatus with an NIR
spectrometer, which allows us to measure the gas phase composition (in time, if
necessary). In this paper we report this new approach to study the adsorption of mixtures
of butane and iso-butane.
2
ExperimentalSection
In a combined simulation and experimental project we set out to assess the adsorption
properties of a series of zeolites. In the present work the adsorption properties of n-butane
and iso-butane on MFI are being studied. The experimental part consists in the validation
of the molecular simulation model, by confirming its results. The experiments were
performed in a constructed in-house manometric apparatus coupled with a NIR
spectrometer (Perkin Elmer, FT-IR system, GX Spectrum). Figure 1 is a scheme of the
experimental set-up.
Liquidpump
A sample of commercial MFI from ZeoIist was used, with a silicon aluminium ratio
(SYAl) of 100, the crystals do not present a regular shape. On figure 2 Scanning Electron
Micrograph (SEM) of MFI crystals is presented. The sample was calcined for 6h at 873K.
The adsorptive gases used were n-butane with a 99.5% purity, and i-butane with
99.95% purity from Praxair. No further treatment was performed on them before their
admittance into the experimental set-up.
For single component and mixtures calibration curves, the NIR spectra of pure gases
are recorded at several pressures and the data gathered are treated as explained in the
result section.
To measure a point of the single component isotherm, pure gas is admitted to the setup with valve 2 closed (figure 1). By closing valve 1 and opening valve 2 the pressure
225
starts to drop, and the final value is measured after equilibrium is reached, and the loading
can be then calculated.
Transient volumetric up-take experiments are performed following similar procedure
of measuring one point of the isotherm, but before opening valve 2, NIR spectra are
recorded in regular intervals. After a short period valve 2 is opened to start the adsorption.
Spectra are recorded until the equilibrium is reached.
Experimental data on single component adsorption isotherms of normal-butane and isobutane, on MFI zeolite, at 373K, for a pressure range of OSkPa to 200kPa,were obtained.
1.o
1.8
=-
1.6
1.4
0.9
0.8
s0.7
E 0.6
1.0
E
0.5
v
;
0.8
0.4
3 0.6
0.3
> 0.4
0.2
0.2
0.1
on .
0.0
1 .OE-05 1 .OE-03 1 .OE-01 1.OEM1 1 .OEM3
1 .OE-05 1 .OE-03 1.OE-0 1 1 .OEM 1 1.OE+03
P(kPa)
P(kPa)
2?
1.2
Figure 3. nButane and i-butane isotherms on MFl at 373K. (- Mol. Simulations, 0 Exp. Results,
Results ref [ 6 ] )
- - - Exp.
226
0.8
h
0.6
0.4
w
9
0.2
0
5000
7000
Wave lengh (cm-1)
9000
i-butane
n-bu tnae
-1.5
- 1
-!
& 0.5
0 Experimental
-Cahbratio
n
-Calibration
0
0
60
120
180
240
60
p Wa)
120
P (kPa)
180
240
0.6
4 0.5
f0.4
s
0.3
>
m 0.2
n-butane
j 0.5
2 0.1
0
0
60
180
240
60
120
P (kPa)
180
240
To calculate the amount of each component in one mixture we use the Net Analyte
Signal (NAS) theory [2]. In figure 6 we can see the NAS calibration curves for n and ibutane.
In figure 7 we present the volumetric up-take experiment results. The time-base spectra
for n-butane are recorded. We can see a overlapping of spectra on the higher region, that
correspond to the initial part before opening valve 1, so the pressure is kept constant for
150s. On the lower part we see high number of spectra overlapping, that correspond to the
equilibrium. These two regions can also be seen on the total up-take curve, the line at
OmmoVg for the initial part between 0 and 15Os, and the flat part at 0.96moI/g for the
equilibrium, reached after 1000s.
Figure 8 shows adsorption data for n-butane and i-butane mixture. The total loading is
represented by the grey symbols, the black symbols represent the partial n-butane loading
and the open symbols the partial i-butane loading. We can observe that the separation
between the two isomers increases with the pressure, but we need to measure more points
in the high pressures region.
227
0.21
1.2
t = loo to 700s
c?.
I
3 0.14
3> 0.4
n
P 0.07
<
0.2 - .
0 7
0
0.00
6500
7500
8500
Wave Lenght (cm-1)
500
time (s)
1000
Figure 7. nButane time-based spectra and total volumetric uptake versus time.
0.6
1.6
h
E 0.8
v
U
$ 0.4
>
0.0
l.E-03
0.2
0
l.E-01
l.E+01
P(kPa)
l.E+03
1200
Figure 8. Mmnm equilibrium data and partial uptake for mixture components versus time.
Conclusions
We conclude that with a manometric set-up coupled to a NIR spectrometer it turns out to
be possible to measure equilibrium and kinetic data for single components and mixtures.
Acknowledgements
This research was carried out within the project CW/STW 349-5203. The authors thank
the Stichting Technische Wetenschappen for their financial support.
References
1. Krishna R., Diffusion of Binary Mixtures in Zeolites: Molecular Dynamics
Simulations versus Maxwell-StefanTheory. Chem. Phys. Lr. 326 (2000) pp 477-484
2. Lorber A., Faber K., Kowalski R., Net Analyte Signal Calculation in Multivariate
Calibration. Anal. Chem. 69 (1997) pp 1620-1626
3. Ruthven D. M., Past Progress and Future Challenges in Adsorption Research. I n d
Eng. Chem. Res. 39, (2000) pp2 127-2131
4. Schenk M. et al., Sep. of alkane isomers by exploiting entropy effects during adsorption on silicalite-1: a CBMC simulation study. Lungmuir 17 (2001) pp 1558-1570
5. Stach H., Lohse U., Thamm H. and Schirmer W., Adsorption Equilibria of
Hydrocarbons on Highly Dealuminated Zeolites. Zeolites 6 (1986) pp 74-90
6. Zhu W. et d.,Adsorption of Light Alkanes in Silicalite-1: Reconciliation of Exp.
Data and Mol. Simulations. Phys. Chem. Chen Phys., 2 (2000) pp 1989-1995
228
Introduction
The adsorption of the homologous alkane series on zeolites and other adsorbents has been
extensively studied by many research groups. These studies demonstrate the existence of
linear relationships between adsorption enthalpy and entropy, and the carbon number [ 141. Contrarily, there are few studies dealing with the adsorption of alkanes in liquid phase.
This can be explained by the lack of selectivity effects that occur in the adsorption of
alkanes on adsorbents in liquid phase. Indeed, classical stationary phases for HPLC show
no separation of alkane mixtures, as a result of the rather weak interactions between the
molecules and the force field exerted by the surface of the amorphous material.
When the alkane molecules are trapped in the pores of a zeolite, much stronger
energetic interactions occur compared to those on amorphous surfaces. Pulse
chromatographic experiments in liquid phase showed a slight increase of the alkane
retention with carbon number on a column packed with a large pore Y zeolite [5]. When
ZSM-5 was used, a zeolite with much smaller pores than Y, very large differences in
adsorption between short and long alkanes were observed in liquid phase.
Among all zeolites, ZSM-5 is undoubtedly the most studied one, both from the
adsorption and catalysis point of view. Several experimental studies reported the
occurrence of a kink in the pure component adsorption isotherms of certain alkanes in gas
phase on ZSM-5 [6-81, and an inflection point in the adsorption enthalpy and entropy
versus zeolite loading curves [9,10]. Generally, the two-step behavior of these linear and
branched alkanes is interpreted in terms of the ZSM-5 channel geometry. For example, it
has been observed that at low partial pressures, isobutane is adsorbed preferentially in the
channel intersections of ZSM-5, while at higher pressures, these branched molecules are
"pushed" into the channel segments, resulting in a significant loss of entropy and a kink
in the adsorption isotherm [ 1 11. The packing and sitting of alkanes in the pore system of
ZSM-5 has been investigated by computational techniques, such as Configurational-Bias
Monte Carlo simulation [12-14]. These simulations all confirm the importance of entropy
effects in the adsorption of alkanes on ZSM-5.
In the present work, we have investigated the liquid phase adsorption behavior of nalkanes on a ZSM-5 zeolite. The saturation capacity of linear C5-C22 alkanes was
determined to study alkane packing effects. Adsorption isotherms of binary mixtures were
229
measured to determine the effect of alkane packing on the competition between short and
long alkanes.
2
Experimental
The H-ZSM-5 zeolite sample used in this study was obtained by deamoniating a NH4ZSM-5 from Zeolyst (CBV 8014, SiOZ/A1203 mole ratio of 80) at 673 K in a muffle oven
in presence of air for 48h.
Experimental adsorption isotherms were obtained by means of batch experiments.
Zeolite samples (-I g) were put in 10 ml glass vials and weighed with a balance. After
regeneration overnight at 673 K, the vials were immediately sealed with a cap with
septum in order to avoid water uptake from the air, and were weighed to determine the
regenerated zeolite mass. Mixtures of two linear alkanes or only a pure alkane in solvent
were added to the sample (each 20 ml). Iso-octane (99% purity, Acros) was used as a
solvent in the adsorption measurements. Immediately after sealing the cap and weighing
the sample, about 10 ml of the mixture was injected through the septum into the zeolite
containing vials, and another 10 ml was added to a vial without zeolite, to be used as
blank sample. Samples were kept at 277 K, to be sure no compounds could evaporate, and
stirred frequently.
Liquid samples were taken with 2 ml syringes after 24 h and 48 h, to verify if
equilibrium between adsorbed and bulk phase was achieved, and analyzed in a gas
chromatograph with flame ionization detector. For every binary mixture, a calibration line
was obtained by analysis of the blank samples, for which the concentration of the
components is exactly known. For each sample the amount adsorbed (qwhte) at
equilibrium was obtained by calculation of the mass balance.
Fig. 1 shows the uptake of pure hexane and decane from their mixture with iso-octane on
ZSM-5. The amounts adsorbed in the zeolite remain constant after 20 hours, indicating
that the experiments were performed under equilibrium conditions. In order to verify that
iso-octane can be used as inert solvent, a comparative experiment was performed in
which the binary adsorption isotherm of hexane and decane was determined using isooctane and 1,3,5-trimethylbenzene as respective solvents. The same adsorption isotherms
are obtained with both solvent (Fig. 1b), demonstrating that iso-octane does not interfere
with the adsorption of the linear alkanes, and that the relative adsorption of the short and
long n-alkanes is not influenced by the nature of the solvent, given that the solvent is not
able to enter the pore system.
Fig. 2a gives the saturation capacity of the C5-C22 n-alkanes, expressed in number of
molecules adsorbed per unit cell. Fig. 2b gives the total number of carbon atoms per unit
cell. For pentane and hexane, about 7.7 molecules are adsorbed per unit cell of ZSM-5.
This corresponds to 39 C atoms for pentane and 45 C atoms for hexane. Although the
number of adsorbed carbon atoms is the same for heptane as compared to hexane, only
about 6.4 heptane molecules are adsorbed per unit cell. A sudden drop is observed
between heptane and octane: only 4.5 octane molecules are adsorbed per unit cell. From
octane on, the number of C atoms adsorbed per unit cell increases steadily, to reach a
plateau of about 55 C atoms adsorbed unit cell.
230
40
20
l W l 2 0 1 4 0
LO
02
LB
04
U r n lh)
08
10
xw
t i 1.............................................................
a 4
e 2
10
11
12
13
14
15
18 20
C.rbmnumbm
10
11
12
13
14
15
18 20
Urbnn m b r
Obviously, the saturation capacity depends both on the dimensions of the adsorbing
molecules, and the geometry of the pore system. The pore system of ZSM-5 is constituted
of linear channels, with a fiee pore diameter of 5.6 x 5.3 A, intersecting with sinusoidal
channels, with a free diameter of 5.5 x 5.1 A (see Fig. 5a). The length of the linear
channel segments between two intersections is equal to 4.5 A, while the length of the
sinusoidal channel segments between two intersections equals 6.65 A. Each unit cell
contains 4 intersections, 4 sinusoidal segments and 4 linear segments. An octane molecule
has a length of 11.1 A, exceeding the length of a linear channel segment and an
intersection, but is also longer than a sinusoidal channel segment. As a result, not all
channel segments can be occupied by C8 molecules, explaining the lower saturation
capacity compared to C5-C7. Even with these shorter molecules, no use is made of all the
available space for adsorption. This is shown in Fig. 2b, where the total number of Catoms adsorbed per unit cell is plotted as a function of the carbon number. Only from C 13
on, a plateau is reached. When the number of adsorbed molecules per unit cell is
multiplied by their molecular length, a plateau value of about 70 A is obtained. This is
longer than the total length of the intersections, linear and sinusoidal channels (66.2 A),
which seems contradictory at fmt sight. However, it should be considered that the kinetic
diameter of the n-alkanes is 4.3 A, leaving an additional 1.1 A at every intersection for
adsorption. This gives a maximal length available for adsorption of 66.2 A + 4* 1.1 A =
70.6 A, which corresponds very nicely to the plateau value. This 100 % occupancy of the
ZSM-5 pores is only possible if the long molecules are able to bend, and occupy both
linear and sinusoidal channels.
231
0.8
0.6
E
0.4
02
0.0
0.2
0.6
0.4
0.0
1.O
02
0.8
0.4
0.8
XCO
XCO
..
ao
02
0.4
0.8
08
10
0.0
0.2
0.4
0.0
0.8
1.0
XQ)
XQ)
In Fig 3%the binary adsorption isotherms of a CB/C12 mixture is shown. C12 is adsorbed
in a very selective way from the mixture, as can be seen in the selectivity diagram (Fig
3b), in which x and y represent the molar firactions in the liquid and adsorbed phases
respectively. This selectivity for the longer chain can be explained by its higher
interaction with the zeolite.
232
A peculiar behavior is observed with a C6K8 mixture (Fig 4), where, at low C6
concentrations (thus a high C8 concentration), the lightest component is adsorbed
preferentially over the heavier alkane. This adsorption selectivity reversal is again
explained by the packing of the molecules in the pores. Since octane can only adsorb in a
!+action of the channel segments, vacancies remain available in which C6 can adsorb, as
is shown in Fig. Sb, where an example is given how the octane molecules can pack in the
linear channels, leaving open space in the sinusoidal channels for hexane. Selectivity
inversion has been observed with a range of binary mixtures, but these data will be treated
elsewhere.
4
Conclusions
The adsorption of linear alkanes on ZSM-5 is governed by geometric and packing effects,
which result in pronounced selectivity effects, and even in an inversion of the normal
adsorption selectivity. These effects are certainly important with respect to catalytic and
separative applications, and will be studied in further work.
Acknowledgements
This research was financially supported by FWO Vlaanderen (G.0127.99). J. Denayer is
grateful to the F.W.0.-Vlaanderen, for a fellowship as postdoctoral researcher.
5
References
1. Bond, C.G., Keane, M.A., Kral, H., Lercher, J.A., Catal. Rev. - Sci. Eng., 42(3), 323383,2000.
2. Ruthven, D.M.,
Kaul, B.K., Adsorption, 4,269-273, 1998.
3. Eder, F.; Lercher, J.A. J Phys. Chem. B 1997,101, 1273-1278.
4. Hampson, J.A.; Jam, R.V.; Rees, L.V.C., Characterization of porous solids I1
Rodriguez, F. et al, Amsterdam 1991, 509,517
5. Denayer, J.F.M.,
Bouyermaouen, A., Baron, G.V., Ind. Eng. Chem. Res., 37 (9),
1998,3691.
6. Richards, R.E., Rees, L.V.C., Langmuir, 1987,3,335-340.
7. Zhu, W.,van der Graaf, J.M., van den Broeke, L.J.P., Kapteijn, F., Moulijn, J.A., Ind.
Eng. Chem. Res., 1998,37,1934-1942.
8. Sun,M. S., Talu, 0. Shah, D. B., J. Phys. Chem., 1996, 100(43), 17276-17280.
9. Yang, Y., Rees, L.V.C., Microporous materials, 12, 1997, 117-122.
10. Millot, B., Methivier, A., and Jobic, H., J. Phys. Chem. B, 1998, 102(17), 32103215.
11. Zhu, W.,Kapteijn, F., Mouiijn, J.A., PCCP, 2000,2, 1989-1995.
12. Maginn, E.J., Bell, A.T., Theodorou, D.N., J. Phys. Chem., 1995,99,2057-2079.
13. Smit, B., Siepmann, J.I., J. Phys. Chem, 1994,98, 8442-8452.
14. Krishna, R, Paschek, D., PCCP, 2001,3,453-462.
233
Introduction
Solid-liquid phase transition (fieezing) in confined space, which is of importance not only
in adsorption but in the nanomaterial fabrication, nanotribology and in the pore size
determination, has recently been explored by several research groups including ours. In
contrast to the long-believed phenomena of freezing point depression in pores[ 11, some
molecular simulation studies have clarified that the freezing point in slit nanospace in
equilibrium with saturated vapor or liquid in bulk can be higher than the bulk, depending
on the potential energy of the confining walls [2,3]. Note that the pore shape other than
slit geometry, and the equilibrium vapor-phase pressure less than the saturated one would
bring depressing effect in freezing point [4,5]. The present understanding of the freezing
in nanospace is roughly reviewed below.
Our study on the first point [2] clarified the following. Depending on the strength of
the attractive potential energy from pore walls, fluid in a slit pore in equilibrium with
saturated vapor showed freezing point elevation as well as depression, and the critical
strength to divide these two cases was the potential energy exerted by the fluids solid state.
The excess attraction relative to the critical one was considered to bring the confined
liquid to a higher-density state that resembles a compressed state, which would result in
the elevated freezing point.
The above result is in accord with other recent studies. Dominguez et al. [6]
examined freezing of LJ fluid in slit pores of purely repulsive and weakly attractive walls,
employing thermodynamic integral technique to determine true equilibrium points. The
freezing points showed significant downward shift, relative to the bulk, in purely repulsive
walls, while the downward shift was much smaller in magnitude for weakly attractive
walls. Further, Radhakrishnan and Gubbins [3] used a different approach of
determination of freezing point in slit pores employing the Landau free energy calculation,
and simple fluid in strongly attractive slit pore was shown to exhibit elevated freezing
points.
234
Now the research effort goes toward experimental verification of the elevation
phenomena in the simplest geometry, a slit. Our main interest is in the range of a few to
several nanomenters. Some experimental studies have already reported fieezing point
elevation in slit pores [7-91,but the materials used were activated carbon fibers (ACFs),
which have only micropores less than 2nm. In such small pores the first layer adjacent to
the attractive pore wall, which is known to form an ordered phase at a temperature well
above the bulk freezing point, will occupy most of the pore spaces, and the freezing
behavior in the interior of the pore space is difficult to be detected. Further, there may
still remain some controversy if a liquid confmed in a larger nanopore would exhibit
elevation unless an experimental verification is made for such a pore.
The employed technique for this purpose was the so-called colloidal-probe AFM
(Atomic Force Microscopy). The results clearly demonstrate that cyclohexane in the
nanoscale slit space between the carbonaceous solids freezes at a temperature above the
bulk freezing point. Though the extent of the elevation itself might look rather small, we
believe that the finding of the definite existence of the elevation would be of much
importance in the research field of the phase behavior in nanopores.
2
Experimental
Laser
figure 1. Schm@ic drawing of AFM apparatus and image of the nanospace formed between surfaces.
235
forcedistance relation. If we look at the system with the separation distance of single
nanometers, the space between the two surfaces would be almost slit geometry because the
radius of the particle (order of 10' pn) is far larger than the separation distance.
A graphite plate (HOPG) and carbon particles, which were made from phenolic resin
by pyrolyzing above 2000"C, were used to form a nanospace with carbonaceous surfaces.
The graphite plate was freshly cleaved before measurement by using Scotch tape.
Cyclohexane, and octamethylcyclotetrasiloxane(OMCTS), whose bulk freezing point
were 6.4"C and 18C respectively, were used for the examination of freezing behavior.
The reasons of the choice were: i)aBity to carbonaceous surface, ii)freezing point near
ambient temperature, and iii)almost spherical molecular shape. Methanol, with bulk
6eezing point of -98"C, was also used as a reference.
3. I
Figure 2 illustrates the force curves between the carbon particle and graphite plate
immersed in cyclohexane at various temperatures above the bulk freezing point. (Note that
the distances shown in the figures are those detrmined from usual mannar of AFM
measurement, and is not the distances between the center of nuclei of surface atoms,
which are often used for simulation results.) As is expected the force at higher
temperature, e.g., at 18.6"C, exhibits typical van der Waals (vdW) force that acts mainly
in the single nanometer range. On the other hand what was NOT expected is its ultrahigh
sensitivity on the temperature. Only about 10 degree C of temperature change brought
multi-fold variation in the force. From theoretical point of view the effect of temperature
on the vdW force would be only from the variation in density of solids and liquid, which
at most would affect only a few percent in this small range of the temperature examined.
0.3
'
17.0"C
c.l
+ ll.0"C
-s
10.0"C
9.0T
8.0"C
E
z 0.2
E
0.1
0-0.1
f.4
-0.2
-0.3I
0
10
I
20
I
0
10
20
I
30
Distance [nm]
Distance [nm]
As a matter of fact, the same measurement in methanol gives the results shown in Fig.
3: Quite naturally the force curves do not show any detectable difference against the
temperature variation. We should, then, not take the abnormal temperature dependence
236
as is apparently shown, but should interpret it on the basis of the insensitivity of vdW
force on temperature.
The observed abnormality can be reasonably interpreted if we look at the trick in the
determination of the separation distance in the AFM measurement, which follows below.
Unlike the surface force apparatus, the AFM measurement does not have a direct
method to detect the distance between the surfaces. Instead, one will take the linear
signal of cantilever deflection against sample displacement as the origin of the surface
distance: The linear signal results because the two surfaces are in contact and move
together. This manner of wall detection usually works well. However, what would
result if the freezing point elevation is the case?
Suppose that the liquid between the two surfaces may freeze when the two surfaces
come close to a certain distance, at which the superposition of the potential energy from
each wall exceeds a critical strength that would be needed for the liquid to freeze. The
two surfaces, then, can never go any closer because of the steric repulsion of the frozen
phase (Fig. 4). The system replies with a linear signal as if it reached the situation of real
contact. The observed force curve would then represent a part of the real vdW force cut
out at this distance, taking this point as the origin of the surface distance, A weak
force thus appears.
0.3
CI
ul
o.2
0.1
a
3
-0.1
.
8
-0.2
-0.3
10
20
Distance [nm]
Figure 4. Schematic illustration of contact
with frozen phase between surfaces.
3.2
Force curves against real separation distance: fieezing point vs. distance
relation
Now we try constructing the real force curves plotted against real separation distance.
The key assumption for this trial would be the insensitivity of the vdW force on the
temperature. The attractive force before the freezing or the apparent contact should stay
almost unchanged. Thus each force curve was slid laterally to exhibit a best fit in the
region of attractive force with long separation distance. The results are shown in Fig. 5.
Each force curve converges into a single curve in longer distance region, which is in
line with the insensitivity of the vdW force on temperature and stands for the validity of
the above assumed interpretation of the apparent phenomena. Then the walls standing
at certain distances for lower temperatures would be a direct reflection of the freezing at a
temperature above the bulk freezing point. Namely, the graphiticlcarbonaceous surfaces
237
in their nature exert strongly attractive potential energy to cyclohexane confined within,
and the superposition of the two potential energies grows with decreasing distance
between them. At the position where the wall stands in Fig. 5 , the potential energy in
the nanospace exceeds the critical value for the confined liquid to freeze. Thus the
distance of the wall gives the pore size needed for the freezing at each elevated
temperature. Quantitative discussion will further be presented in the conference.
We observed similar walls also for the case with OMCTS, though the page
limitation does not allow us to show the results here.
The superposition of the potential energy is typically the case for the micropores.
Note that, however, superposition of potential energy in some larger pores of a few
nanometers would still be sufficient to cause detectable elevation in the freezing point
because the potential energy of carbon surfaces itself shows quite a large value in the unit
of temperature when converted with Boltzmanns constant: It will be more than hundreds
of Kelvins in the vicinity of the surface and can easily be tens of Kelvins even with a
distance of a few nanometers.
Conclusion
An experimental trial for finding the freezing point elevation phenomena was conducted,
employing the so-called colloidal-probe Atomic Force Microscopy. A carbonaceous
nanospace with slit geometry was successfully made up by this technique.
The results demonstrated that cyclohexane in the nanoscale slit space between the
carbonaceous solids freezes when the distance comes down to 4 nm, even at 8.4C,which
is above the bulk freezing point of 6.4C. Measurements with octamethylcyclotetrasiloxane, bulk freezing point being 18C, also detected the freezing behavior at
an elevated temperature of 22C. The detected elevation of a few degree C might be felt
as a matter of less significance, but we believe that the finding of the definite existence of
the elevation would be of much importance in the research field of the phase behavior in
nanospaces.
References
1.
2.
3.
4.
5.
6.
7.
8.
9.
e.g., Patric W. A. and W. A. Kemper, J. Chem. Phys., 42 (1938) 369; Durn J. A., N.
J. Wilkinson, H. M. Fretwell, M. A. Alam and R. Evans, J. Phys. Cond. Matter, 7
(1995) L713.
Miyahara M. and K. E. Gubbins, J. Chem. Phys., 106 (1997) 2865.
Radhakrishnan R. and K. E. Gubbins, Mol. Phys., 96 (1999) 1249.
Kanda H., M. Miyahara and K. Higashitani, Langmuir, 16, (2000) 8529.
Miyahara M., H. Kanda, M. Shibao and K. Higashitani, J. Chem. Phys., 112 (2000)
9909.
Dominguez H., M. P. Allen, and R. Evans, Mol. Phys., 96 (1999) 209.
Kaneko K., A. Watanabe, T. Iiyama, R. Radhakrishnan and K. E. Gubbins, J. Phys.
Chem. B, 103 (1999) 7061.
Watanabe A. and K. Kaneko, Chem. Phys. Lett., 305 (1999) 71.
Sliwinska-Bartkowiak M., R. Radhakrishnan and K. E. Gubbins, Mol. Simul., 27
(2001) 323.
238
D.D.DO
Department of Chemical Engineering, University of QueensIand,St Lucia, QLD 4072, Australia
E-mail: duongd@cheque.uq.edu.au
The density functional theory modified by including the Bender equation of state is applied to the
analysis of high-pressure (up to 50 MPa) adsorption of argon, nitrogen, methane and helium in
activated carbon Norit R1 in temperature range from 298 to 343 K. The approach allows us to
determine the pore size distribution (PSD) and the adsorbent density without recourse to helium
experiments. The PSD obtained with nitrogen at 77.35 K and those obtained with the high-pressure
argon, nitrogen and methane are in fair agreement with each other. However in the latter case the
PSD shows small pores of about 0.3 nm (physical pore width), which do not appear in the 77.35 KPSD due to diffusional limitations. It was shown that the adsorption of helium is not negligible at
room temperature and it cannot be used as an inert gas to determine the adsorbent density. The
approach can be easily extended to near critical gases such as carbon dioxide and ethane.
Introduction
Adsorption of supercritical gases at high-pressure has some features, one of which is that
the adsorption excess vs pressure exhibits a maximum. There are some simplified theories
involving Langmuir, Langmuir - Freundlich, Toth, Dubinin - Astakhov equations for the
absolute adsorption isotherm and 2-Dequation of state (EOS) to the adsorbed phase.
Some approaches were based on Ono - Kondo equations for lattice gas and the simplified
local density theory that utilizes the van der Waals EOS and the Peng - Robinson EOS
modified for the case of confined slit pores. Brief review of these models was presented
earlier [ 13. There are some investigations of supercritical and near to critical temperature
adsorption of gases on the basis of the density functional theory (DFT) [2,3] and the
grand canonical Monte Carlo (GCMC)simulations [4-71. In both cases the PSD obtained
using high temperature and high-pressure gas adsorption and that determined with
nitrogen at 77 K for the same sample of activated carbon was shown to be markedly
different. A group of small pores of the PSD obtained with near critical carbon dioxide
and supercritical methane is not revealed with the low temperature nitrogen adsorption,
which is attributed to diffusion limitations or even blocking these pores by frozen
nitrogen 161. By this reason the PSDs obtained with C02are considered to be more robust
and reliable than those obtained with N2at 77 K. Thus it might suggest that supercritical
adsorption is a suitable means to derive PSD. But there exists one obstacle to this
approach. Since the capillary condensation does not occur in supercritical adsorption the
dependence of amount adsorbed expressed in terms of excess per unit surface area on
pressure is nearly the same for sufficientlywide pores (wider than 6 collision diameters in
the case of methane adsorption [4]). It does not allow us to reliably determine the PSD in
the region of large pore widths and even the total pore volume. This problem may be
239
overcome by increasing the pressure range for experimental isotherms and specifying the
total pore volume, which could be evaluated from N2 adsorption at 77 K.
In this paper we use a modified DFT approach to the data on Ar, N2, CH4 and He
adsorption on activated carbon Norit R1 at pressures up to 50 MPa and four temperatures:
298, 313, 328 and 343 K. Experiments were carried out at Institute of Non-classical
Chemistry of University of Leipzig, Germany, using a magnetic suspended gravimetric
system (Rubotherm PrtlzisionsmesstechnikGmbH, Bochum, Germany) [11. Our aim was
to develope a method of the PSD analysis from high-pressure adsorption data without
recourse to helium adsorption to determine the skeletal density of the adsorbent.
2
Model
The widely used non-local density functional theory [8-101 is known to involve a number
of assumptions. The Helmholtz free energy of a fluid confined in a pore is divided by two
parts, which account for separately attractive and repulsive forces. The former is usually
calculated by integrating the Weeks - Chandler - Andersen (WCA) fluid - fluid potential
over the confined pore on the basis the mean field approximation (MFA). The latter is
modeled by the equivalent hard sphere fluid using the Camahan - Starling equation of
state (CS EOS). The Helmholtz free energy of the hard sphere fluid is supposed to be a
function of a smoothed density, which is defined as a weighted average according to the
T a w n a prescription [el. The solution for a given pore at a specified temperature and a
bulk phase pressure is obtained by minimizing the grand thermodynamic potential with
respect to the density profile across the pore. Mathematically the problem is reduced to a
system of highly nonlinear equations with respect to the set of densities at different
distances from the pore wall, which can be solved by an iteration scheme. In the sub
critical region one may obtain two or more density profiles depending on initial
conditions. In such a case the true density distribution corresponds to the minimal value
of the grand potential. In the case of supercritical gas adsorption only one density profile
is obtained at each bulk phase pressure. The parameters for the fluid - fluid interaction
(the potential well depth m, the collision diameter aff and the equivalent hard sphere
diameter dHS)are chosen in such a manner that the agreement between the bulk phase
properties (dependence of the saturation pressure and densities of coexisting phases on
temperature) and the surface tension and their respective experimental values is
reasonably well. The solid - fluid parameters are calculated by the empirical Berthelot
mixing rule, which sometimes can be corrected using the data in the Henry law region.
For the solid - fluid potential the 10 - 4 - 3 Steele potential is usually used.
Application of the NLDFT to the case of high-pressure adsorption, being principally
the same as in the case of sub critical adsorption, is however accompanied by an
additional difficulty. The problem is that the bulk phase density is comparable with that of
the adsorbate phase and must be described as a function of pressure very precisely. The
Carnahan - Starling EOS does describe this dependence for Ar, Nz and CH4 reasonably
well but its accuracy is not enough to lead to reliable results, especially in the PSD
analysis, which is known to be very sensitive to small experimental errors and hence to
small changes in the governing equations. Moreover, the bulk phase properties near to
critical gases such as COz and C2& the CS EOS cannot fairly correlate at all. The
question is whether the bulk gas could be described by any more accurate equation than
the CS EOS. In the case of high-pressure adsorption the contribution of the central part of
a sufficiently wide slit pore to the excess must tend to zero due to the solid - fluid
interaction becomes very weak, Obviously, it is possible only in the case when the same
240
EOS is applied to the adsorbed phase and the bulk phase. It suggests the following
scheme of a modification of the NLDFT. The Carnahan - Starling EOS is replaced by the
much more accurate Bender EOS [ 111 and then the corresponding molar Helmholtz free
energy is split into three parts: (i) the ideal component, (ii) the excess fiee energy
associating with only repulsive forces and (iii) the component accounting for only
attractive forces. The latter is assumed to be described by the WCA potential in just the
same way done in the original NLDFT. Then the excess free energy is obtained by
subtracting the ideal part and the attractive part (defined for homogeneous fluid) from the
molar Helmholtz fiee energy corresponding to the Bender EOS. At a specified
temperature the excess free energy is considered to be the single-valued function of the
smoothed density, which is defined according to the Tarazona prescription in the case of
inhomogeneous fluid.
The Bender EOS is given by
p = pRT + Bp2 + Cp' + Dp4 + Ep' + Fp6 + (G + Hp2)p3exp(-a,,p2)
(1)
where p and p are the pressure and density, respectively. The constants B, ..., H are
temperature-dependent. Employing this equation, after subtracting the ideal component
and that accounting for fluid - fluid attractive interactions for the molar excess Helmholtz
free energy one can obtain:
F,(p) = Bp + Cp212 + Dp3 /3 + Ep4 / 4 + FpS15
(2)
+(Z/2)[G +ZH-(G +ZH+HpZ)exp(-a,,p2)]+C,p
where Z = l/azo,CO= (2'"16/9)lre&, and NA is the Avogadro number. The term --Cop is
the contribution of attractive interactions in the case of homogeneous fluid. In order to
determine the potential well depth Q and the collision diameter uffthe CS EOS was used
as a first approximation:
Nz
dHS, nm
OK
q&,
M B 7
nm3 K
0.34764
4.1203
98.07
Ar
0.32124
3.7780
113.97
CH4
He
0.36177
6.9560
146.91
0.21592
0.048202
4.79
Discussion
241
the modified NLDFT approach and the PSD was determined using Tikhonov
regularization method. All isotherms at different temperatures were treated
simultaneously (in order to diminish sensitivity of the PSD to experimental errors) using
databases for local isotherms generated for these temperatures. The total pore volume
(0.58 cm3/g)was specified and taken from low temperature nitrogen adsorption. Once the
PSD and the skeletal density had been determined the excess isotherms were plotted.
Figure 2 shows excess argon isotherms at four temperatures.
1 0 2 0 3 0 4 0 5 0
Pressure (MPa)
10
20
30
40
50
Pressure (MPa)
Solid lines in Figures 1 and 2 are calculated for the same PSD. The fitting is excellent,
which means that having determined the PSD from the analysis of one isotherm one can
predict isotherms of other temperatures with high accuracy.
Figure 3 illustratesthe PSD obtained with Ar, N2 and CH4.
Figure 3. Pore size distribution of Norit RI obtained
with different gases: (-) Ar, (-) N1, ( - x - ) CH+ The
pore width is physical, that is H - A, where A is the
separation of adjacent carbon layers in graphite.
242
3 I/
Conclusion
A new approach based on a combination of the non-local density fbnctional theory and
the Bender equation of state was successfully applied to high-pressure (up to 50 MPa)
argon, nitrogen, methane and helium adsorption. The approach allows reliably
determining pore size distribution and adsorbent density, and most importantly it does not
require helium experiments to determine the skeletal density.
Acknowledgements
Support from the Australian Research Council is gratefully acknowledged. The authors
are gratefbl to Dr.Peter Harting for the experimental data.
6
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
1 1.
References
Ustinov E. A. and Do D. D. J. Colloid Interface Sci. 250 (2002) pp. 49-62.
Quirke N. and Tennison S . R. R. Carbon 34 (1996) pp. 1281-1286.
Scaife S., Kluson P. and Quirke N. J. Phys. Chem. B. 104 (2000)pp. 3 13-3 18.
Gusev V. Yu., OBrian J. A. and Seaton N. A. Langmuir 13 (1997) pp- 2815-2821.
Heuchel M., Davies G. M., Buss E. and Seaton N. A. Langmuir 15 (1999) pp. 86958705.
Sweatman M. B. and Quirke N. Langmuir 17 (2001) pp. 501 1-5020.
Sweatman M. B. and Quirke N. J. Phys. Chem. B 105 (2001) pp. 1403-141 1.
Tarazona P., Marconi U. M.B. and Evans R. Mol. Phys. 60 (1987) pp. 573-595.
Lastoskie C., Gubbins K. E. and Quirke N. J. Phys. Chem. 97 (1 993) pp. 4786-4796.
Olivier J. P.J. Porous Muter. 2 (1995) pp. 9-17.
Platzer B.; Maurer, G . Fluid Phase Equilibria 84 (1993) pp. 79-1 10.
243
Introduction
In diffusion and flow of adsorbing gases or vapors through capillaries, a minimum has
been reported in a plot of flow rate versus pressure when the mean free path (k) is
comparable to the capillary radius (r) [1,3,8]. For the tortuous and irregular capillaries of
porous media, on the other hand, the minimum is not expected to appear as reported
theoretically and experimentally [3,9,10]. In our permeation study of n-hexane through
activated carbon, however, a minimum in permeability was observed consistently at
relative pressure of about 0.03 [2], while for benzene and carbon tetrachloride no
evidence of the minimum appearance was found. Such an observation suggests that the
existence of the minimum depends on the properties of permeating vapors as well as the
porous medium. it has been known that the diffusion and flow of sub-critical vapors
through activated carbon is controlled by Knudsen diffusion, gaseous viscous flow and
surface diffusion [4,6]. We argue that the interplay of these three mechanisms may
determine the appearance of the minimum in total permeability, and present iqthis paper
a permeation model which is modified from the Do and Dos model [6].This permeation
model introduces a collision-reflection factor, which takes into account the adsorption
effect on Knudsen permeability at low pressures. In the model surface diffusion is treated
in such a way that the mobility of molecules on the surface increases with surface
concentration due to the reduction of energy barrier with the progress of adsorption. This
paper will present a better description of the three diffusion mechanisms and feasible
reasons for the minimum appearance in the total permeability of n-hexane through
activated carbon.
2
For a given pressure gradient across a porous medium, the mass balance equation can be
described as follows, provided that Knudsen diffusion, viscous flow and surface diffusion
are additive to the total flux.
244
where E is the porosity of the particle, P is the intraparticle pressure and C, is the
adsorbed phase concentration. At steady state the terms in the square bracket on the RHS
of Eq. 1 are corresponding to Knudsen diffusion permeability (Bd, viscous flow
permeability (By) and surface d i m i o n permeability (BJ,respectively.
The pore diffusivity (D,), which is assumed to follow Knudsen mechanism, takes Eq.
2 for non-overlapping cylindrical pore of radius r.
Dk 2r 8RgT 2 - f
(2)
D,=-=-zk 3rk - f
L(1
where f is the fraction of molecules undergoing collision to the solid surface over
reflection From the surface, which is usually taken to be unity in most work in the
literature. Since we have found that the factor f decreases with an increase of pressure
(Carman [3] observed similar behavior in the transient period), we propose the following
pressure dependence form for the factorf for strongly adsorbing vapors:
f = f, +(fb -f,>.exP[-a(P@o)I
(3)
wherefo and fm are the values at the limit of zero pressure and at high pressure (close to
vapor pressure), respectively, which will be obtained directly from experiments. The
viscous flow parameter (Bo) for cylindrical pore is equal to ?/(8rv). The tortuosity factors,
'5k and r, are for diffusive and viscous flow, respectively, which will be calculated from
the permeability of non-adsorbing gases such as helium.
The surface diffisivity (D,) is known to be a function of adsorbed phase
concentration and is equal to the corrected diffisivity (D*$ multiplied by a
thermodynamic correction factor (8lnP/i?lnC,). Assuming that the driving force for
surface diffision is the gradient of the chemical potential and that the mobility constant is
a function of adsorbed phase concentration, Do and Do [6] have introduced the following
form for the corrected surface dihivity:
where Eo, is the activation energies for surface diffusion at the limit of zero pressure.
Dollmand Do, are the corrected surface diffisivities at the limit of zero pressure and at the
infmite temperature and at the permeation temperature, respectively. As the pressure
increases, adsorption occurs on progressively lower energy sites, resulting in the
reduction of energy barrier for diffusion. This is described by the term (I-&/( l+pC,)) in
Eq. 4. The larger the parameter p is, the faster E, decreases with adsorbed concentration.
When p=O, Eq. 4 reduces to the classical Darken equation [5].
3
Experimental
245
other, and is used as the supply reservoir. Thus the supply reservoir was maintained
practically at constant pressure during the c o m e of diffusion and adsorption.
The flux of each adsorbate through the porous solid was measured with respect to
time. Knowing the receiving reservoir volume (V), the cross-sectional area (A) and the
length (L) of the particle, we can determine the total permeability (BJ from Eq. 5 which
gives us a straight line passing through the origin with a slope of BdA$TNL) in a plot of
I~[(P,-P~O)/(P~-P~)]
versus time.
where P1 is the pressure in the supply reservoir, and P2(t) and P; are the pressure in the
receiving reservoir at any t and at PO, respectively. The detailed experimental procedure
and the set-up of permeation measurement can be found elsewhere [2,6].
The total permeabilities of n-hexane, benzene and carbon tetrachloride through activated
carbon were obtained from Eq. 5 and shown in Figure la. At very low pressures a sharp
increase in total permeability was observed for all adsorbates studied. The adsorbed
concentration of these adsorbates [2] increases drastically over this very low range of
pressure, indicating that surface diffusion must play a significantrole in its contribution to
the total permeability since the contribution of gas phase diffusion is expected to be
relatively small. Interestingly, it can be clearly seen in Figure la that only n-hexane
exhibits a minimum in total permeability at reduced pressure of around 0.03. This
phenomenon was consistently observed at three different temperatures. In this range of
pressure, Knudsen diffusion and surface diffusion are expected to dominate the transport
of molecules since gaseous viscous flow is insignificant.
To elaborate the contribution of surface diffusion to total permeability with our
model, several parameters are required. Firstly, tortuosity factors for Knudsen diffusion
(~k) and viscous flow (T,) were found to be 5.66 and 3.10, respectively by comparing the
total permeability of adsorbates with that of inert gases whose flow is governed by
Knudsen d i h i o n and gaseous viscous flow. Secondly, the collision-reflectionfactorfo at
the limit of zero pressure has to be 1.79 for the theoretical Knudsen diffisivity (Eq. 2) to
agree with experimental data. Thirdly, the equilibrium isotherms of the three adsorbates
were well described by the Toth equation. With these parameters, the mass balance
equation (Eq. 1) was solved for receiving reservoir pressure with respect to time by the
combination of the orthogonal collocation method and a standard integration method. All
parameters in Eqs. 3 and 4 at 303K were obtained by matching the simulated results
against permeation results and listed in Table 1.
Table 1. Optimal parameters for n-hexane, benzene and carbon tetrachloride at 303K
c
3
a
Dopo(m%)
p (m3/mol)
Eo,, (J/mol)
n-Hexane
1.79
1.03
2.15 lo3
5.86 x
2.30 x lo4
46900
Benzene
1.79
1.22
2.05 x 10'
7.36 1 0 - l ~
1.75 x lo4
50100
246
Carbon tetrachloride
1.79
1.15
3.16~10'
1.10 x 1 0 - l ~
2.55 x lo4
50000
One would physically expect that as pressure increases the solid surface may get
smoother due to the filling of small pores and cavities with adsorbed molecules, and as a
result the reflection time of gas phase molecules from the surface may become shorter.
The values off, in Table 1 are close to unity as expected and they are in an increasing
order of n-hexane, carbon tetrachloride and benzene. On the other hand, the parameter a
for n-hexane is much higher than that of the others. Since the parameter a in Eq. 3
represents how fast the Knudsen diffusivity increases with pressure, one would expect a
substantial contribution of the Knudsen diffusion for n-hexane to the total permeability at
very low pressures. Also the parameter j3 is a measure of how fast the activation energy
for surface diffusion decreases with adsorbed concentration. As Table 1 indicates, the
surface diffusion permeabilities of n-hexane and carbon tetrachloride are expected to
increase more sharply than that of benzene.
0.00
OlDp
0.01
0.08
0-
0.10
Id)
Carbon Taaachkrida
P,.",.
[P.]
Based on the optimal parameters in Table 1, the three permeabilities (BbB, and B,,)
are plotted in Figure 1 (b, c and d for n-hexane, benzene and carbon tetrachloride,
respectively) at 303K.The theoretical permeabilities calculated from 4 s . 1-4 for the
three adsorbates show very good agreement with those obtained from experiments. As
shown in Figure 1, at very low pressures the contribution of surface diffusion to total
permeability is considerable for benzene and carbon tetrachloride while Knudsen
diffusion is more dominant for n-hexane. Additionally it is interesting to note that the
surface diffusion permeability for the adsorbates studied is found to increase drastically at
very low pressures and then decrease moderately with an increase in pressure, which is in
agreement with out earlier theoretical study [4]. The fractional contribution of surface
diffusion to total permeability is the same order as the maximum adsorbed concentration,
confirming the fact that surface diffusivity is a function of adsorbed concentration.
247
Consequently, it can be clearly seen in Figure 1 that the interplay between Knudsen
diffusion and surface diffusion play an essential role in the appearance of a minimum in
total permeability.
5
Conclusions
The Knudsen diffusion, viscous flow and surface diffusion for strongly adsorbing vapors
are well described at low range of pressures in this paper. The collision-reflection factor
for Knudsen diffusion is found to be not constant but exhibit a modest increase with an
increase in pressure. The dependence of the Knudsen diffision for n-hexane on pressure
is stronger than that of the other vapors. Moreover the activation energy for the surface
diffusion of n-hexane exhibits a faster decreasing behavior in comparison with the others.
Conclusively, the reason for the minimum appearance in the total permeability of nhexane can be attributed by the interplay between the Knudsen diffusion and surface
diffision.
6
Acknowledgements
References
I. Adzurni H.,Studies on the flow of gaseous mixtures through capillaries: 111. The flow
of gaseous mixtures at medium pressures. Bull. Chem. SOC.Jap. 12 (1937) pp. 292305.
2. Bae J . 4 . and Do D. D., Study on diffusion and flow of benzene, n-hexane and C C 4 in
activated carbon by a differential permeation method. Chem. Eng. Sci. in press (2002).
3. Carman P. C., Diffusion and flow of gases and vapours through micropores I. Slip
flow and molecular streaming. Proc.Roy.Soc.(London) A203 (I 950) pp. 55-74.
4. Do H. D. and Do D. D., A new diffusion and flow theory for activated carbon from
low pressure to capillary condensation range. Chemical Engineering Journal 84
(2001) pp. 295-308.
5. Do H. D., Do D. D. and Prasetyo I., On the surface diffision of hydrocarbons in
microporous activated carbon. Chemical Engineering Science 56 (200 1) pp. 435 14368.
6. Do H. D., Do D. D. and Prasetyo I., Surface diffusion and adsorption of hydrocarbons
in activated carbon. AIChE Journal 47 (2001) pp. 2515-2525.
7. Gray P. G. and Do D. D., Dynamics of carbon dioxide sorption on activated-carbon
particles. AZChE J 37 (1991) pp. 1027-34.
8. Knudsen M., Die Gesetze der Molekularstr6mungund der inneren Reibungsstr6mung
der Gase durch R6hren. Annalen der Physik (Leipzig) 28 (1909) pp. 75.
9. Pollard W. G. and Present R. D., On gaseous self-diffusion in long capillary tubes.
Phy~.Rev. 73 (1948) pp. 762-774.
10. Wicke E. and Vollmer W.,Flow of gases through micropores. Chem. Eng. Sci. 1
(1952) pp. 282-291.
248
MODEL
Y. MIURA, Y. OTAKE,S.IWASAWA AND E. G. FURUYA
Dep. lnd. Chem.,Meqi Universiy, Tama-Ku, Kawasaki, 214-8571, Japan
E-mail: egfuruyac@isc.meiji.ac.jp
Introduction
Granular activated carbon (GAC) has been used widely in environmental pollution
control due to its capability to absorb a broad range of organic and inorganic compounds.
To properly design a GAC column, information regarding accurate kinetic data of
intraparticle diffusion rate parameters is required. Intraparticle diffusion is, however, a
complicated process that includes at least two parallel mechanisms: pore diffision and
surface diffusion [7].
In this paper, we will present a procedure to separate pore diffusion and surface
diffusion in GAC adsorption by use of a stepwise linearization. Furthermore, a simplified
method to estimate concentration dependency of apparent diffusivities from breakthrough
curves will be proposed.
Theoretical Considerations
This model was developed for its simplicity to avoid the need to determine
249
Y
Liquid Concentration, c
Using a stepwise linearization technique developed in this study can minimize the
problem associated with the Neretnieks technique. This technique uses a straight-line
section by connecting two isotherm points [(c,,, q,,) and (C,~,qe2)]to approximate the
actual isotherm as presented in equation (4).
The slope obtained by the stepwise method is, therefore, more representative of the actual
slope than that by Neretnieks technique. As seen in Figure 1, the slope (f3) in the
adsorption isotherm curve becomes gentle in high concentration range. Consequently, DS
becomes negligible in comparison with the pore-diffision term Dp/Pppaccording to
Equation (3).
250
XlW'
25
:g
DRCMBR
20
joeg<.O
i
i
!
...i .....-i .......i ....i
. . . .
i
i.
* .i* . i .
.
0.8
1.0
1.2
1.4
5,
XI
0.0
0.2
0.4
0.6
1.6
0.0
'18 Wm3
(a) PNP - CAL systems
0.2
0.4
0.6
0.8
1.2
1.0
1.4
1.6
1/B Wcm?
Figure 3 also includes the correlation between D, and l/P for PNP in of traditional
long column bed (LCB). It is noted that D, in LCB was determined by use of the MTZ
method.
0.30
0.25
0.20
0.15
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
'4 Is/cm3
0.10
-................................................
o
i
'.-_-.-.
Dflm = 0.235
.-.-.W.i.-.-.- 1-.-.a
+.-._..
Dflm
0.22 ( D W M B R )
i
_.
................................................
_.
.............-...;.--.
i
LCB
:
0.0
DWMBR
I
PNP
0
.---*-
Temperature plcl
251
The slopes in Figures 2 and 3 were used in order to calculate the pore diffusivities (D,),
which are independent of adsorbate concentration, by use of Equation (3).
The ratios of Dp to molecular difisivities Dm are plotted against adsorption
temperatures in Figure. 4. The Dflm values are expected to be constant for a particular
adsorbent, irrespective of types of adsorbates and adsorbers over a range of temperatures.
From Equation (3), the value of the surface diffisivity Ds were calculated by
subtracting the pore-diffusivity term Dp/Pppfrom the apparent difisivity D,. The value of
D@, is then plotted against D, for DR and CMBR methods (Figure 5-a) and for LCB
method (Figure 5-b). It can be pointed out from Figure 5-a that that (i) DR and CMBR
methods yield similar estimate of D, and that (ii) intraparticle diffusion of PCP into GAC
is dominated by surface diffusion compared to PNP.
..........
....................
!\AA.....
)
5?
g 0.4 ......,.....
I..
Len-.
.........
...
0.2
soa.
318%
0.0
8 1 0
....................
x10l8
i py. i ....
. i...:...:..:..:
. . . .....
i.......
.
.
.* . . . .. .. .. .. m- .
I
i i i i i
0.0
OR CUBR ffiB
AO A
a m
318%eO
XlOd
8 1 0
4 ldkl
lcn+4
It is also seen fiom Figure 5-b that the extents of Ds contribution to D, evaluated on
LCB method almost coincides with those for DR and CMBR, implying that LCB method
can be applied for the determination of concentration dependency of D,.
Conclusions
The kinetic adsorption studies in different types of adsorbers were performed with
two phenolic compounds of PNP and PCP on activated carbon. A technique of isotherm
stepwise linearization has been proposed and applied to approximate nonlinear isotherms
for GAC adsorption. The results showed that pore and surface diffisivity are estimated
satisfactorily using this stepwise linearization technique. This study also showed that the
apparent difisivity (D,),which possesses concentration dependence, could be estimated
on LCB by applying the technique in high-adsorption region.
References
252
95.
4. Mansour, A. D., von Rosenberg, D. U., and Sylvester, N. D. (1982). AlChE J., 28,
765.
5. Neretnieks, I. (1976). Chem. Engrg. Sci.. 31, 1029.
6. Noll, K. E., Gounaris, V.. and Hou, W. S. (1992). Adsorption technology for air and
water pollution control. Lewis Publishers, Chelsea, Mich., 1 - 20.
7. Weber, W. J. Jr, ed. (1972). Physicochemical processes John Wiley, New York, N.Y.,
199-259.
253
Introduction
Adsorption of ions at surfhces has been one of the classical fields of interest in regard
of catalysis and separation. Among various surfaces, Langmuir monolayers mimic the
structure of cell membranes and hence these biomimetic surfaces are a model system that
enables one to investigate surface phenomena analogous to the membrane surfaces [1 21.
Adsorptivity of various ions to Langmuir monolayers has been known to be quite
different fiom that in the bulk phase after extensive studies done by theoretical models and
empirical techniques involving X P S , neutron scattering, FTIR, etc [3, 41. Most of the
empirical studies were done ex-situ because there exists difficulties in dealing with the
monolayers at the aidwater interface in-situ. Recently, much progress has been reported
especially on the in-situ FTIR spectroscopy for the aidwater interfaces [5,6].
In the present study, we report new results on in-situ near-normal external reflection
FTIR on the monolayers containiig both reactive and inactive moieties to adsorption of
ions. Unlike the conventional ex-situ analysis, it was capable of observing suppressing
effects of mixed monolayer surfaces to ion adsorption.
2
Experimental
Compounds used to form Langmuir monolayers were stearic acid (>99.9%) and
stearyl alcohol (>99.9%) purchased fiom Aldrich. Stearic acid known to bind with
cadmium ions (CdC12, >99.9%, Aldrich) were mixed with stearyl alcohol at varying
compositions fiom 1OO:O to 50:50. Each solution was at the concentration of 1mM in
chloroform (>99%, Fluka).
254
Each mixed solution was spread using a micro syringe on a KSV minitrough
(Finland) containing deionized (DI) water or 1mM aqueous CdCl2 solution both at pH of
5.5. After evaporating chloroform for 30min., the molecules were compressed to form the
close-packed monolayer at the surface pressure of 2OmN/m. After waiting 3Omin to reach
the equiIibrium, the monolayer was deposited onto a clean CaFz substrate for the ex-situ
FTIR analyses by the skimming method to make sure the sampled film to represent the
original monolayer at the aidwater interface. The sample was blown dry by the nitrogen
gas stream, and then scanned 512 times with a FTIR spectrophometer (Perkin-Elmer
Spectrum GX) equipped with a liquid-nitrogen cooled MCT detector at the transmission
mode with an unpolarized i n h e d beam.
For the in-situ FTIR analyses, mixed solutions were spread by the same fashion onto
a house-made minitrough that fitted into the sample chamber of the FTIR instrument. For
every in-situ experiment, the close-packed monolayer was initially formed on DI water
that was then replaced with lmh4 CdC12 solution by careful circulation of the subphase
using a peristaltic pump. The background spectrum was taken for a bare water surface
when the sample was the monolayer on pure water, and was taken for a close-packed
monolayer on pure water when the sample was the one on the cadmium-containing
subphase. The latter technique enhanced the carboxylate peak relating to ion adsorption.
All the experiments were done at room temperature.
3
The ex-situ transmission FTIR results of the mixed monolayers spread on pure water
@H=5.5) are shown in Fig. la. The spectra are adjusted so that methylene stretching
bands (v,CHz, 2918cm-' and vSCH2, 285Ocm-') have the same intensity height. The
carbonyl band (vC=O, 1705-173Ocm~')representing the acidic state of the stearic acid is
not interfered with peaks arising fiom the stearyl alcohol. As the relative amount of the
alcoholic moiety increases the peak area decreases as expected fiom the monolayer
composition, as shown in Fig. lb. It is also noted that the carbonyl band shifts fiom
1705cm" to 173Ocm-', which indicates that lateral hydrogen bonding among carboxylic
head groups becomes to be weaken as the stearyl alcohol molecules are mixed and
inserted among the stearic acid molecules. On another set of experiments of surface
isotherms (of which results not shown), the surface Gibbs fiee energy implies the two
components to be well-mixed at the surface pressure of 2OmN/m at room temperature.
255
0 i o m a o ~ 0 ~ 8 0 m m o o t m
Tbeoretic.1 c.1cUhtion
vc-0
0.2
iw
80
70
80
50
H)
so
10
(a)
(b)
Figure 1. Transmission FTIR results on the mixed monolayers spread on pure water with varying monolayer
composition (stearic acid : strearyl alcohol) (a) and the peak area of the carbonyl band at various composition
(b). The peak areas were normalized with respect to that of pure straric acid case (1OO:O).
The ex-situ transmission results on the mixed monolayers spread on the subphase
containing 1mM CdClz (pH=5.5) are shown in Fig. 2a. At this high concentration of
cadmium ions, every acidic molecule is bound with cadmium ions as indicated by the
complete disappearance of the carbonyl band and the existence of the asymmetric
carboxylate band (v,COO, 1542cm-') at the same time. In general, the peak intensity of
the asymmetric carboxylate band decreases as the relative amount of the reactive stearic
acid decreases, as observed in the case of Fig. 1.
The in-situ near-normal external reflection results on adsorption of cadmium ions to
mixed monolayers are given in Fig. 2b. Since the background spectra are taken for the
close-packed mixed monolayers on pure water at each composition, the methylene
stretching bands are nearly cancelled out. By contrast, the asymmetric carboxylate band
appears with reasonable S/N ratios even without a polarizer-modulator set-up [7].It is
noted that the near-normal incidence of the i n h e d beam resulted in negative signals on
the contrary to that of the grazing-angle incidence.
It is interesting in the in-situ investigation (Fig. 2b) that as the relative amount of the
inactive stearyl alcohols to cadmium ion exceeds 20% the asymmetric carboxylate band
suddenly decreases in its intensity and remains about the same afterwards. In Fig. 2c, it is
clearly seen that the adsorbed amount of cadmium ions at 80% of stearic acid is reduced
by more than half of those at larger compositions of the acid. By contrast, the ex-situ
results showed a linear decrease in cadmium adsorption with the monolayer composition
as well as a certain deviation fiom the theoretical calculation that is different to the case
without adsorption of cadmium ions.
(c)
Figure 2. Ex-situ transmission FTDR results (a), in-situ near-normal external reflection FTIR results (b) on the
mixed monolayers spread on aqueous cadmium solution ( I d , pH4.5) with varying monolayer composition
(stearic acid : streayl alcohol), and the peak area of the asymmetric carboxylate band at various composition (c).
The peak areas were normalized with respect to that of pure strearic acid case (1OO:O).
Conclusions
257
Acknowledgements
This work was supported financially by the Korea Science and Engineering Foundation.
References
1. Vijendra K.A.,Langmuir-Blodgettfilms, Phys. Today (1988) pp. 40-46.
2. Swalen J.D., Allara K.L., Andrade E.A., Chandross E. A., Garoff S., Israelachvili J.,
McCarthy T.J., Murray R., Pease R.F. and Rabolt J.F., Molecular Monolayers and
Films, Langmuir 3 (1987) pp. 932-950.
3. Ahn D.J. and Franses E.I., Ion adsorption and ion exchange in ultrathin films of fatty
acids, AIChE 40 (1994) pp. 1046-1054.
4. Kim T.Y., Lee G.S. and Ahn D.J., Ion separation of binary aqueous solutions at
acidic Langmuir monolayer surfaces, Korean J. Chem. Eng. 18 (2001) pp. 977-985.
5. Geriche A., Huhnerfm H., In situ investigation of saturated long-chain fatty acids at
the adwater interface by external infrared reflection-absorption spectrometry,J. Phys.
Chem. 97 (1993) pp. 12899-12908.
6. Ren Y., Hossain M.M., Iimura K.I. and Kato T., CH3(CH2)COOH/Cd2+system on the
aqueous cadmium acetate solution investigated in situ by polarization modulation
infiared spectroscopy,J. Ply. Chem. B 105 (2001) pp. 7723-7729.
7. Blaudez D., Buffeteau T., Cornut J.C., Desbat B., Escafre N., Pezolet M. and Turlet
J.M., Polarization-modulated FT-IR spectroscopy of a spread monolayer at the
aidwater Interface, Appi. Spectroscopy 47 ( 1993) pp. 869-874.
258
SOLUTION THEORY
P. MONNEYRON, M.-H. MANERO AND J.-N. FOUSSARD
LIPE, Dpt GPI, Institut National des Sciences Appliquees, 135 avenue de Rangueil
31077 Toulouse. France
E-mail: Pierre.monneyron@insa-tlse.jL,manero@ch. iut-tlse3.jL
Pure and binary component adsorption isotherms were determined for three volatile organic
compounds daily used as industrial solvents (methyl ethyl ketone (MEK), toluene (TOL),and 1,4dioxan (DIO))on two high silica zeolites, a desaluminated faujasite Y (Fau Y) and a silidite (Sil Z).
Apart from steric exclusion taking place with TOL-containing mixtures on Sil Z, adsorption
occurred via three phenomena At low filling rates, chemisorption on specific sites happened in
favor of polar or major compound, whereas in the high pressure saturation domain the adsorbent was
selective for the minor compound. In between, micropores-filling had a similar behaviour to
distillation since the component with the lower volatility adsorbed preferentially. Secondly, binary
equilibria predictions were performed using the IAST. On Sil Z, the difference between Langmuir
and Toth model-based calculations of isobaric selective diagrams was small but significant in the
MEK-DIO mixture at low pressures. On Fau Y, IAST calculations lead to an excellent agreement
with experimental data when the adsorbed phase was closed to ideality. RAST correlations
efficiency of fitting was good in some cases. For engineering purposes, Fau Y is to be considered as
a high adsorption capacity adsorbent, whose selectivity can be described qualitatively by the
distillation analogy, and predicted quantitatively with the IAST in case of quasi-ideal mixtures.
Introduction
Volatile Organic Compounds (VOC) are widely found as solvents in industrial processes
and domestic use. Considered as major air contaminants for inducing directly health
troubles, or for being precursors of tropospheric ozone, polluted air streams are mainly
treated by adsorption on a porous solid [6].
Activated carbon is commonly acknowledgedto be very efficient as a VOC adsorbent.
However, in the last decade, interests arose to develop new materials, such as alumnisilicate molecular sieve, towards operating conditions for which activated carbon was
inappropriate due to its inflammability and adsorption capacity dependence on effluent
relative humidity. Apart from hydrophobicity, the advantages of High Silica Zeolites
(HSZ)are notably a thermal and chemical stability, a high steric selectivity and a
complete regeneration at low temperatures [ 1 11. Yet, for adsorption and separation
processes development, organic compounds properties impact on adsorption and
crystalline framework influence on selectivity are to be clarified and efficiently modeled.
This study firstly aims at understanding adsorption properties of two HSZ towards
three VOC (methyl ethyl ketone, toluene, and IP-dioxane), through single and binary
adsorption equilibrium experiments. Secondly, the Ideal Adsorbed Solution Theory
(IAST) established by Myers and Prausnitz [lo], is applied to predict adsorption
behaviour of binary systems on quasi homogeneous adsorbents, regarding the pure
component isothenns fitting models [ 5 ] . Finally, extension of adsorbed phase to real
behaviour is investigated [4].
259
Experimental section
In this study, two commercial HSZ,were used in pellets form, a desaluminated faujasite Y
and a silicalite. The supplier kept undisclosed the chemical nature of the clay binder
together with details of desalumination technique. The main characteristics of adsorbents
are given in table 1.
Table 1. Main characteristics of zeolites.
Type (Symbol)
Crystalline framework
Pore internal diameter (A)
Si02/Al2O3(mol mol-')
Active porous volume (cm3g-I)
Faujasite (Fau Y)
a-cages
13
360
0.24
ZSM-5(Sil Z)
Interconnected channels
(5.7 * 5.1) and 5.4
1880
0.18
The three volatile organic compounds studied (99%), having very different chemical
structure as summarized in table 2, were all used without further purification.
Table 2. Main properties of adsorbates,
property
Symbol
Formula
Molar volume 25C (cm3mol-I)
Vapour pressure at 25OC @Pa)
Dipolar moment (D)
Kinetic diameter (A)
2-butanone
(methyl ethyl
ketone)
MEK
C4H8O
90.14
12.60
2.78
5.2
methyl
benzene
(toluene)
TOL
C7H8
107.51
3.79
0.375
5.8
1,4dioxacyclohexane
(p-dioxan)
DIO
C4H802
85.79
4.95
0
5.3
Batch experiments were performed at 298 K via a standard volumetric method, using
a 1.1 L glass reactor at atmospheric pressure, containing typically 0.5 g of adsorbent,
polluted by liquid VOC injection, leading to an initial concentration of about 0.5 mmol.L-'.
Equilibrium times were 1 and 2 hours respectively for Fau Y and Sil Z, after which the gas
phase was sampled and analysed by chromatography (HP 5890 11). Using the conventional
assumption that the clay binder does not take part in the adsorption mechanism, data were
reported for pure zeolite material. Reproducibility and repeatability of experimental data
were checked by three different manipulators.
In case of binary systems, co-adsorption was performed using three different initial
mixtures being equimolar (Z,
= Zt= 0.5) and rich in component 1 and 2 (respectively 2,
= 0.85 and Z, = 0.15) - whose molar ratio were formerly checked. The selectivity of
adsorbent (qlQ)was either directly represented in an X-Y isobaric equilibrium diagram, or
determined using the following equation, where Xi and 5 are the adsorbed and gas phase
molar tiaction of thcomponent, and plotted versus total amount adsorbed (&).
Xl-Y2
91/2 =-
x2 -yl
260
3.1
Adsorption isotherms were determined in the low partial relative pressure range, &/po 5
0.1). For all compounds, the isotherm curves obtained on Sil Z and Fau Y were
respectively of type I and V of IUPAC classification. Using the assumption that the
adsorbed phase was in the liquid state, micropore fillings were calculated, highlighting the
steric exclusion of TOL on silicalite (52% for TOL versus 87 % for MEK and DIO). This
maximum adsorption capacity of 4 molecules per unit cell, adsorbed at channels
intersections, was commonly observed on pentasil zeolites by other researchers for
aromatics [7], and chlorinated compounds [2]. Contrary to the second step occurring in
the isotherms that they observed, no significant upload in adsorbed quantity of TOL on Sil
Z was found here, as the partial pressure increased up to &bo= 0.35). This difference
was attributed to the initial adsorbent being either directly synthesized silicalite or ZSM-5
with a lower SQAI ratio, or in our case a HSZ where the desalumination step induced a
small decrease in pores dimension. As expected, no exclusion phenomenon was observed
on the large pore faujasite: the difference of pore filling being much smaller (respectively
72, 73, and 82% for TOL, DIO, and MEK) was attributed to differences in molecules
flexibility towards maximum space occupation. These results were consistent with
previous studies carried out on similar systems [8,12].
3.2
Apart from specific adsorption sites - being generally framework aluminum in partially
desaluminated hydrophobic zeolites inducing some polar affinity [3], selective coadsorption on HSZ was reported to depend on adsorbent crystalline framework,
component volatility, initial molar fraction of the gas phase and micropore filling [5,13].
However, considering the different desalumination techniques, various amounts of Extra
Framework Aluminum (EFAL) and silanol group (SiOH) sites can be formed, and may
induce a change of selectivity at low loading [8]. As well, the clay binder can exhibit some
specific adsorption sites fiom its framework hydroxyl groups however small its specific
surface area may be [I]. This co-influence of chemisorption reported previously for an
< 0.5 mmol g-1, leading to a selective
aqueous system [9], was noticed on Fau Y for {aa,
adsorption of component (1) in TOL-containing mixture (fig l.b), and of the major
compound in MEK-DIO binary system.
On both zeolites, qualitative identical adsorption behaviour were observed between
MEK-TOL and DJO-TOL mixtures. On Sil Z (fig. l.a), a low selectivity for TOL
occurred du to the great difference in active volume. With increasing loading, this
tendency increased naturally. However it is strongly suspected that a competitive
adsorption on TOL adsorption sites remained hidden behind this steric exclusion
selectivity, as confirmed by the higher selectivity for MEK predicted by the IAST. Indeed,
in the MEK-DIO mixture at high loading, the Sil Z was found to be selective for the less
volatile compound (DIO). In the same way, this distillation analogy was found for Fau
Y in the micropore filling pressure range, (fig. 1 b). In addition to volatility influence, in
the high loading range, both HSZ show higher selectivities towards minor compound,
inducing for the {Z,= O.I5)-TOL containing mixtures a competitive influence of these
two parameters.
261
45
5 7
40 -
Z1 = 0.15
z 1 = 0.15
a)
0
35 -
z 1 = 0.50
x Z 1 =0.85
E30 4
25 1 2 0 -
x Z1 = 0.85
*.
z 1 = 0.50
**
% o m oroclKrq!ax
5
0
0.5
1.5
2
Q t o t (mmol.g-')
Q t o t (mmol.g-')
Figure 1. Selectivity towards h4EK-TOL mixture, on Sil Z (a) and Fau Y (b).
4.
4.1
+Ex)
_ _ _ IAST
._._
Langrnuir
0.8
0.8
0.6
0.6
(P= 30 Pa)
XMEK
0.4
0.4
0.2
0.2
YMEK
0.2
0.4
0.6
0.8
0.2
0.4
0.6
Figure 2. Isobaric selective X-Y diagrams towards MEK-DIOmixture, on Fau Y (a) and Sil Z (b).
262
0.8
4.2
RAST was applied using Wilson model for activity coefficients and, as shown on figure
2.b, it successfully predict the azeotropic behaviour for the system considered. However
in care of TOL-containingmixtures, experimentallydetermined activity coefficients could
not be fitted over the whole adsorbed phase composition range with only a two adjustable
parameters model.
References
1. Alpay E., Haq N., Kershenbaum L.S. and Kirkby N.F., Adsorption parameters for
strongly adsorbed hydrocarbon vapours on some commercial adsorbents, Gas
Separation and Purijkation 10 (1996) pp.25-33.
2. Bouvier F. and Weber G., Adsorption of a polar or a non-polar chloroalkene on a
ZSM-5 zeolite at 298 K, Journal of Thermal Analysis 54 (1998) pp. 881-889.
3. Brosillon S., Manero M.-H. and Foussard J.-N., Adsorption of acetoneheptane
gaseous mixtures on zeolite: co-adsorption equilibria and selectivities, Environmental
Technology 21 (2000) pp. 457-465.
4. Costa E., Sotelo J.L. Calleja G. and Marron C., Adsorption of binary and ternary
hydrocarbon gas mixtures on activated carbon: experimental determination and
theoretical prediction of the ternary equilibrium data, AIChE Journal 27(1) (1981)
pp.5-12.
5. Garrot B., Couderc G., Simonot-Grange M.-H., and Stoeckli F., Co-adsorption of
1,2-dichloroethaneand 1-bromo,2-chloroethaneon zeolite ZSM-5 from the liquid and
vapour phases, using the Myers-Prausnitz-Dubinin model, Microporous and
Mesoporous Materials 52 (2002) pp. 199-206.
6. Le Cloirec P. Les composes organiques volatiles (COV) dans Ienvironnement
(Lavoisier Tec&Doc, Pars, 1998)
7. Li J.-M. and Talu O., Effect of structural heterogeneity on multicomponent
adsorption: benzene and p-xylene mixture on silicalite, in: M. Suzuki (ed.) Proc.
Int. Con$ on Fundamentals of Adrorption, (Elsevier, Amsterdam, 1993) pp. 373-380.
8. Meininghaus C. K.W. and Prins R., Sorption of volatile organic compounds on
hydrophobic zeolites, Microporous and Mesoporous Materials 35-36(2000) pp. 349365.
9. Monneyron P., Faur-Brasquet C., Sakoda A., Suzuki M., and Le Cloirec P.,
Competitive adsorption of organic micropollutants in the aqueous phase onto
activated carbon cloth: comparison of the IAS model and the neural networks in
modeling data, Langmuir 18 (2002) pp. 5 163-5169.
10. Myers A.L. and Prausnitz J.M., Thermodynamics of mixed-gas adsorption, AlChE
Journal 11(1) (1965) pp.121-127.
11. Otten W., Gail E. and Frey T., Einsatzmoglichkeiten hydrophober zeolithe in der
adsorptionstechnik, Chem.-Znd-Tech.64(10) (1992) pp. 915-925.
12. Rochester C.H. and Strachan A., The adsorption of dioxan by porous silicas, Journal
of Colloid and Interface Science 177 (1996) pp. 456-462.
13. Takeuchi Y., lwsrmoto H.,Miyata N., Asmo S., and Harada M., Adsorption of 1butanol and p-xylene vapor and their mixtures with high silica zeolites, Separations
Technology5 (1 995) pp. 23-34.
Ivh
263
Introduction
Solvent recovery from air by adsorption onto granular activated carbon (GAC) is an
highly exothermic process which may bring about ignition risks on industrial fixed bed
units. Indeed, the saturation of the bed being progressive from the inlet to the outlet, at
each time, the adsorption spreads over a small area. Due to heat accumulating, hot spots
then locally arise. When the temperature becomes sufficiently high to start the oxidation
reactions of the adsorbent or the organic compound, chain mechanisms set up, leading to
ignition. Thus, to insure the efficiency and the safety of the process, prediction of the
temperature maximum attained within the bed is required.
Our previous work mainly paid attention to experimental characterization and
modeling of the thermal behavior of a GAC bed during adsorption of VOCs [ 1-31. One of
our conclusions was that the integral adsorption enthalpy, which is a data depending both
on the nature of the VOC and on the type of activated carbon material employed, has to be
primarily determined in order to accurately predict temperature rises with operating
conditions. Figure 1, which reports the temperature rises observed during experimental
tests conducted with various pollutants at different inlet concentration levels, demonstrates
the strong influence of this data.
The aim of the present study was to quantify the changes in the integral adsorption
enthalpies induced by the nature of the organic adsorbate. For that purpose, energy
measurements were achieved for a wide panel of VOCs, representative of different
264
chemical groups, using one type of carbon adsorbent. A database was thus generated,
which was appropriate for fiuther statistical analysis.
120
100
80
c.
a
60
40
20
20
60
40
- AH
80
100
120
C a (kJ.m")
Figure 1. Maximal temperature rises observed during dynamic adsorption tests of 15 VOCs onto one GAC bed,
the inlet concentration C M varying from 20 to 100 g.m".
Experimental Section .
2.1
One type of GAC (NC60) was mainly employed to set up the adsorption enthalpy
database, with a panel of 44 VOCs. For a few compounds, adsorption energies were also
measured on other GACs. The magnitude of the changes observed were then considered
as indicative of the influence of the characteristics of the GAC. The characteristics of the
GACs employed are listed in Table 1.
Table 1. Main characteristics of the GACs tested
Manufacturer
Name
Raw material
Specific surface area
(m2.g-')
NC60
coconut
Pica
NClOO
coconut
BC120
wood
Chemviron
BPL
coal
Norit
RB2
peat
1063
1783
1675
1043
1013
265
2.2
The whole experimental data are presented in tables 2 and 3. Adsorption energies range
from 40 to 82 kJ.mol%nd are 1.5 to 2 times higher than condensation heats.
Table 2. Experimental adsorption energy database for NC60
VOC
VOC
Adsorption heat
Acetaldehyde
Ethyl acetate
Iso-propyl acetate
Acetone
Ethyl acrylate
2-Bromopropane
Butylamine
Butyraldkhyde
Chloroform
2-Chloro-propane
Cyclo-hexane
Cyclo-hexene
1.2-Dichloro6thane
Dichloromethane
Diethylether
Diisopropylamine
Dimtthoxymtthane
Tetrachloroethylene
Tetrahydrofurane
Toluene
Trichloroethylene
Triethylamine
Trimethylpentane
(k~.mo~-')
48.5
61.2
68.5
50.6
16.2
54.2
14.9
53.2
50.5
49.4
55.4
63.5
51.2
48.6
56.9
14.4
64.2
70.2
49.1
63.1
65.6
81.9
75.3
Adsorption heat
(W.mol-')
Ethyl alcohol
isoiropylether
Formaldehyde
Ethyl-formate
Heptane
Hexane
1-Hexene
1-Hexyne
Isobutylvinylether
Methyl-alcohol
Methylethylketone
Methylethyldioxolane
Methylisobutylketone
2-Methyl-1 -propano1
Pentane
Propyl alcohol
Propionaldehyde
Benzene
Fluorobenzene
Acrylonitrrile
Methylbutanone
48.6
62.2
42.3
51.4
12.9
61.4
63.0
56.9
64.1
40.8
56.2
70.9
67.6
56.6
51.9
50.0
49.4
59.4
61.1
51.2
64.2
Mean
Standard deviation
59.44
9.67
Dichloromethane
Ethyl alcohol
Ethyl-formate
Methylethylketone
Benzene
Fluorobenzene
Acrylonitrile
Methylbutanone
Hexane
Mean
Standard deviation
51.4
56.2
59.4
49.9
55.0
52.8
BPL
46.3
52.1
52.4
61.3
51.2
60.0
51.6
64.0
64.3
50.0
53.1
40.6
46.4
68.3
6.70
60.9
5.71
52.6
4.84
5.94
RB2
48.5
61.4
54.1
62.2
49.2
65.1
52.2
62.8
76.2
8.40
From the standard deviations reported in tables 1 and 2, we notice that the energetic
interactions are sensitive to both the adsorbent and the organic specie. Indeed, energy
deviations observed for a same compound on different carbon materials are in the same
order of magnitude as that measured with different VOCs on one type of GAC.
The energy database for various GACs has to be extended before any quantitative
analysis, accounting for the influence of the intrinsic properties of the adsorbent, could be
achieved. However, we notice that on average, adsorption enthalpies measured on NC 100
and BC120,which have the highest specific surface areas, are lower than on the other
GACs.
266
3
3. I
Statistical models
As a first attempt, a linear model was assumed and a multiple linear regression (MLR) was
267
Results of the best MLR are presented in figure 2, which compares experimental and
computed energies. The best MLR corresponds to the maximum coefficient of
determination ?which was 0.853 on the working data set and 0.879 on the testing data set.
This means that more than 85% of the variability in the data may be explained with the
linear model. Adsorption energies are then predicted with a precision around +/-lo%.
Following the stepwise procedure, 3 explicative variables were discriminated :
+0.0724 M
The effect of the polarisability . and of the ionization potential IP may be directly
related to their impact on the energy of the dispersive forces (London, Debye and
Keesom) which govern physical adsorption onto activated carbon [4]. The lower positive
effect of the molar mass M may be related to the influence of the molecular overcrowding
which increases the surface contact with the solid, leading to more intensive interactions.
,.
ideal line
'-10%
80
70
40
50
60
70
80
90
40
50
60
70
80
90
268
4.3 Discussion
It is noticeable that both linear and non linear modeling approaches explain changes in
adsorption enthalpy data with the same molecular properties. This means that the lack of
agreement observed is not due to the way of combining the explicative variables in the
relationship. A better representation would only be found provided that an other pertinent
molecular property is included among the input variables set.
This study demonstrated that statistical models may be successfblly applied to set up
QSPRs available for prediction of adsorption enthalpy of an organic specie on one type of
activated carbon. But for generalization, the specific influence of the properties of the
GAC have also to be taken into account.
References
1. Prd P ., Delage F. and Le Cloirec P., A model to predict the adsorber thermal
2.
3.
4.
5.
6.
7.
8.
9.
behavior during treatment of volatile organic compounds onto wet activated carbon,
Environ. Sci. Technol.,Environ. Sci. Technol, in press (2002).
Prd P., Delage F. and Le Cloirec P., Modeling the exothermal nature of V.0.C
adsorption to prevent activated carbon bed ignition, Fundamentals ofahorption 7, K.
Kaneto, H. Kanoh, Y.Hanzawa Editors, IK International, Chiba, Japon, (2001) pp. 700 -707.
Delage F., Prd P ., and Le Cloirec P., Mass transfer and warming during adsorption of
high concentrations of VOCs on an activated carbon bed : experimental and
theoretical analysis, Environ. Sci. Technol.,34 (22) (2000). pp. 4816-4821
Ruthwen M.D., Principles of adrorption and ahorption processes, John Wiley &
Sons, New-York, US (1984).
Mocho P., Adsorption de composds organiques volatils sur charbon actif rdgdndration in situ du charbon par chauffage par induction dldctromagnetique,PhD
Thesis, Universitede Pau et des pays de 1 Adour- France (1994).
Terzyk A.P, Rychlicki G., Empirical relationship describing energetics of adsorption
at low coverages of macroporous carbons, J. Thermal Anal., 55 (1 999) pp 101 1- 1020.
Bishop C., Neural networksfor pattern recognition,Clarendon, Oxford, U K , (1995)
Rumelhart D. E., Hinton G. E., and Williams R. J., Learning representations by backpropagation emors., Nature, 323 (1986) pp. 533-536.
Garson G.D., Interpreting neural network connection weights, Al Expert, 6 (1991)
pp. 47-5 1.
269
Introduction
Experimental
270
experiments the balance was kept at 383 K, while the remaining system was kept at a
higher temperature in order to prevent any condensation. A scheme of the set-up is given
in figure 1.
Buoyancy corrections can in the present set-up be made by the in-sifumeasurement of
the density of the gas by means of the weight change of a sinker with a known volume.
This balance is described extensively by Dreisbach ef al. [2].
gas in
@ = Pressuretransducer
tanium sinker
ample holder
In a first series of experiments adsorption was studied using undiluted n- or isobutane. In a second series helium or argon were admitted first, and subsequently (within 5
minutes), n- or iso-butane was admitted to the sample compartment. In both series exactly
the same amount of n- or iso-butane was introduced.
3
3.1
Results
BEA
In Figure 2a and b the results are given for the adsorption of n- and iso-butane at 383 K on
BEA. If there was no influence at all of helium and argon in each figure only two lines
should have been present. From these figures it can be observed that the pre-admission of
helium or argon slows down the rate of adsorption, this being the case to a stronger degree
for argon. Also the equilibrium loading is adversely effected by pre-admission of helium
or argon. The effect on the adsorption equilibrium results in a higher (partial) pressure of
butane in case argon or helium is present, although the same amount of butane was
introduced.
After introducing helium or argon no change in weight could be observed, indicating
that no adsorption of helium or argon is taking place (less than 0.01 pmol He/g or 0.1
pmol Ar/g) before the butane is admitted.
27 1
-c
6
1.00
Im
0.75
0.75
O M
O M
0.25
0.25
0.00 a
50
100
150
I
200
0.00
.-.
50
lime (min)
100
I50
I
m
cim (min)
Rgure 2a and b. The amount adsorbed versus time for n- and iso-butane on BEA at 383K. The indicated
pressures represent the (partial -in 100 Wa He or Ar-) pressures of n- or iso-butane after 200 minutes
equilibrium time.
3.2 MFI
In figures 3a and b the results are shown for n- and iso-butane on MFI at 383K. Basically
the same effects observed for BEA can also be seen in case of MFI.
(iu
(s)
1.00
1.00
31
0.75
0.50
0.25
0.75
0.50
0.25
0.00
0.00
50
100
Is0
200
50
time (min)
100
I50
Mo
time (min)
Figure 3a and b. The amount adsorbed versus time for n- and iso-butane on MFI at 383K. The indicated
pressures represent the (partial -in 100 kPa He or Ar-) pressures of n- or iso-butane after 200 minutes
equilibrium time.
FER
3.3
For n- and iso-butane on FER at 383 K the results are given in figure 4a and b. also in
these figures an influence can be found of the presence of a noble gas. From figure 4b
clearly the conclusion can be drawn that no equilibrium is reached after 200 minutes.
0.00
SO
100
I50
I
200
0.K
time (min)
50
100
I50
time bin)
Figure 4a and b. The amount adsorbed versus time for n- and iso-butane on FEFt at 383K. The indicated
pressures represent the (partial -in 100 Wa He or Ar-) pressures of n- or iso-butane after 200 minutes
equilibrium time.
272
2.00
ij
1
>
130
1.00-
0.3
0.00
10
LO
100
10
10
10
40
80
120
160
200
lime (Inin)
@artid)plcss~rr
Of D - b W e Orps)
Re-admitting of a noble gas influence the adsorption, while admitting a noble gas
subsequently to butane adsorption has no influence at all. This is demonstrated in figure 6
for n-butane on MFI at 383 K.
4
Discussion
As there is no circulation pump present in the experimental set-up, part of the described
phenomenas could be due to poor mixing. Therefore we performed a test in a
microbalance. A BEA sample was pre-treated in a helium flow at 573 K.The sample was
cooled down to 383 K in a helium flow. After cooling down the helium flow was switched
to an n-butanehelium mixture. Comparison with the experiment described before revealed
that the rate of adsorption was faster, but still much slower than without any noble gas
present and that the amount adsorbed was even less than in the described experiments with
a noble gas present.
The presented equilibria are no thermodynamic equilibria. Therefore another test was
performed. After reaching equilibrium during adsorption of n-butane and 100 Wa argon
in FER at 373 K we heated the sample to 573 K during one day and cooled the system
again down to 373 K.We found that the amount adsorbed increased. But also in this case
the amount adsorbed did not reach the value obtained without argon being present. This is
shown in table 1.
Table 1. Amount of n-butane adsorbed on FER at 373 K.
Amount adsorbed
(mm0Vg)
10.6
17.5
12
1.056
No argon
100 Wa argon
100 Wa argon after a temperature cycle.
.876
.968
?he te.mperahue cycle was equilibrium at 373 K, heating to 573 K and cooling down to 373 K.
273
The difference between helium and argon can not attributed to the external mass
transfer, i.e. differences in the binary coefficients. These are DHe,c4= 49.106 m2/s and
DAr,c4=42.106 m2Is.
This reported effect of influence a noble gas is not restricted to zeolites only. We
found the same effect for n-butane on a Carbon Molecular Sieve 5A of Takeda.
The reported influence of a carrier gas for n- and iso-butane was observed before. For
instance K&ger et ul. [7]observed in NMR based diffusivity studies that the self-diffusion
coefficient of cyclohexene in NaX is negatively affected by the presence of argon.
We think that carefully studying the reported literature data on diffusion coefficients
and taken into account whether a carrier gas was used or not could lead to data sets that do
not show the big differencesas thought to be the case.
The influence of a noble gas may be used to improve separation processes as in our
case for MFI the adsorption of n-butane is influenced to a different extent by helium or
argon than is iso-butane. This was reported also by Jwalin et ul. [6] who concluded that
propene and propane could be separated over 5A or 13X zeolites, provided that the
mixture was sufficiently diluted with nitrogen.
Conclusions
Helium and argon, often used as carrier gasses during adsorption studies, have a
negative influence on the rate of adsorption and also on the adsorption equilibrium as
at the same partial pressure less is adsorbed. This is proven for n- and iso-butane on
BEA, MFI and FER.
The influence of argon is more pronounced than that of helium.
The equilibrium is less influenced at higher (partial) pressures.
Re-admitting of a noble gas influence the adsorption, while admitting a noble gas
subsequently to butane adsorption has no influence at all. This suggests that the
observed phenomena is a kinetic effect. Likely, the noble gasses are present in the
zeolite channels but no adsorbed, seriously hamper the diffusion of both n- and isobutane.
The reported phenomenas are not restricted to zeolites; also CMS show the same
effects.
Acknowledgement
This research was carried out within the project CWISTW 349-5203.
References
Calvalante C.L. and Ruthven, D.M., Adsorption of branched and cyclic parafines in
silicalite. 2.Kinetics. Ind Chem. Res. 34 (1 995)pp. 185-191.
2. Dreisbach F. and Losch, H.W., Magnetic suspension balance for simultaneous
measurement of a sample and the density of the measuring fluid. J. Therm. Anal.
Chem. 62 (2000)pp. 5 15-521.
3. Eic M., Micke A., KoEirik M., Jama M. and ZikhnovB A. Diffusion and
1.
274
275
model are replaced by a solid phase diffusion equation and a semi-empirical equilibrium P-C-T
relationship. Two new semi-empirical P-C-T models are also introduced based on modified virial and
composite Langmuir expressions. By varying the heat and mass transfer coeffcients, the model was
calibrated to experimentalpressure and temperatm histories obtained from a commercially viable bed
containing Lm1.M N~.%A~O.M
metal hydride. Overall, the results of this study showed that a fairly
simple numerical model can do a reasonable job in predicting the discharge behavior of a fairly
complicated metal hydride hydrogen storage bed over a wide range of hydrogen demands.
Introduction
The Savannah River Technology Center (SRTC) recently developed an on-board hydrogen
storage bed for a hybrid electricbus, [I] based on the commerciallyviable Lml.MNi4.&lo,m
metal hydride. A schematic of this unique bed is shown in Fig. 1. Due to its inherent
complexity, a mathematical description of the SRTC system is highly desirable for
improving on the design and understanding its dynamic behavior.
\ /
nrnna~iwlaiion
Most of the mathematical models presented in the literature make use of reactor design
equations that include a reaction kinetics equation. However, since the reaction rate tends to
be very fast, the discharge process 60m a metal hydride bed can also be modeled by
assuming solid diffusion as the rate limiting step. In this new approach, the heat and mass
transfer coefficients are obtained by comparing the theoretical discharge curves with the
experimental ones. The extreme heat and mass transfer limits are also explored to gain an
appreciation for the limiting and actual behaviors of the SRTC system. Theoretical
Referring to Fig. 1,the U-tube heat exchanger is approximated as a single coaxial tube with
the diameter doubled. The outside of the column is assumed to be perfectly insulated, and
the water temperature inside the heat exchanger is assumed to be constant throughout the
discharge process. All heat transfer processes between the material and the heat exchanger
are lumped together and represented by an overall heat transfer coefficient. It is further
assumed that the flux variation inside the column is linear. All radial gradients are also
276
ignored. Based on these assumptionsand assuming ideal gas behavior, the 1-D mass balance
is given by
I a7t 7t ae a0 a/
----+-+-=o
8 a~
(1)
e2a t a{ a t
where $, R, 0 and o denote dimensionless loading, pressure, temperature and molar flux,
respectively. The corresponding energy balance, including compression but ignoring
convection effects, is written as
+--
+kh(B-6w)=0
(2)
The intraparticle mass transfer mechanism is based on the following linear driving force
expression (which assumes solid diffusion control):
where k,,, is the mass transfer coefficient, and $*, the dimensionless equilibrium loading, is
obtained directly from the isotherm relationship. The model parameters are defined as inner
radius (ri) 4 . 0 2 m, outer radius (ro) = 0.045 m, length (L)= 1.52 m, heat capacity of H2
(Cpg) = 14.42 kJkgK,heat capacity of solid (Cps) = 0.419 kJ/kgK,mass of metal hydride
(md) = 26.078 kg, mass of aluminum foam (mAl) = I .789 kg, density of metal hydride (pmH)
= 8700 kg/m3and density of aluminum foam (pA,)= 2700 kg/m3. With h and k,,, specified,
Eqs (1) to (3), along with a suitable P-C-T relation are input to FEMLAB and solved
simultaneouslywith the following initial conditions: at t = 0 ,Ic = 7ti , 8 = ei and
4 = 4i. This model utilizes two new P-C-T relationships, denoted modified virial (MV)
and composite Langmuir (CL) [2]. They are
correlated with Lm,.M N&,&tlo,04
0.014
metal hydride data; the results are
The two
shown in Fig. 2.
0.012
experimental isotherms at 3 13 and
333 K, and the numerous P-Tdata
0.010
points at constant loading above and
m
below the phase transition region are 3 0.008
P
correlated equally well by both
2 0.006
models. The corresponding hears of 9
adsorption predicted by the two
0.004
models are also reasonably similar
and relatively constant in the phase
0.002
change region: 28 and 33 kJlmol for
0.000
the CL and M V models,
0.1
respectively.
A
10
P (atm)
100
277
Experimental
The SRTC column is equipped with 16 k-type thermocouples mounted externally on the
stainless steel surface at 4 axial locations with each axial location having four
thermocouples set approximately 90"apart. The pressure inside the column is measured
just at the outlet; and the hydrogen discharge flow rate is controlled with a mass flow
controller. The heat exchanger water temperature and flow rate are fixed at 302 K and
0.32 Us.In a typical discharge run, the bed is filled with hydrogen at 100 SLPM to the
desired pressure (17 to 25 am). The bed is then allowed to cool to the ambient condition.
Finally, the bed is discharged at a constant molar flow rate (5-40 SLPM) and the pressure
and temperatures are recorded.
Six hydrogen discharge experiments were carried out at 5, 10, 15. 20, 25 and 40 SLPM
hydrogen demand. One of these runs was chosen arbitrarily (the 20 SLPM run) to
calibrate the numerical model by varying the h and k,,, until the pressure and temperature
histories from the model matched the experimental data. The performances of the other
five runs were predicted using these coefficients without further adjustment. The heat and
mass transfer coefficients obtained from the M V model were h = 13.24 x
W/cmz/K
and k,,,= 0.1, and those from CL model were 7.57 x
W/cmz/K and k,,,= 0.1. These
values were uniquely defined in each case, with both models resulting in the same k,,,, and
nearly the same h. The factor of two difference in h was most likely caused by the
difference in the plateau heat of adsorption for the two P-C-T models. The CL model had
the lower heat of adsorption (by 5 kJ/mol) and this was consistent with the CL model also
resulting in a smaller value of h.
The experimental pressure and temperature histories obtained during discharge for
three of the experimental flow rates viz. 5, 20 and 40 SLPM are shown in Fig. 3, along
with model predictions from both the CL and MV models using the fitted values of h and
k,,, (Non Ad, Non eq). Note that each experimental temperature history corresponds to the
average temperature associated with all 16 thermocouples. The predictions from both
nonadiabatic-nonequilibrium models utilizing the two different P-C-T relationships (CL
and MV) were quite satisfactory and similar; however, the one based on the MV model
gave slightly better results, especially for the temperature histories of the 20 and 40 SLPM
runs. For this reason, the MV model was chosen to show the extreme behaviors, under
isothermal equilibrium conditions (Iso, Eq) with h = k,,, = 00, adiabatic equilibrium
conditions (Ad, Eq) with h = 0 and k,,, = -, and adiabatic non-equilibrium conditions (Ad,
Noneq) with h =O and k, = k,,, (fitted); these results are also plotted in Fig. 3. In all cases,
the adiabatic predictions deviated markedly from the experimental results, indicating that
the heat exchanger water flow rate was sufficient enough to allow the system to operate
nearer to isothermal conditions. In fact, isothermal-equilibrium conditions prevailed at the
lower flow rate of 5 SLPM, suggesting that the reaction rate was very fast. However, this
was not the case at the higher flow rates, where mass and heat transfer effects dominate.
Even though the pressure histories were predicted quite well in all cases, the models using
the fitted values of h and k,,, failed to predict the leveling off of the temperature history of
the 40 SLPM run. This indicated that the overall heat transfer approach was not rigorous
enough to capture the behavior of the bed at high hydrogen flow rates; more rigorous
278
25
293
20
15
10
273!
(d) 5 SLPM
0
253
0
251
12
12
16
20
--E 15
m
I-
10
273
-1
8
263
'I
-I
(e) 20 SLPM
0.5
253
1
.
(c) 40 SLPM
0.4
0.8
1.2
1.6
1.5
t (hr)
Figure 3. Comparison of various model predictions with the experimental pressure and temperature histories
for 5,20 and 40 SLPM HZflow rates.
Acknowledgement
279
References
1. Heung L. K. On-board Hydrogen Storage System Using Metal Hydride. Hydrogen
Power: Theoretical and Engineering Solutions, Proceedings of the HYPOTHESIS
Symposium,2nd, Grimstad, Norway, Aug. 18-22,1997 (1998) pp. 251-256.
2. Gadre S. A., Ebner A. D., Al-Muhtaseb S. A. and Ritter J. A. Practical Modeling of
Metal Hydride Hydrogen Storage Systems, Znd. Eng. Chem Res. (2002) submitted.
Introduction
Figure I Conceptual illustration for the typical dynamic simulation of a periodic adsorptiou proccss
281
In reality, a practical adsorption process for the separation of gases is often complex
and involves a number of sequential but interacting unsteady state cycle steps.
Accordingly, a precise rigorous mathematical model used to describe such a process
becomes computationally expensive and the solution time-consuming thus making the
optimisation of adsorption processes through dynamic simulation a slow procedure.
Owing to this inherent limitation several researchers have examined improved numerical
techniques to accelerate CSS convergence of adsorption process simulators [ref.2 and
references therein]. Existence of a periodic time boundary, however, encourages the
replacement of the initial conditions by periodicity conditions such that a dynamic system
may be reduced to a steady state system within a confined time period, the time for one
cycle. An instructive illustration is given in Figure 2.
p.rlodkBwnb.ry
sbt.(a)
I..
-ww
CyCllC S t M I y sat.
Figure 2 Conceptual illustrationsof the steady state modelling for direct CSS determination
As seen in this figure, the enforced periodicity condition provides continuity to the system
by linking the starting point towith the ending point tN.In a computational point of view,
this suggests a steady state simulation is feasible by a complete discretisation of space and
time within the confined time length. In fact, the complete discretisation method had been
discussed in an earlier study [ 5 ] and investigated extensively [6].However the application
has been limited to computationally simple problems and was considered an unrealistic
method for complex non-isothermal process simulation owing to computational barriers
121.
The purpose of this study is to examine the capability of this modelling methodology
using readily accessible computing resources such as a Pentium computer and a generalpurpose modellingkimulation environment. The investigation examined a number of
periodic adsorption processes of general complexity such as nitrogen PSA [l], oxygen
VSA [2] and hydrogen PSA [3,4]. From the extensive study, we realised that direct CSS
determination modelling using steady state simulation can provide a remarkably faster
solution than traditional dynamic simulation. Furthermore CSS modelling enables direct
movement from one CSS condition to another CSS condition. However for a dynamic
model further cycles must be simulated until the new CSS condition has been achieved, a
step that can take a significantly longer time than with the direct CSS determination
model (hereafter CSS model).
282
Adsorption beds are essentially transient, spatially distributed systems, where the
properties in the solid and gas phases varying over time in one or more spatial
dimensions. The mathematical description of adsorption beds is usually described by a
series of partial differential equations and algebraic equations. In this paper,
distinguishable features of the CSS model are briefly given.
2. 1
Discretisation Methods
In this work, discretisation of both space and time derivatives was executed, based on
either central finite difference (CFD) or orthogonal collocation on finite elements (OCFE)
discretisation in the spatial domain and backward finite difference (BFD) discretisation in
the time domain.
2.2
Periodicity Conditions
Cyclic Steady State is the condition whereby the state at the end of each cycle is identical
to that at its beginning. For a non-isothermal adsorption system this may be represented
by a mathematical model, comprising material, energy and momentum balances as well
as adsorption equilibrium and kinetic models, the CSS can be expressed by:
Vjce(0,l)
where C, and ?, are bulk and solid concentrations for an individual component and 7^, Ts,
and TW are temperatures at gas phase, solid phase and column wall, respectively. tN is a
cycle time and x denotes a distributed variable along spatial distance L.
3
Several gas adsorption process examples were studied to examine the simulation
performance of the CSS model. Examples include: (1) binary, 4 step N2 PSA using 2
isothermal beds each containing a single CMS layer [1]; (2) binary, 8 step O2 VSA using
2 non-isothermal, non-adiabatic beds each containing a single Zeolite 13X layer [2]; (3) 6
step binary-, ternary-, five component H2 PSA using 2 non-isothermal, non-adiabatic beds
each containing a double layer of Activated Carbon/Zeolite 5A [3, 4]. In this work, the
results obtained by CSS simulation are compared to those by traditional dynamic
simulation. The computing efficiency is assessed in terms of solution convergence and
computational time requirements (all computational results in this paper were obtained
using a 1.7 GHz Pentium 4 computer with 1 GB of physical memory).
In Table 1, a summary of the model assumptions for each example and a comparison
of results obtained using the dynamic simulation and the CSS simulation has been given.
The temporal domain for each example made use of 20 nodes for N2 PSA, 32 nodes for
O2 VSA, and 22 nodes for H2 PSA, together with adapted time element length depending
on each operation step.
283
Process example
0 2 VSA
N2 PSA [13
2 bed, 4 steps
150 s per cycle
[2]
2 bed, 8 steps
60 s per cycle
Adsorbate
N2.02
N2-02
Adsorbent
CMS
Zeolite 13X
Energy balance
Isothermal
Momentum balance
Ergun equation
Equilibrium model
IAST (Langmuir)
Non-Isothermal I
Non-Adiabatic
Ergun equation
Extended Dualsite Lan
Kinetic model
180 s
392 s
Cycle info
Dvnamic
CPutime
Purity
1
I
H2 PSA [3,4]
2 bed, 6 steps
420 s per cycle
H2,
co,
N29 CO2
Activated Carbon I
Zeolite 5A
Non-Isothermal I
Non-Adiabatic
Ergun equation
a,
LRC
Solid phase LDFA
~
95.0 % N2
94.9 % 0
1080 s
91.3 % H2
css
solution
CPUtime
Purity
cycle Time
595 s
176 s
240 s
95.8 % N2
94.2 96 0
90.6 9% H2
Pn.i,inn
Cycle Time s
Position rn
Figure 3 Typical CSS solution of pnssure and gas composition bed prohles for the 9VSA process
284
limitation of this approach and therefore, careful consideration is required in deciding the
number and size of temporal elements.
?{ -
14
L
12
0.9
0
2- 10
zi
0.8'3
2 8
3
$ 6
i?
0.7 8
0.6 I"
Hz PSA
0 I
105
210 315
Cycle Time, s
0.5
420
20
40
Cycle Time, s
60
Figure 4 Typical CSS solution of pressure and gas composition bed profiles for the Q VSA process
(symbols CSS, lines - Dynamic)
In spite of the system size generated by temporal discretisation, it is has been found
that the method can provide a faster solution with acceptable accuracy for highly complex
examples such as oxygen VSA and hydrogen PSA. Furthermore, this modelling technique
becomes much more advantageous if several runs are required to be carried executed. For
example, when executing an optimisation study, the solution of each simulation run
serves as the initial guess for the next simulation run.This allows for rapid transition from
one CSS condition to another CSS condition with the minimum of iterations whereas for
a dynamic simulation fiuther time expensive cycles are required to achieve the new CSS
condition. This is a key benefit for the process engineer, as the technique can offer an
extremely efficient design tool that can be more readily used to determine optimal design
and operating conditions of an adsorption process.
References
1.
2.
3.
4.
5.
6.
Introduction
Zeolite or active carbon has micorpores into which VOC (volatile organic compound) is
adsorbed, resulting in removal or concentration of VOCs. They are usually used as
powder or pellet in packed bed but high energy cost due to pressure drop makes the
application hesitant. Honeycomb formation of the materials is one of the promising steps
to avoid the drawback. However the extrusion cost is also very high and large size
honeycomb is extremely difficult to extrude. Zeolite or active carbon impregnation into
ceramic paper made of ceramic fiber and glass fiber as main components is one of the
developed technologies showing low pressure drop. [ 1,2,3,4,5]
Although several thermal swing data using ceramic rotor were reported,
manufacturing process of the rotor was not described in detail. In this paper ceramic paper
making process from slurry containing ceramic fiber and glass fiber, corrugation,
honeycomb formation, and impregnation of zeolites were described step by step.
For evaluation of the rotor, thermal swing adsorption was tested in a static adsorption
/ desorption test equipment and proper type of adsorbent for target VOCs was
determined.
2
2. I
Experimentation
Ceramic paper was cast on a papermaking machine into a dimension of 0.25mm thickness,
286
50cm width from finely dispersed sluny of mineral fibers in water. The slurry cast on
porous endless wire mesh made of polyester and polyimide was dewatered using
vacuum, pressure rolling and hot air blowing, successively. The final water content of the
formed paper was around 65%. The obtained wet paper was dried in dry oven over 24
hours.
2.2
Corrugation of ceramicpaper
Two sheets of ceramic paper were supplied to a corrugation machine for forming
corrugated sheet having v-shape (2mm height, 4mm pitch) parallel flute, through which
VOC laden air could flow freely. The corrugated sheet was rolled into honeycomb shape,
which had many triangular prismatic parallel flutes and the flowing air did not penetrate
from one flute to another. The ceramic rotor was rolled until its diameter reached lOcm,
before both ends were cut in order to give determined length.
2.3
Organic binder in ceramic honeycomb rotor was removed by heating it for 5 hrs in 600C
before impregnation of zeolite. Heat treated rotor was soaked in zeolite (UOP HISIV
1000 and HISIV 3000) dispersed slurry with silica sol (Nissan Chemical ST-30) or
alumina sol (Nissan Chemical AS-520) as a binder. The amount of binder addition was
varied to 3, 5,7 wt?h.BET surface area and SEM micrograph was analyzed with respect
to type of binder and its amount.
2.4
287
(a)honeycombmtci (sideview)
3
3. I
BET surface areas of the HISIV 1000 and HISIV 3000 zeolites were 585 and 419 m2/g,
respectively. In order to determine proper type of inorganil: binder, equilibrium loading
amount of toluene into zeolite impregnated paper was measured. HISIV 1000 zeolite
showed that zeolite adhered by silica sol adsorbed more toluene than zeolite adhered by
alumina sol at low partial pressure as shown in Figure 2. Thus silica sol was used as a
binder for binding zeolite between fibers of the ceramic paper.
The BET surface areas of the HISIV 1000 impregnated with 3,5, 7 % silica sol as a
binder were 147, 159, 165 m2/g,respectively. Those of HISIV 3000 impregnated with 3,5,
7 % silica sol were 138, 137, 129 m2/g, respectively. HISIV 1000 zeolite impregnated
with 3, 5, 7 wt% silica sol had loading capacities of 5.2, 5.7, 5.7 wt% of toluene at 1 1.5
mmHg, respectively. HISIV 3000 zeolite impregnated with 3, 5, 7 wt% silica sol had
loading capacities of 4.7, 4.4, 4.5 wt% of toluene at 11.5 mmHg, respectively. Using 5
wt% of silica sol was the best selection of the binder system.
288
10
10
11
Umrcb)
Figure 2. Equilibrium adsorption curve of toluene on HISN lo00 impregnated ceramic paper
3.2
Adsorption properties
289
Acknowledgements
We thank Ministry of Science and Technology and Greenhouse Gas Research Center for
financial support.
References
1. Kodama A., Goto M., Hirose T. and Kuma T., Temperature profile and optimal
2.
3.
4.
5.
rotation speed of a honeycomb rotor adsorber operated with thermal swing, J. Chem.
Eng. Japan 27 (1 994) pp. 644-49.
Mitsuma Y., Yamauchi H., Hirose T., Analysis of VOC reversing adsorption and
desorption characteristics for actual efficiency prediction for ceramic honeycomb
adsorbent, J. Chem. Eng. Japan 31 (1998) pp. 253-57.
Kodama A., Goto M., Hirose T. and Kuma T., Experimental study of optimal
operation for a honeycomb adsorber operated with thermal swing. J. Chem.. Eng.
Japan 26 (1993) pp. 530-35.
Krishna S. M., Murthy S. S., Experiments on a silica gei rotary dehumidifier, Hear
Receovey Systems & CHP. 9 (1989) pp. 467-73.
Kodama, A, Goto M, Hirose T. and Kuma, T., Performance evaluation for a thermal
swing honeycomb rotor adsorber using a humidity chart, J. Chem. Eng. Japan. 28
(1 995) pp. 19-24.
290
Introduction
Figure 1. Homogeneous catalyst recycling by Reverse Flow Adsorption (feed alternatesi between A, and
I
In this paper, the Hard and Soft Acids and Bases (HSAB) theory [4] is applied to
select potential adsorbents for the reversible adsorption of transition-metal complexes.
2
Approach
Ligand
- Metal + Ligand
Metal - Ligand
Metal + Ligand
(b)
Figure 2. (a) Transition-metal adsorption by an immobilized ligand and (b) ligand adsorption by an
immobilized transition-metal.
292
We studied two groups of adsorbents, based on their interactions with the Co(I1)
transition-metal center or PPh3 ligands:
0
Experimental
The three selected carriers were: Amberlyst A21 (4.8 [mmol N/g dry], Sigma-AIdrich),
polymerbounded PPh3 (3.0 [mmol P/g dry], Sigma-Aldrich) and Amberlyst 15 (4.7
[mmol H/g dry], Sigma-Aldrich). The Amberlyst 15 was firstly washed with de-ionized
water (Millipore) in a column. The functionalization of the Amberlyst 15 was done by
contacting the resin with either 0.1 [mM] CoCl2 (98 [%I, Sigma-Aldrich) or 0.1 [mM]
AgN03 (extra pure, Sigma-Aldrich) aqueous solutions. During the ion-exchange, the
hydrogen of the Amberlyst 15 was exchanged for the transition-metal. The exchange was
done until maximum loading was reached. All four adsorbents were pre-rinsed with deionized water. Then, the remaining water was rinsed out of the resin with methanol (p.a.,
Merck). The remaining methanol was rinsed with 1-butanol (p.a., Merck). The adsorbents
thus prepared were taken fiom the column and used in the adsorption experiments.
The adsorption characterizations of the various adsorbents were done via batch
adsorption experiments. The series of nitrogen and phosphorous functionalized
= 0.3 [gr]) were contacted in erlenmeyer flasks with 10 [ml] of
adsorbents
dichlorobis(triphenyIphosphine)cobalt(II) (98 [%I, Sigma-Aldrich) at various
concentrations of 1, 2, 4 and 8 [mM]. The Ag' and Co2+functionalized adsorbents were
conctacted with 10 [ml] PPh3 solutions of 2, 4, 8 and 16 [mM]. The erlenmeyer flasks
were then equilibrated at 90 ["C] in a thennostated shaking water bath for 15-16 [hr]
(approximately 5 times the real equilibration time). The liquid phases were decanted and
analyzed. UVNis spectroscopy (Shimadzu 2501) was used for the determination of the
PPh3 concentrations at 265 [nm]. The Co(I1) concentrations have been analyzed by AAS
(Varian Specrtaa 1 10). After adsorption, all equilibrated samples were contacted with 10
[ml] of fresh I-butanol for 15-16 [hr] at 90 ["C] to investigate the reversibility of the
adsorption. The equilibrium concentrations after desorption of the relevant components
were measured as described above. The amounts adsorbed were calculated from the
differences in initial and equilibrium amounts. The loading of the adsorbents after
adsorption and desorption are expressed with respect to the number of functional sites - N,
P, Ag' or Co2' - in the adsorbents.
293
Experimental results
The results of the Co(II) adsorption and desorption experiments over the nitrogen and
phosphor functionaiized adsorbents are presented in figure 3. The Co(II) loading onto
these two selected adsorbents is shown as a function of the equilibrium concentration of
Co(I1) in the liquid phase.
0.0
2.0
4.0
6.0
Go@)
[&I
Figure 3. Co(1I) adsorption (closed squares) and desorption (open squares) onto nitrogen functionalized
Amberlyst A21 and Co(II) adsorption (closed triangles) and desorption (open triangles) onto phosphorous
functionalized polymerboundedPPh,.
It can be concluded from figure 3, that the Co(II) adsorption onto Amberlyst A21
(closed squares) is strong. This adsorption is reversible, as the desorption results (open
squares) are located on the adsorption isotherms. The poIymerbounded PPh3 adsorbent
shows a less strong, but reversible Co(II) adsorption (closed triangles). The stronger
Co(II) adsorption by the nitrogen functionalized adsorbent was expected from the HSAB
theory. For both adsorbents, no PPh3 adsorption has been observed.
The experimental results of the PPh3 adsorption and desorption on both transitionmetal - Ag+ and Co" - functionalized adsorbents are shown in figure 4 as a function of
the equilibrium PPh3 concentration.
Because the immobilized Ag+ can be exchanged for Co2+from the homogeneous
model catalyst, the transition-metal functionalized adsorbents have only been contacted
with PPh3 solutions. Thus, to avoid the exchange of an immobilized transition-metal,
Reverse Flow Adsorption requires two separate adsorption beds. The transition-metal
center has to be recovered before the adsorption of the ligands. Figure 4 demonstrates that
the PPh3 adsorption (closed triangles) onto Co2+functionalized Amberlyst 15 is weak.
The low degree of adsorption is caused by two effects: 1) the interactions between Co2+
and PPh3 - as predicted by the HSAB theory - are small and 2) the steric effects of the
SOigroups with the relatively large PPh3. One Co2+is immobilized onto two SOi groups.
As predicted by the HSAB theory, the Ag+ functionalized Amberlyst 15 shows a
larger PPh3 adsorption (closed squares) compared to the immobilized Co2+. The
experimental results - the open symbols - indicate that the PPh3 desorbes from the
transition-metal functionalized adsorbents. However, no complete desorption was
observed, indicating that the desorption time has been taken to short.
294
0.0
2.0
4.0
6.0
8.0
CPPh3
10.0
12.0
14.0
16.0
[d]
Figure 4. PPh3 adsorption onto (closed squares) Ag' and (closedtriangles) Co2' and desorption from (open
squares) Ag' and (open triangles) Co2' functionalized Ambedyst 15.
Conclusion
To apply Reverse Flow Adsorption, a combination of two adsorbents has to be used for
the reversible adsorption of a homogeneoustransition-metal catalyst. The transition-metal
center can be adsorbed by a suitable ligand immobilized onto a solid carrier, while the
ligand is adsorbed by an immobilized transition-metal. Two groups of adsorbents have
been studied, based on the HSAB predictions on the interactions with the Co(I1)
transition-metal center or PPh3 ligands:
0
295
1 Introduction
Process modelling is a key enabling technology for the development, design and optimization of every adsorption process. However, its success is critically dependent upon the
accurate description of adsorption equilibriumand kinetics. Molecular simulation has now
developed to the point where it can be useful for quantitative prediction of those properties. Although there are several molecular simulation methodologies currently available,
bridging techniques, i.e. computational methods used to bridge the range of spatial and
temporal scales, are still largely underdeveloped. Here, we present a new molecular simulation method that bridges the range of spatial scales, from atomistic to macroscale, and
apply it to solve the perturbation equations for a multicomponent, isothermal stirred-tank
adsorber under equilibrium controlledconditions.
2 Problem formulation
Consider an isothermal stirred-tank adsorber under equilibrium-controlledconditions. q
is the bulk porosity (volumetric fraction of the adsorber filled with fluid phase), qp is the
porosity of the adsorbent, Fi 2 0 is the amount of component i added to the adsorber in
the inlet stream, and Wi 2 0 is the correspondingamount removed in the outlet stream;
both fi and Wi represent amounts scaled with respect to the adsorber volume.
The differential material balance to the ith component of an m-component mixture in
the adsorber yields
where ci and qi are the concentrationsin the fluid and adsorbed phases, respectively. Since
the fluid phase is assumed to be perfectly mixed,
dWi =yidW = c i d C ,
(2)
where yi is the mole fraction of component i in the fluid phase and dG is the differential
volume of fluid (at the conditions prevailing in the adsorber)removed in the outlet stream,
scaled by the adsorber volume. Substitution of Eq. (2) into Eq. (1) gives
q dci
296
(3)
In Eq.(4) the superscript denotes the state at which the variable is evaluated and
Given that the inlet value A FYI is an input parameter, the terms on the r.-h.-s. of Eq. (7)
are known quantities. To simplify the notation, the r.-h.-s. of Eq. (7)is condensed into a
single parameter denoted by wi and the superscripts are dropped. Eq. (7)can be written in
this shorthand notation as
(q
+ AG)ci + (1 - q)qpqi =
Wi.
(8)
This equation requires a closure condition which consists of fixing the value of either AG
or the pressure P at the new state.
Here we show that Eq. (8), together with the conditions of thermodynamic equilibrium for an isothermal adsorption system (equality of chemical potentials between the two
phases), can be solved using the Gibbs ensemble Monte Car10 (GEMC) method in the
modified form presented in the next section.
3 Simulation method
In the GEMC method' the two phases are simulated as two separate boxes, thereby avoiding the problems with the direct simulation of the interface between the two phases. The
system temperature is specified in advance and the number of molecules of each species
i in the adsorbed phase, Nip, and in the bulk, N ~ Bmay
, vary according to the constraint
NjB Nip = Ni, where Nj is fixed.
and Nip, the following expression is obtained:
If Eq. (8) is rewritten in terms of N ~ B
where NA" is avogadro's number and Vp is the volume of the box simulating the adsorbed
phase. The value of Cj has been expressed as a function of Vp instead of the volume VB of
the box simulating the bulk fluid. The reason for this is that Vp is always fixed, whereas,
as we shall show below, VB must be allowed to fluctuate during the simulation when the
297
pressure is an input parameter. Obviously, for Eq. (9) to be valid the values of VB and Vp
must be in accordance with the relative dimensions of the physical problem, i.e.
Since the GEMC method inherently conserves the total number of molecules of each
species, Eq. (9) is automatically satisfied by every sampled configuration provided that
each Ci turns out to be an integer number. This feature makes the Gibbs ensemble the
natural ensemble to use when solving Eq.(9). Unfortunately,in general it is not possible to
size VB and Vp according to Eq. (10) and Eq. (9) so that each Ci is an integer number. To
overcome this problem, Eq. (9) is satisfied statistically by allowing Ni to fluctuate around
the target value Ci so that the ensemble average gives
(Ni) = Ci.
(11)
It is shown in detail elsewhere2 that if an equation of state for the fluid phase is known,
the bulk box does not have to be explicitly modelled computations on the bulk box amount
to just updating the value the NiB as the configuration changes. Thermodynamic equilibrium between the two boxes is achieved by allowing them to exchange particles and by
changing the internal configurational of volume Vp. The probability of acceptance of the
latter moves (molecule displacement, rotation, or conformational change) is the same as
for a conventional canonical simulation:
min{1, exp(-pAU)],
(13)
where B = l / k ~ Twith
, kg the Boltzmann's constant, and AU is the internal energy
change resulting from the configurational move.
The transfer of particles between the two boxes forces equality of chemical potentials.
The probability of accepting a trial move in which a molecule of type i is transferred to or
from volume Vp is, respectively,
298
How the equation of state is actually employed to compute depends on the type of
problem being solved. If AG is an input parameter, Vg is fixed throughout the simulation
and the gas mixture is further specified by its number density p ~ ~ +=k (NB k)/ VB.
If, on the other hand, the pressure is fixed, its value defines the state of the mixture. The
statistical mechanical basis for Eqs. (14) and (1 5) is discussed elsewhere.2
All that remains to completethe simulation procedure is to generatetrial configurations
whose statistical average obeys Eq. (1 I). To get the best statistics Ni = NiB Nip must
fluctuate with the smallest amplitude around the target value Ci, which is the case when
Ni takes only the two integer values int(Ci) or int(Ci) 1. It is straightforward to derive
that for Eq. (1 1) to hold, the probability densities of finding the system in one of the two
configurationsmust be
nl(N + int(Ci)) O( 1 - S i ,
N ( N i + int(Ci)
+ I ) oc S i ,
(17)
where 6i = Ci - int(Ci). In order to sample this probability distribution, a new type
of trial move must be performed which consists of an attempt to change the system to
a configuration with int(Ci) or int(Ci) 1 particles. It is highly recommended that the
box for insertionhemoval of the molecule always be the bulk box (except for the rare
cases that NiB becomes zero). This choice is most suited for adsorption From the gas phase
where, in general,the bulk phase is much less dense than the adsorbed phase and, therefore,
more permeable to particle insertions. Furthermore, given that the bulk box is not actually
modelled the molecule insertionhemovalmove amounts to just updating the value of N ~ B .
4 Application example
Due to lack of space, the few results presented here are primarily intended to demonstrate
the validity of the proposed method. The pore space of the adsorbent is assumed to consist
of slit-shaped pores of width 15 A, with parameters chosen to model activated carbon. The
porosity values are fixed at q = 0.45 and q p = 0.6. The feed stream is a ternary gas mixture
of H ~ / C H ~ / C ZThe
H ~ .vapor-phase fugacities were computed from the virial equation to
second order, using coefficients taken from Reid et aL3
Methane and ethane were modelled using the TraPPESunited-atom potential in which
CH4 and the CH3 group are considered as single Lennard-Jones interaction centers. The
LJ parameters for hydrogen, ~ / k g= 38.0 K and 0 = 2.915 A, were taken from Turner
et aL6 The potential cutoff was set at 14 A, with no long-range corrections applied. The
interactions with the carbon walls were accounted for using the 10-4-3 Steele p~tential.~
The cross-term LJ contributionsbetween all molecules were calculated using the LorentzBerthelot mixing rules. The simulations were equilibrated for 1O4 Monte Carlo cycles,
where each cycle consists of N attempts to change the internal configurations of volume
VP (equally partitioned between translations, rotations and conformational changes) and
N / 3 attempts to transfer molecules between boxes. Each particle molecule attempt was
followed by a trial move to adjust the total number of molecules of that type.
299
Table 1. Results of simulations.The subscripts indicate the estimated error in the last digit of the value.
The simulations reported here consisted of pressurizing an initially evacuated adsorber with four mixtures of different compositions. These simulations are very much like
the traditional flash calculations of chemical engineering thermodynamics applied to an
adsorption system. The first set of runs, which we refer to as set G-NVT,is equivalent
to solving Eq. (4) with c!') = 0, 41') = 0, AF!') = yj"AF(') 2 0, closure condition
A G ( ' ) = 0, and the equilibriumpressure as output of the simulation. Then, a second set of
runs (G-NPT) was performed with the same feed mixtures and the pressure fixed at the values obtained from the G-NVT runs. In this case ( VB)is an output of the simulation. Finally,
a third set of runs (GCMC) was camed out to check the validity of our simulation technique. These runs consisted of standard multicomponent GCMC simulationswith mixture
fugacities calculated from the virial equation of state using the pressures and gas-phase
compositionsobtained in the G-NVT runs.
The results obtained are listed in Table 1. The three sets of runs give the same results
to within the statistical uncertainty of the simulations, which attests to the viability of the
proposed method. The total number of molecules employed in the G-NVT and G-NPT runs
is given in the 8th column of the table. They were purposively set to noninteger values to
test the efficiencyof the method in generatingtrial configurationswhose statistical average
obeys Eq. (1 1). As can be easily verified, there is very good agreement between (NB)
(Np) and the imposed N value for every run. The theoretical approach presented here
represents a successful attempt to develop an ab-initio or first-principles computational
methodology to predict the macroscopicbehavior of an adsorption process from knowledge
of the intermolecularforces and structural characteristicsof the adsorbent.
References
1. A.Z. Panagiotopoulos,Molec. Phys. 61,8 13 (I 987).
2. J.P.B. Mota, J. Chem. Phys, submitted (2002).
3. R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and Liquids, 4th
ed. (McGraw-Hill, Singapore, 1987).
4. W.A. Steele, f i e Interaction of Gases wih Solid Surfaces (Pergamon,Oxford, 1974).
5. M.G. Martin and J.1. Siepmann,J. Phys. Chem. B 102,2569 (1998).
6. C.H. Turner, J.K. Johnson,andK.E. Gubbins,J. Chem. Phys. 114,1851 (2001).
Introduction
(1)
The first work on the doping of NaAlK with Ti used solution chemistry techniques,
whereby nonaqueous solutions of N a A l b and either TiC13 or Ti(0Bu"k catalyst
precursors were decomposed to solid Ti-doped NaAlb.' Zidan et aL2 and other
investigators3-' discovered later that a further lowering of the dehydrogenation
temperature was highly dependent on the doping and homogenization procedures. They
also found that Zr when mixed with Ti improved the dehydrogenation reversibility of
N a A l b over Ti alone. These favorable effects of using mixed metals as the dopant
generated interest in trying other combinations of mixed metal catalysts. The objective of
this study is to show the effects of Ti, Fe, Zr and their combinations on the H2 desorption
kinetics of NaAlh.
2
Experimental
TiC13 (Aldrich), FeC13 (Aldrich, 99.99%. anhydrous) and ZrCb (Aldrich, 99.9%) were used
as received as the catalyst precursors. Crystalline NaAl& (Fluka) was purified fiom a THF
(Aldrich, 99.9%,anhydrous) solution and vacuum dried. The dried N a A l b was mixed with
301
Resultsanddiscussion
Figure la shows the TGA results for catalyzed NaAl& with 1 to 4 mole% TiC13. The 4
mole% Ti sample exhibits the best behavior with respect to the H2 desorption kinetics,
while the 1 mole% Ti sample has the highest H2 capacity. In the recent study by Sandrock
et al,6 they found that the TiC13 was completely reduced by Na in the NaAl& to form
NaCl and most likely zero-valent Ti. This solid state reaction can be written as:
(1-x)NaAl&+xTiC13+( 1-4x)N~+3xNaCl+xTi+3xAl+6xH~
(3)
where x is the mole fraction of TiC13 in the NaAl&. This reaction shows that the H2
capacity depends on the amount of TiC13 in the sample. Theoretically, after doping with 4
mole% Ti, the H2 capacity decreases to 4.6 wt%; the experimental value obtained here is
very close to this value at 4.5 wt%. Clearly, the Tic13 loading has a negative effect on the
H2 capacity. In contrast, the TiC13 loading has a positive effect on the H2 desorption
kinetics, which increases with increasing TiC13loading.
Figure 1b shows the TGA analyses for NaAl& doped with 4 mole% each of the three
different metal chlorides. The 4 mole% Ti sample exhibits the best behavior with respect
to the H2 desorption kinetics, followed by 4 mole% Zr and then 4 mole% Fe. This result
confirms that Ti by itself is the best catalyst with respect to the kinetic behavior. Figure 2a
shows the TGA analyses for NaAlH., catalyzed with 4 mole% metal, but in different
combinations and with each containing with 1 mole% Fe. The 1 mole% Fe-3 mole% Ti
sample exhibits the best behavior with regard to the Hz desorption kinetics and again the
kinetics increase with increasing Ti loading. Figures 2b, 3a and 3b compare the 1 to 3
302
5.0
A
f 4.0
3.0
2.0
1.o
0.0
50
150
100
200
cc)
Figure 1. TGA analyses of NaAIH4doped with a) 1 to 4 mole% Ti; and b)
varying amounts of the three pure metal chloride catalysts.
mole% Ti samples with different amounts of Fe and Zr and Ti itself. All the mixed metal
samples with the same Ti loading have similar profiles, i.e., the samples with 1 or 2
mole% Ti exhibit similar kinetics and Hzcapacity. However, by comparing with Ti alone
at the same loading, the 1 or 2 mole% Ti mixed with different metals show an improved
kinetic profile, while losing some Hzcapacity. Surprisingly, the 1 mole% Fe-3 mole% Ti
sample is better than the 4 mole% Ti sample with respect to HZdesorption kinetics, but it
does nothing for improving the kinetics of the second reaction depict in eq 2. This
synergistic behavior with the Fe-Ti mixed catalyst system is very interesting and needs to
be explored in more detail. In general, however, all the samples containing Ti exhibited
the best behavior.
303
4.0
1.o
0.0
5.0
4.0
3.0
20
1.o
0.0
Figure 2. TGA analyses of NaAI& doped with 4 mole% metal in different combinations
with each containing a) 1 mole% Fe; and b) 1 mole% Ti.
Conclusions
These results continue to prove that doping NaAlh with transition metals, especially Ti,
improves the Hz dehydrogenation kinetics. However, more research needs to be done to
lower the dehydrogenation temperature even further, especially for the second reaction
depict in eq 2. In this study, the effect of the different transition metals played an
insignificant role in reducing the temperature or increasing the kinetics of the second
reaction. Other metals and metal combinations are currently being explored for this
reason, and to further reduce the temperature (increase the kinetics) of the first reaction.
304
5.0
4.0
I
1::
2KTklxzr+l%F.
ao
0.0
4.0
3.0
2.0
1.0
0.0
Figure 3. TGA analyses of NaAlH4doped with a) 4 mole% metal with at least 2 mole%
Ti and varying amounts of Fe and Zr; and b) 1 mole% Fe-3 mole% Ti, and 4 mole% Ti.
5
Acknowledgements
1
2
3
4
305
Introduction
Colloidal silica gels have been applied to numerous industrial fields such as thermal
insulation, catalyst supports, filters and sorbents[11. Their industrial performance is
dependent not only on their chemical structures but also on their physical pore structure,
which comprises pore sue, pore size distribution, pore volume and surface area.
Therefore, it is important to elucidate the relationship between the pore and chemical
structures and the performance efficiency.
From the viewpoint of materials processing, the pore and chemical structures are
affected by three kinds of processing conditions: one is concerned to the parameters of
sol-gel based synthesis (hydrolysis and condensation) route[2-5], another is related to the
aging and drying conditions of the wet gels[5-10], and the third is in close relationship to
the calcination conditions of the dried gels[ 1 11.
C. J. Brinker et al. showed that the pore size of silica gel increased by the simple
immersion in a basic solution[4]. R. K. ller has summarized the dependence of solubility
of amorphous silica in the aqueous solvent as a hnction of pH[1]. The solubility gently
decreases at the low pH values, reaches a minimum at pH 7-8, and shows a steep
increasing behavior above pH 8, as pH increases. It is expected that the aging of silica gel
in basic solutions increases the pore size due to the activated particle growth by the
Ostwald ripening process. Therefore, it is important to investigate the structural and
chemical change of silica gels during the aging in basic conditions.
In the present study, monodisperse spherical silica gels were prepared by aging a
monodisperse spherical silica gel precursor in different basic conditions, and then the
effect of the basic strength in aging process on the pore and chemical structures were
investigated.
306
Methods
2. I
Generally, it is known that in the SFB process, particle size of silica gels is affected
by the processing parameters such as temperature, time, [NH3], [TEOS] and volume ratio
of H20 to EtOH. In the present study, the particle size was controlled to be 50 to 50Onm
307
by changing the volume ratio of H2O to EtOH and mH3], the addition amount of the base
catalyst.
Figure 1 represents the average particle size of the synthesized silica gels as a
function of the volume ratio of H20 to EtOH and mH3]. As the volume ratio of H20 to
EtOH increased, the particle size increased to maxima at about 0.1 of volume ratio of H 2 0
to EtOH, and then again decreased. In addition to the volume ratio, the content of NH3
affected the particle size. The particle size increased as the content of NH3 increased.
Figures 2(a) to (c) represent SEM images of the silica gels synthesized in the mixed
solvents with (a) 0, (b) 0.25 and (c) 0.67 volume ratio of H20to EtOH, respectively. In all
cases, the addition amount of NH3 in the synthesis process was 6ml. Without relation to
the volume ratio of H20 to EtOH, all the synthesized silica gels were monodisperse and
spherical. Also it was clearly shown that the particle size evaluated by the SEM analysis
was well in accord with the particle size results characterized by the laser scattering
method as shown in Fig. 1.
G. H. Bogush ef al. have suggested that the growth of silica gel in the SFB process
should be governed by an aggregative growth mode1[13-14]. This model states that the
particle growth occurs due to an aggregation of primary particles that are nucleated in a
308
supersaturation of silica, and nowadays their model is generally accepted for the growth of
silica gel in a sol-gel process.
If the growth of the synthesized spherical gel is governed by the agglomeration
model, it is expected that the silica gels have high specific surface area, because the
spherical gels are composed of primary nanogels.
R. K. Iler has systematically summarized the dependence of solubility of amorphous
silica on pH[ 11. As pH increases, the solubility of amorphous silica gently decreases at the
lower pH, reaches a minimum at pH 7-8, and shows a steep increasing behavior above pH
8. The growth of primary particles in Ostwald ripening process will be activated by the
increment of NH3 content in the aging process. It is expected that the pore size can be
systematically controlled by aging the gels in different basic conditions, in other words, by
controlling the growth rate of primary nanogels. From the SEM analysis, it was known
that there was no spherical morphology change before and after the aging process in basic
conditions.
To confirm that the spherical silica gel comprises of primary nanogels, the pore
structure was analyzed by the BET analysis. Contrary to the expectations, the precursor
and aged silica gels have relatively very low specific surface area. In Table I, the specific
surface area of the precursor and aged silica gels was presented. As the addition amount of
NH3 increased, the specific surface area increased.
Table I Specific surface area of the precursor and aged gels
Addition amount of NH3
0
0.01
fml\
Specific surface area
(m2/g)
16.6
16.6
0.1
10
17.6
19.9
24.1
The fact that the silica gels had low specific surface area means that the synthesized
silica gels were so dense. Therefore, the aggregative growth model suggested by G. H.
Bogush et al. might be impertinent for the silica gel prepared in the SFB process.
Fig. 3. Cumulative pore volume curves of precursor and aged silica gels as
a function of average pore diameter.
The cumulative pore volume curves as a hction of average pore diameter were
calculated to elucidate that the spherical silica gels are dense, and represented in Fig. 3. It
309
was clearly shown that all the silica gels have micropores with the pore diameter less than
20A and diffuse mesopores with the 10 to 20Onm of pore diameter. The diffuse mesopores
originated in the randomly loose packing of the spherical silica gels.
To investigate the detailed size distribution of the micropores, the BET analysis was
minutely conducted at the very low pressure of N2.Fig. 4 represents the detailed
incremental pore volume curves as a function of average pore diameter. It was clearly
shown that the pore diameter of the micropores was about I5.k irrespective of the aging
conditions.
Fig. 4. Incremental pore volume pore diameter curves for silica gels aged
with (a) 0.5. (b) 2 and (c) 4 ml of N H 3 .
It is interesting to answer the question where did the micropores originate in?. Fig. 5
represents the XRD patterns of the silica gels before and after the aging process. It is
obvious that there was no trace for the progress of crystallization during the aging process.
Therefore, it was concluded that the micropores didn't originate in the lattice pore in
crystalline phase.
,r I.0
I.
I,
(0
I.
I0
310
Fig. 6. Si-NMR spectra of the silica gels (a) before and (b) after the
aging process with 6 ml of N H 3 aqueous solution.
Conclusion
Under the consideration that silica gels prepared by SFB process were so dense,
the growth of silica gels in SFB process was governed by Ostwald ripening process
rather than the agglomeration model. Silica gels prepared by base-catalyzed routes
such as the SFB process are not suitable for the preparation of adsorbents due to the
small specific surface area. Also, the aging process in basic conditions is not suitable
to control the pore and chemical structures of silica gel.
In the presentation, the effect of synthesis and aging conditions on the pore and
chemical structures of silica gels will be introduced and then the relationship between
pore and chemical structures and dehumidificationbehavior will be discussed.
Acknowledgements
This work was financially supported by National Research Laboratory Program (Korea
Ministry of Science and Technology).
31 1
References
1. R K. Iler, The Chemistry of Silica: Solubility, Polymerization, Colloid and Surface
Properties, and Biochemistry (John Wiley & Sons, New York, 1979)
2. C. J. Brinker and G. W. Scherrer, Ultrastructure Processing of Ceramics, Glasses, and
Composites (Wiley, New York, 1984).
3. C. J. Brinker and G. W. Scherrer, Sol-gel Science (Academic Press, New York, 1990).
4. A. Yasumori, M. Anma and M. Yamane, Phys. Chem. Glasses 30 (1989) 193.
5. D. C. L. Vasconcelos, W. R. Campos, V. Vasconcelos, W. L. Vasconcelos, Muter. Sci.
& Eng. A334(2002) 53.
6. M. Yamane and S . Okano, Yogyo-Kyokai-Shi87(8) (1979) 56.
7. R. Takahashi, K. Nakanishi and N. Soga, J. Non-Cryst. Solids 189( 1995) 66.
8. P. J. Davis, C.J. Brinker and D. M.Smith, J. Non-Ctyst. Solids 142(1992) 189.
9. P.J. Davis, C.J.Brinker, D. M.Smith and R. A. Assink, J. Non-Cryst. Solids 142(1992)
197.
10. J. H. Harreld, T. Ebina, N. Tsubo and G. Stucky, J. Non-Cryst. Solids 298(2002) 24 1.
11. Z. J. Li, C. R. Liu and Q. S. Zhao, J. Non-Ctyst. Solids 265(2000) 189.
12. W. Stiiber, A. Fink, E. Bohn, J. Colloid & Inter. Sci. 26(1968) 62.
13. G. H. Bogush and C. F. Zukoski IV,J. Colloid& Inter. Sci. 142(1991) 1.
14. G. H. Bogush and C. F. Zukoski IV, J. Colloid & Inter. Sci. 142(1991) 19.
312
Introduction
Lithium ion batteries have dominated the market of portable secondary batteries, due to
their higher energy densities and longer shelf lives. In this battery system, carbon
materials that can store a significant amount of lithium ions within their structure are used
as the anode material. There are numerous types of carbon materials, but in commercial
cells, graphitic carbons are mostly used due to their high stability. However, as there is a
limit in the lithium ion capacity in this type of carbon (372 mAhg-), and materials with
capacities close to this limit have already been developed, worldwide scale research is in
progress to find alternative anode materials that possess higher capacities.
Among various types of carbon materials, hard carbons, which are predominantly
formed by graphene sheets stacked like a house of cards [4], is a potential alternative.
However, although most hard carbons possess large lithium ion reversible capacities, their
irreversible capacities are also rather large, making them difficult to be used in
commercial batteries. It is widely recognized that a large part of this irreversible
capacity arises from the formation of a passivation layer on the outer surface of the carbon
[2]. In hard carbons, such layers are also likely to be formed within its pores, which
leads to an increase in irreversible capacity. Previously, we showed that the irreversible
capacities of hard carbons highly depends on their pore structures, and hard carbons
which pore openings are small enough so that C02cannot penetrate into them tend to have
smaller irreversible capacities [ 5 ] . However, the pore volume of such hard carbons tends
to be small, and it is hard to expect large reversible capacities from such materials.
As there are a wide variety of hard carbon precursors, there is a high possibility to
obtain a hard carbon with a large pore volume and small pore openings by combining
precursors of different natures. In this work, hard carbons were synthesized by
carbonizing combinations of various phenolic resin precursors. The lithium ion
capacities of thus obtained carbons were also measured. From the obtained results,
313
strategies to obtain hard carbons with large reversible capacities and small irreversible
capacities are proposed.
2
Experimental
One feature of phenolic resins is that they are usually synthesized via several stages.
First phenols react with formaldehyde by the catalysis of an acid catalyst and novolac
resin is formed.
These novolacs are usually cured with agents such as
hexatnethylenetetramine and a thermosetting resin is obtained. Hard carbons can be
obtained by carbonizing this thermosettingresin.
A wide variety of hard carbons can be obtained by carbonizing mixtures of phenolic
resins derived fiom different phenols that are at different synthesis stages. In this work,
first various phenolic resins were synthesized from combinations of different phenols and
formaldehyde. The phenols employed were pure phenol, o-cresol and 3,5-xylenol.
Note that the relative reactivities of these phenols with formaldehyde are 1:0.26:7.55,
respectively. Next mixtures of phenolic resins derived from different phenols that are at
different synthesis stages were combined and carbonized at 1273 K for 1 h, yielding
various types of hard carbons.
The pore volumes of the obtained hard carbons were measured using the molecular
probe method [3]. Adsorption isotherms of the probe molecules were measured at 298 K
using an adsorption apparatus (Be1 Japan, Belsorp 28). The employed probe molecules
were C02, C2H6, n-C4Hlo and i'C4H10 (minimum molecular dimensions: 0.33, 0.40, 0.43
and 0.50 nm, respectively). By applying the Dubinin-Astakhov equation (n-2) [11 to the
measured isotherms, the limiting micropore volumes corresponding to the minimum size
of the adsorbed molecules were determined.
Measurements of the lithium ion reversible and irreversible capacities of the samples
were conducted using a two-electrode cell at a constant current of 25 mAg-'. Cut off
voltages were set to 0 and 2.5 V. Lithium metal was used as the counter (reference)
electrode. The carbon electrodes were constructed by supporting ball-milled carbon to
copper foil using PVDF. The electrolyte used was a 1 M LiC104-EC/DEC(1: 1) solution
(Mitsubishi Chemicals). Celgard 2400 (Hoechst Celanese) was used as the separator.
3
Through preliminary experiments, it was found that the pore structures of carbonized
phenolic resins differ significantly when different phenols are used for synthesis. When
the reactivity of the phenol with formaldehyde is high, the resulting carbon tends to have
small pore openings, and if low, the pore volume tends to become large. Therefore the
carbonization of a combination of phenolic resins, one derived from phenols with high
reactivity and the other fiom phenols with low reactivity, is expected to give hard carbons
with large pore volume and small pore openings.
314
0
0.30
0.35
0.40
0.45
0.50
0.55
315
500
IReversibleCapacity1
[IrreversibleCapacity
Theoretical 400
Capacity ---- -372 mAh g-l
300
200
100
0
Sample A
Acknowledgements
This research was partially supported by Industrial Technology Research Grant Program
in '01 from New Energy and Industrial Technology Development Organization of Japan.
316
References
1.
2.
3.
4.
5.
317
DMITRY I. SHVETS
Institute for sorption and problems of endoecology NAS of Ukraine.13. General Nawnov Str...
Kiev-I64,03680, Ukraine
E-mail: a!shvetz@isne.kiev.u: dshvetz@isDe.ldc.net
The properties of bioactive carboncontaining sorbents are consided during clearing liquid
hydrocarbonaceouspropellant from sulfurcontaining substances. It was revealed, that the superselectivity
is stipulated by availability in bioactive carboncontaining sorbents of clusters and carbon nanotubes. It
was shown, that a type of clusters, their concentration, natm and the sizes of nanotubes are defining at
sorption of sulfurcontaining substances. It was found, that the purified solar oil contains minimum
amount of admixtures and conforms the requirements of the world standads. The mechanism of
superselective sorption with allowance of nanoclaster structuresis discussed.
1.
Introduction
The diesel fuel recently involves the increasing notice both technologists, and consumers.
For making solar oil use alcohols, carbohydrates etc. Despite of the successes, achieved in
this direction, rather acute there is a problem of quality of propellant, namely contents of
toxic admixtures, first of all elementcontaining. It is stipulated by that element (Cl, 0, N,
S) - containing liquid carbohydrates and the hydrocarbons (i.e. propellant with
admixtures) at combustion will derivate toxic products of the special danger, which one
harm as the person, and ozone layer of the Earth. Therefore, problem of purification of
liquid carbohydrates and hydrocarbons from toxic admixtures is one of most significant
for today for a propellant industry.
The technologies applied for clearing of propellant from toxic admixtures are rather
diverse; however degree of clearing remains insufficiently high and does not correspond
to increasing requirements. Not subjecting criticism any of existing methods, in operation
is considered an opportunity of clearing of components of solar oil - liquid carbohydrates
and hydrocarbons from sulfurcontaining substances with usage new of bioactive
carboncontainingsorbents with nanocluster structures in porous space.
2. Methods
As objects of study there were used new modifications of carbon materials vegetative
(carbon material with heterostructures of a radical type), organocarbon (nanotube), carbon
(puffed up graphite) nature and also combined carboncontaining composite. Modification
of sorbents conducted during their synthesis (heat treatment at fixed temperature) or by
processing carbon materials by special (ecologically clean) reagents at ambient
temperature. As toxic matters used petroleum, oil products, and also various fuels
containing toxic substances of a various type - aromatic substances, asphaltenes, resin,
sulfurcontaining substances, dispersible sulfur etc. Analysis of properties of carbon
materials and sorbed products carried out with usage of physicochemical methods,
atomic-adsorptive analyzer, and also with applying of methods ESR-,IR-, UV-, X-ray
spectroscopy, Zpotentiometry etc.
As the object of investigation diesel fuel @F) was used. DF- is the product of cokechemical production, containing asphaltenes, soots, paraffins, sulfur-, nitrogen- and
To obtain the composite meeting our requirements we varied its composition, taking
different amounts of the components and modifying their properties.
Experimental results showed that carbonmineral composites are much better than
others adsorbents, for example, the mineral one. A good selectivity of carbon materials
made us to assume that it is a carbon substance is responsible both for selectivity and
synergistic effect of adsorption too. From our point of view one of the reason of such a
behavior could be specially organized carbon structures such as intermediate complexes
(clusters), which possess peculiar electron properties only to them. Probably similarly
toxic substances are adsorbed, such as phenols, cresols, quaiacol, aldehydes,
polyatomic alcohols, ethers etc. (Table 1).
Table 1. Efficiency of decontaminationof some aqueous solutions from organic pollutants by &on
andcarbonrmn
' eral* materials
modified
concentration,m@l
POUUtPDt
Phenol
Cresol
Quaiacol
Ethers*
Aldehydes*
Polyatomic alcohols*
Initial
Final
2.1
4.8
Decontamination level, %
100
100
lo4
4.0. lo4
279.2
100
13.2
0.036
0.4
95
92
100
3,7
319
can be seen from fig.3, the most cleaning degree is reached at use sorbent of mixed type
only, where synergic effect is maximal.
Efficiency of refining different mixtures with the usage of the combined sorbents was
established to be significantly higher than in the case of initial unmodified sorbents. The
observed synergism proposes new approaches to the selection of components of the
carbomineral sorbents.
A. X
'9
4%
100
80
1 -NSP
60
2.Nsz
3-Nso
40
20
&NST
S-WW
S-NYNM
our investigationshave shown, not only mixed sorbents capable to show superselectivity
and provide high purifying degree of fuel from impurities. As it is seen from fig.5, similar
320
Fig. 3. Influencecondition of heat treatmenton the type of DF purification by sorbents of different type (2.5.8 heat treatment of s o h t by stages;3.6,9 -heat treatment of sorbents mixture; 1.4.7 - sorbent without heat
treatment)
+petroleum
-)Ioil
1
Material type
Wg.5. The influence of CadJoncontaining
nanotubes n m (1 - 3 cadJon nature. 4 - 6
organic nature)on the efficiency of the oilproducts
adsorption from water surface
effect of superselectivity is observed for carbon nanotubes. The reasons of the anomalous
effect of such type are yet to be explained, however even today we can say about it value
for practical purposes for obtaining of high pure ecologically harmless kinds of biofuel.
321
space additional sorption of toxic substances can be happened. Its possible that impact of
such factor is significant, but its role in process of purification (as the role of OH-groups
and acidic centers) is not dominant.
Nature of surfacesions also play significant role in purification process
Confmnation for benefit of further mentioned argument is the fact, that exactly after the
thermo-handling of natural materials degree of purification of DF is increasing, but type of
natural sorbents is greatly influencing ). And we can suggest, that with structural-sorption
parameters nature of surfaces ions also play significant role in purification process. In
sorption process one materials saturated by toxic admixtures of DF and changes their color;
another one doesnt change their color. This fact confirms possible role of surfaces ions
nature. This fact takes a great attention, because it allows to suggest, that surfaces centers
are not only the sorption centers, but in the same time they are catalytically manyfunctional centers of clusters type, Independent confirmation of these suggestion is a point,
that quantity of purified fuel in counting of it per lgramm (>20 g/g) exceeds any variants
(practical and theoretical), from volume of sorption pores Vs = 0,6-0,7 cm3/g and density
of admixtures d=0,8 g/cm3for sorption of 20 g of admixtures 25 cm3 of volume is needed,
and really system has 1,8-2,0 cm3, i. e. only sorption scheme of purification is unreal.
Relatively to the possibility of proceeding of the sorption-catalyticprocess, it is shown by
the fact , that functional-depended thermo-handling strictly increasing purification degree,
as in absolute values, such in effectivity.
4. Conclusions
So. ?resented experimental results shows, that at first time weve found the effect of overselectivity, based on fact, that in oxides systems of mixed type, passed through the
functional-depended thermo-handling, it is formed, clusters center and carboncontaining
nanotubes nature , providing the possibility of proceeding of over selective sorptioncatalytical process of purification of liquid hydrocarbons from toxic admixtures
References
1. Shvets D. I., Adsorption Science and Technology 17 (1999) pp. 709-714
2. Shvets D. I., Carboncontaining sorbents of mixed type: properties and applying in
extreme situations, Curbon-02 In Prossiding International Conference on Carbon,
September 15-20,2002 Beijing, China. ISBN 7-900352-03-7/16-03.
3. Shvets D. I., Kravchenko O.V., Urvant O.S. ,The applying of mixed carboncontaining
sorbents for removal of oil products from the water surface, Curbon-02 In Prossiding
International Conference on Carbon, September 15-20, 2002 Beijing, China. ISBN 7900362-03-7/IG-03.
4. Shvets D.I., Lapko V.V., Urvant O.S., Sorption-catalytic purification of diesel fuel
from toxic admixtures by oxides systems of mixed type, Adsorption Science and
Technology 21 (2003) (in press).
5. Shvets D. Biocatalysys on the basis of carbon - and carbon-mineral sorbents and their
property.Ros. 5 European Congressjn Catalysis. Limeriick, Iceland. 2001. p.129.
6. Baiker A. Chem. Rev., 99 (1999), pp. 453-454.
7. Sagave P.E.Chem. Rev., 99 (1999), pp. 603-605.
8. Shchukin E, Amelina E, Izmailova V. In Roc. NATO Advanced Research Workshop
Role of interface in Environmental Protection, Miskolc - Hungary, 2002, p. 6.
322
9.
323
TITANOSILICATEETS-10: SYNTHESIS,CHARACTERIZATIONAND
ADSORPTION FOR HEAVY METAL IONS
[GEORGE)X.S . ZHAO*, J. L. LEE AND P.A. CHIA
Department of Chemical and Environmental Engineering, National University of Singapore, I0 Kent
Ridge Crescent, Singapore I 1926; E-mail: cliens0,nus.edu.sg
Microporous titanosilicate ETS-I0 was synthesized in the absence of organic template and
characterized using XRD, FTIR, Raman, and nitrogen adsorption. The adsorption properties of
heavy metal ion PbZ+on ETS-I0 were studied by measuring the adsorption kinetics and equilibria
using a batch-type method. Highly pure ETS-I0 was obtained without the presence of ETS-4. The
adsorption rate of heavy metal ions on ETS-I0 is extremely rapid, less than 5 seconds is required to
attain maximum adsorption capacity in a 10 moYL solution with a batch factor of 200 m u g . The
kinetic data can be fitted by pseudo-second-order model whereas the equilibrium data is better fitted
to Langmuir isotherm than to Freundlich isotherm. The maximum adsorption capacity of Pb2+and
Cu as predicted by the Langmuir equation was 1.12 and 0.578 mmol/g, respectively. The
remarkable adsorption rate coupled with the high adsorption capacity promise potential applications
of ETS-I0 for the removal of heavy metals present in drinking water and wastewater.
Introduction
Heavy metals such as lead (Pb) are common groundwater contaminants that must be
controlled to an acceptable level according to the increasingly stringent environmental
regulations. The heavy metals, especially Pb present in drinking water are extremely
detrimental to human beings. Depending on the existing form of the metals, they can be
removed by different technologies such as chemical precipitation, membrane filtration, ion
exchange, and adsorption [l]. Unfortunately, none of them affords reducing the heavy
metals to an acceptable low level at a minimal contact time, which is of significance in the
treatment of waters, especially in purification of drinking water.
ETS-10, a microporous titanosilicate ETS-10 discovered by Engelhard in 1989 [2] is
zeolite material with a pore-opening size of 0.8 nm [2-4]. The basic anhydrous formula of
as-synthesizedETS- 10 is Na1.5&.5TiSi5013.
Unlike conventional zeolites, the framework of
ETS-I0 is constituted fiom SiO, tetrahedra and TiOs octahedra by corner-sharing oxygen
atoms [3]. The presence of each tetravalent Ti atom in an octahedrum generates two
negative charges, which are balanced by exchangeable cations Na+ and K+.Such a unique
framework property manifests itself a promising and potential ion exchanger for many
cationic metal ions that are present in waters such as Pb2+,Cd, Cu2+,Zn2+,etc. However,
adsorption data of heavy metals on ETS-10 have been hardly available [5,6]. Al-Attar and
Blackbum compared the uptake properties of uranium on ETS-10 materials synthesized
with different Ti sources and noted that the method of ETS-10 preparation has a
considerable effect on the uptakes of uranium [5]. Kunicki and Thrush [6] observed that
ETS- 10 and ETAS- 10 (Al-containing ETS- 10) displayed an extraordinarily rapid
adsorption rate towards Pb2+.The concentration of Pb2 was reduced to a negligible amount
fiom 2000 ppm in a very short contact time at a liquid to solid ratio of 100:2.4 (g:g).
Unfortunately, adsorption equilibrium data were not available.
324
Motivated by the work of Kunicki and Thrush [6], we have carried out a systematic
study on the adsorption equilibria and kinetics of several heavy metal ions including PbZ+,
Cd2+,Cu, Zn2+and Ni2+on ETS-10 using a batch-type technique. Our observations have
not only confirmed that ETS- 10 does exhibit a remarkable adsorption rate towards heavy
metal ions but also demonstratedthat the maximum adsorption capacity of Pb on ETS- 10
is as high as 1.12mmoVg according to the prediction of Langmuir model. This is the highest
uptake that has been observed on zeolite materials [ 11.
In this paper, we present the unusual adsorption properties of ETS- 10 towards heavy
metal ions Pb2+and Cu2+.Adsorption equilibrium and kinetic data are reported. Fitting of
the experimental equilibrium results to both Langmuir and Freundlich isotherms and the
kinetic data to both pseudo-fist- and pseudo-second-orderkinetic models is described.
2
Methods
The method of synthesis of ETS-10 was similar to that reported by Yang and co-workers [7].
The synthesis recipe was 8NaOH:2KOH:TiF.,:5.7Si02:350H~0.
Sodium silicate solution
(Merck) and TiF4(Aldrich) were used as the Si and Ti source, respectively. All chemicals
were used as received.
Samples were characterized by using X-ray diffraction (XRD) on a Shimadzu
XRD-6000 diffractometer (CuKa radiation), physical adsorption of nitrogen on a
Quantachrome NOVA 1000, Fourier transform infrared (FTIR) spectroscopy on a Biorad
spectrometer using the KBr method, Raman spectroscopy on a Bruker FRA 106/S
FT-Raman spectrometer, and scanning electron microscopy (SEM) on a Joel JSM-5600LV.
Adsorption of heavy metal ions on the ETS-10 sample was conducted using a
batch-type method at room temperature (23 OC). For kinetic measurement, 1 g of air-dried
ETS-10 was added to 100 ml of solution pre-acidified by nitric acid under shaking so as to
generate a solution of pH = 5.8. Then, 100 ml of 20 mmoVL Pb(NO& (or Cu(N03)z)
solution was added to obtain a mixture with an initial Pbz+(or Cu2> concentration of
approximately 10 mmoVL, a final pH value of about 5.0 and a batch factor (ratio of liquid
volume to solid mass) of about 0.2 L/g. 5 ml of the mixture was withdrawn at an appropriate
time interval by using a 5 ml syringe and rapidly filtered through a 0.2 pm nylon membrane
filter. The filtrate was collected in a sample valve and analyzed for Pb (or Cu), Na and K
concentrations using a spectrometer (Perkin-Elmer Analyst 300). The amount of metal
adsorbed at time t (s), qc(mmovg), was deduced from the mass balance between the initial
concentration (Co)and concentration at time t (CJ. The experimental data were fitted to
pseudo-second-order equation (t/q, =l/vo +t/q,) [8], where k (g/mmoVs) is the adsorption
rate constant, qc(mmoVg) is the amount of metal adsorbed at equilibrium, and vo (mmol/g/s)
is the initial adsorption rate which is kq;.
Adsorption equilibrium data were collected in a similar way as the kinetic
measurement. The equilibrium time was 10 min, which, according to the kinetics data, was
found to be sufficiently long to attain adsorption equilibrium. The experimental data were
fitted to both the Langmuir isotherm ( q , = q,,,bC,/(1+ bC,) ), where qm (mmol/g) is the
maximum adsorption capacity, C, (mmol/L) is the equilibrium concentration of the heavy
metal ion in solution, and b (L/mmol) is the Langmuir constant, and the Freundlich isotherm
(4,= KC:),where K and n are constants.
325
3
3. I
Fig. 1 depicts the XRD pattern, Raman and ETIR spectra of the ETS-I0 sample used in this
study. The XRD pattern is identical to that of ETS-10 materials reported previously [2,7],
showing that the sample is a pure ETS-I0 phase without the presence of ETS-4 impurity (it
has been shown that ETS-4 is a thermodynamicallymore stable phase than ETS-10 and it is
normally present in an ETS-I0 product [9]). The Raman spectrum (left-hand insert) further
confirms the purity of the sample. A most intense peak at 728 cm", assigned to Ti-0-Ti
stretching in comer-shared Ti06 chains [lo], and a small band at 305 cm-', attributed to
Ti-0-Si bending [1I] can be seen. The absence of any peak above 800 cm-' on the Raman
spectrum further confirms the inexistence of ETS-4 in this sample [10,111. The observation
of a main band at about 1024 cm-' due to Si-0 stretchingand a few small bands at 668,570
and 434 cm-' because of Ti-0 stretching, Si-0 rocking and 0-Ti-0 bending, and 0-Si-0
and 0 - T i 4 bending and Ti-0 rocking, respectively, on the FTIR spectrum (right-hand
insert) is consistent with the literature data of ETS-10 [121.
SEM image (not shown) displays cuboid-shape crystals of about 5 pm, but incomplete
crystal growth was also observed. The specific surface area of this sample calculated by
using BET model was about 258 m2/g.
I
728
a
E
Ba
r
.-
200
600
800 1000
Raman shift (cm-l)
1200
400
400
aoo
1200
Frequency (cm-l )
10
15
20
25
30
35
40
Two theta
Figure 1. XRD pattern, Raman spectrum (insert,left) and FTIR spectrum (insert, right) of
as-synthesized ETS-10
3.2
Fig. 2 shows the adsorption kinetics of Pb2+ on ETS-10 together with the
pseudo-second-order kinetic curve. It is seen that the adsorption rate is extremely fast.
Under the experimental conditions, less than 10 s was required to attain saturation
adsorption. When the concentration of Pb was about 2.5 mmoVL, Pb2+was not detected
326
Experimetnal data
Langmuir isotherm
Experimetnal data
Pseudo-second-ordvr model
40
60
BO
0.00
100
0.05
0.10
0.15
ce (m mol/L)
3.3
Fig. 3 shows the adsorption isotherm of Pb2+ on ETS-10. The experimental data were fitted
to both Langmuir and Freundlich isotherms and the results are included in Figure 2 as well.
The parameters derived from the two models are presented in Table 1. As can be seen, the
Langmuir isotherm predicts the experimental data much better than the Freundlich isotherm.
The maximum adsorption capacity of Pb2+ on ETS-10 as predicted by the Langmuir
isotherm is 1.12 mmol/g or about 232 mg/g. Such a high adsorption capacity of Pb2+ on
zeolite materials had never been observed [1]. The adsorption of Pb2+ on a commercial
zeolite NaY sample (Si/Al = 2.45) was measured as well and the results showed that its
maximum adsorption capacity towards Pb2+ was about 56.3 mg/g, much less than ETS-10.
The adsorption of other heavy metals including Cd2+, Cu2+ and Zn2+ on ETS-10 and zeolite
NaY was also studied and compared. A similar adsorption behavior was observed, namely,
the adsorption rate of these metal ions on ETS-10 was extremely fast and the adsorption
capacity was much higher on ETS-10 than on zeolite NaY. The maximum adsorption
capacity of Cd, Cu and Zn on ETS-10 was found to be all around 0.5 mmol/g while it
became about 0.2 mmol/g on zeolite NaY.
Table 1. Langmuir and Freundlich Parameters for Pb2* Adsorption on ETS-10
Freundlich model
n
A:(mmol L 1/n g 1 )
1.50
0.102
M/n
/v
0.932
Langmuir model
qm (mmol g"1) b (L mmol"1)
1.12
480
327
I?
0.992
3.4
Conclusion
Introduction
Porous materials can be classified, according to the pore size, into microporous materials
with ore size smaller than 20 A, mesoporous materials with pore size between 20 8, and
500
and macroporous materials with pore size larger than 500 A. Microporous and
mesoporous materials have been studied extensively and have found wide applications in
many areas, such as adsorption, separation and catalysis. One of the frequently used
methods of synthesizing porous materials is template strategy. A well-known example is
the Mobils liquid-crystal templating mechanism by which many mesoporous materials
can be made. This discovery provides an opportunity of treating and processing relatively
large molecules. However, when macromolecules such as enzymes are dealt with,
macroporous materials with an ordered pore structure and uniform pore size are desired.
OMMs were first synthesized for the purpose of photonic a lications because of their
3D spatial structure with periodically varied reflective index!Since
then, OMMS with
various chemical compositions have been prepared and they have been demonstrated to
find wide applications in the fields other than photonics? With the availability of porous
inorganic-organic materials: and the successful synthesis of surfactant-mediated highly
ordered mesoporous organosilica materials, organic-inorganic macroporous composite
materials would afford high application potentials in adsorptiodmembrane separation. In
addition, OMMs are a suitable material for processing macromolecules such as enzymes.
In this paper, the synthesis and characterization of highly ordered macroporous materials
with various chemical compositions and functionalities (silica, organosilica, titana,
titanosilicate, aliumina) are presented. The application potential of the OMMs in
adsorptiodseparationare analyzed and discussed.
1,
329
2. I
Methods
Synthesis of OMMS by using self-assemblystrategy
The synthesis strategy of OMMs is similar to the conventional template method (see Fig.
1). The template used is self-assembled microspheres instead of single molecule or
surfactant micelles. Colloidal microspheres with uniform size and morphology are
induced to spontaneously organize into a crystalline lattice (artificial opals), which could
have a face-centered cubic (fcc) or a hexagonal-closed-pack (hcp) structure or the
combination of them depending upon experimental conditions. The artificial opals are
slightly annealed to improve the stability of the crystal structure and to form connecting
necks between the adjacent spheres. Then the voids among the opals are tilled with
another material such as oxides, polymers, and hybrid materials, etc. Finally, the artificial
opals which act as the template are removed, leaving behind an OMM.
li
Self Assembly
Witration
removai
Polystyrene (PS) spheres were prepared with emulsifier free emulsion polymerization.
Silica spheres were prepared following the modified Sttiber method! All chemicals were
used without further purification.
330
2.3
The formation of artificial opals was achieved by using a number of methods including
sedimentation, filtration, evaporation, and drip method.
2.4
Opal annealing
After the opal forming, annealing was used. The PS opal was heated in oven at 110 '
C
(slightly higher than the glass temperature of PS) for 5 to 10 min.
2.5
Opal injiltration
Infiltration of the artificial opals was carried out by either filtration, or chemical vapor
deposition, or soaking method.
2.6
Template removal
The template was removed either by calcination at 550 OC for the PS opal or by chemical
etching in HF solution for silica spheres.
2.7
Characterization
Samples were characterized by using scanning electron microscope (SEM) (JEOL JSM5600LV), transmission electron microscope (TEM), physical adsorption, FTIR, Raman.
3
3.1
Opal annealing
The opals obtained by self-assembly are mechanically unstable because there is only Van
der Waals force between spheres. The subsequent infiltration process could easily destroy
the ordered colloid arrays. So we annealed the opals of polymer sphere to increase their
stability. As a result, there would form interconnections between spheres, which come
from the slight melting of the sphere surfaces. These necks can provide the opal with
necessary mechanical stability. In addition, they are important for producing inverse opal
structure. After infiltration, when the samples are treated with calcinations, these necks
can act as channels for the transport of the products formed during calcination like COz.
331
Figure 2. Self-assembled artificial opals fabricated with different methods: (A) sedimentation, (B)
filtration, ( C ) evaporation, and (D) flow-controlled evaporation.
3.3
Figure 3. SEM images of (A) PS opal infiltrated with SiOz, (B) after removal of template of (A), (C)
macroporous Ti02 prepared via core-shell method, and (D) macroporous organosilica materials
332
Conclusion
References
1. Imhof A. and Pine D. J., Ordered macroporous materials by emulsion templating,
Nature 389 (1997), pp. 948-951.
2. Vlsov Y.A., Xiang Z. B., Sturm J. C. and Norris D. J., On-chip natural assembly of
silicon photonic bandgap crystals, Nature 414 (2001), pp. 289-293.
3. Xia Y.,Gates B., Yin Y.and Lu Y., Monodispersed colloidal spheres: old materials
with new applications,A h . Muter. 12 (2000), pp. 693-713.
4. Subramania G.,Constant K., Biswas R., Sigalas M. M. and Ho K.-M., Inverse facecentered cubic thin film photonic crystals, A h . Muter. 13 (2001), pp. 443-446.
5. Stein A., Sphere templating methods for periodic porous solids, Micropor. Mesopor.
Muter. 44-45 (2001), pp. 227-239.
6.Loy D. A. and Shea K. J., Bridged polysilsesquioxanes. Highly porous hybrid
organic-inorganic materials, Chem. Rev. 96 (1995), pp. 1431-1442.
7. Inagaki S., Guan S., Ohsuna T. and Terasaki O., An ordered mesoporous organosilica
hybrid material with a crystal-like wall structure, Nature 416 (2002), pp. 304-307.
8. T. Okubo, T. Miyamoto, K. Umemura and K. Kobayashi, Colloid Polym. Sci., 2001,
279,1236.
9.Okubo T., Miyamoto T., Umemura K. and Kobayashi K., Seed polymerization of
tetraethyl orthosilicate in the presence of colloidal silica spheres, Colloid Polym. Sci.
279 (2001), pp. 1236-1240.
333
Adsorption ofN2,O~and Ar in zeolite A and X exchanged with silver, cerium and europium at 15 and 30C
temperatures has been studied. Silver exchanged zeolite A show higher adsorption capacity and selectivity
for nitrogen compared to Zeolite CaA.Enhanced Nitrogen interactions of nitrogen molecules with AgA are
also observed in very high heat of adsorption (38kJmor'). AgA also exhibits argon selectivity over oxygen
atypical of zeolites. Both cerium and europium exchanged Zeolite X show oxygen selectivity over nitrogen
in Henry region which has been attributedto interaction of oxygen with non-stoichiometric oxides of these
cations apparentlyformed inside zeolites cavities.
Introduction
Zeolites are of immense interest in gas and chemical industries for purification and
separation due to their unique adsorption properties. The extra framework cations
invariably present in zeolites play significant role in determining their adsorptive properties
[l]. In particular, if coordinately unsaturated metal ions can be incorporated inside the
zeolite cavities, novel adsorption behavior may be fashioned on the basis of coordination of
guest molecules. Exchangeable transition metal ions in activated zeolites are generally
coordinately unsaturated and readily form complexes with a variety of guest molecules [2].
This is due to the van der Waals and Coulombic interactions between the extra framework
cations and the guest molecules. Synthetic zeolites of type A, X and mordenite having alkali
and alkaline earth metals as the extra framework cations have been extensively studied and
are mainly used as the nitrogen selective adsorbents for the adsorptive separation of oxygen
from air [3,4,5,6,7,8]. However, there are few studies on the adsorption behavior of
transition or rare earth cation exchanged zeolites. In the present paper, we report the
adsorption of nitrogen, oxygen and argon in some transition and rare earth metal ion
exchanged zeolite A and X.
2
Methods
2. I Cation Exchange
Commercially available zeolite A and X from Zeolites and Allied Products Mumbai
India was used as the starting material without any further purification. For exchangingwith
transition and rare earth metal ions, the zeolite was mixed with 0.1 M aqueous solution of the
specific cation and refluxed at 80C for 4 hours. The zeolite was filtered and washed with
distilled water until the washings were free fiom ions and used for the adsorption
measurements after drying. The percentage of ion exchange was determined by Atomic
Adsorption Spectroscopy after acid digesting the sample.
334
Structuralchanges due to the cation exchange, if any, was determinedby measuring the
X-ray powder diffraction with Philips X'Pert M P D system using Cu Kctl(l= 1.54056) in
the 20 range 5 to 65.
2.3 Adsorption Isotherms
Oxygen, nitrogen and argon adsorption at 15C and 3OoCwas measured using a static
volumetric system (Micromeritics ASAP 20 10, USA), after activating the sample at 350C
under vacuum for 8 hours. Dosing of the adsorbate gas was done at volumes required to
achieve a targeted set of pressures ranging from 0.5 to 850mmHg. The adsorption and
desorption were completely reversible, hence it was possible to remove the adsorbed gases
by simple evacuation.
2.4 Heat of Adsorption
Isosteric heat of adsorption was calculated from the adsorption data collected at
different temperatures using Clausius - Clapeyron equation.
&dH" = R [alnpl/[a( 1IT)] 1 0
where R is the universal gas constant, 8 is the fraction of the adsorbed sites at a pressure p
and temperature T. A plot of Inp against 11T gives a straight line with slope of A,,+H"/R.
3.
Results
335
200
400
600
800
Pressure in mmHg
A%r
M
12
30
25
20
15
10
5
0
Pressureinnun&
Figure
336
Europium exchanged zeolite X also shows higher heat of adsorption (-47 klmof')
value for oxygen. Samples having specific Europium loading displays oxygen adsorption
selectivity over argon and nitrogen in Henry' s region only which is shown in Fig.3.
II
CeX
Eux
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
II It
200400600800
20
40
60
80
Pressure in mmEIg
Figure -3 Adsorption Isotherm measured at 3OoCon CeX & EuX
The isosteric heat of adsorption on various zeolite adsorbents are given in table 1
Table-I Heat of Ahorption in kJ mot'K' at O.04mmoUg Coverage
Sample
Nitrogen
Oxygen
Argon
25.01
20.51
AgA
38.77F
NaX
22.45
15.62
13.98
CaX
29.15
15.23
14.12
Agx
37.86
15.84
14.76
CeX
17.57
69.48
EUX
16.10
46.90
15.60
Discussion
337
the adsorbates molecules for zeolitic adsorbents. However, in case of zeolite adsorbents
used for the air separation, the main factors influencingthe nitrogen adsorptioncapacity and
selectivity are the difference in the quadruple moment of the adsorbate molecules and
accessibilityand the charge density of the cations [4,5].
Silver ions are reported to form neutral and charged silver clusters in the zeolite cavities
on vacuum dehydration at higher temperature [9].These coordinately unsaturated species
interact very strongly with nitrogen molecule [5].The other major factor contributing
towards the interaction of silver zeolite with nitrogen is enhanced polarization interactions
between AgA and nitrogen molecules. Ag+ ion with higher polarizing power compared to
Na'/Ca'2 ions and nitrogen molecules with relatively high polarizability interacts strongly
with each other resulting into enhanced adsorption for nitrogen.
The argon selectivity showed by the silver zeolite A can be explained in terms of the
difference in polarizability values. Argon having polarizability higher than that of oxygen
shows relatively high adsorption capacity and selectivity.
Higher interaction of oxygen molecules with CeX may be explined in terms of
interaction of oxygen molecules with non-stochiometricoxides of cerium probably formed
inside zeolite cavities due to interaction of cerium with zeolitic framework oxygens. Cerium
is known for its non-stochiometric oxides, which are oxygen selective.
Acknowledgements
References
1. R.M. Barrer, Zeolites and Clay Minerals as Sorbents and Molecular Sieves; Academic
338
D. Kavitha
1. Introduction
The conventional methods for removal of dyes using alum, femc chloride, coconut shell
based activated carbon etc., are not economical in the Indian context. Pollard el QL, [l]
and Namasivayam [2] have reviewed non-conventional adsorbents used for the removal of
dyes and heavy metals. Adsorption of acidic and basic dyes by activated carbon and bone
char [3] acid dye on bagasse pith [4] and orange peel [5], acidic and basic dye by biogas
residual sluny [6] and banana pith [7] have been reported. Industrial solid wastes like
Fe(III)/Cr(III) hydroxide for the removal of congo red [8] and red mud for the removal of
procion orange [9] have been investigated. Dyeing wastewater treatment using organic
coagulant and Fentons reagent [lo] and ozone [ l l ] have also been examined. The
photocatalytic oxidation and photoelectrocatalytic oxidation of rhodamine B using the
Ti/TiOz have been investigated and compared [12]. Biosorbents like chitosan beads for
reactive dye [13] and mixed culture of bacillus species and pseudomonas stutzeri for
methyl red [14] have been studied. Coir pith is a waste byproduct of coconut coir
industries in southern India. It is a soft biomass separated from the coconut husk during
the preparation of coir fiber. The purpose of this work was to investigate the removal of
methylene blue by coir pith carbon as a model study.
2. Experimental
339
meter(Elic0, model LI-107, Hyderabad, India). The dye solution was separated fiom the
adsorbent by centrihgation at 20,000 rpm for 20 min and its absorbance was measured.
Effect of pH was studied by adjusting the pH of dye solutions using dilute HCl and
NaOH solutions. Effect of adsorbent dosage was studied with different adsorbent doses
(25-600 mg) and 50 ml of 10,20,30,40 mg& dye solutions. For desorption studies, the
adsorbent that was used for the adsorption of 10,20 mg/L of dye solution was separated
from the dye solution by centrifugation. Then the spent adsorbent was agitated with 50
ml of distilled water, adjusted to different pH values for 60, 80 min. The desorbed dye
was estimated as before. For temperature studies, adsorption of 10 mg/L of methylene
blue by 200 mg of adsorbent was carried out at 35,40, 50 and 6OoC in the thermostated
rotary shaker.
340
3.5. pH effect.
The per cent removal was >90% in the pH range 2-1 1. At pH 2, though positively
charged surface sites on the adsorbent do not favor the adsorption of dye cations due to
the electrostatic repulsion, dye removal was still high (>90%). As the pH increased, the
removal increased slightly. This suggests that the chemisorption might play a major role
in the adsorption process. A similar trend was observed for the adsorption of methylene
blue by clay [19] and rhodamine B by biogas residual slurry [20]. The per cent desorption
was <lo% in the entire pH range 2-10 though there was slight increase from 0.5 to 9.0.
Insignificant desorption at different pH values confirms that chemisorption is the major
mode of adsorption process.
3.6. Effect of temperature
Increase of temperature increased the per cent removal. The change in standard free
energy, enthalpy and entropy of adsorption were calculated using the following
equations:
(4)
AGO = -RTlnK,
where R is gas constant and K, is the equilibrium constant and T is the temperature in k.
Values of AGO were found to be in the range -9.239 to -13.57 (kJ/mol).
According to van't Hoff equation,
logloK, =
Values of ASoand &were
AS0/2.303R
AHo/ 2.303RT
(5)
Positive values of & show the endothermic nature of adsorption. Similar results have
been reported for the adsorption of methylene blue by clay [19].The negative values of
AG'indi~te the spontaneous nature of adsorption for methylene blue at 35, 40, 50 and
60' C. The positive values of ASosuggest the increased randomness at the solid /solution
interface during the adsorption of dye on coir pith carbon. Equilibrium data at different
temperatures for the adsorption of dye on coir pith carbon do not follow the first order
kinetic model but follows the second order kinetic model. The second order rate constants
were in the range 0.357-0.879g/mg/min.
4. Conclusion
The present study shows that the coir pith carbon is an effective adsorbent for the removal
of methylene blue from aqueous solution. Adsorption follows Langmuir isotherm. Kinetic
data follow second order kinetic model. The adsorption capacity was found to be
5.87mg/g. The results would be useful for the fabrication and designing of wastewater
treatment plants for the removal of dye. As the raw material, coir pith is discarded as
waste in coir industries, the treatment method using coir pith carbon is expected to be
economical.
341
REFERENCE:
1
2.
3.
4.
5.
6.
7.
8.
9.
10.
S.El-Kadri ,'0.
Dabbit and H. Kakhia, Treatment of wastewater containing
dyes used in the Syrian textile industry, J. of Chem. Tech. Biotech., 77,
11.
437443,2002.
12.
13.
14.
15.
16.
17.
18.
19.
20.
343
Introduction
The purity of oxygen product from air separation by equilibium controlled Pressure Swing
Adsorption (PSA) is limited to 95% by the presence of argon, which has the same
adsorption characteristics as 02.To meet the need of high purity 0 2 or Ar, cryogenic
distillation and catalytic hydrogenation are normally applied. Attempts to separate 02-Ar
mixture using kinetically controlled PSA have been reported in the literature [ 1,2]. The
present work is a part of the study aimed at choosing a suitable adsorbent and developing
feasible PSA cycles to separate 02-Ar mixture. Three CMS samples, Bergbau-Forschung
(BF) and two Takeda CMS (Takeda 1, Takeda 2) and a modified 4A zeolite (Union Carbide
RS-10)were investigatedfor this purpose. Although PSA processes may operate at elevated
pressure, the equilibrium and kinetics in the linear range are often used to give an
approximation for the initial screening of adsorbents. A proper kinetic model is crucial to
any dynamic simulation of PSA processes. While it is generally agreed that in CMS
adsorbents, the dominant resistance for gas diffusion is in micropores, three different
mechanisms have been suggested for transport in the micropores: distributed pore interior
resistance (pore model), barrier resistance confined at the pore mouth (barrier model) and a
combination of both (dual model) [3]. The dual model seems to best capture the uptake data
measured in this study. The bidispersed pore model developed earlier in this laboratory [4]
for kinetically controlled air separation has been modified to include dual transport
resistance in the micropores.
2
344
where DJr: (s-) is time constant accounting for distributed pore resistance and kb (s-) is
transport coefficient accounting for banier resistance. On RS-10, micropore diffusion
followed the pore model. Pore model was simulated by assigning a large value to in eq
(1).
1
Fig 1. B r e a k t h r o u g h o f A r in Takeda 2
1
F i g I. Uptake of A r r t 293K
0.8
0.6
t0.4
0.8
0.6
0 0.4
0.2
0.2
cxpat 293 K
-model
*ot,.,(s
..bj(O
60
200
400
600
800
1000
the
linear range) together with Henrys constants K are listed in Table 1. Representativematch
between experimental and model uptake curves is shown in Figure 1. It is obvious that the
9 and cannot be predicted by the
uptake curve (plotted vs. t) for Takeda2 is of shape
pore model. The same observation was also true for the other CMS samples.
t(s)
Table 1. Equilibramand kinetics of Arand o2 adsorption on the 4 samples in the linear range
To validate the results from the volumetric method, breakthrough experiments were
also conducted using helium as carrier gas in columns packed with CMS samples. The
volumetric data predicted the breakthrough performance very well, as may be seen from
Figure 2.
3
Referring to O2 data [3] listed in Table 1, Ar diffuses much slower in all adsorbents. The
kinetic selectivity is defined by: a, - q~/ C A ,where qi is the average concentration in the
q B /cB
adsorbed phase.
Considering only micropore transport with constant parameters, the single component
uptake by pore diffusionin RS-10, following a step change in gas concentration, is given by
$ cotpn+ L -1 = 0; L = kb
30, :1.
345
Fig 3. Kinetic i e l e e t i v i t y
2o
t(s)
40
60
PSA simulation
PSA simulations were performed using a modified two-bed Skarstonn cycle without
external purge for the production of Ar [7,8]. The bidispersed pore model for kinetically
controlled air separation developed by Gupta and Farooq [6] has been extended to
incorporate dual resistance observed for transport of oxygen and argon in the CMS samples.
In view of space limitation, only some important features are highlighted here.
Adsorption equilibrium was represented by extended Langmuir isotherm with the same
saturation capacity (qs) for both adsorbates and constants (bi) following Arrhenius
temperature dependence:
3.950
4.451
4.475
kl*
(IO-~S-')
pb
98.4
2.07
5.56
6.08
The above equations are written for componentA. Similar equations apply for component B.
The concentration dependence of pore diffisivity followed Darken's equation. However,
the concentration dependence of the barrier coefficient was much stronger than that
expected from the analog of Darken's equation, which following other studies in this
laboratory [3,9], was represented by:
( h o = K"),
)I
346
(kio)Aris the limiting value obtained in the previous section. Representative results are
shown in Figure 5 and the extracted pb values are given in Table 2. Some simulation results
are summarized in Table 3.
Table 3: PSA simulation results
1.
PR: pressurization;BD; blowdown; HP: high pressure adsorption;SP: self purge.
.
2. Productivity: in units of cc(latm)/hr/cc adsorbent.
Feed composition: 95% 02 and 5% Ar on molar basis; temperature: 293 K; number of cycles: 25.
Bed length: 40 cm, bed radius: 1.9 cm; bed voidage: 0.35; particle radius: 0.159 cm; particle voidage: 0.33.
The purity of Ar in the high pressure cycles was limited to 50%. The purity and
recovery were improved in subatmosphericcycles with a consequent loss of productivity. In
blowdown steps, oxygen product was also concentratedto 96-98% with recovery up to 90%.
It is noted that 3 and 1 atm are the pressures of O2product in the two main industrial PSA air
separation methods, Lindox process and VSA process [2], respectively.
Studies are underway to further improve the purity and recovery of the argon product.
The results will be presented at the conference.
3.5
CI
E
-E
2.53
2
:
1.5
ij
9"
0.5
10
-model,
no
0
0
0.1
0 2
C(mmbl/cc) 0.3
0.4
0.2
q,q.
0.4
0.6
References
1 . S. Hayashi; M. Kawai; T. Kaneko. Dynamics of high purity oxygen PSA. Gus. Sep.
Furif: 1996, 10, 19.
2. Salil U. Rege; Ralph T. Yang. Kinetic separation of oxygen and argon using molecular
sieve carbon. Adsorption. 2000,6, I5
3. Huang Qinglin; S M Sundaram; S Farooq. Revisiting transport of gases in the
micropores of carbon molecular sieves. Submitted for publication.
4. Gupta, R. and Farooq, S. Numerical Simulation of a Kinetically Controlled Bulk PSA
Separation Process based on a Bidisperse Pore Diffusion Model. Proceedings of the 81h
APCChE Congress, Vol. 3, p. 1753-1756, August 16-19, 1999, Soul, Korea.
5. Loughlin, K. F; Hassan, M. M.; Fatehi, A. I.; Zahur, M. Rate and equilibrium sorption
parameters for nitrogen and methane on carbon molecular scieve. Gas Sep. fur$ 1993,
347
7,264.
348
1 Introduction
349
3 Model
It is assumed that the DR PSA unit is able to separate and purifjl
where 'I[;= PH/PL.~ A , Iis assumed to be equal to YA,F to avoid diluting during
blending. For a system with linear isotherms [6], all the gas that is
required to pressurize the column that just underwent the feed step comes
fiom the blowdown of the other column, i.e., Nw=Na. By defining
S=NFE/NF,the resulting relationship follows for the purge to feed ratio (y),
REand RL fkom local equilibrium theory for linear isotherms [6]:
(2)
(3)
(4)
Prepresents the relative affinity of the bed for the heavy component over
the light one (B) [5] and is equal to PA/& with fi given by
&
Pi = E + (1 - &)ki
i=A,B
(5)
where ki the dimensionless Henry's law constant and E is the bed void
fraction. The dark rectangle located on the LHS of the column undergoing
feed in Fig. 1 indicates that the location of the feed is not necessarily
restricted to a fixed position; it can be anywhere in between ZF,,,,~" and
ZF,ma. The former ensures no breakthrough takes place at the bottom of
the bed, while the latter ensures the feed concentration does not change
when mixing with the upstream flow. The expressions for ZF,min and ZF,ma
are given by [6]:
351
4 Discussion
Table 1 shows results for different values of p, 'II and S, for YA,P0.2, L=l
. REand RL are obtained directly from Eqs (2)
m, b 2 0 s and a p ~ 4 . 0 5 y,
to (4), and yA,2 is obtained from Eq. (1) with YA,I=YA,F. ATBTis the
dimensionless feed time defined according Eq. (8), for which ZF,min in
Eq.(6) is zero, i.e., it is the time above which breakthrough of the pure
heavy component always takes place [6].AZ~RBT
is half this time. ZF,min,
ZF,- and UF are obtained from Eqs. (6) to (8), respectively, using ATII~BT.
Recall that perfect separation was assumed, i.e., y ~ , ~ and
=0 y~,~1.0;
this necessarily results in 100% recovery for both components. However,
for this DR PSA process to be feasible, R ~ l l . 0 which
,
was always the
case. What is even more remarkable is that the separations were achieved
1S)! These results suggest that in reality it may be
at relatively small z (I
possible to separate a binary mixture into nearly pure components at high
recoveries with a minimal expenditure of energy using the DR PSA
concept. It is also interesting to note the strong influence of 6and /3 on
While the first result is obvious, the second is not and due to the fact that
as the relative affinity for the heavy component increases (i.e., smaller p )
the amount of solute that desorbs during the feed step also increases,
which directly impacts the total gas leaving the bed. Notice the minuscule
impact of the three parameters on RE. Equation (3), as with Eq (4) for RL,
shows no dependence on 'II, a result that comes directly form the
application of equilibrium theory, and the fact that complete separation is
being achieved. RL is also independent of p: no matter the species in the
gas mixture one value of RLleads to the same result in all cases. The effect
of /3 on ZF,min, ZF,-, and UF is also strong, revealing that longer recti@ing
sections are needed for smaller /3. For the same reason, UF has to be
smaller. Finally, for small /?,only the rectifying section was required for
the separation.
352
Table 1. Theoretical prededictions showing the feasibilityof the DR PSA concept for
different values of and .
6
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
& &
3.38 0.95
Y&Z
AfBT
&I/ZBT
uF(cmls)
q,min(@
0.024
0.211
0.000
2.353
0.174
0.174
0.174
0.186
0.164
0.146
0.194
0.194
0.194
0.194
0.197
0.194
0.191
0.187
0.021
0.011
0.002
0.011
0.011
0.011
0.211
0.211
0.211
0.319
0.145
0.073
0.003
2.128
1.087
0.185
1.087
1.087
1.087
32.990
30.189
16.327
2.920
16.327
16.327
18.327
16.327
1.2 0.01
1.2 0.1 3.75 0.96 0.11
1.2
1 7.50 0.98 0.56
1.2
10 45.00 1.00 0.93
1.1
1 8.18 0.98 0.56
1.3
1 6.92 0.98 0.56
1.5
1 6.00 0.98 0.56
1.2 0.01 0.84 0.84 0.01
1.2 0.1 0.94 0.85 0.11
1.2
1 1.88 0.92 0.56
1.2
10 11.25 0.99 0.93
1.1
1 2.05 0.92 0.56
1.2
1 1.88 0.92 0.56
1.3
1 1.73 0.92 0.56
1.5
1 1.50 0.92 0.56
0.043
0.022
0.004
0.022
0.022
0.022
0.660
0.604
0.327
0.058
0.327
0.327
0.327
0.327
0.015
0.026
0.015
0.015
0.015
0.330
0.466
0.004
0.302
0.163
0.029
0.163
0.163
0.163
0.163
0.466
0.466
0.033
0.177
0.317
0.177
0.177
0.177
0.177
0.466
0.482
0.466
0.452
0.428
5 Acknowledgements
References
1 Ruthven, D. M., Farooq, S. and Knaebel, K. S., Pressure Swing
Adsorption, VCH, New York, 1994.
2 Diagne, D., Goto, M. and Hirose, T., Numerical Analysis of a Dual
Refluxed PSA Process during Simultaneous Removal and
Concentration of Carbon Dioxide Dilute Gas from Air, J. Chem. Tech.
Biotechnol., 65 (1996) pp. 29-38.
3 Ebner A. D., and Ritter, J. A., Equilibrium Theory Analysis of
Rectifying PSA for Heavy Component Production, AIChE J. 48 (2002)
pp. 1679-1691.
4 Mclntyre J. A., Holland C. E., and Ritter J. A., High Enrichment and
Recovery of Dilute Hydrocarbons by Dual-Reflux Pressure-Swing
Adsorption, Ind. Eng. Chem. Res. 41 (2002) pp. 3499-3504.
5 Knaebel K. S., Hill, F. B., Pressure Swing Adsorption: Development of
an Equilibrium Theory for Gas Separations, Chem. Eng. Sci., 40
( 1985) pp. 235 1-2360.
6 Ebner A. E. and Ritter J. A., Dual Reflux PSA for the Complete
Separation of Binary Gas Streams, AIChE J., submitted (2002).
353
separation process combining membrane permeation and pressure swing adsorption (PSA) is
presented. The membrane performs most of the bulk separation operating in counter-current flow
mode to maximize the average driving force and therefore providing the most efficient arrangement.
Permeate and residue streams are fed to the PSA at different steps of the cycle for higher purity and
enhanced recovery.
Our simulation work shows that the efficiency of the pressurization and high-pressure adsorption
steps increase, thereby improving the separation performance as compared to a standalonePSA. The
process has been successfully applied to the bulk separation of a mixture of 50/50 HdCI-4 and
preliminary results have been obtained for COZ/CHJand Hz/COz/C& mixtures. The H~/CHJmixture
was selected because it is a challenging separation to show the benefits of the hybrid process since
the selectivity between CH& on activated carbon is high, making the PSA alone a very efficient
separation process for this mixture. Nevertheless, even in this unfavorable case the membrane
enhances the separation performance. It is expected that using the operating pressure of the PSA bed
as the driving force for membrane permeation minimizes recompression work and enhances
productivity.
1 Introduction
Membrane permeation and PSA are frequently considered as alternatives
to the conventional cryogenic gas separation processes. In a PSA process
the adsorbent is regenerated by reducing the partial pressure of the
adsorbate, which is accomplished by lowering the total pressure or by
using a purge gas. With the present generation of membrane modules, the
PSA process gains an advantage in the high-purity region while the
membrane system is more advantageous when product purity requirements
are less severe'. It is therefore it is reasonable to expect that an optimized
gas separation process integrating membrane and PSA improve product
purity and/or recovery as compared to the two-standalone systems.
2 Process Description
Fig. 1 shows the integrated cyclic process developed for bulk separation of
an A+B mixture, using a membrane and a dual-bed PSA unit. The process,
as presented here, operates under the assumption that the least adsorbed
component A permeates faster. The cycle starts with an incomplete
pressurization (PRI) of one bed with the permeate, which is stored in the
354
M)
I20
180
240
300
360
420
lime,.
Bed 1
Bed2
Munbruc
Figure 1 Flowsheet of hybrid membranaPSA process. Steps: pressurization (PR = PRI + PRz), high-pressure
adsorption (HPA), co- and counter-curred blowdown (CD, BD), Purge (PG);A : stream enriched in less
adsorbed component, B: stream enriched in strongly adsorbed component. Pressure histories of the integrated
cycle at CSS.
355
3 Theoretical Modeling
3.I Membrane Unit
The individual (i = 1,...,iVc- I ) and global material balances in the residue
(k= 1) and permeate (k= 2) sides of the membrane are
where 0 < z < Lm,Ak and A m are the cross-section and permeation areas,
respectively. If Qiis the permeance of species i, then its molar flux can be
= Qi(P,yiql
-P2yi.?). For a binary mixture (A+B) the
Written as
permeation flux of the less permeable species (B) can be expressed in an
, ~ ) , a = Q ~ Q is
A the
alternative form as F ~= ~, ~ /~a ( p~-, ~P ~,~.J, I ~where
ideal membrane selectivity.
e.,l+2
(-)
at T
az
z:
at
where 0,is the intraparticle effective diffusivity and rp the particle radius.
356
Multicornponent adsorption equilibrium is modeled using the LangmuirFreundlich (LF) isotherm model with the literature data given in [5].
The model equations were discretized in the spatial coordinate z using
a control-volume formulation with high-order flux correction applied to
the convective terms. The resulting large-scale stiff system of differential
algebric equations (DAEs) and process scheduling were solved using the
gPROMS simulation package.
4
94
0
96
92
*s
88
*
8
e
90
86
84
82
I 0
80
78
44
50
56
62
68
74
80
Feed, L(STP)
44
50
56
62
68
74
80
Feed, L(STP)
Figure 2 Impact of feed flow rate on H2 product purity and recovcry for standalonc PSA (A, f H = 35 bar; A,
= 25 bar) and for integrated system (0,
f H = 35 bar; m,
= 25 bar).
357
100
95
90
$
85
0.8
tt!
0.6
y
s
0.4
0.2
80
75 I
0
I
0.05
0.1
0.15
0.2
0.25
0
0
0.2
0.4
0.6
0.8
P/F
dL
Figure 3 Impact of P/F ratio on product purity and recovery for standalone PSA (Hz:A, purity; 0,recovery,
Ch: 0, purity;
recovery) and for integrated system (Hz:A, purity; m, recovery, Ch: *, purity;
,
recovery). CH4 concentration profiles in the PSA bed for a single and for the integrated system. PSA alone: 0
end of PR1(9s), 0 end of PRt(3Os), A end of HPA. Integrated process: H end of PRl(9s). + end of PRz, A end
of HPA.
*,
higher feed throughput than the standalone PSA (Fig.2). Increasing the
purge to feed ratio increases H2 purity and C& recovery steadily, with loss
of H2 recovery and dilution of the CH4 product stream. The H2 recovery
and CI& purity for the hybrid system are higher than those for the
standalone PSA (Fig.3). The concentration profiles for the hybrid process
are sharper than those for the PSA alone, which enhances the separation
performance of the combined process (Fig.3). The reason for this is that,
unlike in a conventional PSA, the beds in the hybrid system are fed with a
varying-composition gas stream, initially rich in the more permeable but
less adsorbed component, which is progressively enriched in the other
component having opposite behavior. The results obtained show that the
coupled process increases the efEciency of the PR and HPA steps, thereby
improving the separation performance as compared to a standalone PSA.
5 Acknowledgements
I.A.A.C. Esteves thanks FCTMCT (Portugal) for a doctoral fellowship.
References
D.M.Ruthven et al., Pressure Swing Adsorption, VCH Pub.( 1994).
D.T.Coker, B.D.Freeman, GKFleming, AIChE J 44 (1998) pp. 1289-1301.
E.Drioli, M.Romano, I..Eng.Chem.Res. 40 (2001) pp.1277-1300.
R.T.Yang, Series on Chem. Eng., Imperial College Press Vol. l(1997).
R.T.Yang, S.J.Doong, AIChE J 31 (1985) pp.1829-1842.
6. R.T.Yang, S.J.Doong, AIChEJ 32 (1986) pp.397-410.
7. R.W.Baker, Ind.Eng.Chem.Res.41(6) (2002) pp.1393-1411.
1.
2.
3.
4.
5.
358
adsorption
Introduction
Economical 13Cseparation is very important, not only for its use as an isotopic label in
nuclear magnetic resonance chemical analysis and medical diagnosis, but also to provide a
means for the removal and fixation of radioactive carbon (carbon-14) in the nuclear power
industry.
I3C is normally separated from l3C/''C CO or 60m I3CI1'C CH4 by cryogenic
separation factor is 1.007,
processes. As the separation factor is quite low (the 13CO/12C0
and the '3CH4/12CH,separation factor is 1.003), the cost of separation is very high. The
applications of I3C are therefore limited to use in the laboratory as a chemical reagent: its
use for industrial purposes is not viable. However, it is well known that CO is strongly
adsorbed on Na-X type zeolites'). Studies of the adsorption of CO on zeolites suggested
that some types of zeolite showed selectivity towards I3CO in the binary '3CO/12C0
system'). We therefore evaluated the relationships between the selective adsorption of
13
CO and a) the type of zeolite crystal, b) the Si02/A1203 ratios, and c) the chemical
modifications.
Experimental
A gaseous mixture of CO (13C/12C
= 0.01 1, natural abundance) and helium as a carrier gas
was introduced into a small column of zeolite pellets for a selected time, then desorbed by
evacuation of the column.
Apparatus
A small-column adsorption apparatus was used to determine the adsorption
359
equilibrium and the rate characteristics of a bicomponent mixture of "CO and I3CO
(Figure-I). The column was loaded with 10-15 g of zeolite sample pellets, prepared by
extrusion as 1.dmm-diameter cylindrical samples. The samples were first heated to 400 K
in air for 2 hours to remove surface water, and then at 723 K, so that the adsorbents were
regenerated and became thoroughly free of pre-adsorbed water vapor. The column was
then placed in a refrigerator at a constant temperature of 2 13 K.
The inlet flow rate and pressure
were controlled by a mass-flow
controller. The mass flowmeter at the
outlet of the column detected changes
in the flow rate, and a sampling line
leading to the quadra-pole mass
spectrometer was placed at the exit,
for measuring the I2CO, I3CO, and
helium concentrations in the exiting
gas. The column was evacuated by a
~,
vacuum pump, with v-3 Opened and
Figure-l. Small c-1- apparatus for '3CO/12CO
V-1 and V-2 closed. When the
separation evaluationusing PSA.
column pressure reached the
desorption pressure, V-4 was opened, and helium was supplied for a countercurrent purge.
The amount of gas desorbed by evacuation was measured by a rotary flowmeter connected
to the outlet of the vacuum pump. "CO, "CO, and helium concentrations at the desorption
stage were not measured, but these values were determined from the mass balance
between the inlet and outlet at the adsorption stage.
Procedure
The adsorption pressure was adjusted by means of a pressure gauge installed on the
inlet gas line. The programmed sequence of the adsorption experiment was as follows: (1)
Valve V-1 was opened, the inlet gas of CO concentration cOl
(I = I; I2co,I = 2; I3c0,I =
3; He) was introduced into the column, and the column pressure reached the adsorption
pressure Pa. This process took about 5 seconds. Valve V-2 was then opened, and
adsorption in the column fiom the inlet gas took place (adsorption step). During this
period, the flow rate and concentration of CO, GI,and C,,, were measured. (2) Valves V-1
and V-2 were closed, V-4 was opened, and the column was evacuated (desorption step).
At the end of the desorption step, the pressure was below 13 Pa after 600 seconds. (3) As
V-3 was also opened under evacuation, helium was supplied as a countercurrent purge to
remove CO thoroughly (countercurrent purge step). (4) With V-3 closed and V-4 still
open, the column was re-pressurized to the adsorption pressure with helium. The
measurement conditions are summarized in Table 1, and the samples that were screened
are listed in Table 2. The adsorption temperature was one parameter examined in this
study, and a sequence controller was programmed for each set of conditions, so that steps
( 1 x 4 ) were repeated over more than 4 hours. The total amount of desorbed gas G2 was
determined from the gas collected at the exit of the rotary flowmeter.
360
See Table 2
1/16". 2 gram
6W RI N/ninute
CO 10 vol K. Ha 90 vol K
( W F ratio
:Natural abundance 0.011)
Adsorption tcrosrature
Adsorption pressure
Dssorption pressure
Adsorption time
213-298K
120 kPa
1 kPa
180 seconds
361
I d a qas m e ( d W b r c N
Figure-Za).
Outlet "CO concentration.
Figure2b).
Outlet 13c0concentration.
4
<
Ida
(PI m e (
Figure-3.).
Temperature dependency of
"CO and "CO equilibrium
constants of Na-LSX.
drVbrtd3
Figure-2c).
Outlet ~ 3 c 0 / 1 z cisotope
0
ratio.
I3COselectivity of Na-X
As a strong selectivity of Na-LSX towards I3CO was suggested by the screening test,
the adsorption behavior of Na-LSX towards I3CO and I2COwas evaluated. The adsorption
equilibrium constants of 13C0 and l2C0 ( B 13 and B 12, respectively) on Na-LSX were
determined at 2 13-273K (Figure-3a).
The lower the temperature, the greater were B 13 and 12. B 13 was greater than B
12 at all the temperatures studied. In this case, the separation factor cx in the binary
system '3CO/'2C0 is defined by Equation 3.
a = B 1318 12
(3)
The temperature dependence of the 13C0 separation factor of Na-LSX was studied
(Figure-3b). The separation factor increased with increasing temperature and reached a
value of 1.1 at 213 K. This separation factor for gas-phase adsorption on Na-LSX is
extremely high compared with the cryogenic separation factors for 13CH4/12CH4
(1.003)
and for '3CO/12C0(1.007). The mechanism for the separation is illustrated in Figure4 it
can be assumed that the interaction energy (mainly vibrational energy) between 13C0and
Na at the SIU site, which forms the active adsorption site, is greater than that between
l2C0 and Na at this site, and the statistical residence time of 13C0at Na at the SIU site is
greater than that of 1 2 ~ ~ 3 ) .
362
s1.20,
Y
1 1 00
&?
Figure 3b).
Temperature dependence of 3CO/zC0
separation factor.
Figure 4.
3CO/2C0separation mechanism.
13
We are studying a system for the enrichment of a desorbed gas, by using a parallel
flow purge. When the adsorption is completed, the desorbed gas is supplied as a parallel
flow to the tower to substitute l2C0with 13C0for a three-tower VPSA unit (Figure 5).
We assumed that the enrichment performance of this VPSA unit can be calculated by
using a PSA simulation involving the parallel purge ratio R. The parallel purge ratio R is
defined in Equation 4.
R = Gp/Gd
(4) Gp; Gas rate of parallel purge, Gd; Gas rate of desorption
The relationship between the separation factor and the enrichment ratio was
calculated (Figure-@. As the CO separation factor of Na-LSX at 213K is 1.1, it is
predicted that the enrichment ratio for a single stage of this VPSA will be 2.5.
3.
%D
icw Ipr
(1w
Figure-5.
1.
Summary
Isotope separation by means of gas-phase adsorption is quite a new area of study. In
the screening test for selective adsorption of 13C0 on zeolite samples from the binary
system 3CO/12C0,it was found that Na-LSX (Si02/A1203ratio 2.0) adsorbed 13C0
selectively at low temperatures, and that its 13C0separation factor reached 1.1 at 213 K.
Compared with cryogenic separation, this separation factor is extremely high.
363
References
364
Molecular Sieve
Jeong-Geun Jee, Tae-Hoon Kwon, and Chang-Ha Lee'
Department of Chemical Engineering, Yonsei University, Seoul,Korea
Tel.: +82-2-2123-2762, Fax: +82-2-312-6401, E-mail: leech9vonsei.ac.k
Four different PSA cycles using CMS were compand for producing high purity oxygen over 99%
as well as the high productivity. The cyclic performances such as purity and recovery of four different
PSA processes were investigated experimentally under the n o n - i s o t h e d condition. The binary
955 ~01.46)mixture was used as a feed gas for PSA experiments. As a result, the process I with
purge (BD2) after product (BDI) step produced the oxygen with about 98% purity and 66% recovery
while processes ll and Ill with product (BD2) after purge (BD1) step produced about 99.2 to 99.9%
purity and 56% recovey. Also,the process IV replacing the purge step in processes I to III with PE step
produced the 9 product with very high recovery about 78% as well as high purity about 99.7%.
Because the cyclic performances of the suggested processes were significantly affected by the diffusion
rate, the modified LDF model incorporating concentrationdependent rate parameter that was evaluated
(wh,
from the Darken equation was proposed and successfully applied to the process simulation.
Key words: Q?PSA, CMS. concentrationdependent rate, nitrogen impurity
1. Introduction
High purity oxygen gases such as those having high purity of 99% or more are greatly
demanded industrially such as a welding gas, medical use, oxygen inhalation, combustion
process or a cylinder filling materials. Needless of this increasing demand on the high
purity oxygen, only a cryogenic process has been recognized as an effective method for
producing high purity oxygen product (99+ vol.%). However, its economical efficiency is
established only by the large-scale production of several tens of tons per day. Hence, when
a small amount of oxygen is used, the costs become extremely high because the above
high purity oxygen gas obtained from cryogenic plant is transported in the form of liquid
by using a tank lorry or packed in gas cylinders to supply it dividedly [ 11.
In that reason, many researchers suggested and have developed the PSA or VSA
processes for producing the high purity oxygen (99+ vol.%) since the mid 1980's. And the
most of these studies adopted a two-stage process consisted of zeolite bed for the firststage and CMS bed for the second. However, the additional equipment costs to set up the
second adsorption unit and the great product loss in CMS bed are a hindrance for
producing a high purity oxygen gas at a low cost. Therefore, the optimization of CMS
PSA and the development of new process to maximize the productivity need to stay
predominant over the cryogenic process.
In this study, the binary (Oz/Ar,9 5 5 vol.%) mixture assumed as the composition of the
products of equilibrium-controlled PSA process was used as a feed gas and CMS as
adsorbent. Also, four different PSA processes which have two-stage countercurrent
blowdown and one-stage cocurrent purge (or PE) steps with a different cycle sequence are
compared to c o n f m and develop both the high purity and high recovery oxygen
producing adsorption processes.
In a kinetically controlled separation system using CMS or zeolite 4A as adsorbents, it
is necessary to use more accurate rate model. Therefore, concentration dependent
diffusivity model based on Darken equation combined with Langmuir-Freundlich isotherm
was applied and each result was compared with the experimental data.
365
2. Mathematical models
All of the governing equations containing mass, energy, and momentum balances were
presented in our previous studies [2]. And, the boundary and initial conditions of
governing equations are presented below.
<Boundary conditions for feed pressurization, adsorption, cocurrent purge, and
pressurizing pressure equalization steps>
=o
; qi (z,O) = 0
(4)
The multi-component adsorption equilibrium was predicted by the LRC model and the
sorption rate into an adsorbent pellet was described by the following modified LDF
model.
<Adsorption rate model: Darken equation + L F isotherm>
Farooq et al. [3] introduced a variable di hi vi t y model to a kinetically controlled PSA
separation process. They pointed out that the Darken equation with the Langmuir
isotherms predicted the experimental data better than the constant difisivity assumption.
Based on those results, following concentration dependent diffisivity model was
presented as the adsorption rate models.
Though the ideal gas assumption would cause some error in predicting result, the
reasonableness of the above suggested models can be explained by HI0 (Higashi, Ito,
Oishi) model (Higashi et al., 1963) which is based on the random walk of molecules. The
HI0 model was same with the model 4 in this paper when the single layer adsorption was
assumed.
3. Experimental
The schematic diagram of PSA apparatus was shown in Figure 1. The adsorption beds
were made of stainless steel pipe with a length of 100cm, ID of 2.2cm, and wall thickness
of 0.175cm. The beds were packed with CMS from the Takeda chemical company.
Calibrated three resistance temperature detectors (RTD, Pt 1000) were installed at the
positions of 10, 50, and 80cm fiom the feed end in order to measure the temperature
variations inside the bed. The two pressure transducers were located at the feed and
product ends in order to measure the bed pressure variation. The feed flow rate was
366
Each process was consisted of conventional PSA steps such as pressurization (PR),
adsorption (AD), blowdown (BD), purge (PU), and pressure equalization (PE) steps.
However, the flow direction of all the steps except blowdown step was cocurrent.
Furthermore, the idle time was applied to keep the cyclic symmetry.
As can be seen in Table 1, the first blowdown step produces oxygen in the process I.
Then, the second blowdown gas is used as a purge gas for the other bed. Also, the one bed
is operated from the PR step to BDl step during the other bed inevitably undergoes idle
step. The desorption pressure at the end of BD1 step was 1.5atm at process I while 3.2atm
at processes 11 to Tv. However, the desorption pressure at the end of BD2 step was
ambient pressure at all the processes. Based on the cyclic sequence of process I, the
following modification was executed through process I1 and IV. In the process 11, the
purposes of two blowdown steps are opposite to the process I. Moreover, the idle step
(ID) between two blowdown steps is applied. And one bed is operated from @e ID1 step
to BD2 step during PR step in the other bed. The process I11 is nearly same as the process
I1 except non-idle step between two blowdown steps. Furthermore, only one idle step
exists and the PR step is hanged from the BD2 step to the middle of ID step. In the
process IV, the purge step in process I11 was replaced by PE step to maximize the
productivity and recovery with maintaining the high purity.
BED ll
PRf I A D T I
ID
BD13.
( 0 2 produced)
BD2 3.
(Purge)
PUT
367
PRf
AD?
PUT
BD14
BD2L
~~
0/0aObMOOOWmoQ9
368
Table
cyclic
Table
2. Ex 2. Experimental and predicted
A processes.
1 -
5. Acknowledgement
The financial support of the Carbon Dioxide Reduction and Sequestration R & D Center
(COO2-0103-001-1-0-0) is gratefully acknowledged.
6. References
1. Haruna K. Process for Producing High Purity Oxygen Gas from Air. US Patent
4,985,052, 1991.
2. Yang J., Lee C.-H., Adsorption Dynamics of a Layered Bed PSA for Hz Recovery from
Coke Oven Gas.AZChE J. 1998,44,1325.
3. Farooq, S.; Rathor, M.N.;Hidajat, K. A Predictive Model for a Kinetically Controlled
Pressure Swing Adsorption Separation Process. Chem. Eng. Sci.. 1993,48,4129.
4. Higashi, K., Ito, H., and J. Oishi, J. Aromic Energy SOC.,5, 846 (1963).
"."
369
1 Introduction
370
Experimentals
2. I
Materials
The deodorant activity of the deodorizing fiber was determined using chromogenic
gas detector tubes (Gastec, Japan) to determine the degree of photodegradation of the
odor molecule with Ti02 photocatalysts incorporated glass fibers in the gas phase during
illumination with UV lamp. The gas phase solution was prepared by the evaporation of
inserted 0.1 mL each solution (ammonia, methyl mercaptan and acetaldehyde). These
experiments were carried out using a reservoir chamber of a Pyrex flask (1 L) illuminated
by a 40W UV lamp (40 W,Ushio) with 20 cm distance between the UV lamp and sample
flask. For all experiments, the glass fiber supported with Ti02 was introduced into the
flask. Each 0.1 mL odor molecule solution was added to the sealed chamber flask.
Then, the flask was incubated for 10 min at 45 'C to make phase transition from liquid
phase to gas phase. For each chamber flask, the initial concentration of odor molecules
was about 500 ppm and UV light irradiation was started from the initial concentration.
371
20
30
40
--'
50
'
60
'
-1
70
2Theta (deg.)
Figure 1. Low angle XRD panems of Ti& supported on glass fiber calcinated at 450 OC,500 "C and 750 "C
afIer coating with 5 wt?hTi02 sol solution.
The representative low angle XRD difiactograms for TiOz coated glass fibers
calcinated at 450 "C,500 OC and 750 "C for 1 hr after coating with 5 wt?! Ti02 sol
solution are shown in Figure 1.
This shows that the main phases at 450 OC and 500 "C are pure anatase, but the
calcinations temperature higher than 500 OC,the rutile phase begined to appear and major
phase of rutile appeared on the calcinations temperature at 750 "C. The increase of firing
temperature above 500 OC results in the phase transition fiom anatase to rutile. This is
already reported in previous literature [3, 51. The anatase phase is the more
photocatalytically active allotropic form of Ti02.
Most of the previous studies have been tried with photocatalytic mineralization of
organic pollutants using active TiOz photocatalysts as an effective method for water and
air purification. However, the use of powdered photocatlysts in technological applications
has many manipulation problems during processing. Such technological problems have
been tried to be solved by incorporation of Ti02 photocatalysts on the solid substrate,
glass fibers or fibers. The incorporation of TiOz photocatalysts on the glass fibers or
polymer fibers can increase the active surface area of Ti02 photocatalysts by
immobilization on the surface. In the present study, the TiOz photocatalysts has been
tried to incorporate on the surface of glass fibers by sol-gel process. This kind of study
has not been reported so far.
372
The overall photocatalytic activity was chosen as the rate of decomposition of odor
molecules such as NH3, CH3SH and CH3CH0. Figure 2 shows that the degree of
photodegradation of NH3 molecule on the uncoated glass fiber, T i 4 photocatalysts
coated glass fibers twice and five times with 5 wt?? TiOz sol and calcinated at 450 'c.
The photodegradation rate of NH3 increased with increasing Ti02 sol coating number. The
same results were obtained for the photodegradation of CH3SH and CH3CHO.
Figure 3 shows the degree of photodegradation of NH3 during with Ti02
photocatalyst uncoated glass fiber, TiOz photocatalyst coated glass fiber with 3 wt?hTiOz
sol and calcinated at 450 "C,TiOz photocatalyst coated glass fiber with 5 W h Ti02 sol
and calcinated at 450 "C, TiOz photocatalyst coated glass fiber with 5 wt?! Ti02 sol and
calcinated at 500 "C and TiOz photocatalyst coated glass fiber with 5 wt?? Ti02 sol and
calcinated at 750 OC under the system of UV light illumination. The photodegradation
efficiency of NH3 molecule was greatly increased as increasing concentration of Ti02 sol
for the coating of glass fiber up to 5 wt?? at the cacination temperature of 450 "C. This is
interpreted as the increased concentration of TiOz sol solution results in the higher number
of coated TiOzphotocatalytic particle on the glass fiber surface. This enables to increase
the photodegradation efficiency of NH3 molecule. The photodegradation efficiency of
NH3 molecule was abruptly decreased with increasing calcinations temperature to 500 OC
and then 750 "C. This is possibly caused by the phase transition of Ti02 photocatalyst
coated on the surface of glass fiber from anatase to rutile phase. As it is already known,
the anatase phase has the higher photocatalytic effect than the rutile phase. So increased
calcinations temperature fkom 450 "C to 500 "C and furthermore to 750 "C decreases the
photodegradation efficiency of NH3 molecule due to phase transition of Ti02
photocatalyst coated on the surface of glass fiber. The same results were obtained for the
photodegradation of CHsSH and CH3CH0.
373
Acknowledgements
This study was supported by research grants from the Brain Korea 2 1.
References
1. Ollis D.F. and Al-Ekabi H., Photocatalytic Purification and Treatment of Water and
Air; Elsevier, Amsterdam (1993).
2. Aguado M.A. and Anderson M.A., Solution factors affecting the photocatalytic and
photoelectrocatalytic degradation of formic acid using supported Ti02 thin films J.
Photochem. Photobiol. A: Chem. 94 (1 996) pp 22 1-229.
3. Ding X.Z.and He Y.Z., Study of the room temperature ageing effect on structural
evolution of gel-drived nanocrystalline titania powders. J. Muter. Sci. Left. 15 (1996)
pp 320-322.
4. Hermann J.M., Tahiri H., Ait-Ichou Y., Lassaletta G. and Gonzales-Elipe A.R.,
Characterization and photocatalytic activity in aqueous medium of Ti02and Ag-Ti02
coatings on quartz. Appl. Catal. B 13 (1 997) pp 2 19-228.
5. Robert D., Piscopo A., Heintz 0. and Weber J.V., Photocatalytic detoxification with
TiO, supported on glass-fibre by using artificial and natural light. Catalysis Today 54
(1999) pp 29 1-296.
6. Brezova V., Blazkova A., Karpinsky L., Groskova J., Havlinova B., Jorik V. and
Ceppan M., Phenol decomposition using M"'/Ti02 photocatalysts supported by the
sol-gel technique on glass fibres. J. Photochem. Photobiol. A: Chem. 109 (1997) pp
177-183.
374
Introduction
Many inorganic ion exchangers have been studied for the removal of strontium and cesium ions, due
to their high selectivity for specific cations, thermal and radiation stabilities [1 51. In spite of those
advantages, they have been liited in their extensive applications because of the pressure drop
problem in column operation when they are used in microcrystallineor powdered form. To solve this
problem, in the case of synthetic zeolites, clay minerals are often used for pelletization, but it still
causes dissolution of clay minerals in aqueous solution.
For these reasons, the studies on the preparation of composite adsorbents using organic binder such
as polymer have been vigorously performed[6-12]. PAN(polyacrylonitri1e) has been viewed as one
of the most favorable binding materials, due to its physico-chemical properties such as excellent
bead formation, strong adhesive force with inorganic materials, good solubility for organic solvents
and chemical stability[lO].
Many researchers have studied the preparation and evaluation of the physico-chemical properties of
PAN-based composite adsorbents. In spite of some successful results on the preparation and
evaluation of the PAN-based composite ion exchangers, further studies on the preparation and
characterizationof various kinds of composite ion exchangers are still required.
Therefore this study focused on the preparation of PAN-4A and PAN-KCoFC composite ion
exchangers and characterization of their physico-chemical properties for the removal of Sr and Cs
ions in acid solution.
EXPERIMENTAL
To prepare PAN-KCoFC and PAN4A composite beads in which the inorganic powder content is
80 percent, the given amounts of inorganic powders were dispersed in DMSO(dimethylsu1furoxide)
solvent and then mixed with PAN(polyacrylonitri1e) polymer and a few drops of TWEEN-80
375
sufactant to make homogeneous composite dope. The detail procedures for preparation of
composite beads were the same as described in our previous study[ 1I]. Pore size distribution and
porosity of the prepared composite beads were measured by mercury porosimeter(Micrometrics,
AutoPoreIII). The pore structure and the distribution of the powders in the composite beads were
observed by scanning electron microscope(JE0L Co., JSM 5200).
Ion exchange tests for strontium and cesium ions were carried out to determine ion exchange
equilibrium isotherms in single component system. Ion exchange equilibrium isotherms were
obtained in batch system where the dosage of adsorbent and the pH were fixed constant at
0.2
1omWO.Ig and 2, respectivly, while the solution concentrations were varied between 0.0002
N.
q,bc
1+bc
376
where q (meq/g) and c (meq/mL) are the equilibrium concentrationsin the solid and liquid phases,
respectively, and q,(meq/g) is the saturation concentration in solid phase, and b, the coefficients
fitted to the experimental data.
The results in Fig. 7 indicate that the Langmuir model fits the data. The ion exchange capacities of
the PAN-KCoFC and PAN-4A composite ion exchangersobtained by modeling the experimental
data using Langmuir model were 1.07 meq (Cs)/g and 2.90 meq (S?)/g, respectively. These values
are almost 80% of those for KCoFC and 4A powders, respectively. This fact is obviously due to the
difference in inorganic contents between them. It also indicates, taking into account the 80%
inorganic content in the composite ion exchanger, that the PAN binder provides a smooth pathway
for ion transfer without blocking the adsorption sites.
CONCLUSION
PAN-KCoFC and PAN-4A composite ion exchanger beads containing about 80Y0inorganic powders
were prepared to evaluate ion exchange behavior for cesium and strontium in acid solution. The acid
and radiation stability tests confirmed that the composite ion exchanger beads were stable in acid
solutions of more than pH = 2 and against radiation dose less than I .89 MGy, respectively. Also, ion
exchange tests proved that the prepared composite ion exchangerscould effectively be used for the
removal of cesium and strontium ions in acid solution.
ACKNOWLEDGEMENT
This project has been carried out under the Nuclear R&D program by MOST
REFERENCES
1. Jung K.T., Shul Y.G., Moon J.K., OH W.J.,Waste treatment and immobilization
technologies involving inorganic sorbents, IAEA-TECDOC-947( 1992-1996) 193.
2. Marageh M.G., Husain S.W., and Khanchi A.R., Selective Sorption of Radioactive Cesium and
Strontium on Stannic Molybdophosphate Ion Exchanger, Applied Radiation and Isotopes 50
(1999) 459.
3. Mimura H., Letho J., Harjula R., Ion Exchange of Cesium on Potassium Nickel
Hexacyanoferrate(II)s, J. of Nucl. Chem. Technol. 34(5) (1997) 484.
4. Moon, J. K , Kim, H. T., Shul, Y. G., Lee, E. H. and Yoo, J. H., Ion Exchange Behavior for
Mixed Solution of Sr and Cs Ions with Potassium Titanate, HWAHAK KONGHAK 38(6)
(2000) 847.
5. Liang T., Hsu C., Sorption of Cesium and Strontium on Natural Mordenite, Radiochimica Acta.
61(1993) 105.
6. Mardan A., Rumana, A., Mehmood, A., RAza, S. M. and Ghaffar, A., Preparation of Silica
Cobalt Hexacyanoferrate Composite Ion Exchanger and Its Uptake Behavior for Cesium, Sep.
Puri. Technol. 16 (1999) 147.
7. Mariamichel A., Kishnamoorthy S., Synthesis and Characterization of New Composite Ion
Exchangers, Scientific & Industrial Research 56 (1 997) 680.
377
8. John J., Sebesta F., Motl A., Composite Absorbers Consisting of Inorganic Ion-Exchangers and
Polyacrylonitrile Binding Matrix. Leaching of Cs-137 fkom Cemented NiFC-PAN Absorber,
Radiochimica Acta. 78 (1997) 131.
9. Sebesta F. and John J., An Overview of the Development, Testing, and Application of
Composite Absorbers, LA-12875-MS 1995.
lo. Sebesta F., John, J., Motl, A. and Watson, J., Proc. 5 Int. Conf. on on Radioactive Waste
Management and Environmental Remediation 1995, Berlin, p.36 1.
11. Moon J.K., Kim, K. W., Jung, J. H., Shul, Y. G. and Lee, E. H., Preparation of
Organic-inorganic Composite Adsorbent beads for Removal of Radionuclides and Heavy Metal
Ions, Radioanalyticaland Nuclear Chemistry, 246(2) (2000) 299.
12. Xue T.J., McKinney A., Wilkie C.A., The Thermal Degradation of Polyacrylonitrile, Polymer
Degradation and Stability 58 (1997) 193.
@)
(a)
Figure. 2. SEM images of the fracture(a) and magnification of macro pores(b) of PAN-KCoFC
composite ion exchanger beads.
378
(a)
( b)
Figure 4. SEM images of the fiacture (a) and magnification of macro pores(b) of PAN-4A
composite ion exchanger beads.
Average Pore
Diameter
Porosi
0.08 Frn
75.70
Figure 5. Pore size distribution and porosity data of the PAN-KCoFC composite ion exchanger
379
Average Pore
Diameter
0.14 pm
Porositv
73.67
Figure 6. Pore size distribution and porosity data of the PAN-4A composite ion exchanger
'f
1.o
0.0
0.w
0.05
0.w
0.10
0.05
0.10
0.15
Figure 7 Ion exchange isotherms of the composite ion exchangers and the pure inorganic powders.
(a) PAN-KCoFC and KCoFC, (b) PAN-zeolite 4A and zeolite 4A.
380
0.20
Introduction
Recently, rotor-type adsorption systems attract much attention, because the systems
can effectively control humidity and air pollutants such as volatile organic compounds
(VOCs), nitrogen oxide ("Ox) and sulfuric oxide (SOX). Gas remediation efficiency is
principally concerned to the gas capturing ability of the adsorbents impregnated into the
ceramic honeycomb rotor such as zeolite, silica, activated carbon, etc. Therefore, it is one
of the most important works to develop the adsorbent with good absorption-desorption
behaviors.
Nowadays, rotor-type dehumidification and air-conditioning systems are spotlighted
and begin to be industrialized, because the systems don't use CFCs which are known to be
representativechemicals destroying an ozone layer in earth. Generally, silica gel is used as
a dehumidifier in the dehumidification and air-cooling rotor. Therefore, it is important to
improve the dehumidification efficiency of silica desiccant in this field.
The dehumidification efficiency of silica desiccants very depends on the synthesis
and aging conditions such as pH[1,2]. But, there seems to be a limit to improve the
dehumidification efficiency by using pure silica desiccants.
Recently, Kuma et uf. have reported that the M-rotor treated with aluminum sulfate
showed better performance for dehumidificationthan the S-rotor treated sulfuric acid[3,4].
Dinnage et uf. have reported that the titanium silicate-impregnated ceramic sheet shows
better dehumidificationbehavior than the aluminum silicate-impregnated sheet[5].
In the present study, the silica ceramic sheets with Ti, A1 and Mg ions modified were
prepared and then their dehumidificationbehaviors were investigated. Finally the origin of
the superior dehumidification efficiency of Ti or Al-modified silica desiccants will be
discussed.
381
Methods
Ceramic sheets were prepared by a modified paper-making process with using AI2O3
and Si02 fibers. The detailed preparation conditions of the ceramic fiber sheet will be
reported, elsewhere.
Metal(Ti, Al, Mg) silicates were impregnated into the ceramic sheets by as-following
two-step process. The first step was the process to prepare silica-embedded ceramic sheets
and the second step was to incorporate Ti, Al and Mg ions into the silica-impregnated
ceramic sheets.
At first, the ceramic sheet with thickness of 0.2mm was tailored to the rectangular of
which width and length was 50 and 60mm, respectively. Then, the rectangular ceramic
sheets were dipped into a sodium silicate aqueous solution at 25C for Smin. The sodium
silicate aqueous solution was prepared by mixing 80wt?h of sodium silicate glass (No.3,
Shinheungjpsan, Korea) and 20wt?h of water. The dipped ceramic sheet was dried at
80C for 5min. The ceramic sheet was dipped and dried at the same conditions, one more
time. The dried ceramic sheet reacted with a sulfuric acid aqueous solution for 6hrs to
form silica gels on the ceramic sheet. In the sulfuric acid aqueous solution, the content of
the sulfiuic acid (Aldrich Chemical Co., USA) was 5wt%. After the silica gel formation
process, the silica-coated ceramic sheets were aged in the sulfuric acid aqueous solution at
pH 3 for 17hrs, and then washed in pure water at 25C for 5min to remove some
impurities such as sodium and sulfate ions from the silica-impregnated ceramic sheet.
The silica-impregnated ceramic sheets were dipped in three kinds of metal sulfate
aqueous solutions at 45OC for 3hrs. In the metal sulfate aqueous solutions, 1Owto/o of
Ti(S04)2 (Junsei Chemical Co., Japan), A12(S04),(Showa Chemical Co., Japan) and
MgS04 (Junsei Chemical Co., Japan) were dissolved, respectively. The dipped
silica-impregnated ceramic sheets were washed in pure water at 45C for lhr to remove
sulfate ions. After the washing process, the metal silicate-impregnated ceramic sheets
were dried at 200C for lhr and then used for the evaluation process of dehumidification
behavior.
Microstructure and pore structure of the prepared ceramic sheets were characterized
by SEM(XL30, Phillips, Holland) and BET(ASAP2400, Micrometrics, USA) analysis.
The dehumidification efficiency was evaluated by measuring the weight increment of the
adsorbent-impregnated ceramic sheets before and after the exposure to the 50% of relative
humid condition at 35OC for 3hrs. Also, the H20 adsorption isotherms were obtained by a
lab.-made mass equilibrium adsorption system on which the suspension balance
(Rubertherm magnetic suspension balance) is attached on.
3
Figures l(a) to (c) represent SEM images of (a) bare, (b) silica-impregnated and (c)
titanium silicate-impregnated ceramic sheets. In the bare ceramic sheet, there is large open
volume between ceramic fibers and the adhesion between ceramic fibers was induced by
the silica sol, an inorganic binder. On the other hand, in the silica or titanium
silicate-impregnated ceramic sheets, there was no free volume between ceramic fibers. In
the two cases, the open volume was fulfilled by the impregnated silica or titanium silicate
adsorbents. It was interesting that many microcracks were shown in the titanium silicate
382
phase located between ceramic fibers, compared with the silica-impregnated ceramic
sheet.
Fig. 1 SEM images of (a) bare, (b) silica-impregnated and (c) titanium
silicate-impregnated ceramic sheets.
w1
wz
(9)
0.4140
(9)
0.8043
ws
(9)
0.9308
Dehumidification
efficiencY (%1
32.41
0.7601
0.8687
32.52
Magnesium Silicate
0.4262
Aluminum Silicate
0.4140
0.7903
0.9222
35.05
Titanium Silicate
0.41 50
0.8036
0.9528
38.39
W, : weight of ceramic sheet Mom impregnation. Wz : weight of ceramic sheet after impmgnafhm. WS : weight of
adrorb.nt-impregMted ceramic shed after dehumidification teat at 35C and 50% of relative humidity, Dehumidification
efficiency (K) = IWs-W,) I (Wz-W,) x 100
383
384
P-
88
-B
IW
100
0
> 5 0
0
0.0
0.2
0.4
0.8
1.0
0.8
Relative Pressure
Fig. 3.
.....
10
100
lo00
Conclusion
The ceramic sheets with aluminum silicate or titanium silicate adsorbents showed
better dehumidification behavior than the silica and magnesium silicate-impregnated
ceramic sheets. The superior dehumidification efficiency originates om the well
developed micropores.
385
Acknowledgements
This work was fmancially supported by National Research Laboratory program (Korean
Ministry of Science and Tschnology).
References
1. Kuma, Shirahama, Izumi, US. Patent 5,753,345 (1998).
2. Kuma, Toshima, Shirahama, Noriaki, Izumi, Horaki, US. Patent RE37,779 (2002)
3. Kuma, Tosimi, Okano, Hiroshi, US.Patent 4,911,775 (1990)
4. Kuma and Hirose, J. Chem. Eng. Japan, Vol. 29, No. 2,376 (1996).
5. Dinnage, Paul A., Tremblay, Gerard, U.S.Patent 5,505,769 (1996)
386
Introduction
387
2. I
Methods
Zirconia Cottoit&@nthesis
When 0.4 M ZrOCI2.8H20 was used, the weight fraction and the pH of the final
colloidal solution were -5 wt.% and -0.5, respectively. To compare the PICA
performance of the synthesized colloids with that of the Nyacol colloids, it was
concentrated by reverse-osmosis. For reverse osmosis, stirred cell from Amicon with an
ultrafiltration membrane (50,000 MW cut-off) was used and pressure up to 50 psi was
applied. After reverse osmosis, water was added to increase the pH. By repeating this as
many times as necessary, 20 wt.% colloids at pH 1.75 were prepared.
For a PICA experiment, urea (U) from Fisher Scientific company was added to a new
30 ml polystyrene reactor. Formaldehyde solution (F) from Mallinckrodt company in a
separate beaker was added to a reactor to start the reaction. ([U]+[F])/[Zr02] and [U]/[F]
ratios were kept at 1.5 and 0.75, respectively. Reaction was quenched with water when the
secondary particles started appearing (-15 min). Particles were washed with water three
times, then with isopropanol twice. The particles were, then, filtered and dried in a
vacuum oven. At this point, the weight of particles was measured. The particles were
burned at 350 OC for two hours to remove polymers on the surface, then sintered at 750 OC
for six hours and 900 "C for three hours. After burning and sintering, the weight of
particles was again measured to get yield and polymer content. The surface area and the
pore size distribution of these particles were measured using Micromeritics nitrogen
sorptometer. S-800 SEM (scanning electron microscopy) from Hitachi was used to
observe the final particles.
3
3. I
Results
Zirconia Colloids Synthesis
We find that the synthesis as reported by Bleier and Cannon [7], but changing the salt
concentration, is capable of reproducibly making 100 - 250 nm (average diameter)
zirconia colloids with a narrow distribution (standard deviation always smaller than -50
nm). However, we note that there is a maximum in the final particle size at 0.2 M
ZrOC12.8H20 (for which the pH is 0.9). Figure 1 shows the effect of the initial salt
concentration on the final particle size. Note that there is a correlation between the salt
concentration and the pH of the solution; the pH falls with higher salt concentration
because of zuconia ion hydrolysis. If too much salt is supplied (> 0.4 M),the yield is
limited to L 80 %. The highest concentration we obtain (pH < 0.9) is ca. 5 wt. %.
300
250
200
150
100
50
0'
0.0
0.2
0.4
0.6
0.8
[ZrOCI;8H20] (M)
1.1
0.9
0.5
0.4
PH
Figure 1. Final particle size vs. initial [ZrOC12.8H20] (the axis at the bottom indicates the initial pH of the
solution).
3.2
In order to compare the PICA performance of the synthesized colloids with that of
commercial colloids from Nyacol, 5 wt.% colloids were concentrated to 20 wt.% and pH
was adjusted to 1.75 as described in the experimentalsection.
After urea and formaldehyde were added to our colloids, small particles appeared in
-5 minutes, and they grew until the secondary particles appeared in -15 minutes. This is
shilar to the PICA performance of the Nyacol colloids [1,2]. After sintering, the yield
was -7 % and the polymer content was -70 %. The surface area of these particles was -20
m2/g. Figure 2 shows the SEM pictures of final PICA particles made from our colloids;
clearly, they are very porous and show the irregular shapes.
4
4. I
Discussion
Zirconia Colloid Synthesis
One spec%= goal was to see whether simply adjusting the salt concentration could
provide starting marerid for PICA process. Of our trials, a solution of 0.4 M
ZrOC12.8H20with
HCI is optimal for the procftrction of monodisperse -100 nm
colloids because:
t 0p.m
Figure 2. SEM micrograph of PICA particles made from the synthesized colloids.
Since we would ideally like to produce even more concentrated sols (ca. 20 wt. %).
we wish to better understand the effect of the initial salt concentration. It is helpful to
consider the solubility of zirconia in water. The solubility of zirconia is reported by Baes
and Mesmer [ 111. At low pH range the solubility increases sharply with acidity. For the
systems with no added acid, the limited yield - when the initial concentra$on of salt is
higher than 0.4 M (pH 50.4) - may be attributed to the very high solubility of zirconia at
low pH.
4.2
The differences of the final PICA particles using the synthesized colloids and the
Nyacol colloids are summarized in Table 1. It should be noted that the reactant
concentrations and the burning procedure were optimized for the Nyacol colloids, but not
for our colloids. The different polymerization kinetics in the PICA reactions using our
colloids instead of Nyacol colloids causes the very high polymer content, which also leads
to lower yield, smaller particles, bigger pores, irregular shape, and a broader distribution.
We also ascribe big pores to the unoptimized burning procedure. Thus, in order to
reproduce PICA particles made from Nyacol colloids, it is essential to reoptimize the
reactant concentrations of PICA reactions using our colloids.
Table 1 Comparison of PICA particles using the synthesized and the Nyacol (V-66 batch) colloids
Synthesized colloids
Yield (%)
7.0
15.0
70.0
40.0
1000.0
400.0
Final distribution
broad
narrow
Shape
irregular
spherical
1.O 4.0
3.0 5.0
Acknowledgements
References
1. Amen M.J., Kizhappali R., Cam, P.W. and McCormick A.V., J. Muter. Sci.29 (1994)
pp.6123-6130.
2. Sun L., Annen M.J., Lorenzano-Porras F., Can P.W. and McCormick A.V., J.
Colloid Intevace Sci. 163 (1994) pp. 464-473.
3. Iler R.K. and McQueston H.J., US Patent No. 4,010,242 (1977).
4. Blumenthal W.B., The Chemical Behavior of Zirconium (D.Van Nostrand Company,
Inc., New York, 1958) pp. 125-132.
5 . Matsui K. Suzuki H. and Ohgai M., J Am. Ceram. SOC.78 (1995) pp. 146-152.
6. Aiken B. Hsu W.P. and Matijevic E., J. Muter. Sci. 25 (1990) pp. 1886-1894.
7. Bleier A. and Cannon R.M., In Better Ceramics Through Chemisny 11, ed. by C.J.
Brinker, D.E. Clark and D.R. Ulrich (Materials Research Society, Pittsburgh, 1986)
pp. 71-78.
8. Fegley B., White P. and Bowen H.K., Am. Ceram. Bull. 64 (1985) pp. 1115-1120.
9. Bartlett, J.R.,Woolfiey J.L., Percy M., Spiccia L. and West B.O., J. Sol-Gel Sci.
Tech. 2 (1 994) pp. 2 15-220.
10. Lerot L., Legrand F. and De Bruycker P., J Muter. Sci. 26 (1991) pp. 2353-2358.
11. Baes C.F. and Mesmer R.E., The Hydrolysis of Cations (John Wiley & Sons, New
York, 1976) pp. 152-159.
391
1 Introduction
392
2. I Materials
The soil used in all experiments was obtained from coal-mine region in Samchok,
Korea. Soil sample was air-dried and screened through a US standard No. 10 mesh (2mm)
sieve to remove coarse firagments. The fraction of organic carbon in the soil sample was
determined to be 0.14% from TOC analysis using MULTI N/C-300 Total Carbon
Analyzer (Analytic Jeni. AG., Germany). Phenanthrene. SDS and radio-labeled
phenanthrene (9-14C, 13. IrICV-hnol) were purchased from Sigma Chemical Co.(St. Louis,
MO USA). APU particles were synthesized by polymerization of urethane acrylate
anionomers (UAA) as described by Kim et al. [12]. Table 1 shows the molar ratios of
reagents used in the synthesis of the UAA precursors. The hydrophilicity and the
hydrophobicity of the synthesized polymer can be modified by changing these molar
ratios. APU made from UAA 2:8 has the highest hydrophilicity, while that from UAA 6:4
has the highest hydrophobicity.
Table 1. The molar ratio of reagents in the synthesis of various APU particles
mn-m-p
Types of APU
UAA 218
UAA5:5
UAA 6:4
--
Reagents
PTMG/DMPA/TDI/2-HEMA
PTMGIDMPAITDI/2-HEMA
PTMGIDMPNTDIR-HEMA
----*
Molar ratio
0.2/0.8/1.5/1.5
0.5/0.5/1.5/1.5
0.6/0.4/1.5/1.5
-*,?,**vc-<y
2.2 Methods
2.2.1 Adsorption of SDS or APU particles onto soil
A batch equilibrium method was employed to measure the sorption isotherm of SDS or
APU particles in the soil-water system. Samples were prepared in duplicate by mixing
1.OOg of soil and SDS or APU solutions (IOmL) of various concentrations in glass vials
with an open-port screw cap, which was fitted with a Teflon-lined septum. The vials were
shaken in a mechanical rotary tumbler for 72 h at room temperature. After equilibrium
partitioning was attained, 5 mL of the samples were centrifiged at 15000g and
concentrations of SDS or APU in the supernatants were estimated as total organic carbon
fractions using Pharma Total Organic Carbon Analyzer.
393
transferred into scintillation vials containiig lOmL of Ecolume cocktail, and the
concentration of 14C-phenanthrenein the aqueous phase was measured using a Liquid
ScintillationCounter (LSC).
2.2.3 Extraction of phenanthrene sorbed in soil using APU or SDS
In the sorption experiment of APU particles or SDS onto soil, APU particles exhibited
relatively low degree of sorption onto soil than SDS (Figure1.). It is believed to be due to
the highly cross-linked structure of APU. Sorption isotherm of phenanthrene in the test
soil was shown in Figure 2. As shown in Figure 3, phenanthrene showed the lower
solubility in APU solutions than in SDS solutions. Hence APU particles seem to have the
lower affinity with phenanthrene than SDS with phenanthrene. However, at low
concentrations ofAPU particles or SDS (below 2100mg/L,CMC of SDS), APU particles
showed the higher extraction efficiency of sorbed phenanthrene than SDS did (Figure 4).
At higher concentrations of APU particles or SDS,the extraction efficiency of APU was
almost same as that of SDS,even though APU particles exhibited the lower solubilization
of phenanthrene than SDS micelles in the absence of soil. Extraction of phenanthrene
from soil using interfacial agents seems to depend not on their affiity with phenanthrene
but on the degree of their sorption onto the soil.
2.0
..... ..o...
..
U A A 2:8
1.8
t-UAAS:S
3--
0.4
0.2
...
...
....
.......
!
0
Figure 1. Distribution of SDS or APU between soil and aqueous phase. (F& =
[SurfJJ([Surfl,*f,)
= ([mg of surfactant sorbed in soil/g of soil])/([mg of
surfactant in aqueous solution/mL]*fractional organic carbon content of the
soil)
394
w5
0.0
0.1
0.3
0.2
0.4
0.5
........ 0 .......
395
0.5
CI
0.4
ui
1
z
Y
F
5
0.3
(II
a
B
0.2
P,
-#
e
.s
*
0.1
I
0.0
0
Aknowledgements
396
8.
397
YOSHIMI SEIDA
Institute of Research and Innovation, Takuda 1201, Kashiwa, 277-8501 Japan
E-mail: seida@iri.or.jp
Introduction
Porous carbon materials have been considered as an effective material for many
engineering use such as catalytic support, battery electrode, capacitor and gas storage
material. For such applications, the carbon materials should have high mesopore content
so that ions and large molecules can penetrate and adsorb efficiently in pores. Mesopores
act as the main transport arteries for the adsorbates and contribute significantly to their
adsorption. Reports that study the synthesis of the mesoporous carbons have been
increasing recently [4,6,7,9,10]. Synthesis through activation of precursors with metal
ions is one of the ways to obtain the mesoporous carbons [2,8]. However, there are not
many reports that studied rigorously the effect of the metal ions andor metals on the
mesopore formation. In the present study, synthesis of mesoporous activated carbons was
performed through a heat-treatment of an ion-exchange resin with Fe ion in a series of
gases. The synthesized activated carbons were characterized in terms of specific surface
area, pore size distribution, produced phase and crystallite size of the produced Fe
compounds in the activated carbons. Effects of the condition of heat-treatment
(carbonization) and the iron in the resin on the mesopore formation of the activated
carbons were examined to elucidate a role of the introduced Fe on the mesopore
production.
398
Results
From TG/DTA analysis of the dried resin with Feythe resin was found to show a major
weight loss with an exothermic thermal decomposition at 473-873 K followed by a slight
endothermic weight decrease at above 873K. About 2 0 W ? of the carbonized resin
remained at 1273K.
(a)IW%N,
(b)25%H,
(c)IW%H,
Figure 1 shows the SEM photographs of the activated carbons synthesized in the
series of gases at 973 K (Sample
No.3, 7 and 13). The resins lost their initial snherkal
shape after the heat-treatment and showed expanded single carbon b lo ck The
carbonization of the resin occurred through the
a-Fe
liquefaction at 473-87313. Macroporous
I
structure was observed in the crushed samples
synthesized in 100% H2 (Fig.1c). On the
contrary, non-porous structure with glassy
surface was observed in the crushed samples
synthesized in 100% N2 and 25% H2 (Fig.la,
b). Any iron-based particles were not observed
by the SEMEDX analyses of the surfaces
shown in Fig.1 under their resolution except
for the samples with Q/Q~c=0.41 and 0.53
0
10 20 30 40 50 60 70
(No.5,9 and 16).
2 0
Figure 2 shows the XRD diffraction
fig. 2 XRD pamm of me semples
patterns of the samples No. 3, 7 and 13.
Formation of graphite-like carbon, which was
with Fe
identified from the diffiction peak at around
---- lWhH, 26.2 degree [4], was observed in all the
samples synthesized with Fe. Dominant Fe
compounds produced in the activated carbons
were identified from the diffiction patterns as
FeJC for the samples synthesized in 100% N2
and a-Fe for the ones synthesized in 100% H2,
respectively. The a-Fe produced in the
activated carbons was hardly removed by a
1
10
100
repeating wash using 1N HN03 and N&Cl
Pore diameter [nm]
under ultrasound. The a-Fe was stable against
Fig3 Pore size dishibution, Dv, of
oxidation for more than one year in the air.
the synthesized activated carbons
These results indicate that the a-Fe Droduced
in the activated carbons may =be
0.8
immobilized in a carbon matrix.
The pore size distributions, D,, of
o
the synthesized samples (Sample No.1,
3 , 7 and 13) are shown in Figure 3. The
samples synthesized with Fe contain
mesopores with 2.0-30 nm in diameter. $ 0.4
The pores with more than 4 nm in 2
diameter increased largely by the g
synthesis in 100% H2. The sample a 0.2
synthesized without Fe did not produce
mesopores. Figure 4 shows the effect of
the introduced amount of Fe and gas
0.10 0.53 0.10 0.41 0.10 0.41
during the heat treatment on the pore
and above
nm in
Fig.4 Effect of introduced amount of iron on the pore
diameter. The total pore volume
volume of the activated carbons synthesized at 973K
in a series of gases
increased with the increase of Fe in the
Q,Q,
,"
-P
Discussion
The introduced Fe contributes to increase the specific surface area and mesopore of the
activated carbon as shown in Fig.3. The Fe ions migrate in the resin to form nanoparticles
of Fe compounds during the heat-treatment. Along with the formation of the particles of
Fe compounds, the mesopore of the activated carbon may also be produced at the sites
where the Fe compounds migrated. In the case of a-Fe, the a-Fe particles may act as a
catalyst for gasification of the carbons around the particles in Hz atmosphere at above
401
873K [1,3], which would result in the drastic increase of the mesopore in the activated
carbons synthesized in 100% H2. Based on these mechanisms of the mesopore
production, control of the particle size of the Fe compound should be important to
produce mesopores. The size of the particles can be controllable through adjustment of
the introduced amount of Fe in the precursor, dispersion of Fe at the preparation stage of
the precursor and the condition of heat-treatment such as heating rate and treatment
temperature. The conditions should be optimized depending on precursors. We also
confirmed the effectiveness of the present method in selective increase of mesopores of
activated carbons using used coffee beans and tea leaves wastes. The results will be
presented in the next paper.
5
Conclusion
The mesoporous activated carbons with large mesopore volume can be obtained from the
resin exchanged with Fe ion through the heat-treatment in hydrogen atmosphere. The key
factors to obtain the highly mesoporous activated carbon are (1) the introduction of Fe
with high dispersion and (2) the size control of Fe compounds produced during the heattreatment through adjustment of the introduced amount of Fe and the condition of heattreatment.
References
402
Introduction
403
Experimental
2.1. Reagents
The chemicals used in this study were sodium chloride, magnesium chloride, calcium
chloride, potassium chloride, trichloroacetic acid (TCA), trifluoroacetic acid, a-d glucose,
sodium citrate dihydrate, sodium hydrogen phosphate, hydrochloric acid, and iron (11)
sulfate heptahydrate. These chemicals were purchased from Sigma (St. Louis, MO, USA).
The HPLC grade solvent, acetonitrile was 6om J. T. Baker (PhilipsburgNJ, USA). Water
was distilled and deionized prior to use.
(min)
vol. %
100
90
10
80
20
10
65
35
20
50
50
30
100
404
(a)
(b)
Figure 1. Photograph showing the sample preparation process. (a) leukocytes in the upper
side and erythrocytes in the lower side (b) peptides in the upper side and
erythrocytesand proteins in the lower side.
The peptide extracts by TCA from the fresh human blood and the stored human bloods
during 3, 5 , and 7 days were experimented. The specific character of the peptides
formation is a change in quantity of the peptides in the extract. The accumulation of the
peptides in the extracts probably explained by the fermentative peptides proteolysis,
which is the decomposition process of the proteins and peptides catalyzed by the special
ferments.
The identification of the some peptides was carried out in this work. Some standard
substances of the peptides for the procedure of the identification were used. Other
peptides were identified based on the retention times by previously constructed database.
The qualitative determination of the peptides in the extract was made on the retention
times of the standard peptides substances. The chromatogram of the peptides by fresh
sample is shown in Fig. 2, while that in 7 days is shown in Fig. 3. The five peptides in the
extracts were identified, and for coding structure of the peptides we used one letter for a
code.
12
16
Time (min)
Figure 2. Separation of peptides from human blood by RP-HPLC (fresh sample, injection
volume lo,&)
0.08
0.04
0.00
12
18
20
Time (rnin)
406
human blood caused degradation. These conditions had influence on the formation of the
peptides. It is expected that more concrete understanding of peptide-separation will
provide very useful information to the hnction of peptides in human blood.
Acknowledgements
The authors gratefully acknowledged for the financial support by Center for Advanced
Bioseparation Technology in Inha University.
5
Reference
1 . A. A. Karelin, M. M. Filippova, 0. N. Yatskin, E. Yu. Blishchenko, I. V. Nazimov,
and V. T. Ivanov, Proteolytic Degradation of Hemoglobin in Erythrocytes Yields
Biologically Active Peptides, Peptide Science, 4 (1 998), 27 1-28 1.
2. V. Casal, P. J. Martin-Alvarez, T. Harraiz, Comparative prediction of the retention
behaviour of small peptides in several Reversed-phase high-performance liquid
chromatography columns by using partial least squares and multiple linear
regression, Analytica Chimica Acta, 326 ( I 996), 77-84.
3. Zukowski J., Pawlowska M., Nagatkina M. Armstrong D. W., Highperformance Liquid Chromatographic Enantioseparation of Glycyl dipeptides and
tripeptides on Native Cyclodextrin Phases, Mechanistic Considerations, Journal of
Chromatography.629 (1993), 169- I 79.
4. T. Harraiz, Sample preparation and Reversed-phase high-performance liquid
chromatography analysis of food-derived peptides, Analytica Chimica Acta, 352
(1997), 119-139.
5. Florance J., Galdes A., Konteatis Z., Kosarych Z., Langer K., Mamtcci C., High
Performance Liquid Chromatographic Separation of Peptide and Amino Acid
Stereoisomers,Journal of Chromatography.41 4 (1 987), 3 13-323.
6. Apffel A., Peptide mapping, Journal of Chromatography. 712 (1995), 177-190.
7. Seiler P., Peptide bank regulatory peptides, Journal of Chromatography A . 852
(1999), 273-283.
8. lvanov V. T., Karelin A. A., Philippova M. M., Nazimov 1. V., Pletnev V. Z.,
Hemoglobin as a source of endogenous bioactive peptides: the concept of a tissuespecific peptide pool, Peptide Science, 43 (1997), I 7 I - 188.
9. Blishchenko E. Yu., Mernenko 0. A., Yatskin 0. N., Ziganshin R. H., Philippova M.
M., Ivanov V. T., Karelin A. A., Neokyotorphin and neokyotorphin (14):secretion
by erythrocytes and regulation of tumor cell growth, FEBS Lett, 414 (1997), P. 125128.
407
Introduction
Experimental
2.1 Reagents
The Acanthopanm senticosus was purchased from Korea Siberian Ginseng
Association(cily, Korea). Methanol, acetonitrile and twice distilled water were filtered by
using decompressing pump (Division of Millipore, Waters) and filter film(FH-0.5 m).
The extracted sample was concentrated using a rotary evaporator from LABO-THEM
SW 200, Resona Technics Co.(city, Korea)
3. I Solvent &traction
Because many kinds of components existed in Acanthopanax senticosus, when the
trunk powder of the plant was extracted by ethanol, a large amount of impurities were
included except for the interest component acanthoside-D. As acanthoside-D is soluble in
water, a partitioning step with waterhexane as the partition solvents was used to remove
the impurities before fiuther refining. In this procedure, non-polar components were
moved into hexane layer and polar components including acanthoside-D were moved into
water layer. The water layer was concentrated, and then it was dissolved in methanol and
refined by the preparative recycle HPLC.
250
'i
200-
150
100
Acanthoride-D
lo
15
20
25
30
35
410
411
10
15
20
Time (mia)
412
I Introduction
Various materials have been used for biosorbents to remove toxic metals from process or
groundwater. Ones selected by the US Army Corps of Engineers in 1997 [l] for further
study include chitosan, peat moss, seaweed (algae), and lignin. Work in our laboratory has
shown that uptake by peat moss [2] and algae [3] occurs by an ion exchange mechanism in
which an existing proton or metal is displaced in the process:
M2' + 2 (HX) R (MX2) + 2H'
M ~ ++ (c~x,)R ( M X ~+) Ca2+
Recently we reported that uptake by a krafi pine lignin also occurs by these ion exchange
reactions [4].
Lignin is a major component of plants where it serves as a binding agent for cellulose
and other materials, and the kraft process of paper production, heating with alkali and
sulfide, produces polyhydroxy phenolic, carboxylic acid, and sulfide functional groups in
a soluble black liquor mixture [5]. Acidification precipitates this modified lignin as a
powder, hereafter referred to as lignin, a 20B30% by product in the manufacture of paper.
Constancy of values of K,"
and K,, for wide ranges of initial concentrations
demonstrate validity of these displacement processes and prove that uptake in these systems
is not simple adsorption. Furthermore, it was found that the stoichiometry for Sr and Cd
uptake by Ca-loaded lignin is one metal sorbed for one Ca released. This observation for
metals of very different binding strengths is difficult to rationalize with adsorption models,
but is in complete agreement with an ion exchange process.
413
The finely divided powder (200-300 mp) used in the above study is difficultto separate
from purified water in large scale and is not suitable for column applications. This work
describes a novel formulation of this powder into a solid workable into various forms
effective for heavy metal uptake.
2 Methods
Kraft pine lignin, kindly provided by MeadWestvaco, Charleston, SC as their lndulin AT
product, was converted to a completely acidified form, HLg, by treating a suspension of 6.0
g of lignin in 40 mL of water with dilute nitric acid to pH 1.5 and stirring for 30 min. After
centrifugation,the solid HLg was washed twice with water and to a suspension in 40 mL of
water was added calcium hydroxide powder (50 mg per g HLg, unless stated otherwise).
After stirring for several hours, the resulting CaLg was centrifuged, washed twice with
water, and air-dried overnight.
A plastic material was made by mixing 1.O g of CaLg with 0. I g of clipped, glass wool
and then adding 0.6 mL of DMF which contained 60 mg of a polysulfone resin (Aldrich,
average MW 30,000). Thorough mixing gave a uniform mass of putty-like, plastic material
which could be rolled into a cylinder. Flattening by further rolling gave a strip which could
be cut into various shapes: strips (typically 0.3 x 4 x 10 mm for 0.1 g), chips, or flat pieces.
Hard material can be formed by heating for 20 min at 70 OC and then cooling to RT. This
hard material is referred to as modified lignin MLg.
Concentrationswere determined by atomic absorption (AA) with a Perkin-Elmer Model
2380. For amounts of sorbed metals, the solid was treated with 0.01 M HN03 for 30 min
followed by centrifugation and AA analysis of the aqueous layer.
3 Results show uptake occurs by ion exchange with potential practical applications
3.1 Recovery of DMF
A strip of MLg made with 20 mg of calcium hydroxide was heated to 120 OC and held at that
temperature of 20 min. A stream of nitrogen passing over the sample in a glass tubing was
collected at Dry Ice temperature. The weight of condensed gases was essentially the same
as the amount of DMF used in the sample preparation.
3.2Structuralstabikty in water
A 40-mm long plastic strip was glued to the end of strip MLg. This plastic strip seived as a
pointer to provide more accurate measurements. The MLg strip was extended horizontally
40 mm from the edge of a support block and a small weight (ca. 0.3 g) hung at the junction
to cause a bending in the MLg. The extent of bending was measured as the vertical
deflection of the pointer end and the sample immersed in water. After one week, the sample
was dried at 70 OC for 20 min and re-tested. After six weeks there was no significant change
in the degree of bending.
414
Strips of MLg, ca. 0.2 g each, were immersed in 20 mL of solutions 0.5 to 10 mM in Pb. Pb
uptake occurred with an equivalent amount of Ca released. Similar results were found for
Ca release on Cd uptake. This Cd uptake was rapid, as shown by an experiment in which a
0.1 g MLg strip was immersed in 25 mL of a 0.2 mM Cd solution, and 65 % of the Cd was
sorbed within 10 minutes.
The fact that one mole of Ca is released for one mole of Pb or Cd sorbed onto MLg shows
that the process is one of ion exchange rather than adsorption. This stoichiometry cannot be
explained by the biotic ligand model, also an adsorption model which assumes that metals
act independently, even when metal competition is included [6].
Advantages to this modified lignin include: stable structure; re-usable; recovery of
solvents for re-use; high capacity, determined by the amount of calcium hydroxide used;
rapid; effective in batch or column operations.
References
1 . Bailey S., Olin T. J. and Bricka R. M., Low-cost sorbents: a literature summary,
Technical Report SERDP-97-1(U. S . Army Corps of Engineers, Vicksburg, MS, 1997).
2. Crist R. H., Martin J. R., Chonko, J. and Crist, D. R. Uptake of metals on peat moss: an
ion exchange process, Environ. Sci. Technol. 30 (1996) pp. 2456-2461.
3. Crist R. H., Martin J. R., Carr D., Watson J. R., Clarke J. and Crist D. R. Interaction of
metals and protons with algae. 4. Ion exchange vs. adsorption models and a
415
reassessment of Scatchard plots; ion exchange rates and equilibria compared with
calcium alginate, Environ. Sci. Technol. 28 (1994) pp. 1859-1866.
4. Crist R. H., Martin J. R and Crist D. R. Heavy metal uptake by lignin: comparison of
biotic ligand models with an ion exchange process, Environ. Sci. Technol. 36 (2002)
pp. 1485- 1490.
5. Marton J. Reactions in alkaline pulping. In Lignins Occurrence, Formation, Structure,
and Reactions, ed. by Sarkanen K. V. and Ludwig C. H. (Wiley, New York, 1971) Ch.
16.
6. Meyer J. S. A mechanistic explanation for the ln(LC5O) vs In(hardness) adjustment
equation for metals, Environ. Sci. Technol. 33 (1 999) pp. 908-912.
416
Y. G. SHUL
Dept.. of Chemical Engineering,Yonsei Universiw, 134 Shinchondong Seoa'aemoongu, Seoul,
Korea
E-mail: shulyg@bubble.yonsei.ac.kr
A study on the electrosorption of U(VI) onto a porous activated carbon fibers (ACFs) was performed to treat
uranium-containing lagoon sludge. Effective U(VI) removal is accomplished when a negative potential is
applied to the activated carbon fiber(ACF) electrode. For a feed concentration of 10@-350mg/L,
the
concentration of U(VI) in the cell effluent is reduced to less than ImglL. The adsorbed uranium could be
desorbed from the ACF by passing a IM NaCl solution through the cell and applying a positive potential on the
electrode.
Introduction
For the removal of uranium (VI) fiom waste streams, a variety of physical and
chemical methods such as precipitation, coagulation, ion exchange and adsorption have
been used. But, these techniques have been restricted in application due to their limited
capacity when the concentration of U(VI) in the waste water is relatively high[l]. As an
efficient electrochemical method for the removal of high concentration uranium,
electro-deposition on carbon materials has been extensively investigated and used very
effectively[2]. For uranium having a high reduction potential, electro-deposition is not a
practical method. An alternative to electro-deposition is electro-sorption, that is,
adsorption of the metal cations onto a negatively charged carbon surface.
Electrosorption technique, which may use the electrical potential as the 3d driving
force to the traditional adsorption and ion exchange mechanism, has reversible
characteristics of purifying waste solution by adsorption and concentrating contaminants
by desorption. Carbon materials satis@ the basic requirements for an efficient electrode
material, and have good radiation and chemical-stability.Especially activated carbon fiber
(ACF), which can be easily made into a variety of types (textures or sheet), has a high
specific surface area and electrical conductivity.
In this study, we conducted the experiments on a selective adsorption of uranium
(VI) fiom a high concentration of chemical salt to investigate the technical feasibility of
the electrosorptionprocess using ACF as an electrosorption adsorbent.
2
Experimentals
417
electrode(ACF) was placed on a platinum mesh used as a current collector and supporter.
The counter electrode was platinum wire and the Ag/AgCI electrode was used as the
reference electrode. All the potentials reported in this paper are relative to this reference
electrode. The electro-chemical cell was connected with a potentiostat (EG&G Model
273). The fixed flow rates through the cell were controlled by a peristaltic pump.
Various type of salts such as NaCl, NaN03 and NH4N03 were tested as the supporting
electrolyte.
3
Test on the electrosorption with 100 mg/L U( VI) feed onto the ACF felt at various
negative potentials in the range of - 0.3 to - 0.9 V (vs. Ag/AgCl) was carried out. The
uranium concentration in the effluent from this test is shown in Fig. 1.
-0.w
* - -0.w
+-O.w
t-
0.7
0.6
0.3
418
0.1c
0.08
0.a
0
I!
0.04
0.02
0.00
lime, rrin
Fig. 2. Long term test of U(VI) electrosorption.
The adsorbed uranium could be desorbed up to 92% for 1 Oh by passing a 1 .OM NaCl
solution through the cell and applying a potential of +1.2V (Fig. 3).
The electrosorption behavior of U(VI) with a variation of solution pH at -0.9 V is shown
in Fig. 4. As the solution pH was lowered, the adsorbed uranium decreased. At pH 2.1,
the eftluent uranium concentration is 5Omg/L at the beginning but rapidly increases to
200mg/L in about 6h, showing an extremely low uranium sorption capacity. The
electrosorption at pH 3 and 4 shows very similar results except for the slightly higher
uranium removal during the first hour of electrosorption at pH 4.
The effect of
electrolyte concentration was studied and the results are shown in Fig. 5 . It can be seen
that uranium adsorption extents and kinetics increased with the increase of electrolyte
concentration. It is due to the increase of ionic mobility and decrease of ohmic voltage
drop resulting from the increase of electrolyte concentration. As ionic mobility
100
'
'
'
'
80-
s .
.-c.
'
'
M -
01
-*1 0 0 2 0 0 J o o 4 0 0 5 0 0 m
419
Tim,rnin
Fig. 4. Electrosorption of U(VI) with variation of solution pH.
lime, nin
Fig. 5. Electrosorption of U(VI ) with variation of electrolyte concentration.
420
Acknowledgements
This project has been carried out under the Nuclear R & D Program finded by the
Ministry of Science and Technology
References
1. Lenhart, J.J., Figueroa, L.A., Honeyman, B.D., Kaneko, D., Colloids Surf. 120
(1997) pp. 243-254.
2. Farmer, J.C., Bahowick, S.M.,H a m , J.E., Fix, D.V., Martinelli, R.E., Au, A.K.,
Carroll, K.L., Energ. Fuels 11 (1997) pp. 337-347.
421
1 Introduction
The irradiation of nuclear fuels in power reactors leads to the production of atoms of a
wide range of fission products, ranging in atomic mass from 70 to 160. These fission
products include three of PGM, i.e., palladium (Pd), rhodium(Rh) and ruthenium(Ru).
The PGM are valuable and important as noble metals, but their natural resources are
rather limited. Due to the increase in utilization of PGM in the automotive and dental
industries, in electronic and electrical devices, in the production of ultrapure hydrogen,
and as an industrial catalyst. The demand for PGM continues to grow in a steady manner.
The noble metals generated by fission can be an important alternative resource to meet
the increasing demand [4]. In order to separate the PGM from high-level radioactive
liquid waste(HLLW), various recovery methods have been studied, for example, lead
extraction, solvent extraction, precipitation, adsorption and ion exchange methods
[ 1,3,4,5,7]. Recently, Kondo, Y et a1.[4] investigated precipitation behavior of PGMs
from simulated high level liquid waste. And Wei, Y.Z.,et a1.[7] reported that the anion
exchanger AR-0 1 with a benzimidazole group especially shows significantly strong
adsorption of Pd(I1) from nitric acid solution.
In this work, batch and column experiments were carried out to investigate the ion
exchange characteristics including the effects of the ionic group of ion exchangers, the
concentration of nitric acid, the feed rate and also the elution characteristics of Pd(1I) by
various eluents for obtaining the optimal separation conditions.
2 Experimental method
Commercial strongly basic anion exchangers such as IRN-78 and Dowex 1x8 were used
as anion exchangers for these experiments. The resins were pretreated with 10 % sodium
hydroxide solution, washed with distilled water, converted into nitrate form with nitric
acid, and dried overnight at 50'c in a convection oven. Reagent grade nitric acid was
diluted with distilled water to obtain a desired concentration varying from 0.1 to 7 M. The
422
nitric acid solution of Pd(I1) was prepared by dissolving Pd(N4)2 into the nitric acid
solution.
In batch experiments, 1 g of an anion exchanger and 20 ml of a platinum group metal
containing solution were put in a glass flask and the flask was set in the mechanically
shaking water bath maintained at 20'c or 609: for 24 hours. It was then taken out and
centrifuged for 5 minutes at 3000 rpm, and the metal concentration in the solution was
measured by inductively coupled plasma atomic emission spectroscopy (ICP Model:
Jobin Yvon JY38 plus, polychromator, JYOCY).
The column experiments were carried out in a glass column of 1.5cm internal
diameter and 30cm length filled with 5g of ion exchange resin. Pd solution was percolated
through the packed column at a flow rate of 1.O ml/min controlled by a peristaltic pump
(EYELA SMP-21, Japan). The effluent samples were collected at regular intervals by the
fraction collector (Model: Adventec SF-2 100) and analyzed for Pd concentration by ICP.
The distribution coefficient (&) of metal is defined as the ratio of the metal
concentration in the resin of the ion-exchanger to that in the solution [2,7]. Thus, Kd
value was calculated by the following equation,
50
40
30
:Dower 1x8
-0-
10
15
20
25
Time (hr)
Time (hr)
Fi.2.
The ion exchange reaction of anionic complexes in nitrate media is generally expressed as
following equation [7],
423
where ,'R Pd(N03)i, and vA denote the fixed ionic group, the counter ion(anionic
complex of Pd), and the charge number of the counter ion, respectively.
Fig. 2 shows the effect of ionic groups on the adsorption of Pd(II) from nitric acid
solution onto the several anion exchangers. These results were compared with those from
the anion exchanger named AR-01 with quaternary and tertiary benzimidazole groups and
the several conventional anion exchangers such as IRA 900 and IRA-93ZU cited in the
literature [7]. As shown in Fig. 2, anion exchangers such as Dowex 1x8 and Dowex 2x8
with an ionic group of quaternary methyl ammonium have higher ion exchange capacity
than anion exchangers such as IRN 78 and IRA-93ZU with a conventional amine group.
The anion exchanger AR-01 with a enzimidazole group especially shows significantly
strong adsorption of Pd(II) from nitric acid solution, the distribution coefficient (Kd)
value for the adsorption of Pd(II) was about 2000-3000 at 0.1 M of nitric acid solution
171.
Fig3 shows the effect of the nitric acid concentration on the adsorption of Pd(I1) in
the range of 0.1 to 7 M by Dowex 1x8 and IRN 78. the optimal nitric acid concentration
was shown to be in 2 3M.
The ion exchange characteristics of Pd(II) in packed column filled with 5g of anion
exchange resin at 2.0 M nitric acid solution are shown in Fig. 4. The ion exchange
capacity of Pd(II) by Dowex 1x8 was higher than that by IRN 78 at 2.0 M nitric acid
solution. Breakthrough by IFW 78 occurred at 40 ml volume treatment when Pd
concentration was 172 ppm, while breakthrough volume by Dowex 1x8 was 100 ml. This
result shows a similar trend to the results in batch experiments, Dowex 1x8 with ionic
group of quaternary methyl ammonium has higher ion exchange capacity than IRN 78
with conventional amine group.
0.4
'
0.2
I
0
Contentratiin of
0.0
HNO, (N)
50
-c-
4-
100
150
: IRN 78
:Dower 1x8
200
250
300
350
Treated Volume, ml
Fig. 4. Breakthrough curve for Pd(ll) sdrorplion by anion
exchsngen [ Pd con.: 172 pprn. nitric acid con.:
2.0 M. feed rate: 1 mumin 1
Fig. 5 shows the effect of feed rate on the adsorption of Pd(1I) in the packed columns
by Dowex 1x8. As shown, the ion exchange capacity of Pd(I1) decreased as feed rate
increased. When feed rate was 1 ml/min, breakthrough point occurred at 100 ml treatment
and the bed was saturated at 3 10 ml treatment. When the feed rate increased 3.5 mumin,
however, the breakthrough volume for Pd(l1) adsorption decreased to 48 ml and the bed
was saturated at 150 ml treatment.
The elution characteristics of Pd(I1) in packed bed filled with 5 g Dowex 1x8
saturated with Pd(I1) by various eluents are shown in Fig. 6.
As shown in Fig. 6, the capacity for the elution of Pd(I1) by 0.5 M thiourea and 0.1 M
424
0.8
"O
,;!Lr
0.4
I?
02
0.0
50
Treated Volume, mi
Treated Volume. ml
perfectly eluted by 0.5 M thiourea and 0.1 M nitric acid mixed solution. However, the
elution capacity of Pd(I1) by low concentration of nitric acid was very low.
4 Conclusions
Ion exchange and elution characteristics of Pd(I1) by several anion exchangers in the
batch and column were investigated. Based on experimental results, the ionic groups of
anion exchangers affected the ion exchange capacity for the adsorption of Pd from nitric
acid solutions significantly. Anion exchangers such as Dowex 1x8 with the ionic group of
quaternary methyl ammonium had a higher capacity than anion exchanger such as IRN 78
and IRA-93ZU with amhe group for the adsorption of Pd(I1) from nitric acid solution in
the batch and column experiments. Especially, new type anion exchanger, AR-01 with
quaternary and tertiary benzimidazole groups showed very strong adsorption of Pd(I1)
compared with other conventional anion exchangers. The optimal nitric acid
concentrationwas shown in the 2 3 M.
The elution characteristics of Pd(I1) in the batch and packed column showed that Pd
could be easily eluted by 0.5 M thiourea and 0.1 M nitric acid mixed solution. The
capacity for the elution of Pd(II) by 0.5 M thiourea and 0.1 M nitric acid mixed solution
was high compared with the other eluents such as nitric and hydrochloric acid solutions.
Based on these experiments, to separate Pd(l1) effectively by an ion exchange method
from radioactive liquid waste, the development of anion exchanger with the high ion
exchange capacity for Pd(I1) may be important.
References
1. Beamish, F.E., A critical review of methods of isolating and separation the six
platinum metals, Tuluntu, 5, (1960), pp 1-35.
2. Helfferich, F.,Ion Exchange, McGraw-Hill, New York (1962).
3. Jensen, G.A. et al. .J., Recovery of noble metals from fission products, Nucl. Technol.,
65, (1984), ~~305-324.
425
4. Kondo, Y and Kuboto, M., Precipitation Behavior of Platinum Group Metals from
Simulated High Level Liquid Waste in Sequential Denitration Process ,J. Nucl. Sci.
Technol.,29(2), (1992), pp140-148.
5. Navratil, J.D., Ion exchange technology in spent fuel reprocessing,
J. Nucl. Sci. Technol, 26(8), (1989), pp735-743.
6. Rizvi, G.H. et al., Recovery of fission product palladium from acidic high level waste
solution, Sep. Sci. Technol.,3 1(13), (1 996), pp 1805-18 16.
7. Wei, Y.Z.,et al.,"Adsorption and Elution Behavior of Platinum Group Metals In Nitric
Acid Medium", Proceeding of IEX'96, 174, Royal Society of Chemistry (July, 1996).
426
E-mail: hmoon@chonnam.ac.b
2
E-mail: ldhO928@yahoo.com
The background organics in water and wastewater are necessary to fractionate into groups or
components according to the difference in adsorbability. In this study, the background organics were
!hctionatedin terms of the adsorptive strength described by the Freundlich isotherm constants k and
n with the assumption that the fractionated components differ in the value of k but have the same
value of fl based on IAST (Ideal Adsorption Solution Theory) using binomial concentration
distribution.A simple CharaCterLationprocedure for water and wastewater to chantcterizeDoc in t e r n
of adsorbabilitywas proposed and applied to three types of organic mixture contained in different water
sources. The composition of each organic mixture was successfully evaluated to describe the IAE
(Integral adsorption experiments)data of the total organic carbon using this characterization procedure.
1. Introduction
427
considered for use in wastewater and water treatment plants within Korea. The conditions
undex which they were studied can be related directly to practical applications in terms of
carbon dose and contact time. It can be shown that the availability of advanced
characterization techniques offers the potential for predicting the adsorbability of DOC
without precise knowledge of the chemical structures present in the water and wastewater.
2. Experiments
Adsorption experiments with PAC (James Cumming & Sons LTD, Australia) were carried
out by varying the amount of activated carbon dosed to 1 L of 0.45 pm filtered sample.
The PAC-HA, PAC-WB and PAC-CB based on coconutshell, wood and coal were used in
this study.
The materials chosen for the investigation in wastewater and surface-water were
DOC. DOC concentration was measured using W-Persulfate TOC analyzer
(DOHRMANN Phoenix 8000). Batch adsorption experiments were performed at different
RPM (50, 100, 150 and 200) to obtain the data required for the design and operation of
membrane-PAC hybrid system for the treatment of real-wastewater and surface-water. A
schematic diagram of the membrane-PAC hybrid system used in this study is shown in Fig.
1. The suspension of PAC particles and wastewater was delivered from a stock tank to a
CFMF cell by peristaltic pump. The dimensions of the filtration channel in the CFMF cell
are 6 cm, 0.6 cm and 0.036 cm of length, width and thickness respectively. The CFMF
cell has 9 filtration channels and the total membrane area is 3.24 X lo4' m2.A
spiral-mixing device was made by winding PVC tube with diameter of 6 mm around a
column 110 rnm in diameter. The PAC and solution were sent together into a mixing
device and went through to the CFMF cell.
The main modification in the characterization procedure was to assume a simple discrete
428
CT
=cci
i=l
zi = cioI [ ( n I n K J
+ ( M I V ) ( r I I n ) ] (3)
c(n
N
i=l
/ nK
-1=o (4)
CiO
Y + (M I V
/n)
429
100 ND
F(%) = - [Gev- Gcal)/
,G
],
( N D :Number of data)
ND m=l
Table 2. Characterization results of surface-water on PAC
1000
HA-Wastewater
WB-Wastewater
I00
s?
t
10
't
0.02
0.04
0.06
0.08
0.1
0.1
10
CT,mgRrDOC
M N , kgIm3
430
o WBSurfacewater
0 HASurfacewater
100
L
6 2
10
1
1 I
0.1
0
0.02
0.04
0.06
0.08
0.1
I I
I I l l 1
I I I I U
10
Cr. +DOC
W ,k@
4
0 RPM= 50
3.5
&
RPM=100
0 RPM=150
WFA+ChPracterizatioA
2.5
1.5
P
u 2
1.5
1
0.5
Oe50
10
20
30
40
SO
60
Tim, nin
20
40
60
80
5. Acknowledgements
This study was supported by a research fund provided by the ARC (Australia) - KOSEF
(Korea) joint research.
References
1. Y. Matsui, A. Yuasa, F. Li, and F. Li, J. Environ. Eng., 124, 11, (1998) p. 1099.
2. Maccormick A. B., The application of microfiltration in water and wastewater
treatment, In Modern Tech. in Water and Wastewater Treatment, CSIRO Publishing,
Australia, 1995, p. 45.
3. H. Moon, H. C. Park, and C. Tien, Chem. Eng. Sci., 46, 1. (1991) p. 23.
4. Chi Tien, Adsorption Calculations and Modeling, Butterworth-Heinemann, USA,
1994, p. 167.
431
Introduction
Problems associated with the removal of heavy metals in effluent waters from several
different industries have become controversial issues in the world. Especially, chromium is
one of the undesirable heavy metals because it affects human physiology, accumulates in
the food chain, and causes several ailments [ 1,2].
The methods employed for the removal of Cr ions from wastewater include
precipitation [3], ion-exchange [4], membrane [ 5 ] , and solvent extraction [6]. However,
these treatment methods have not widely practiced due to their high cost and for low
feasibility small-scale industries.
Two classes of materials that are used extensively as heterogeneous catalysts and
adsorption media are microporous (pore diameters 5 -20 A ) and mesoporous (-20 - 500
A ) inorganic solids [7]. In 1992, the discovery of a new family of mesoporous molecular
sieves designated M41S had been reported by researchers at the Mobil Coporation [S]. The
MCM-41 material possesses a uniform hexagonal array of linear channels constructed with
a silica matrix like a honeycomb. These materials have very high surface area, ordered pore
structure, and extremely narrow pore sue distribution. Pore size can be controlled by
intercalation of layered silicates with a surfactant species [9]. Because of their large areas
and well-defined pore size and pore shape, these materials have great potential in
environmental and industrial processes.
Brown et ul. [ 101 reported that selective Hg2+adsorbent could be synthesized by using
silica, also Dai et ul. [l 11 synthesized selective Cu2' adsorbents the adsorption of bents
using MCM-type mesoporous silica. However, little research has been reported for noble
metal ions using mesoporous silica.
The main objective of this work was to investigate the surface and adsorption
properties of the MCM-41 by using pH, acidhase value, and XRD and BET isotherms.
Also, it was assessed how these properties affect the adsorption of Cr( II1) and Cr(V1).
432
2. I
Experimental
Synthesis of MCM-41
A MCM-41 has been synthesized following a procedure of Ryoo and coworkers [ 121.
The fust procedure used colloidal silica (Ludox HS40,39.5wt???SO*, 0.4 wt?? Na20, and
60.1 wt?? H20,du Pont) as the silica source and 25% cetyltrimethylammonium chloride
(CTMACI, Aldrich) solution as surfactant. A solution of sodium silicate was prepared by
combining 1.00 M NaOH solution with colloidal silica. The sodium silicate solution was
dropwise added to a polypropylene bottle containing a mixture of 28 wt?? aqueous NH3
solution and CTMACI solution with vigorous magnetical stirring at room temperature. This
mixture was heated for 4 d at 373 K. The pH of the reaction mixture was adjusted to 10.2
by dropwise addition of 30 wt?? acetic acid with vigorous stirring. Subsequently, the
precipitated product, MCM-4 1 with CTMA template, was filtered, washed with distilled
water, and dried in an oven at 370 K. The product was calcined in air under static
conditions using a muffle furnace at 770 K for 24 h.
2.2
Characterization
The pH of MCM-41 was measured with ASTM D 3838. About 1.Og of dry MCM-41
was added to 20 ml of distilled water, and the suspension was shaken overnight to reach
equilibrium. Then the sample was filtered, and pH of the solution was measured. The
surface fbnctional groups of the samples were determined by Boehm's titration method
[ 131. In the case of acid value, about 1.Og of the sample was added to 100 ml of 0. I N
NaOH solution and the mixture was shaken for 24 h. Then the solution was filtered through
a membrane filter and titrated with 0. IN HCl. Likewise, the base value was determined by
converse titration.
XRD patterns were obtained at room temperature, using a Rigaku Model D M X Ill
B (CuK, X-ray source). All samples were scanned under the same conditions (28 = 1.2 10"). N2 isotherm was measured by using an ASAP 2400 (Micromeritics) at 77 K. Prior to
each analysis, the samples were outgassed at 298 K for 6 h to obtain a residual pressure of
less than I O 3 torr.
2.3
Adsorption of Chromium
The adsorption efficiency of Cr ( 111) and Cr (VI) on the MCM-41 sample was
obtained by using stoppered flasks containing 0.lg of MCM-41 in 100 ml of aqueous
solution of chromium chloride (CrC13 6H20) and sodium chromate (Na2Cr04* 4H20),
respectively. Also, the initial pH of the solutions (CrC13 6H20 and Na2Cr04 4H@)
were adjusted to about 3 and 5 by using 0.1 N HCI and 0.1 N NaOH. The amount of
chromium adsorbed was determined by ICP-AES.
It is well known that surface properties should play an important role in the process of
gasAiquid adsorption on MCM-4 1.
433
XRD pattern of the MCM-41 sample synthesized in the present work was presented in
Figure 1. The XRD pattern was comprised of one very intense line, three weak lines, which
could be indexed to (loo), (1 lo), (200), and (210) diffraction lines characteristic of a
hexagonal structure of MCM-4 1, respectively. This feature was generally attributed to the
formation of Si-0-Si bonds by condensation of Si-OH groups present in the as-synthesized
material. The hexagonal unit cell (a,,) could be calculated by Eq. (1)
a,, = 2d,,J3
As a result, hexagonal unit cell (a,,) value, containing pore walls, WBS about 48.3 A .
,
4
.
6
110
24.2
2w
20.9
.
8
(
10
28
Figure 1. Typical X-ray diffraction patterns of synthesizedMCM-41 sample.
The pore structure parameters were included in Table 2. It was found that the BETS
surface area and the pore volume were 803 m2/g and 0.83 cm3/g, respectively. Also, the
BJH pore size distribution shows MCM-41 material with a quite narrow pore diameter
distribution centered around 25.8A. Thus, the framework walls are 22.5A thick.
Adsorption behavior of Cr(lll) and Cr(VI) ions from aqueous solutions of chromium
chloride in the concentration of 50 mg/L on the samples are shown in Figure 2. All
adsorption isotherms were also carried out by adjusting the initial pH of solution by using
0.1N HCI and 0.1N NaOH and without adding any buffer to control the pH constantly
[ 14,151.
434
MCM-41
a
803
1414
25.8
0.8264
22.5
' : Total pore volumed: BJH Average pore diameter' : Pore wall thickness ( A )
The initial adsorption rate increased rapidly. Also, it was seen that adsorption amount
of Cr( 111) on MCM-41 had higher than that of Cr(VI). This was due to the presence Si-0-Si
and Si-OH groups that were easily dehydrogenatedby hydrogen bonding between hydroxyl
groups on surface MCM-41 in aqueous solution. Thus, This result was probably explained
that surface hydroxyl group of MCM-41 enhanced adsorption of Cr(lll) cations, as it
suppressed the adsorption of Cr(VI) anions.
0
D
Time (mill)
Figure 2. Adsorption of Cr(II1) and Cr(VI) on MCM-41 as a knction of contact time.
Conclusions
In this work, the effects of the surface and adsorption properties of the MCM-41
sample on chromium adsorption were investigated. As a result, It was found that the
presence Si-0-Si and Si-OH groups that were easily dehydrogenated by hydrogen bonding
between hydroxyl groups on surface MCM-41 in aqueous solution. Also, adsorption
amount of Cr( 111) on MCM-41 had higher than that of Cr( VI). This result was probably
explained that surface hydroxyl group of MCM-41 enhanced adsorption of Cr( 111) cations,
as it suppressed the adsorption of Cr(Vl) anions.
435
References
1. R. C. Bansal, J. B. Donnet, and F. Stoeckli, Active carbon, Marcel Dekker, New York
(1988).
2. S. J. Park and Y. S. Jang, Pore structure and surface properties of chemically modified
activated carbons for adsorption mechanism and rate of Cr(VI), J. Colloid Interjiuce
Sci. 249 (2002) 458-463.
4.
5.
6.
7.
8.
9.
14. S. J. Park and W. Y. Jung, Adsorption behavior of chromium (111) and (VI) on
electroless Cu-plated activated carbon fibers, J. Colloid Inrerjiuce Sci. 243 (2001) pp.
3 16-320.
15. S. J. Park and J. S. Kim,Anodic surface treatment on activated carbons for removal of
chromium (VI), J. Colloid Interjiuce Sci. 239 (2001) pp. 380-384.
436
Introduction
In recent years, activated carbons fibers (ACFs) because of their high surface area,
microporous character, and the chemical nature of their surface have been considered
potential adsorbents for the removal of heavy metals from industrial wastewater [I-31.
The properties of ACFs are determined by their microstructure, it is therefore important to
investigate the microstructure of ACFs in terms of specific surface area, micropore
volume, pore size distributions, surface chemistry and so on. Also, the adsorption
properties of carbonaceous adsorbents are dependent on not only the porous structure but
also the surface chemistry [3,4].
It is known that surface oxides on carbon surfaces are formed by means of thermal
treatment at high temperature, ozone treatment, and liquid treatment of the chemical
aqueous solution [5]. Also, anodic oxidation of fibers in electrolytes can produce a variety
of chemical and physical changes in the fiber surfaces [6].The main aim of oxidation of
carbon surfaces is obtaining a more hydrophilic surface structure with a relatively large
number of oxygen-containing surface groups [7]. The existence of surface functional
groups on carbons such as carboxylic, phenolic, lactonic and acid anhydrides has been
postulated as constituting the source of surface acidity [8,9]. Also, these surface groups
make the carbon surface hydrophilic and enhance its ion exchange capacity so that these
carbons are potential adsorbents for the removal of metal ions from industrial and
domestic wastewater.
In this work, ACFs are modified by anodic oxidation treatments with acid (H3P04)
and base (NI&OH) to obtain oxygen-containing groups. Surface hctional groups on the
carbon surfaces are investigated by XPS and acid-base values. Nz adsorption isotherm
characteristics, including the specific surface area, micropore volume, and total pore
volume, are determined by BET. And the adsorption amounts of Cr(VI), Cu( II ), and
Ni( II) ions on ACFs are using UV/vis spectrophotometer (UV) and inductively coupled
plasma atomic emission spectrometer(ICP-AES).
437
Experimental
0.05 g of each of the activated carbon fibers were placed in contact with 150 ml
solutions of 20 ppm concentrations of sodium chromate (Na2Cr04 4H20), cupric
chloride (CuC12 * 2H20), and nickel chloride (NiC12 6H20) for the adsorption of Cr(VI),
Cu( 11), and Ni( II) ions. The initial pH of the Cr(VI), Cu( II), and Ni( II) solutions was
adjusted with 0.1 N HCl and NaOH. The bottles were sealed with parafin film and then
shaken on a time sequence (10,20,30,40,50,90, and 180 min) at 25 c at a frequency of
100 strokedmin using a shaking bath. At the end of the reaction period, each reaction
mixture was filtered to separate the Supernatant and activated carbon fibers. The adsorbed
amount of Cr(VI) was measured by using the pink color complex developed between
diphenyl carbohydrize and chromium ions in an acidified solution with a UV/vis
spectrophotometer(UV S-2100, Scinco) at an absorbance of 540 nm [3].
430
1200
900
600
uw)
The residual copper and nickel ions were analyzed by ICP-AES (Jovin-Yvon UltimaC). The amount of adsorbed heavy metal ions was obtained by calculating the difference
of each concentration of heavy metal ions before and after adsorptions.
3
3. I
Figure 1 shows the XPS survey scan spectra of the nontreated and the anodic
oxidation treated ACFs. The CISand Ols peaks of ACFs are appeared in 284.6 and 532.8
eV, respectively [13]. As a result, the relative intensity of Ols peak is increased by the
anodic oxidation treatment. This is clearly attributed to the increasing of oxygen groups
on the ACFs surfaces.
Boehm titration results are presented in Table 1. As seen in Table 1, oxygen
functional groups of surface-treated ACFs are increased. These results can be explained
that the anodic oxidation treatment of the ACFs surfaces produces various oxygen
functional groups, i.e., carboxylic, lactonic, and phenolic groups.
Table 2 shows microstructural properties, including specific surface area, micropore
volume, and total pore volume of the ACFs. The specific surface area of the pure-ACFs,
A-ACFs, and B-ACFs are 1944, 1430, and 1937 m2g-', respectively. That is, the BET'S
specific surface area is decreased by 26% for A-ACFs compared to the pure-ACFs, but BACFs have no significant change. Also, total pore volume and micropore volume of
surface-treated ACFs are decreased. This is due to the increase of oxide functional
groups, which are attributed to the block of the micropores.
Carboxylic (meq/g)
3
40
4
Lactonic (meq/g)
40
230
80
439
Phenolic (meq/g)
70
140
70
Pure-ACFs
A-ACFs
B-ACFS
1944
0.787
1.027
1430
1937
0.243
0.560
0.343
0.701
The results of percentage removal of metal ions with contact time for the initial
concentration of metal ions are shown in Figure 2. It is observed that the initial adsorption
rate increases rapidly. The percentage adsorption of metal ions increases with increasing
the agitation contact time and the percentage adsorption of metal ions of surface-treated
ACFs is always superior to that of pure-ACFs. This is because at higher dose of adsorbent
due to the increased surface functional groups, more adsorption sites are available,
causing higher removal of metal ions. Also, A-ACFs show lower percentage adsorption
of metal ions than B-ACFs. It seems to be due to the pore blocking by surface oxide
groups, resulting in decreasing the specific surface area.
40
80
1 2 0 1 6 0 :
40
80
IP
la
Tl(min)
Conclusions
In this work, the anodized ACFs were studied in the adsorption characteristics in
terms of the microstructures and surface functional groups. In the results of XPS, acidbase values, and BET, the specific slirface area of surface-treated ACFs was decreased,
whereas, oxygen-containing functional groups of surface-treated ACFs were increased.
As expected, the increased surface fhctional groups led to an increase of the adsorption
of heavy metal ions. In case of A-ACFs, the adsorption of heavy metal ions was increased
by an increasing of oxygen-containingfunctional groups, in spite of a decrease of specific
surface area. In conclusion, the surface functional properties of ACFs made a major
important role in increasing the heavy metal adsorption in aqueous solution.
References
1. M. Suzuki, Activated carbon fiber: Fundamentals and applications, Carbon 32 (1994)
pp. 577-586.
2. J. B. DOMet, R. Y.Qin, S. J. Park, Ryu S. K., and Rhee B. S., Scanning tunnelling
microscopy study of activated carbon fibers, J. Muter. Sci. 28 (1993) pp. 2950-2954.
3. S. J. Park,B. J. Park, and S. K. Ryu, Electrochemical treatment on activated carbon
fibers for increasing the amount and rate of Cr(VI) adsorption, Carbon 37 (1999) pp.
1223- 1226.
4. Z. Ryu, H. Rong, J. Zheng, M. Wang, and B. Zhang, Microstructure and chemical
analysis of PAN-based activated carbon fibers prepared by different activation
methods, Carbon 40 (2002) pp. 1 144-1147.
5. J. B. DOMet and R. C. Bansal, Active Carbon, 2nd ed., (Marcel Dekker, New York,
1990) pp. 145-204.
6. S.J. Park and J. S. Kim, Anodic surface treatment on activated carbons for removal
of chromium(VI), J. Colloid Interface Sci. 239 (2001) pp. 380-384.
7. J. W. Shim, S. J. Park and S. K. Ryu, Effect of modification with HN03 and NaOH
on metal adsorption by pitch-based activated carbon fibers, Carbon 39 (2001) pp.
1635-1642.
8. H. P. Boehm, Chemical identification of surface groups. In Advances in Catalysis,
ed. by Weisz P. B. 16 (1966) pp. 179-287.
9. S. J. Park and Y. S. Jang, Pore structure and surface properties oftchemically
modified activated carbons for adsorption mechanism and rate of Cr(VI), J. Colloid
Interface Sci. 249 (2002) pp. 458-463.
10. S. Brunauer, P. H. Emmett, and E. Teller, Adsorption of gases in multimolecular
layers, J. Am. Chem. Soc., 60 (1 938) pp. 309-319.
11. J. H. de Boer, B. G. Linsen, T. Plas, and G. J. Van Zonder, Studies on pore systems
in catalysts, VII. Description of the pore dimensions of carbon blacks by the t-method,
A Card. 4 (1 965) pp. 649-653.
12. G. Horvath and K. Kawazoe, Method for the calculation of effective pore size
distribution is molecular sieve carbon, J. Chem. Eng. Jpn. 16 (1983) pp. 470-475.
13. S. J. Park and W. Y. J u g , Effect of KOH activation on the formation of oxygen
structure in activated carbons synthesized from polymeric precursor, J. Colloid
Interjiace Sci. 250 (2002) pp. 93-98.
441
experimental data mathematically described using empirical external mass transfer and intra-particle
diffusion models. The experimental data show conformity with an adsorption process, with the
removal rate heavily dependent on both external mass transfer and intra-particle diffusion.
Introduction
Methods
The dolomite used has a typical chemical composition of 44%MgC03and 53% CaC03.
The raw dolomite was charred in a furnace at 850C for a period of 6- 18 hours producing
a CaC03/Mg0 porous structure. Specific surface area was measured using BET nitrogen
adsorption employing a Sorptomatic 1900.
A reactive dye, Levafix Brilliant Red E4BA was used. The research investigates the
effect of: mass-volume ratio, initial dye concentration and agitation speed. For variation
in mass-volume ratio, the mass of the dolomite ranged from 1.06g to 4.25g i 0.002g in
1.7 dm3 of solution (dye concentration of 400 mg dmj, impeller speed 400rpm). For
variation in concentration, the initial concentration of dye solution ranged from 400 mg
dm-3to 1000 mg dmm3(mass volume ratio of 17g per 1.7dm3of solution, impeller speed
400rpm). For variation in yitation rate, the speed ranged from 100-5OOrpm (mass
volume ratio of 17g per 1.7 dm of solution, dye concentration of 400 mg dm).
442
An empirical model was used to calculate the external mass transfer coefficient, kF [4,12].
The change in fluid phase concentration with time Ct is related to kF ,concentration at the
surface C, and specific surface S, by:
dt
Hence at t = 0 a plot of CdC0 will yield a slope of -kFSs. The plot of CJC0 against time
can be curve fitted and the slope as t + 0 can be calculated fiom the curve fit relationship
and not just the first two data points.
The intra particle diffusion model (single resistance) assumes external mass transfer
is significant only at initial stages. The internal diffusion parameter, k, is calculated from
the plot of dye adsorbed qt versus square root of time [S].
qr = k(to.)
(3)
The BET analysis on dolomite and charred dolomite is shown in Table I. There is a
rise in surface area on charring of the dolomite due to the calcining process which
effectively creates a porous structure.
Table 1. BET nitrogen adsorption analysis. Dolomite charring temperature = 800C.
Dolomite Sample
raw dolomite
6 hr charred dolomite
12 hr charred dolomite
18 hr charred dolomite
0.7
19.5
23.0
36.0
443
the relative increase in competition for available adsorption sites override the increase in
driving force for the adsorption urocess at elevated dye concentrations.
0.0
0.8
0.7
0,s
O
-0.5
0.4
0.3
0
0.2
0.1
.. .
0
0
0
: It
0
Concentration
(mgdm)
1000
800
600
400
kf (cm s)
0.0260
0.0352
0.0555
0.0834
Agitation
(rpm)
100
200
300
400
kf (cm s-l)
0.045 1
0.0507
0.0679
0.0834
0.1425
0.1535
0.1249
0.63
1.25
2.50
kfin this work is higher that that calculated elsewhere using other adsorbents, and
would indicate that mass transfer in the reactive dye - charred dolomite system is very
high [I]. The magnitude of kffor variation in agitation rate indicates that kfincreases with
increase in impeller speed. Since kf = D/6, where 6 is the effective thickness of the
Nernst layer which is smaller the greater degree of agitation, then a linear plot of In kf
versus In (rpm) would be expected [6]. The correlation in Figure 2 is described by the
equation ks = 3.58 x 10-2(rpm)0.14
.Rate of internal mass transfer is in most cases the
rate-determining step, more notably in the case of large molecular weight dyes [lo]. The
single resistance model used assumes diffusion occurs in the pore structure of the
adsorbent and that this diffusion is described by Ficks second law. The intra particle
diffusion parameter, k, is defined as the gradient of the solid phase concentration qs,
versus the square root of time. This line can often be linearised into regions representing
different stages of mass transfer of adsorbates into adsorbents [7]. The initial stage
represents external mass transfer, with the following stages representing intraparticle
diffusion in the macro, meso and micropore structure of the adsorbent. In figure 3, after
the fmt minutes where external mass transfer is the dominant process, there is a single
linear relationship between qs and to.. The single linear stage (table 3) would indicate that
intra particle diffusion occurs in pores of a similar magnitude. The results of the BET
analysis indicate a low surface area and pore volume, hence much of the internal structure
of the charred dolomite consists of macropores, with little or no branched pores.
Concentration (mgdm)
1000
800
600
400
0.63
1.25
2.50
k (mg minaO)
0.98
4.76
8.25
0.98
Results indicate the rate of intra particle diffusion is dependent upon initial dye
solution concentration with an increase in C, giving a corresponding increase in
magnitude of k. In the case of intra particle difision being the only rate determining step
it was found that k varied with the square root of the initial concentrations used [2, 121.
The effect of an increase in sorbent mass is an increase in the surface area for adsorption.
The trend in k was possibly due to the effect of the increase in surface area increasing the
value of k which is a rate parameter and not a diffusion coefficient. Results from other
investigations into the removal of metal ions indicated that the removal from solution was
related to the volumes of precipitation of their hydroxides formed in the presence of
dolomite [8,9]. In this investigation there was no evidence of a precipitate.
4.0
-2 ,
3.5 J
7.0
Figure 2. Correlation between external mass transfer coefficient and agitation rate
45
rmfs
0630
25
Figure 3. Solid concentration versus square root of time for different initial concentration
Conclusions
Batch kinetic data on the removal of reactive dye from solution using thermally charred
dolomite have been well described by empirical external mass transfer and intra-particle
diffusion models. It was found that external mass transfer and intra-particle diffusionhad
rate limiting effects on the removal process which were attributed to the relatively simple
445
macropore structure of the charred dolomite particles. These analyses, plus a visual
inspection would appear to indicate that adsorption is the likely removal mechanism in
the process.
4
References
Allen S.J., McKay G and Khader K.Y.H., Intraparticlediffision of a basic dye during
adsorption onto sphagnum peat. Em Poll 56 (1989) pp. 39-50.
2. Allen S.J.,Brown P., McKay G. and Flynn O., An evaluation of single resistance
transfer models in the sorption of metal ions by peat. J Chem Technol BiotechnolS4
(1 992) pp. 27 1-276.
3. Boynton R.S., Chemistry and Technology of Lime and Limestone. (Intersci, New
York, 1967).
4. Furusawa T. and Smith J.M., Fluid-particle and intraparticle mass transport rates in
slunies. Ind Eng Chem Fundum 12 (1973) pp. 197-203
5. Furusawa T. and Smith J.M., Intraparticle mass transport in slurries by dynamic
adsorption studies. AIChEJ 20 (1 974) pp. 88-93
6. McKay G. and McConvey I.F., The external mass transfer of basic and acidic dyes
by wood. J Chem Technol Biotechnol31 (1 98 1) pp. 401-408
7. McKay G., Blair H.S. and Gardner J., The adsorption of dyes in chitin 11.
intraparticlediffusion processes. J Appl Polymer Sci 28 (1983) pp. 1767- 1778
8. Staszczuk P., Stefaniak E. and Dobrowolski R., Characterisation of thermally treated
dolomite. Powder Technol 92 (1997) 257
9. Stefaniak E., Dobrowolski R. and Staszczuk P., On the adsorption of chromium V1
ion dolomite and dolomitic adsorbents. Adrorption Sci and Technol 18 (2000) pp.
107-115.
10. Walker G.M.and Weatherley L.R.,Adsorption of acid dyes from aqueous solutionthe effect of adsorbent pore size distribution and dye aggregation. Chem Eng J
(2001) (accepted).
11. Walker G.M., Hanna J-A and Allen S.J., Investigations into the adsorption of reactive
dye, phosphate and nitrate by dolomite. (Fundamentals of Adsorption 7, 2001,
Nagasaki Japan.
12. Weber W.J. and Moms J.C., Kinetics of adsorption on carbon fiom solution. JSun
Eng Div A X E (1 963) April pp.3 1-58.
1.
446
Introduction
447
Experimental
2.1 Materials
2.1.1 Proteins
Bovine serum albumin (BSA) and bovine hemoglobin (BHb) were purchased from
Sigma Chemical Co., USA, catalog number A-7906 and H-2500, and no finther
purification was performed.
2.1.2 Monomers
Styrene (s) and methacrylic acid (MAA) were obtained from Junsei Chemical Co.,
Japan, are stabilized by monoethyl ether hydroquinone (MEHQ), therefore, an inhibitor
remover column (Aldrich Chem. Co., USA, catalog number 306312) was used for
removing MEHQ.
2.2. Preparation of microspheres
All microspheres were prepared using soap-free emulsion polymerization.
Carboxylated microspheres were prepared by batch copolymerization. Batch
copolymerization was performed with main monomer, S, lwt?! of co-monomer, MAA,
and 0.4WtOh of initiator, KPS. All weight fiactions were based on the amount of main
monomer, S. These microspheres were named CM-1 for low carboxylated PSRMAA,
respectively.
2.3. Permeate flux Procedure
A stirred cell equipped with a 0.22Cm membrane filter was charged with 30 mL of latex,
the dispersion of microsphere. The specific surface area was adjusted to 0.19 m2 per 1mL
and the ionic strength was calibrated to 0.0 1. At the constant stirrer speed, buffer solution
was introduced into the stirred cell until steady state flux was attained. Protein solutions
were introduced with step of pulse injection. The permeate flux was measured
continuously with an electronic balance (Precision plus, Ohaus Co., USA) by a data
acquisition system. The electronic balance was connected to a PC through a RS 232C
interface. The surface charge density of microspheres was varied as 0.45, 5.94, 9.14 and
10.25, and the stirrer speed was varied as 300,400 and 600rpm.
448
Conclusion
449
References
450
20
--
0.32
d 300 rpm
400 rpm
0.30
--
1.2
1.0
0.8
3
0
0.28
'8
0 0.2a
2
0.24
0.6
0.4
0.22
0.2
0.20
0.0
200
400
300
500
600
1.2
1.o
,
0
50
1W
150
200
250
300
50
100
150
200
250
Time (min)
Time (min)
45 1
300
1.Introduction
Activated carbon is a porous carbon material. It has been produced from many
different carbonaceous materials, including coal, wood, coconut shells, and peat. The
major manufacturing processes of the activated carbon are carbonization and activation.
Organic sludge is rich in carbonaceous organic material; therefore it has the potential to
be converted into activated carbon if pyrolysed under controlled conditions or with some
chemical treatment. The few studies 11-3 1 have been made on the pyrolysis behavior of
the organic sludge and on the physicochemical properties of the reclaimed adsorbent. The
effects of preparation condition parameters such as the concentration of activating agent,
heating temperature, dwell time, heating rate were investigated.
Several authors 14-51 have studied the effects of KOH on carbonization of
carbonaceous materials. Marsh et al. indicated that the oxygen of alkali could remove
cross-linking and stabilizing carbon atoms in crystallites at the activation temperature
range of 550 900C. After activation reaction, a new structure of the microporosity of the
activated carbon was created when potassium salts and carbon atoms from the internal
volume of the carbon were removed. Later, Otowa et al. also pointed out that high
452
temperature and high KOWcarbon ratio produced large pores in the carbon structure, due
to the presence of K20,derived from KOH, expanded the carbon atomic layers. When the
temperature exceeded 700 c ,a considerable amount of K was formed by the reduction of
K20 with carbon. Since the inner carbon atoms were consumed, pores were formed in the
structure. Carlos et al. indicated that chemical activation of olive-mill wastewater with
KOH produced activated carbons with much lower ash content, higher nitrogen surface
area and much better developed porosity than in the case of either its chemical activation
with H3P04 or its physical activation with C02 at 840C.
Fractal geometry has been used to describe the structure of porous solid and
adsorption on heterogeneous solid surface 16-81 . The surface fractal dimension D was
calculated from their nitrogen isotherms using both the fractal isotherm equations derived
from the FHH theory. The Frenkel-Halsey-Hill (FHH) adsorption isotherm applies the
Polanyi adsorption potential theory and is expressed as:
In N=constant + S lnA
where N is the amount adsorbed, and Anis the adsorption potential defined as:
A=-AG=RTh(I/X).
For smooth surface, the parameter S is assumed to be equal to -1/3, while for a
fiactal surface, S is a function of the surface fractal dimension, D. If the van der waals
attractive forces are dominant between adsorbent and adsorbate, then S is equal to
(Ds-3)/3 (91 . For higher surface coverage where the adsorbent-adsorbate interface is
controlled by the gadliquid surface tension, S would be equal to (D-3) 10,ll I .
According to the FHH model, on a In N vs. In A plot, the slop of the straight-line part
should be equal to S.
The objective of this research work was to use the surface fractal theory to analyze
the adsorbent from industrial sludge at various conditions. Effects of activated
temperature, activated time and activated agent on the specific surface area and pore
volume surface of adsorbents were investigated.
2.Experimental
A dewatered sludge was collected from the wastewater treatment of PET
manufacture process. The sludge was put in oven at 103 Cfor 24 hours. The water
content of the industrial sludge was about 75%. The dry sludge was put into a quartz tube
located in the furnace for carrying out the pyrolysis process. The pyrolysis was conducted
in a fixed bed, using nitrogen to carry away expelled gases. The temperature was
controlled at 600 C for 2 hrs.
The product, the sludge char, after the carbonization process was activated. The
chemical activation with activated agents (KOH and H3P04) orland physical activation
with C02 were used in the activation process. The activated temperatures were controlled
at 500 - 8OOC for 0.5 to 2 hours. The various concentrations of KOH and H3P04were
controlled at 0 to 7M.The various concentrations of H3P04 were controlled at 0 to30 %.
Nitrogen adsorption and desorption isotherms for the sludge adsorbent were
measured using the standard N2-BET test (Micromeritics Instrument Corporation
ASAP2000). The properties of the sludge adsorbents were also characterized by the BET
surface area method. The surface fractal dimension D was calculated from their nitrogen
isotherms using both the fractal isotherm equations derived from the FHH theory.
453
Table 1. The specific surface area, pore diameter, and fractal dimension of the sludge
adsorbent with H3P04 at various activation conditions.
Note:
1.
2.
3.
The assumption that Van Der Waals foeces are dominant between the adsorbate
and the adsorbent
S: the slope of the line of In(VNm) against In(1n PO/P) for sludge adsorbent
D: the surface fractal dimension
In generally, the value of the fractal dimension, D, from the fractal FHH model is
from 2 to 3. But in this study, when the sludge char was activated by only H3P04 at
various activation temperatures and times, most slopes, S, of the lines of ln(VNm) against
ln(1n POP) for the.N2 adsorption isotherm data of the sludge adsorbents are smaller than
-1/3. The D values of the sludge adsorbents are smaller than 2. These are derived based
on the assumption that Van Der Waals forces are dominant between the adsorbate and the
adsorbent. The D values of the sludge adsorbents from H3P04 activation are 1.1 2.2,
indicating the presence of a regular and smooth surface. The D values of the sludge
adsorbents with steam activation are 2.2 and 2.6, indicating a partially irregular surface
and semi-microporous structure.
The specific surface areas, pore diameters, and surface fractal dimensions of the
sludge adsorbents with KOH at various activation conditions are shown in Table2. As in
shown, when the sludge chars were activated by KOH agent, the specific surface areas and
the pore diameters of the sludge adsorbents are 19 - 36 m2/g and 58 to 98 A, respectively.
When a steam and KOH agent simultaneously activated the sludge chars, the specific
surface areas and the pore diameters of the sludge adsorbents are 133 - 499 m2/g and 19
to 32 A, respectively. It is also observed that the optimum activation condition of the
sludge char, based on the highest specific surface area, was found to be with 100% steam
and 7MKOH agent at 700'c for 1 hr. The pore diameters of the sludge adsorbents
decrease as the surface area of the sludge adsorbent increased. The phenomena could be
ascribed to the fact that the sludge chars would not decompose completely to provide
enough specific surface area at a shorter activation time, a lower activation temperature,
or a lower concentration of KOH, however that a sintering effect resulted in the reduction
of the surface area at longer activation time or a higher activation temperature, or a higher
concentration of KOH. Moreover, the result of analysis for the surface areas and pore
diameters of the sludge adsorbents in Table 2 shows that the parameter of a steam than
KOH agent for activation process is more important.
Table 2. The specific surface area, pore diameter, and fiactal dimension of the sludge
adsorbent with
KOH at various activation conditions.
S: the slope of the line of ln(VNm) against h(ln POP) for sludge adsorbent
D1: the assumption that Van Der Waals foeces are dominant between the adsorbate
and the adsorbent.
D2: the assumption that a higher surface coverage with gaslliquid surface tension as
the controlling factor at the adsorption interface.
When the sludge chars were activated by KOH agent orland a steam at various
activation temperatures and times, most slopes, S, of the lines of In(V/Vm) against h(ln
POm) for the N2 adsorption isotherm data of the sludge adsorbenst are larger than -1/3.
The D values of the sludge adsorbents are almost larger than 2.5, whether these are
derived based on the assumption that Van Der Waals forces are dominant or surface
455
tensions are controlling factors. The D values of the sludge adsorbents fiom KOH agent
orland steam activation are 2.7-2.9 (Van Der Waals forces are dominant) and 1.9-2.8
(surface tensions are controlling factors). From the Figurel, the D values of the sludge
adsorbents increase as pore diameter decreased. The sludge adsorbents are suggested that
have strong micropore structures and irregular surfaces, when the sludge chars were
activated by a steam and 7M KOH agent for 700'c. According to N2 adsorption isotherm
data of sludge adsorbent with KOH at various activation temperature, Fig. 2 shows that
plots of ln(V/Vm) against ln(hPO&) exist a strong linear correlation. The slopes, s, of the
lines of ln(V/Vm) against h(ln POR) for sludge adsorbent gradually increase as the
activation temperature increased. Furthermore, the optimum activation condition for the
sludge adsorbent with 7MKOH and steam occurs at 700 'c for lhr.
3 -
29
428
8 27
- a0
-+
0 0
'1 26
s =
+ +
24
2.3
I22
& 21
+VanDerWallsfO~dominant
2
1.9
Figure 1. The correlation of pore diameter and fractal dimension of the sludge
adsorbent from KOH activation process
A 7MKOH0.5hr600C
I .6
1.5
1.4
1.3
1.1
' - -
0.R
0.7
0.6
o,5
0.4
0.3
.A
= -0.1 1 3 6 r + 0 . 4 1 9 5
R' = 0 . 9 4 23
;..---.......,.
o.;
-.A
= - 0 . 2 9 1 ~+ 0 . 4 2 8 8
--.
. .- P
---
0.2
0.1
R' = 0 . 9 8 3 7
-------l__
.
.
.-
7MKOHOShr700'C
-...A
-.
- 0 . 0 7 7 6 ~+ 0 . 4 3 6 6
R'= 0 . 9 5 4 8
A
0 '
-5
4.5
-4
4.5
-3
-1.5
-I
-1.5
.I
4.5
0.5
In( In P O P )
456
of porous solid. The D values of the sludge adsorbents from H3P04 activation are 1.1
2.2, indicating the presence of a regular and smooth surface. The D values of the sludge
adsorbents with steam activation are 2.2 and 2.6, indicating a partially irregular surface
and semi-microporous structure. The D values of the sludge adsorbents from KOH agent
orland steam activation are 2.7-2.9 (Van Der Waals forces are dominant) and 1.9-2.8
(surface tensions are controlling factors). The sludge adsorbents are suggested that have
strong micropore structures and irregular surfaces. However, the D values of the sludge
adsorbents increase as pore diameters decreased.
Reference
44(200 1)45-5 1
3. Chiang, P.C., You, JH., Use of sewage sludge for manufacturing adsorbents, Can.
J. Chem. Eng. 65( 1987) 922-927
4. Carlos Moreno-Castilla et al.,Chemical and physical activation of olive-mill waste
water to produce activated carbons, Carbon 39(2001) 14 15-1420
5. Jia Guo and Aik Chong-Lua,Effm of surface chemistry on gas -phase adsorption by
9.
Avnir D, Farin D, pfeifer P., Molecular fiactal surfaces,. Nature 1984; 308:
(2001).
26 1-263
10. Avir D, jaroniec M.,An isotherm equation for adsorption on fractal surfaces of
heterogeneous porous materials, Langmuir, 1989;5 (6)143 1-1433
11. Yin Y,Adsorption isotherm on hctally porous materials, Langmuir 1991;7
(2):216-2 17
457
Introduction
In the food, medical, and pharmaceutical industries, amino acids, peptides, and
proteins play very important roles. Their purities must be high because of using for
human body. For separation and purification of amino acids, peptides, and proteins,
adsorption and ion exchange processes are generally used in these industries.
In our previous works [l-31, we reported experimental and theoretical equilibrium
isotherms for adsorption of L-glutamic acid in the single component system on
polyaminated highly porous chitosan (hereafter called PEI-CH), weakly basic ion
exchanger, and crosslinked chitosan fiber. We found that the adsorption of L-glutamic
acid, which is a kind of acidic amino acid, was controlled by the acid/base neutralization
reaction between neutral L-glutamic acid (zwitterion, A 3 and those adsorbents.
In this work, we investigate the possibility of using ChF for adsorption of acidic
peptide. The experimental equilibrium isotherm and mechanism for adsorption of acidic
peptide is presented and discussed.
2 Experiments
We used the crosslinked chitosan fiber (hereafter called ChF) in this experimental
study. ChF was fabricated by Fuji Spinning Co., Japan. Fig.1 shows the unit molecular
structure of chitosan which was transformed from chitin by deacetylation. Chitin is a
natural biopolymer which is contained in the shell of arthropods. Chitosan was
crosslinked to make an adsorbent with acid, alkaline, and chemical proofs. The
fabrication method of ChF was presented elsewhere.[5,6].
Glutathione (Peptide Institute Inc., Japan) was used as the acidic peptide in this
experimental work. It has important role in biochemical oxidationheduction reaction.
The structure is shown in Fig.1.
~
458
CH20H
CH*OH
~ \
0
H
?IH
H
EGDE-Residue
HOOC-H2C-HN-
NH2
Chitosan
0
II
C-
CH2CH
\0/
0
II
CH-NH- C-
I
CH2
I
SH
~
EGDE
yoo(CH2)2- FH
NH~+
Glutathione (;type
where Co and C are the initial &d equilibrium concentrations of the peptide in the
solution (kmol/m3), respectively. q denotes the equilibrium concentration of the peptide
in adsorbed phase. (kmoVkg dry fiber). V and Ware the volume of the solution (m3) and
the weight of adsorbent (kg dry fiber), respectively. All experiments were carried out at
298 K.
'1
r
q=QKC/(1+KC)
298K
p 3 . 91 molkg
~ = 7 . 2x
3 ~02m3flun~i
0.01
0.02
0.03
OO
Table 1
pH
No adjustment
K[m3/moll
7.23 X 102
3.22 X 102
3.2k0.2
4-
I
I
Fig.No.
3.91
4.63
2
4
*it
?
&[moVkgdry fiber]
5 -
t,
c -
9
1
1 - 7
,'
74.
I
II
:* -
,'.'
',
,,a
460
The pH of the solution was adjusted by using HCI or NaOH aq.. When 2<pH<4.5,
pH4.8, and pH>10.5, glutathione is adsorbed on ChF. In other pH regions, it is not
adsorbed on ChF.
Glutathione dissociates in the aqueous solution as follows:
where A',
A*,A-,
A2;
and A3- are R,,(-COOH)(-COOH)(-SH)(-NH3+),
R&-COO)(-COOH)(-SH)(-NH3+), R,,(-COO)(-COO-)(-SH)(-NH3'), Rp
(-COO-)(-COO-)(-S-)(-NH3+),and %(-COO-)(-COO-)(-S-)(-NH2), respectively.
For example, the structure of A* is shown in Fig.1.
In the region of 2<pH<4.5, the A*type of glutathione is dominant in the solution. So
that type of glutathione may be adsorbed on ChF. Yoshida et al. [I J and Yoshida and
Kishimoto [2] reported that the adsorption of L-glutamic acid on PEI-CH, weakly basic
ion exchange resin, and ChF is controlled by the acidbase neutralization reaction between
the carboxylic group of the neutral L-glutamic acid (A? and the fixed amino group of the
adsorbents. This may suggest that glutathione is also adsorbed according to the
following, an acidbase neutralization reaction:
R-NHz + &(-COO-)(-COOH)(-SH)(-NH33
(7)
A 0.03
~ = 3 . 2x
2 1o2m3km~i 0.04
rn
0
'
0.01
0.05
0.05
461
Fig. 4 shows the equilibrium isotherms for adsorption of glutathione on ChF at the
constant pH (=3.2M.2). The experimental adsorption isotherms of glutathione were
correlated well by the Langmuir equation (2) by using Q and K are listed in Table 1.
The coefficient of correlation is 0.966. Since the equilibrium isotherm is independent of
the initial concentration, the mechanism for adsorption of glutathione may be
chemisorption. Since in this pH region, type A* of glutathione is dominant in the
solution, it is selectively adsorbed on ChF. We investigated the equilibrium isotherms
for adsorption of glutathione at the pH=l .O, 2.0, 6.4, and 1 1.8*0.2 in this work. Those
isotherms were unfavorable rectangular, and glutathione was adsorbed little on ChF at
those pHs.
4 Conclusion
(1) The experimental equilibrium isotherm (q-C curve) for adsorption of glutathione on
ChF was independent of the initial concentration of glutathione.
(2) The adsorbed amount of glutathione on ChF was effected by the pH value of the
solution on the q-pH curve, significantly.
(3) It appeared that the adsorption of glutathione correlated by the Langmuir equation
well.
References
[I] H. Yoshida, N. Kishimoto, and T. Kataoka, fnd. & Eng. Chem. Rex, 34, 347-355
(1995).
[2] H. Yoshida, and N. Kishimoto, Chem. Eng. Sci.,50,2203-2210 (1995).
[3] N. Kishimoto and H. Yoshida, Sep. Sci. & Tech.,30,3 143-3163 (1995).
[4] H. Yoshida, N. Kishimoto, and T. Kataoka, fnd. Eng. Chem. Rex, 33,854-859 (1994)
[5] H. Yoshida, A. Okamoto, H. Yamasaki, and T. Kataoka, Fundamentals of Adsorption,
Kodansha, Tokyo, 767-774(1993)
[6] H. Yoshida, A. Okamoto, and T. Kataoka, Chem. Eng. Sci., 12,2267-2272(1993).
462
H. YOSHIDA
Department of Chemical Engineering, Osaka Prefecture University,I - I Gakuen-cho Sakai
599-8531, Japan
E-mail: yoshida@chemeng.osakafu-u.ac.jp
With the aim of repeatedly reusing the solution used to season salted ume (Japanese apricot), we
investigated its desalting and deacidification by electrodialysisand adsorption. Although NaCl and
acids could be easily removed from used seasoning solution by electrodialysis, useful substances
such as amino acids were removed at the same time. Chitopearl CS selectively adsorbed citric acid
in the used seasoning solution without also adsorbing useful substances. The equilibrium data of a
citric acid, which was a main organic acid, were correlated by the Langmuir equation. The
saturation capacity decreased with increasing concentrations of NaCl in the solution but the
equilibrium constant did not change. The breakthough curves of citric, malic and acetic acids in
used seasoning solution on Chitopearl CS were investigated. Chitopearl CS can be regenerated
using 1 N NaOH solution.
Introduction
Pickled ume (Japanese apricot), a traditional delicacy in Japan, are prepared in the
following manner. Ume h i t are first preserved in salt for about 2 months (ume
fruitsalt = 4 kg:l kg). The salted ume are then washed with water and immersed in a
seasoning. NaCl and organic acids are extracted from the salted ume into the solution
during the seasoning process, which means that about 30 % of the solution has to be
replaced before it can be reused. As new seasoning solution is expensive and used
solution contains considerable amounts of amino acids and sugars, an economical means
of treating used seasoning solution for reuse is greatly desired. The removal of NaCl and
organic acids from used solution by combining electrodialysis and adsorption, without at
the same time removing useful components, were investigated.
Experimental Section
A laboratory electrodialysis system (CS-0 type; Asahi Glass Co., Tokyo) was used. The
system consisted of cation-exchange membranes (CMV; 14 sheets) and anion-exchange
membranes (AMV; 10 sheets). The ion exchange resin used in this study was Chitopearl
CS, which was the effective for removing organic acids [l, 21. The physical properties of
Chitotearl CS were shown in Tablel. Adsorption isotherms were measured by the batch
method. The resin particles were contacted with each solution at 298 K for 7 d. The
breakthrough curves were measured using the column (1 cm i.d.) in which Chitopearl CS
beads packed at 298 K.
463
As shown in Table 2, NaCl and total acids concentrations in used salted ume seasoning
solution were 1.5 and 5 times new seasoning solution, respectively. However, total
nitrogen concentration in the used salted ume seasoning solution was largely remained.
Figure 1 shows the removal of NaC1, total acid (TA), and total nitrogen (TN) at 10 V.
These results showed that while electrodialysis could remove NaCl fiom used seasoning
solution, the removal of acids was slow and was accompanied by decreasing TN. It is
thought the acid removal rate might be slow because the molecular weight of citric acid
(192 Da), which exists abundantly in the solution, is larger than those of NaCl(58 Da) and
glutamic acid (147 Da).
2
3
4
Time (h)
Figure 1. Changes in each component by electrodialysis.
Wi.0, initial weight of i component.
0
2.5
1 500
0.01
1
0.1
CN.CL(kmol m-9
Figure 2. Effect of NaCl on saturation capacity (q,) and
equilibrium constant (K).
464
Figure 2 shows the effect of NaCl on the adsorption isotherm for citric acid on Chitopearl
CS. K and qowere calculated by the Langmuir isotherm equation.
40KC
'= 1 +KC
where q, C, K, and qodenote the adsorbed phase concentration of organic acid (kmol m-3
wet resin), concentration of organic acid in the liquid phase (kmol m-3), equilibrium
constant (m3 kmol-I), and saturation capacity (kmol m-3 wet resin), respectively. qo
decreased with increasing CN&l,but K was constant. When CN&l= 0.1 km01/m3 (5.8 kg
m-3),40 was reduced to about half the value at CNacl= 0 lanol m-3and the resin could not
> 1 kmol m-3. The above results showed that the lower the
adsorb citric acid when
concentration of NaCl was, the greater the adsorption of organic acid became. We
therefore used electrodialysis to first reduce the NaCl in the used seasoning solution.
NaCl was reduced almost linearly by electrodialysis, for 3 h, at which time its
concentration was only 0.2 kg m-3. The removal of organic acid by CS was then tested
using this solution.
10
20
30
40
50
60
V/w ((masolution)(g wet resinP)
Figure 3 shows the degree of removal of each component from the solution. TA
decreased but TN and direct reduce sugar (DRS), which were useful substances, did not.
1.2
0.6
0.4
0.2
0-
0.02
0.04
0.06
0.08
0.1
c (lunol m3)
Figure 4. Adsorption isotherms of citric, malic and acetic acids in used salted
ume seasoning solution on CS.
0 ; citric acid, A; malic acid, 0 ; acetic acid
465
Figure 4 shows the adsorption isotherm of citric, malic and acetid acids in the solution on
CS. A citric acid was selectively adsorbed compared with other organic acids. This
result is consistent with the adsorption on a weakly basic exchanger described previously
[31.
1.4
1.2
1
0.8
virgin
Ztimcs
citricacid
citricacid
ciaicaeid
0.6
0
0
Jtimcs
0.4
0.2
0
1000
4000
3000
2000
5000
Time (sec)
Figure 5. The breakthrough curve for adsorption of citric, rnalic and acetic acids on CS.
Uf,superficial velocity; H, bed height; C, fluid phase concentraion
Figure 5 shows the breakthrough curves for adsorption of organic acids in the solution on
CS packed column. They are little affected by the repeat time. Figure 6 shows the
eluent curves using 1 kmol m-3 of NaOH. Acetic acid adsorbed on CS was desorbed
with increasing the adsorption of citric acid and malic acid. Subsequently malic acid
adsorbed on CS was desorbed with increasing the adsorption of citric acid. Finally only
citric acid in used seasoning solution was adsorbed.
R e p l d NnS
0
0.3
-E
0
0
A
V
A
0
0.2
*8
L,
cilncacid
citricacid
citricacid
mvlic acid
mdicacld
nidicacid
aucticnd
irtlicacid
prrlicacid
virgin
2 rim
3 limv
virgin
2 times
3 rimer
virgin
2 times
3 times
Us = 0.05 rm
0.1
0
I200
Time (sec)
466
References
1 . Takatsuji, W. and Yoshida, H., Removal of organic acids from wine by adsorption on
weakly basic ion exchangers: equilibria for single and binary systems, Sep. Sci.
Technol. 29 (I 994) pp. I473 - 1490.
2. Takatsuji, W. and Yoshida, H., Adsorption of organic acids on polyaminated highly
porous chitosan: equilibria., Ind. Eng. Chem. Res. 37 (1998) pp.1300 - 1309.
3. Takatsuji, W. and Yoshida, H., Adsorption of organic acids on weakly basic ion
exchanger: equilibria for binary systems, A. I. Ch. E. J. 44, (1998) pp. 12 I6 - 122 1.
467
P.C . WANKAT
School of Chemical Engineering, Purdue University, West h f q e t t e , IN 47907. USA
An one-column process was developed to simulate a four-zone SMB using just one column and four
storage tanks. The basic principle of this process is identical to a four-zone SMB. A systematic
design for one-column process was carried out for the separation of two amino acids, phenylalanine
and tryptophan. The process was compared with a four-zone SMB by computer simulation using
Aspen Chromatographym. Operating parameters were obtained h m the triangle theory. The
simulation yielded the product purity of the one-column process to be 92.0% and 85.6% for
phenylalanine and tryptophan, respectively, while 92.8% and 87.8% for the fowzone SMB. The
recovery yields of the one-column process were 93.0% and 84.0% for phenylalanine and tryptophan,
respectively, while 94.0% and 85.5% for the four-zone SMB. The low purity and yield of the
one-column process were due to the fact that the concentration profiles are destroyed in the fluid
phase after mixing in the collection tanks, but maintained in the solid phase. The one-column
process would be usefbl to reconstruct an existing conventional chromatographyto a SMB process.
Introduction
The simulated moving bed (SMB) technology was developed in the early 1960s by UOP
for large-scale hydrocarbon separations in plants [l, 21. Recently, SMB is extensively
used for the separation of enantiomers [3,4],amino acids [5,6], and protein desalting [7].
The SMB system simulated counter-current movement; this is done with a series of
packed bed by periodically advancing the input (feed, desorbent) and output port
(raffinate, extract) along the solvent flow direction.
The solute of lower affinity with adsorbent moves along the fluid direction, while
solute of higher affinity with adsorbent moves along the counter direction [8]. The main
advantage of SMB system is the fact that it is a continuous process with high purity and
recovery, and low eluent consumption. For successful separation, appropriate zone flow
rate and switching period should be selected. The design methods of SMB have been
proposed in the literatures [9-111. In this study, the one-column process was simulated
using single column and four tanks to compare with the conventional SMB system. The
operating conditions were obtained by equilibrium theory, assuming a negligible mass
transfer resistance.
2
2.1
Theory
Design of SUB process
The operating parameters are chosen to achieve successful operation, such as maximum
productivity, maximum yield, minimum desorbent consumption. There are two major
methods to obtain these operating parameters: one is the periodic moving port analysis
468
19-1 11 and the other is the continuous moving bed analysis [12, 131. The latter is
represented by the triangle theory. The optimum operating conditions for an SMB in this
study was obtained from the triangle theory [lo, 14, 151, where the separation
performance is controlled by the flow-rate ratios between each zones of the SMB unit:
mj
=-
Q,t* - v&*
v I-&
where mj is the flow rate ratios in the four zones of the SMB, Q, is the volumetric flow rate
in zone j , V is the volume of the column, t* is the switching time, and E* is the total
column porosity.
The triangle theory is acknowledged as one of the most effective design tool for SMB.
Although this theory neglects mass transfer resistance and axial dispersion, it provides a
useful approximation of the real SMB behavior.
2.2
When solute concentrations are sufficiently low and isotherms are in the linear range, the
following correlation can be used to estimate the lumped mass transfer coefficient (Kf)
[l 11:
1
R2
-=
+- R
K, 15&,D, 3k,
where R is the sorbent particle radius, Dp is the effective intraparticle diffisivity, and kf is
the film mass transfer coefficient. kf is estimated from the correlation of WilsonGeankoplis [16]. The Wilke-Chang correlation was used to estimate the Brownian
diffisivity, D. The effective pore diffisivity was obtained from the Mackie-Meares
correlation [ 171:
where
E,
siEz
si
si
&,
is the
One-column process
A conventional SMB can be divided into four zone; zone I is between desorbent and
extract, zone II is between extract and feed, zone III is between feed and raffinate, zone
IV is between raffinate and desorbent as shown in Figure 1. Each column plays the role of
different zone during each period between switching time. For example, column 3 plays
the role of zone III during the fKst switching period, zone I1 during the second
469
Figure lschematic diagram of a four-zone SMB process during four switching periods. The weakly adsorbed B
(rafinate) moves up in zone 111 while strongly adsorbed solute A (extract) move down in this zone. For each
switching period in four column four zone SMB,columns play the role of different zone.
period, zone I during the third period, and zone IV during the fourth period. One column
can perform the role of four zone during one cycle of four switching time. This is the key
concept of the one-column process. Only one column and two tanks are needed in a period.
To provide liquid with appropriate concentration to a column during a cycle, four tanks
are needed. A simplified flowsheet of the one-column process is given in Figure 2.
t+4
+ +t- I
tew
Figure 2. A simplified flowsheet of one-column process using a single column and four tanks.
470
b,,t e l
Discussion
The separation of two amino acids [5, 61, phenylalanine and tryptophan, was tried using
one-column process. The adsorption isotherms of two amino acids were obtained by
multiple frontal chromatography [ 5 ] . The equilibrium adsorption data were fitted by
Langmuir isotherms as follows;
1 .74
c,
11 .95
c,
r-
System parameter
G r a t i n g parameter
2. 5
0.89
1000
Interparticle porosity (E iJ
0.35
zone Ill
7.29
intraparticle porosity (c p)
0.55
zone IV
2.36
21 1
feed
raffinate
4.93
extract
5.99
desorbent
5.92
mass
transter
(l/min)
coefficients
phenylalanine
tryptODhan
tryptophan
zone I
8.28
zone II
2.29
1.83
1.83
53.82
The simulation results of one-column process and four columns four zone SMB were
presented in Table 2. The purity and yield are defined as follows;
where E and R are abbreviations for extract flow rate and rafinate flow rate, respectively.
471
500
1500
loo0
2wo
3wo
Time (min)
Figure 3. Simulated concentration profile of one-column process. Solid line is for tryptophan and dashed line
is for phenylalanine.
Table 2. Simulation results of one-column process and four columns four-zone SMB.
Purity(%)
Phe
Yield(%)
4 columns SMB
92.8
Trp
87.8
92.0
85.6
Phe
Tip
94.0
93.0
85.5
84.0
The results using the Aspen Chromatography simulator showed the product purity of
one-column process of 92.0% and 85.6% for phenylalanine and tryptophan, respectively,
while 92.8% and 87.8% for four-zone SMB. The recovery yields of one-column process
were 93.0% and 84.0% for phenylalanine and tryptophan, respectively, while 94.0% and
85.5% for four-zone SMB. The low purity and yield of the one-column process comparing
with those of four-zone SMB was due to the fact that the concentration profiles are
destroyed in the fluid phase after mixing in the collection tanks,but maintained in the
solid phase. The one-column process can be applied to reconstruct an existing
conventional chromatography to a SMB process. As the operating conditions of this work
have not been optimized based on purity and yield, the optimization and experimental
work with the two amino acids using one-column process are under way to compare with
the simulation results.
5
Acknowledgements
This study has been supported by the ERC for the Advanced Bioseparation Technology,
KOSEF.
472
References
1. Broughton D. B., Molex: Case History of a Process, Chern. Eng. Prog., 64 (1968)
pp.60.
2. Broughton D. B., Neuzil R. W., Pharis J. M., and Brearley C. S., The Parex Process
for Recovering Paraxylene, Chem. Eng. Prog., 66 (1970) pp. 70.
3. Ching C. B., Chu K H., Hidajat K., and Ruthven D. M., Experimental Study of a
Simulated Counter-current Adsorption System: VII. Effects of Non-linear and
Interacting Isotherms, Chem. Eng. Sci.,48 (1993) pp.1343.
4. Rodrigues A. E., Loureiro J. M., and Pais L. S., Separation of I7l-bi-2-naphthol
enantiomers by continuous chromatography in simulated moving bed, Chem. Eng.
Sci.,52 (1997) pp. 245-257.
5. Wu D., Xie Y.,Ma Z. and Wang N. -H. L., Design of SMB Chromatography for
Amino Acid Separations,Ind. Eng. Chem. Res. 37 (1998) pp. 4023-4035.
6. Xie Y.,Wu D., Ma Z. and Wang N. -H. L., Extended Standng Wave Design Method
for Simulated Moving Bed Chromatography: Linear Systems, Ind. Eng. Chem. Res.
39 (2000) pp. 1993-2005.
7. Hashimoto K., Adachi S. and Shirai Y., Continuous Desalting of Proteins with a
Simulated Moving-bed Adsorber, Agric. Biol. Chem. 52 (1988)pp. 2 161.
8. Wankat P. C., Rate-Controlled Separations, Glasgow/London (1994).
9. Ruthven D. M. and Ching C. B., Counter-Current and Simulated Counter-Current
Adsorption Separation Processes, Chem. Eng. Sci.44 (1 989) pp. 10 1 I 1038.
10. Storti G., Mazzotti M., Morbidelli M. and Carra S., Robust design of binary
counter-current adsorption separation processes, A.I.Ch.E.J. 39 (1993) pp. 47 I.
11. Ma Z. and Wang N. -H. L., Standing Wave Analysis of SMB Chromatography:
Linear Systems, A.LCh.E.J. 43 (1997) pp. 2488-2508.
12. Ching C., Ruthven D. M. and Hidajat K., Experimental Study of a Simulated
Counter-Current Adsorption System: 111. Sorbex Operation, Chem. Eng. Sci. 40
(1985) pp. 1411.
13. Hashimoto K., Adachi S., Noujima H. and Maruyama A., Models for separation of
glucose-fructose mixture using a simulated moving bed adsorber, J. Chem. Engng.
Japan. 16 (1 983) pp. 400-406.
14. Gentilini A., Migliorini C., Mazzotti M. and Morbidelli M., Optimal operation of
simulated moving-bed units for non-linear chromatographic separations 11.
Bi-Langmuir isotherm, J. Chromatogr. A. 805 ( I 998) pp. 37-44.
15. Mazzotti M., Storti G. and Morbidelli M., Operation of simulated moving bed units
for nonlinear chromatographic separations, Margalef R., J. Chromatogr. A . 769
(1 997) pp. 3-24.
16. Wilson, E.J. and Geankoplis, C. J., Liquid Mass Transfer at Very LOWReynolds
Numbers in Packed Beds, Ina! Eng. Chem. Fundam. 5 (1 966) pp. 9.
17. Mackie, J.S. and Meares, P., The Diffusion of Electrolytes in a Cation Exchange
Resin Membrane, Proc. Roy. SOC.London, Ser. A 267 (1955) pp. 498-506.
18. Slater, M.J., The Principles of Ion Exchange Technology, Butterworth, Heinemann,
Boston. (1991).
473
ISAO MOCHIDA
Institute of Advanced Material Study,Kyushu Universiv 6-1, Kasugakoen, Kasuga-shi, Fukuoka
816, Japan
It becomes obvious that SOX in flue gas can be removed continuously over active carbon fibers (ACF)
subjected to surface treatment such as heat treatment. Pitch based ACF shows highest activity for continuous
removing of SOX among several types of ACFs. It is considered that Pitch based ACF can make surface
hydrophobic property higher than other types. The flue gas treatment technology using ACF is a semidry
oxidative de-SOX process which is effective around temperature of 273-353 K. In addition, this process can
produce by-products such as sulfuric acid, and sulfates, and is applicable in the field of flue gas treatment to
which the conventional de-SOX technologies could not be applied for economical reasons. Therefore, this new
technology is expected to be useful in reducing environmental load not only in Japan but also globally.
1. Introduction
There is worldwide and increasingly the discharge of the sulfur dioxide with the use of
fossil fuel. Especially, the discharge in the Asia region increases recently, but the
environment countermeasure has been retarded for the problem of economical efficiency.
Though in the advanced nation, the limestone gypsum method is mainly used as stack gas
desulfurization facility, it is the method in which both cost of equipment and operational
cost are expensive.
On the other hands, it becomes obyious that SOXand NOx in flue gas can be removed at
room temperature by using active carbon fibers (ACF) subjected to surface treatment such
as heat treatment [l, 21. The flue gas treatment technology using ACF is a semidry
oxidation type de-SOX method which is effective even around room temperature. In
addition, this technology enables by-products such as sulfuric acid, sulfates, nitric acid,
and various nitrates to be recovered, and is applicable in the field of flue gas treatment to
which the conventional de-SOX method, such as the limestone gypsum method, could not
be applied for economical reasons.
2. Experimental
2.1 Characteristicsof ACF catalyst
To evaluate the basic characteristicsof de-SOX over ACF, comparison was made between
4 kinds of commercialized ACFs under the untreated condition. Table 1 shows the
474
cellulose-type (Toyobo co.,ltd.) ACFs have high oxygen content, PAN-type (Toho tenax
co.,ltd.)ACF has high nitrogen content, and pitch-type (Adall co.,ltd.) ACF has the largest
carbon content, which indicates that the compositions of raw materials may exert great
influence on the chemical properties of ACFs
Table 1
Comparison of the properties of ACFs made of different raw materials
Pitch type ACF PAN type ACF
Composition formula of raw materials
Carbon content in raw material (%)
[CluHs$lO]n
93. I
[C3NH3ln
67.9
[&Hs~Oliln
76.6
[CsH~oOsln
44.4
10 to 18
7 to 15
0.9 to 2.0
500 to 1500
9toll
1.0 to 1.2
900 to 2500
0.22 to 1.2
1.8 to 4.4
30 to 40
1OOOto1500
2.7 to 2.8
7
470
15 to 19
0.2 to 0.7
950 to I500
0.2 to 0.6
700 to 2500
0.3 to 1.6
to 2
10 to 20
200t01200
1.0 to 2.8
7
460 to 480
22 to 68
900 to 2200
to 400
2 to4
20 to 37
7000t08000
to 2.0
470
17 to 50
to 300
22 to 90
950 to 2400
to 380
1 to 1.8
6 to 10
1000 to 2000
30 to 58
2.2
475
100
80
-A.Phenol-ACF
60
40
20
0
0
5
10
Reaction time(h)
15
476
I00
80
8
8
60
40
20
10
15
Reaction time(h)
477
References
1. Mochida et al., Continuous Removal of SO2 in the Model Flue Gas over PAN-ACF
with Recovering Aqueous HzSO~,
Chemistry Letters, pp. 1899 - I902 (1 993)
2. Mochida et al., Oxidation of NO into NOz over Active Carbon Fibers, Energy & Fuel,
Vol. 8, No. 6,1341 (1994)
3. T. Ohlubo et al., High-temperature treatment effect of microporous carbon on orderd
structure of confined S02, Chem. Phys. Letters, 329, pp.71-75 (2000)
4. M. Ruike et al., J. Colloid Interface Sci. 207, pp.355 (1998)
478
1 Introduction
It is well-known that the nature of NG composition has a negative impact on ANG technology due to the deterioration of the adsorbent capacity on extended cyclic operation.
Although this problem has been addressed by some authors, either experimentally or theoretically, the single- and multi-componentadsorption data reported to date, as they apply
to natural gas, are still rather scarce.
The main purpose of the present work is twofold (i) to report an extensiveset of singlecomponent adsorption isotherm data of the more common natural gas components on activated carbon, and (ii) to present a means of extrapolatingthe measured data to higher
alkanes in order to be able to span the whole composition of a typical natural gas. There
is experimental evidence that for the n-alkanes series this can be done using the Adsorption Potential theory, as demonstratedrecently by Holland et al. on Westvaco BAX- 1 100
carbon, and assumed previously by US.^.^
'
2 Theory
The Adsorption potential theory has been used extensively for correlatingadsorption equilibria on porous adsorbents. It states that for a given gas-solid system the volume of the
adsorbed phase, W, is a function of the adsorption potential,
w =qvm = W@),
(1)
where q is the amount adsorbed at equilibrium and V,( 7') is the adsorbed-phase molar
volume, which is temperature dependent. The adsorption potential is defined as
7 = R T ln(P,/P),
(2)
where P is the equilibrium pressure at temperature T and P , ( T ) is the saturated vapor
pressure of the adsorbate. At high pressure, however, P and P, should be replaced by
the corresponding fugacities, f and fs,to correct nonideal gas behavior. The functional
relationship between & and W is characteristic of the particular gas-solid system and is
usually referred to as the characteristiccurve.
*Author to whom correspondence should be addressed (e-mail: pmota@dq.fct.unl.pt).
479
which is characteristic of a given adsorbent and can be equally applicable to all adsorbates. The practical applicabilityof this feature is limited by our ability to predict affinity
coefficients,but this has been greatly improved by Wood' who has recently published an
extensive compilation of experimental p values for gases and vapors and showed that p is
highly correlated to the molecular parachor accordingto
p = 8.27 x 10-3(Parachor)o.90.
(4)
Under conditions below the critical temperature, T,,of the adsorbate, Vm is assumed
equal to the molar volume of the saturated liquid at system temperature. Above T , the
adsorbedphase is ill-defined, and this has led to different approximationsbeen proposed for
V,. Likewise, in the supercritical region the concept of vapor pressure does not exist and
f s in Eq. (2) must be replaced by a pseudo-vaporpressure.In the present work we followed
the suggestionsof Agarwal and
and estimated f , and Vm at temperaturesabove
Tc as follows:
where f c is the critical pressure of the adsorbate, Tb and vb are the temperature and molar
volume of the liquid adsorbate at the normal boiling point, and 52 is an estimate of the
thermal expansion coefficient of the adsorbate in a superheated liquid state, which for light
gases is SZ 2 . 5 ~ K-'.
3 Experimental section
The carbon selected for study is a coal based, high activity (109 %CTC), extruded carbon
(2 mm diameter pellets) from Sutcliffe Speakman Carbons Ltd (SSC). The carbon was
characterized using N2 adsorption at 77 K and mercury porosimetry. An analysis of the
chemical nature of the carbon surface using the PZC method and Bohem titration revealed
that its surface is mostly clean of acidic groups.
x
4and tert-butyl mercaptan (TBM) on
The adsorption equilibria of the n-alkanes C 1
SSC carbon were measured gravimetrically using a high-pressure magnetic suspension
balance from Rubotherm, driven with in-house-developedLabview software. TBM is currently one of the more widely used odorants for natural gas. All gases employed are CPgrade and were obtained from Praxair Portugal Gases, SA.
The adsorption data of the n-alkanes were measured accordingto standard procedures:
the adsorption chamber was pressurized with the pure gas at approximately the desired
pressure and then sealed. Then, the pressure and the change in the mass (weight) of the
carbon sample were recorded until equilibrium was reached. On the other hand, obtaining
reliable adsorption equilibriumdata for TBM at the very low concentrationsusually found
in natural gas (0-25 mg/Nm3) was a more challenging task. In this work they were determined by recording the weight change of the carbon sample upon saturation with various
feed concentrationsof TBM diluted in an inert carrier. The measurements consisted of exposing the adsorbent sample to a single calibratedmixture of TBM and helium (6.74ppmv)
circulating at different pressures. This was realizable in practice because in our adsorption
apparatusthe pressure can be spanned and accuratelymeasured over a wide range. Preliminary adsorption tests with pure helium showed that its adsorption was negligible compared
with that of TBM,even at the low partial pressures considered in this work, and that helium
could be safely used as the carrier gas without the need for correction of the results.
The flow of the feed stream and the pressure in the adsorption chamber were both fixed
using a mass flow controller, located at the inlet port, and a back-pressure regulator placed
at the outlet. Each measurement was started by circulating the feed gas through the sample
chamber and continued until the recorded weight change attained a steady value. These
experimentstook considerablymore time than those of the alkanes using the conventional
gravimetric procedure. During each experiment the feed stream to the adsorption chamber was routed through a coil immersed in a second temperature-controlled thermostatic
bath in order to maintain consistent isothermal conditions at the entrance to the adsorption
chamber. When the sample weight attained a steady value, the inlet port was slowly closed
while maintaining a constant pressure in the chamber by means of the back-pressureregulator. Then, a final reading of the weight change of the sample was taken. Since this final
reading was taken with the inlet port closed, the measured value of the sample weight is
not erroneouslymasked by the drag exerted by the circulatinggas during the equilibration
phase.
4
The gravimetric measurements, as well as all other conventional adsorption methods, rather
than giving the total amount adsorbed, q, give just the amount in excess, qex,with respect
to that of bulk gas occupying the same volume as the adsorbed phase. However, to apply
the adsorption potential theory the required variable is q and not qex.In this work, q was
estimated from the measured qex value by assuming that the adsorbed-phase volume is
equal to the total pore volume of the ~ a r b o n Vs
, ~ = 0.850 cm3/g, determined from N Z
adsorption at 77 K:
4 = qex
+ VSP&
(6)
where pg is the density of the bulk gas phase at the equilibrium pressure and temperature.
The success of Wood's correlation, Eq. (4), led us to use it for estimating the /? values
for the adsorbates C3+, which are clearly vapors at ambient temperature;on the other hand,
the /? values for the adsorbates C2-, which have critical temperatures close to or below
ambient, had to be obtained experimentally by superposing the corresponding adsorption
data onto the characteristic curve of the higher alkanes. We believe that the reason for
this is the difficultyin calculatingdensities of condensed,adsorbed phases at temperatures
approachingand exceeding critical temperatures.
481
-1
h
-2
1-3
$
-5
-6
I 0-4 x Q (J/mol)
Figure 1 displays the experimental characteristic curve obtained and the B values employed to generate it. The existence of very little scatter in the data demonstrates that the
isotherms of the various adsorbates were successfully correlated as a single temperatureindependent characteristic curve. This fact corroborates the applicability of the Potential
theory to the carbon under study.
To obtain a workable isotherm model for future process simulation, the experimental
o
0.20
0.12
0.20
0.08
0.10
0.04
2
P
0.00
0.00
2 0 4 0
6 0 8 0 1 0 0
10
20
30
40
0.50
0.30
0.20
0
0.10
0.00
0.00
0
10
15
P (bar)
Figurc 2. Singlc-component adsorption equilibria of the normal alkanc scrics q - C 4 on SSC carbon. Symbols
denote experimental data and lines represent predictions from the D-A isotherm model with parameters given by
Eq. (8) and pl = 0.47, 82 = 0.65.83 = 0.76,84 = 0.93. The average error over 364 data points is 6.8%. The
temperatures (K) are (Cl) 284,298,323; (C2) 287,299,314,324; (C3) 284,298,323; (C4)273,288,298,324.
0.09
0.06
0.03
0
0.0
0.8
1.6
2.4
104xP (bar)
Figure 3. Low-pressure adsorption equilibrium for TBM on SSC carbon. Symbols represent experimental data,
and lines represent predictions from the D-A isotherm model with parameters given by Eq. (8) and &BM = 1.05.
The avetagc error over 2 1 points is 4.1%.
characteristic curve was successfully fitted using the Dubinin-Astakhov (D-A) equation.
For a pure component,this isotherm model can be written as
W = Wsexp(-vb"),
(7)
where Wsis the specific pore volume and y and n are parameters. The regressed values are
Ws= 0.856cm3/g,
y =4.402~
(J/mol)-'*, n = 1.09.
(8)
The isotherm model is compared directly to the experimental adsorption data in Figures 2
and 3. The plots show that there is good agreement between model predictions and the
experimental data for all of the adsorbates. Furthermore, the regressed value of W s is in
excellent agreement with the total pore volume determined from N 2 adsorption at 77 K. It
is also somewhat surprising to observe that most of the TBM measurements were in the
nonlinear range of the isotherms even at the low concentrationsconsidered in this study.
Acknowledgements
The authors thank SutcliffeSpeakmanCarbons for providing the carbon samples and characterizing them using N2 adsorption and mercury porosimetry. This work was supported
by the European Community through contract No. ENK6-CT-2000-00053. I. E. acknowledges the financial support of FCT/MCT (grant PRAXIS XXL/BD/19832/99).
References
483
1. Introduction
To date, activated carbon is the most universal adsorbent for VOCs control. However,
some disadvantages for the application of activated carbon include its flammability,
difficulty in regenerating high-boiling point solvents and required humidity control. On
the positive side, activated carbon fiber has uniform size and dimension, higher adsorption
capacity, faster adsorption and desorption rates than activated carbon, and ease of
handling [1,2]. These features obtain adsorptive system size reduction and added adsorbed
vapor selectivity. In these respects, activated carbon fiber, as alternative to activated
carbon inefficiencies, is an excellent micro-pore adsorbent.
In this study, we focused ow attention on investigating the adsorption dynamics in
column packed with activated carbon fiber. By optimizing the breakthrough curve data
with a mathematical model, effective overall mass transfer coefficient was obtained. And
it can be given reasonable predictions compared with the experimental data of
breakthrough curve.
2. Methods
2. I Materials
Pitch-based activated carbon fiber, Nano-10 (Nanotechnics Co., Korea) [3], was used
as the adsorbent. Using the adsorption of nitrogen at 77 K, the BET specific area for
Nano- 10 was measured by an automatic sorption analyzer (Quantachrom Autosorb- 1).
Nano-10 has a BET surface area of 1453 m2-g-',total pore volume of 0.4096 cm3*g-'and
484
mean pore diameter of 22 A. Prior to the experiments, the adsorbent was kept in a drying
vacuum oven at 423 K for more than 12 h to remove impurities.
1.6
0.136
Particle porosity
0.21
0.35
Column diameter, cm
1.7
Column length, cm
3.1
3. Data Handling
Generally, there are four steps are included in the mass transfer mechanisms of the
adsorption process. These steps are fluid-film transfer, pore diffusion, surface adhesion,
and surface diffusion. The rate of surface adhesion for physical adsorption on the surface
of porous adsorbents is very rapid, enough to be assumed instantaneous relative to the
other transfer rates [ 5 ] .
The complex heterogeneous structure of fiber is replaced with an effective
homogeneous structure having an equivalent rate of mass transfer. Coefficient of mass
diffusion through the effective homogeneous activated carbon fiber is defined as the
effective diffisivity (D&. Deffis then used to explain the mass transfer of adsorbed vapors
through the original activated carbon fiber complex structure [6].
0.357(NRe)0.64
(Nsc)0.33
DM
,
kf =E
2%
The Knuhen difision coefficient:
485
3<N~,<2000
(1)
D,= D,,,
exp(-E,, 1R T )
(3)
(4)
The resulting equation of the overall mass transfer coefficient could be expressed as
follows:
To represent the adsorption dynamics in column, the linear driving force (LDF)
approximation model for overall mass transfer coefficient was applied. The LDF model
for gas adsorption dynamics is frequently and successfully used for analysis of column
dynamics because it is simple, analytic, and physically consistent [7]. We assumed that the
velocity of the gas in column is constant, and radial temperature, concentration and
velocity gradients within the bed are negligible in this model. With the ideal gas-law
assumption, the set of equation for this work is as follow:
Mass balancefor component i:
- 01.-
a2yr i3yl
i3yl
az2 +-+-+-+az
at
RT
I-&
an,
PpX=O
dn.
)=
at
k , ( q0 - n i )
Adsorption equilibrium :
Toth
N=
mP
(b + P' )"I
486
(7)
Although the model equation included the axial dispersion coefficient (DL),
plug flow
was approximated by assigning a very large value to the Peclet number (S/DL). This is
because the effect of axial dispersion is quite negligible in a small column and the model
with the second derivatives can give more stable numerical results.
4. Results and Discussion
Activated carbon fiber has much steeper breakthrough curve than that of other
adsorbent in that adsorbate vapors in an activated carbon fiber with only micropores reach
the adsorption sites through micropores without the additional diffusion resistance of
meso- or macropores, and it was required for very short time to reach C / CO= 1 [8].
Breakthrough curves of toluene and trichloroethylene reflected the effect of fed
concentration and flow rate of solvent-laden gas as shown in Figure 1. It is obvious that
high feed concentration also makes steeper breakthrough than low concentration. This is
due to the fact that the higher bulk concentration can make the greater concentration
driving force between bulk and solid phase. And, when the feed concentration is lower, a
longer time is required for reaching the column saturation.
Adapted a nonlinear regression technique, the results of calculation were given the
following relationships:
kToluene
kTrichloroeihyletw
= 0.091x [P]o.920[~]o.5@
= 0.0712 x [P]o.769[~]o.671
In Eqn. (1 1) and (12), k is overall mass transfer rate coefficient, P is partial pressure (in
kPa), and u is interstitial bulk fluid velocity (in d s ) in column. Because of the lack of
experimental data, the correlation can only be available in the experimental range, the
partial pressure of 0.1 1 to 0.35 kPa for toluene and trichloroethylene, and the interstitial
bulk fluid velocity of 0.22 to 0.46 d s .
References
1.
487
7.
Sircar S. and Hufton J. R., W h y Does the Linear Drving Force Model for Adsorptio Kinetics
Work?, Adrorption, 6 (2000), pp. 137-147.
8. Motoyuki S., Activated CarbonFiber: Fundamentals and Applications, Carbon, 32 (1994), pp.
577-586.
1.o
0.8
$=
0.2
0.6
U
0.4
02
0.0
0.0
10
20
30
Time Ela&
Time Elapsed, m h
50
40
mm
1.o
0.8
?-
0.6
0.4
0.4
0
0
0.2
0.2
0.0
0
20
40
80
0.15mls
0.25 mls
0.35 mls
0.0
80
40
80
80
Time Elaplcd. m h
Figure 1. Experimental and predicted breakthrough curves for toluene and trichloroethylene
488
Introduction
There has been considerable effort to solve and diminish ecological and
environmental problems such as air pollution, acid rain, soil pollution, and etc [I]. It has
been well known that the acidic gases, such as, SO2 and NO, are major components of
air pollution. Carbons have been used as not only a reducing agent itself but also
catalyst support for the purpose of removing pollution sources such as NO,, SO,, and etc
[2-41.
The catalytic conversion of NO into O2and N2 by using carbon with the metal (Ni,
Fe, Cu, K, Ca, Pd, Sn, and Na) prepared by impregnation and precipitation with an
aqueous solution of metals has been investigated for a long time. It has been found that
the carbon supported with copper is the one of the best catalytic effect to transform NO
into O2and N2 either in the presence of O2 or in the absence of 0 2 [5-71. In this system
above, oxygen over the ACF/Cu is used as not only a modifier to play a role in changing
metallic copper into copper oxides known as active species for NO removal, but also an
accelerator to produce CO to be reducing agent, resulting in promoting NO conversion
~~91.
The electro-copper plating from an aqueous solution of a copper ion has an
electrochemical mechanism involving the electron transfer with an external source of
electric current. Copper is autocatalytically deposited on the carbon surface as a
function of reaction time [101.
In the present study, a novel surface treatment of microporous carbon, so-called
electro copper plating which has been used in the application fields is provided to
introduce copper onto activated carbons. And, the catalytic reduction mechanisms of
NO over ACFdCu prepared by electrolytic copper plating have been studied.
489
2
2. I
Experimental
Materials and Sample Preparation
Virgin ACFs, AW2001, supplied by Taiwan Carbon Co. was used in this work. To
sensitize the surface of ACFs were immersed in a solution composed of acidified tin
chloride solution at concentration of 5 gel-' for 5 min at room temperature, and followed
by a rinse with distilled water. The ACFs were successively subjected to a copper
electroplating in copper plating solutions with varying treatment time.
2.2
Measurements
The identification and amount of copper on the activated carbons were evaluated
by energy dispersive X-ray analysis (EDX, Hitachi, S-246ON) and inductively coupled
plasma (ICP, Atomscan 25, Thermo Jarrell Ash Co.), respectively. For the test of NO
conversion of ACFs, fixed-bed column made of quartz was used after N2purge at 300C
for 30 min before reaction. The outlet gas was checked by a NOx meter (Ecom@A plus,
ECOM America Ltd.) with time on stream for the catalytic reaction NO-Cu in the
presence of oxygen. The conversion of NO was estimated from the concentration of NO
at the input and output of the column [1 1,121.
Fig. 1 shows the copper contents on the ACFs/Cu catalysts. It is found that virgin
ACFs show no copper peak. Cu5 and CulO, however, show copper peaks, and it is
increased with plating time. This result shows that copper contents are depended on
plating time if other conditions are same.
Fig. 2 shows the NO conversion on the ACFs/Cu catalysts by copper electroplating.
Nitric oxide is converted into the nitrogen and oxygen on ACFs and ACFs/Cu catalyst
surfaces at 500C. As an experimental result, it shows that all of the samples prepared
by electrolytical copper plating represent higher NO conversion than that of unplated
one. In the presence of 02,the higher the content of copper on the ACFs is, the higher
the conversion is, until the reaction time on stream of about 20 h.
Figs. 3 and 4 show the X-ray diffraction profiles of the ACFs/Cu catalysts before
and after catalytic reactions, respectively. The copper metal (Cu), which the diffraction
patterns revealed around 26 43 and 50 on ACFs/Cu, is oxidized to CuzO (28 36 and 42)
during NO catalytic reduction process. The surfaces of ACFs/Cu catalyst are found to
scavenge the oxygen released by catalytic reduction of NO, which can be explained by
the presence of another nitric oxide reduction mechanism between ACFs and ACFs/Cu
catalysts.
490
ACFdCulO
2 111
1.10
1.1
.#a
,.om
.
.
U
7.1
..
*.P
110 %.la
%la
.
.
l
a
*.la
-*.lo-" .I
*.la
la 1
. u.1. Y.U
1000
0.
750
ACFs
ACFICu5
ACF/CulO
0
.Y
8
8
2
L
500
250
0
0
50
100
150
It is clearly seen that the copper species of Cu5 and CulO before NO test is only
metallic copper. And the CuO peak intensities increase with increasing the reaction time
on stream, which is implied by the fact that the sintering of CuO is taking place. From
the results above, the state of metallic copper is changed into copper oxides by oxygen
in this system, resulting in high NO conversion.
491
20
40
2 Theta (degree)
Figure 3. X-ray diffraction profiles of the ACFslCu catalysts by electrolytic copper plating: (a) ACFs, (b)
ACFslCuS, (c) ACFslCulO.
20
40
60
2 Theta (degree)
Figure 4. X-ray diffraction profiles after the NO-ACFslCu catalysts reaction at 500C: (a) ACFs, (b) ACFsICuS,
(c) ACFsKulO.
Conclusion
In this work, the copper content and the net heat of adsorption due to the amount of
copper content on ACFs are increased with increasing the plating time, resulting in
improving the NO conversion as the reaction time on stream increases. As the
experimental results above, it is seen that the copper metal deposited on the ACFs
appears to be increasing the ability of NO removal for the catalytic reactions of NO-Cu
and NO-C in the presence of oxygen. From which, it is clearly found that CulO is a very
prominent catalyst for removing NO. Consequently, it is said that electrolytical copper
plating on ACFs is a useful method in the preparation of the AC/Cu catalysts for NO
conversion.
492
References
1. S. Calvert and H.M. Englund, Handbook of Air Pollution Technology, John Wiley &
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
493
Introduction
2
2.1
Experimental
Materials and Electrolytic Cu-plating
For the present investigation,the ACFs were supplied by Taiwan Carbon Co. AW2001
494
(weight: 45 g/m2, thickness: 0.3 mm, and specific surface area: 2121 m2/g). Cu-deposited
ACFs were prepared by Cu electroplating at constant velocity and same electric current.
Electrolytic copper plate and graphite club were used as the anode and cathode, respectively.
The samples were denoted in as-received, Cu-2, Cu-5, Cu-10, and Cu-20 with different
plating times, such as, 0,2,5, 10, and 20 seconds, respectively.
2.2
The surfaces of ACFs were analyzed using a VG Scientific LAB MK-I1 X-ray
photoelectron spectrometer (XPS). The spectra were collected using a M g b X-ray source
(1253.6 eV). The pressure inside the chamber was held below 5x10-' torr during analysis.
Both survey XPS spectra are recorded at a 45 O take-off angle.
Nitrogen isotherms were measured by using an ASAP (Micromeritics) at 77K.
Prior to each analysis, the samples were outgassed at 573K for 10 - 12 h to obtain a
residual pressure of less than
torr. The amount on nitrogen adsorbed was used to
calculate specific surface area, and the micro pore volumes determined from the BET
equation [ 141 and t-plot method [151, respectively. Also, the Horvath-Kawazoe model
[161was applied to the experimental nitrogen isotherms for pore size distribution.
2.3
NO Conversion Test
For the present experiment, gas chromatograph (DS6200 model, Donam Korea) and
thermal collect detector were used to measure NO conversion. Reactor temperature was
sustain constantly at 500C using P.I.D. temperature controller (UP-350,Yokokawa) and
gas flow rate was maintained 10 mVmin by mass flow controller; GMC 1000, MKS). All
samples were heated under Helium purge at 150C for 1 hour to remove residual H 2 0
before NO conversion test. The NO conversion was determined from the concentration of
NO at the outlet reactor. Prior to each analysis, NO standard curve was gained using 300,
600, and 1000 ppm NO gas.
3
3. I
495
1200
900
300
Mx)
cu-5
cu- I0
cu-20
1709
1620
1534
1060
1.145
0.906
0.83 1
0.809
0.526
1.216
0.997
0.9 12
0.889
0.572
94
91
91
91
92
12.7
12.9
12.7
12.9
12.3
as-received
BET surface area
(mag-)
Micropore volume
(cm.g-)
Total pore volume
(cm3.g-)
Fraction of
Micropore (%)
Average pore diameter
(A)
Table 1 shows the structural properties of the ACFs studied. As shown in Table 1, all
samples have welldeveloped micropore and microporosity of Cu plated ACFs are decreased
as compared that of as-received. Also, the volume Gslction of micropom is decreased with
increaSing of Cu content on ACFs. It can be seen that the copper plating shows pore-blocking
phenomena owing to deposition of copper metal on ACFs [13]. Specific surfice areas are
decreased result h m micropore volume h m t-plot method was decreased.
496
3.2
NO Conversion
4 cu-20
50
100
150
200
250
300
Conclusions
In this work, the effects of the surface properties and pore structure of the copper
plated ACFs on NO removal were investigated. As experimental results, tHe copper metals
appeared to be an increasing of the characteristics of NO removal in spite of the
decreasing of adsorption properties, including specific surface area, micropore volume,
and microporosity of the ACFs. In addition, NO conversion was linearly increased with
increasing the copper content in the ACFs. It could be concluded that the copper content
in ACFs played an important role in improving the NO removal, due to the catalytic
reactions of C-NO-Cu. It is then noted that copper electro-plating treatment on ACFs is a
useful technique for the removal of NO with a viewpoint of high functional metallic
catalytic system.
497
References
1. K. E. Noll, V. Gounaris, and W. S. Hou, Adsorption technology for air water
pollution control, Lewis, Michigan (1992).
2. S. Calvert and H. M. Englund, Handbook of Air Pollution Technology, John Wiley &
Sons, New York (1984).
3. B. J. Park, S. J. Park, and S. K. Ryu, Removal of NO over copper supported on
activated carbon prepared by electroless plating, J. Colloid Interface Sci. 217 (1999)
pp. 142-145.
4. Z. Zhu, Z. Liu, S. Liu, and H. Niu, Catalytic NO reduction with ammonia at low
temperatures on V20dAC catalysts: effect of metal oxide addition and SO2, Appl.
Catal. B: Environmental 29 (2001) pp. 267-276.
5. Y. Hu and E. Ruckenstein, The catalytic reation of NO over Cu supported on mesocabon
mimbeadsofullrahighsurfkcearea,J.Catal. 172(1997)pp. 110-117.
6. E. Ruckenstein and Y. Hu,Catalytic reduction of NO over CdAC, Ind Eng. Chem.
Res. 36 (1997) pp. 2533-2539.
7. P. Denton, A.Giroir-Fendler, Y. Schuurman, H. Praliand, C. Mirodatos, and M.
Primet, A redox pathway for selective NO, reduction: stationary and transient
experiments performed on a supported pt catalyst, Appl. Catal. A: General 220
(2001) pp. 141-152.
8. S. K. Ryu, S. Y. Kim, N. Gallego, and D. D. Edie, Physical properties of silver-containiing
pitch-based activatedcarbon fibers, Carbon37 (1999) pp. 1619-1625.
9. T. W. Chung and C. C. Chung, Increase in the amount of adsorption on modified activated
carbon by usingneutron flux irradiation,Chem. Eng. Sci. 54 (1999) pp. 1803-1809.
10. S. J. Park and K. D. Kim, Adsorption behaviors of C02 and NH3 on chemically
surfaceaeatedactivatedcarbons,J. Colloid InterJace Sci. 212 (1999) pp. 186-189.
11. S. Lowell and J. E. Shields, Power surface area and porosity, Chapman & Hall,
London (1993).
12. S. J. Park and J. B. Donnet, Evaluation of the distribution function of adsorption site
energies based on the Fermi-Diracs law in a monolayer, J. Colloid Inteflace Sci. 200
(1998) pp. 46-5 1.
13. S. J. Park and Y. S. Jang, Interfacial characteristics and hcture toughness of
14.
15.
16.
17.
18.
498
Introduction
The oxygen activated sludge process using oxygen for wastewater treatment is being
generally used in U.S., Japan, etc., and it is well known that its efficiency is also good. But
the reason why the oxygen activated sludge process is not used on a large scale is that the
cost of oxygen feed is higher than the cost of air feed.
Generally, the methods to provide oxygen into wastewater are divided into two. One of
them is to inject liquid oxygen through a pipe line or tank-lorry, and the other is to inject
the gaseous oxygen by 02- PSA(Pressure Swing Adsorption)[l]. In this study, in the
case of injecting oxygen produced by the 02-PSA, the oxygen recovery of PSA for
oxygen concentration, the amount of oxygen transferred into wastewater, and wastewater
treatment efficiency for oxygen concentration were examined.
2
2. I
Theory
0 2 - PSA Process
The maximum purity of 02-PSA is 95% due to the separation of argon in produced gas,
and usually it is 90-93%. The purer the 02-PSA is, the lesser its oxygen recovery
becomes, so the flux of product gas decreased. That means the drop in economical
efficiency of 02-PSA[2]. The concentration of 02-PSA can be generally changed by
tuning P f f ratio(Purge/Feed ratio), and the more PIF ratio increases, the smaller the flux
of product gas becomes. So, when producing highly concentrated oxygen, the power cost
to produce I kg oxygen increases[3].
2.2
The oxygen activated sludge process is a method applying highly concentrated oxygen to
activated sludge process, and it can be used more widely and has higher treatment
efficiency comparing with the activated sludge process. This oxygen process can maintain
499
high sludge concentration, and its retention time is shorter, and it occupies smaller place
comparing with the air activated sludge process. This enables one to reduce the initial
construction cost. Generally, the oxygen process is 2-3 times of MLSS(Mixed Liquor
Suspended Solid) comparing with the air process, and even operating it for 1/3 of the
general retention time, its overall treatment ratio is same as that of air process or better.
Therefore, the oxygen process makes an efficient operation possible in short retention
time, and it provides more oxygen per unit power and makes an operation possible in the
high concentration of dissolved oxygen as well. Furthermore, because the power with
small shearing stress can operate in high concentration of dissolved oxygen, the sludge
which is well deposited and concentrated can be produced, and the amount of excess
sludge decrease. Generally the activated sludge process has a slow treatment speed and
produces much excess sludge. Because this excess sludge treatment costs a lot, it should
be considered by terms of operation expense. The minimal DO(Disso1ved Oxygen) of
activated sludge is about OSmgA, and it is well-known that 1-2mgA or more would be
proper. The OUR(0xygen Uptake Rate) increases at around the entrance of drain, and
decreases low near the exit of drain[4].
I"
w&ta s w e
The Closed type in the oxygen activated sludge process is a method increasing the
efficiency of oxygen by shutting the upper part of aeration tank tight and separating the
aeration tank into 3-4 parts. As a diffuser, the surface aerator is used, and the 02-PSA is
used as an oxygen producer. The open type is a method not covering the top of aeration
tank,and its aeration tank is divided into several parts like the closed type.The open type
used a diffuser specially manufactured to increase the efficiency of oxygen, etc., and
comparing to the closed type, its initial installation cost is low and its power expense
needed to dissolve oxygen is also low, and it is easy to maintain. But the efficiency of
oxygen seems to be worse than the closed type.
500
3. I
Methods
A pilot plant with 1Om3/&y wastewater treatment capability was manufactured. It consists
of raw collection tank,aeration tank,settling chamber and effluent tank, and the aeration
tank is divided into 3 parts. The top of aeration tank can be opened and closed, and the
flow of bubble and the shape of flock in the aeration tank can be observed through a
window. And by attaching a return pipe, materials can be returned from the settling
chamber to the aeration tank,and its drainage becomes easy by attaching a drain valve on
each part of aeration tank.Surface aerator was attached on each part of reaction tank, and
each aerator has an inverter to control the speed of revolution, and the height of aerator
can be changed. Analytical devices are 3 DO meters, MLSS meter, pH meter, and ORP
meter, etc. These are connected to a computer to automatically save their data, and for
sample analysis, CODcr, CODw, TN, TP, etc. were measured with Hach(USA) reagent.
Wastewater used for the experiment was from the joint wastewater disposal plant in the
complex of H-pharmaceutical company, and in the wastewater CODM,, was
1000-3000mg/l. All test devices and analysis equipment were installed indoors, and
oxygen aeration was used in the daytime when wastewater is discharged, and in the
nighttime, the air aeration was used to increase the activity of microbes.
3.2
Based on the results of adsorption test and breakthrough test, etc. oxygen with 93% purity
was produced by using ZMS(Zeo1ite Molecular Sieve) 5A adsorbent, and its flow was
1.5Nm3/h.The air input flow was 22Nm3/h,and the recovery rate was aimed to be 30%.
The 02-PSA pilot plant consists of a compressor for air supply, freezer, after-cooler for
cooling, air receiver tank, 02-product tank,air actuated valve, control box, etc. On the
adsorption tower, 4 RTDs are installed from its upper part to its lower part to change
temperature when adsorbing or removing it. To control feed, purge and product, MFM
was installed for each function.
4
Conclusion
Fig. 2 shows the efficiency of wastewater treatment and the recovery of OZPSA
according to the oxygen concentration. As Fig. 2 shows, the higher the oxygen
concentration becomes, the lower the recovery of 02- PSA becomes. But, the efficiency
of wastewater treatment was about 96% in 60% oxygen concentration, and it was 88% in
90% oxygen concentration. This shows that the highly concentrated oxygen is not
essential for the oxygen activated sludge process. Namely, when using a product gas with
60% oxygen concentration, the efficiency of wastewater treatment is better. Fig. 3 shows
the amount of oxygen transferred into wastewater and total dissolved oxygen according to
the oxygen concentration. The oxygen transferred amount into wastewater gradually
increases when its solubility increases because of high oxygen concentration. But it is
observed that the total dissolved oxygen does not increase continually according to the
oxygen concentration, and it decreases when the oxygen concentration rate reaches about
60%. This is because when the oxygen concentration increases, the recovery rate of
501
02-PSA decreases, so the amount of product gas is reduced, and the total oxygen amount
decreases. That means even though the oxygen concentration is high, the recovery of
02-PSA can decrease, then the amount of product gas produced in the 02-PSA becomes
reduced. Finally the total oxygen dissolved in wastewater is reduced.
In the case of pharmaceutical wastewater, it shows when its oxygen concentration was
60%, the amount of total dissolved oxygen is the most. According to the condition and
concentration of wastewater and the recovery of 02-PSA used in other wastewater
treatment plants, the optimal, and most economical oxygen concentration and operating
conditions will be decided. This study shows that oxygen with 90% concentration or
higher doesn' t have the best treatment efficiency and economical value.
Figure 2. Oxygen recovery ratio and Wastewatertreatment efficiency for oxygen concentration
F '
K.18 -
4-
0,.
A*AA4Tkk
F,,
z 3
A'
0
0
'
ut
$00.9
$
9K
w
w
-1 0 .99
a
w
-06
5:
9
. X3
A'
-03 A
- 1122
A
A
I- 0 3
fo
- 1s
A 'A
3 12-
-A-
00
00
a,
40
60
80
I-
1w
0, CONCENTRATION[%]
Figure 3. Oxygen transferredamount and total dissolved oxygen for oxygen concentration
502
References
503
Introduction
One of modification techniques of the quartz crystal sensor for the determination of
organic vapor is organic film coating on the surface of the electrode. Yet the organic film
coating has problems with its implementation and maintenance in spite of its good
selectivity. Because the adjustment of film thickness is difficult, the reproduction of the
film-coated sensors is also dificult and the sensitivity of the sensors depends largely upon
the film condition. In addition, they are not utilized in the environment of large
temperature variation.
Carbon coated sensors have high stability and endure harsh environment in application,
though they are not selective to organic substances. Kim et al. [l] investigated the
stability of a carbon-coated sensor to find that it is very stable and easy to regenerate by
simple thermal treatment. The sensor is fabricated from the process under very high
pressure, and therefore it is difficult to fabricate and expensive. Chao and Shih [2]
introduced a simply prepared carbon sensor. The coating of fullerene (C,) is readily
made from dropping a drop of dissolved carbon in solvent and drying without any binding.
However, its maintenance is not simple and hard to be utilized in harsh condition. In
another study [3], hllerene derivative has been applied to detect various organic
molecules.
Coating the molecular sieve on one electrode of a quartz crystal oscillator is conducted
to fabricate a gas sensor in this study. The detection performance of the sensors with two
different pore sizes of the molecular sieve is examined from their implement in the
determination of methanol, ethanol and n-hexane concentration in air. From the
performance test, the ruggedness, sensitivity and selectivity of the sensor are investigated.
2
2. I
Experimental
Sensor Preparation
An AT-cut quartz crystal having base frequency of 8 MHz (Sunny Electronics Co.,
Korea) is utilized to prepare the sensor. The electrode of the crystal is silver finished. Two
504
pore sizes of 4 and 5 A molecular sieve (Yakuri Pure Chemical Co., Japan) having pellet
size of 1/16 inch is used, and for binder the phenol resin (Novolac, Dong Kwang Chem.
Co., Korea) having average molecular weight of 400, purity of 99% or above and particle
size of 200 meshes with 13 % hardener of hexamethylenetetramine is added.
The coated crystal is cured in a drying oven of 160 "C for an hour to make the particles
bound on the surface. An SEM photograph of the crystal is exhibited in Fig. 1. In the
figure,dark particles are binder resin and grayish particles are molecular sieve. At lower
left comer there is a large particle of molecular sieve and resin bound.
2.2
Experimental Procedure
The experimental setup is demonstrated in Fig. 2. Air is provided from a blower and a
portion of the air is vent through a bleeding valve. An objective organic vapor is obtained
by passing some of the air to be fed to the measuring cell through an Erlenmeyer flask of
0.2 L capacity containing liquid of the organic substance.
The adjustment of organic vapor concentration is carried out from manipulating the
valves installed in the line of gas flow. The flow rate of mixed gas flow during frequency
measurement is maintained at 0.4 Llmin. all the time by controlling the valve installed at
the bottom of the flow meter. Experiment is conducted at room temperature.
505
The detection performance of the molecular sieve coated sensor is examined from the
measurement of frequency variation while different concentrations of organic vapor
contained air are contacted to the sensor surface. While organic vapor contained air flows
continuously with constant flow rate of 0.4 L/min., the variation of frequency is
monitored and the outcome is converted to the organic concentration. In order to examine
the process of adsorption and desorption of the organic vapor on the molecular sieve
coated on the sensor surface, fresh air and organic substance contained air are alternately
provided.
Figure 3 shows the experimental result of the determination of methanol with 5A
molecular sieve coated sensor. In the beginning, fresh air is supplied, and then methanolcontained air is provided. The concentration of methanol is measured by taking the
sample of 1 mL with a sampling syringe from the gas flow line and by analyzing it with a
gas chromatograph. The decrease of frequency indicates that the coated molecular sieve
adsorbs the methanol and there is a mass change on the sensor surface. After the decrease
is settled, fresh air is fed to desorb the methanol adsorbed on the molecular sieve. The
frequency increases again, and it retums to a little more than the initial value. Because the
experiment is conducted in a flow system, some drift in the initial frequency is
accompanied. After the frequency with the air is kept at a steady value, sample flow of a
higher concentration is introduced to determine frequency variation with different
concentration of methanol. These measurements are conducted for four different
concentrations of methanol- contained air in flow. The incompleteness of frequency
recovery with fresh air supply is linearly increased for the last three runs, but the
frequency shift with methanol is distinctive and proportional to the concentration of
methanol.
-800 awrc.inppm
-m
75
2 M x ) 4 w o 6 o o o 8 o o o
t
i (set.)
In case of ethanol, the sensitivity of the sensor to ethanol-contained air is about 1/5 of
that of methanol. Because the 5A molecular sieve is designed for the separation of the
molecular size of methanol, ethane and propane or smaller, the 5A molecular sieve coated
sensor gives much less sensitivity with ethanol contained air. Unlike other solid particle
coated sensor, such as activated carbon sensor, the molecular sieve coated sensor has
selectivity to the molecular size of detecting material. The outcome presented in Fig. 3
indicates that the sensor coated with 5A molecular sieve satisfactorily discern methanol
vapor from bigger molecules, but it does not separate from small molecules. When 4 A
molecular sieve coated sensor is implemented to detect methanol, the same result of
measuring ethanol with 5 A molecular sieve sensor is yielded as shown in Fig. 4. In other
506
-250
oncinm
-mo
taa
20m
3ooo
urn0
tirn ( u c l
Figure 5 shows the relation between methanol concentration and frequency shiA with 5
A molecular sieve coated sensor. This indicates the measured frequency shift gives the
concentration of organic vapor.
Conclusion
In order to give selectivity to a solid particle coated quartz crystal sensor having
ruggedness and stability with easy maintenance, the coating of two difference pore sizes
of molecular sieve is exercised here. The applicability of the sensor as a gas sensor is
examined by monitoring the adsorption and desorption of organic vapors on the
molecular sieve. The measurement is conducted in a system of flowing air to prove the
ruggedness of the sensor in practical implementation.
From the frequency measurement for different concentrations of organic substance
contained in air, it is shown that the sensor can detect the concentration of different sizes
of organic materials. A good recovery of the sensor to the initial condition is shown, and
the ruggedness is proved from implementing the sensor in a flow measurement system.
The sensor is produced from readily available materials with a simple process, and it is
easily regenerated fiom heat treatment.
Acknowledgements
Financial supports h m the Korea Science and Engineering Foundation and the Korea
Research Foundation are gratefully acknowledged.
507
References
1. J.-M. Kim, S.M. Chang, Y. Suda and H. Muramatsu, Stability study of carbon
graphite covered quartz crystal, Sensors and Actuators, A 72 (1999) pp. 140-147.
2. Y.-C. Chao and J.-S. Shih, Adsorption study of organic molecules on fullerene with
piezoelectric crystal detection system, Anal. Chim.Acta, 374 (1998) pp. 39-46.
3. J.-S. Shih, Y.-C. Chao, M.-F.Sung, G.-J.Gau, C.-S. Chiou, Piezoelectric crystal
membrane chemical sensors based on fullerene C60, Sensors and Actuators B 76
(2001) pp. 347-353.
508
measurements were made for dichloromethane on the adsorbents. Computer calculations were
carried out to simulate the experimental results using the Stop40 method to show the calculated
results coincide well with experimental results. The method is usefil to predict the performance of a
solvent recovery system operated by PSA.
Introduction
The possibility of the PSA process to separate eficiently and economically the
components of some mixed-gas streams have made the process to be used many other
applications, as suggested in many references.
As the PSA process is operated at lower temperature, without heating in regeneration,
it was thought not to be advantageous as for solvent recovery. As a result, it was not fully
studied yet, compared with the recovery by thermal regeneration.
In this study, the solvent recovery by PSA with resin adsorbent and high silica zeolite
was tested. As a first step, CH2C12was chosen as solvent and the following items were
examined.
1) Isotherms and dynamics of CH2C12 adsorption for commercial resin and high silica
zeolite adsorbents were measured by a flow type gravimetric method.
2) CH2C12recovery from air was tried to obtain basic data, using a PSA system, consisted
of two columns.
3) A numerical calculation of PSA operation were performed with the Stop 62 Go method
and results were compared with the experimental results.
2. I
Experimental
Adsorption equilibrium
509
rate (1 00 cm3/min.) and various constant concentrations was fed to the measuring device
as feed gas through two mass flow controllers (for diluting line and for concentrating
line). Concentrations of feed gas were determined by a gas chromatograph (SHIMAZU
GC-7A). Finally, the weight increase due to adsorption for each sample (EX20P and PQUSY) at equilibrium was measured.
Adsorption isotherms of CH2C12on each sample at 303.15 K are shown in Fig. 1.
Solid lines in Fig. 1 are those correlated with Langmuir equation. Equilibrium parameters
for each sample are shown in Table. 1. From the results, the sample PQ-USY was found
to be better to use for PSA operation.
,-52.0
Saturated amount
adsorbed : q%/d
PQ-USY 0.260
EX2OP
2.2
0.220
Adsorption equilibrium
constant : K [i/kPa]
0.1250
0.0718
9" KP
Experimental procedure
PSA unit was consisted of two columns. First, a column pressure was raised by stream
of gaseous feed to 200 kPa (pressurization step). Then product gas was taken out through
pressure control bulb (adsorption step). The other column was evacuated and regenerated
at lower pressure (40 kPa) by feeding purge or backwashing flow, taken from the product
gas. The roles of two beds were reversed periodically. Pressurization, adsorption,
evacuation and backwashing purge were set to 20, 700,20 and 700 seconds, respectively.
Solenoid valves were controlled by a key board programmer to achieve the sequence. Air
from compressor passed through a silica gel column to make the air dry. The dried air was
introduced to a bubbler to load CH2C12vapor and was mixed with the dried air stream for
dilution. The solvent-laden air of constant flow rate (1000 cm3/min.) and constant
concentration (0.8 ~01%)was fed to one of the columns as feed gas. The flow rate of the
gas was measured by a mass flow meter.
The adsorption columns were of 27 mm in i.d. and 300 mm in length. A certain
amount of regenerated adsorbent was packed into each column, as shown in Table. 2.
Temperature was set to 303.15 K by use of a constant temperature bath. A thermocouple
was inserted into the column at 15 cm from the bottom. The concentration changes in
product gas were measured until a cyclic steady state was obtained. Concentration of
feed, product and exhaust gases were determined by a gas chromatograph (SHIMAZU
GC-7A) equipped with a thermal conductivity detector.
510
3.1
As for ylksav (Bed density/Overall mass transfer coefficient), one of the key
parameters of PSA simulation, the simulated break through curves for various ylksav by
Stop-Go method were compared with the experimental curve as shown in Fig.4 to obtain
a reasonable value. There, break through operation and simulations were equal to
pressurization step and adsorption step of the PSA operation. Langmuir constant and
saturated amount adsorbed were equal to the result of adsorption equilibrium experiment.
The other parameters and operation conditions were set to be equal to those of the PSA
operation as Table. 2. From this comparison, in the case of PQ-USY, suitable value of
y h a v were 150 sec, in the case of EX20P, this is 20 sec.
PQ-USY
- 1.2 1
EX20P
Time [min]
Time [minl
3.2
3.2.1
PSA operation
Fig. 5 shows the relation between yield against purity of product gas for PQ-USY and
for EX20P, respectively at a cyclic steady state. Yield is defined as follows:
Yield [-3 = Total amount of product gas per cycle / Total amount of feed gas per cycle
and the purity is defined as follows:
Purity[-]=l-C/Co
511
92
94
96
Purity
98
100
[%I
3.3
PSA simulation
Experimental data were compared with the results of simulation by Stop-Go method
as shown in Fig. 4, 5. Fig. 4, 5 were obtained for dynamic steady operation, regarding
four conditions of the purge gas ratio(R), i.e., R=0.50,0.97,1.46 and 2.72, respectively.
Fig. 4 shows changes of concentrations of CH2C12 in product gas with time in cases
with various purge ratios. Fig. 5 shows the relation between yield and product purity.
From these comparisons, it can be said that the experimental behavior can be simulated
rather well by this simulation method.
0.25
0.20
0.15
1.46
2.72
0.05
0.00
0-
0 10 20 30 40 50 60
70
Cycle [-I
80
90
100
3.3.I
Simulation
Since the experimental results are well simulated, this Stop-Go method can be
possible to predict the behavior in the column, such as the distribution of the amount
adsorbed in the axial direction. Fig. 6 tells the distribution of amount adsorbed at various
positions with purge. This result might be useful in considering axial distribution of the
amount adsorbed in PSA operation and to decide an effective length of column.
512
Bottom
50
Z3O
ZO
10
n
0
10
20
30
40
50
Cycle [-I
Conclusion
The product gas and the exhaust gas were measured for dichloromethane-laden air
feed by PSA system using a resin adsorbent and a high silica zeolite as adsorbent. The
PSA method for solvent recovery with each adsorbent seems to be technically feasible.
The high silica zeolite gave better performance than the resin adsorbent, as expected from
their isotherms.
Also, It was confirmed that the experimental data could be well simulated by the StopGo method. Further, it might be possible, to simulate the condition within the column,
such as the distribution of the amount adsorbed, and to estimate the effect of operational
factors.
513
Fixed-bed adsorption experiments of laboratory-scale were carried out to m o v e organic solvent vapors by
several types of adsorbents. Binary adsorption equilibria of azeotmpic mixture-HSZsystems showed two
azeotropic points. Those experiment data were compared with molecular simulation by the Grand Canonical
Monte Calm (GCMC) method. Experimental results for single and binary component system, including
azeotropic mixture systems, could not be in agreement with the simulation result correlated satisfactorily. But it
turns out that the tendency of the simulation result is the same as the experiment result
Introduction
Discharge of organic substances into air has been strongly prohibited since some
decades ago, to preserve comfortable natural environment. Though hydrocarbons,
alcohols and chlorinated hydrocarbons had been used as the degreasing agent in
industries, these solvents may also affect to our environment, and it is necessary to
remove them from air as much as possible. This study was performed aiming at
presenting useful data for the design of adsorption processes, especially the removal of
the solvent vapors as above from air by adsorption. The soIvents used were
trichloroethylene (TCE) and iso-propanol (PA).
Molecular simulation has now become powerfil means for the study of adsorbed
molecules in high silica zeolites, and GCMC method is especially u s e l l for predicting
adsorption equilibria. However, idormation on forcefield parameters and charges are
often inadequate, even in systems where the structure is well known.
514
2.1
Experimental
Solvents used were toluene (TOL), benzene (BEN), iso-propanol (PA), n-propanol
(NPA), ethanol (EtOH), tetrachloroethylene (PCE), and trichloroethylene (TCE),
respectively, and their binary mixtures were also prepared.
The adsorbents used in this study were high silica zeolite (HSZ) (Y-type from
TOSOH Corp., Ltd Japan.).
Experiments were carried out using a flow method, for BEN-EtOH*, NPA-TOL*,
NPA-PCE*, PA-TCE*, BEN-PA, and BEN-NPA systems, respectively (*: means
azeotropic mixture).
Adsorbents were packed in a glass column of 0.1Om length and 0.0156m i.d.
Experimental conditions were as follows: linear flow rate; 0.2 d s , influent concentration;
in the range of 0.004-0.2 moVm3, and temperature; 298 K.
2.2
Molecular Simulation
Cerius2 (MSI Inc.) was used throughout the simulations. Adsorption equilibria was
carried out by GCMC method for same systems of experiments. Adsorbent model was
pure silicious Y type that was same type as experimental adsorbent. Simulation forcefield
parameters were new forcefield parameter obtained by Mellot et al"]. Solvent charges
were determined with Charge-Equilibration method, respectively.
3.1
Breakthrough Curves
Fig.1 shows several types of breakthrough curves obtained for PA-TCE -Y-type
zeolite system. For this system, reversal of the order of breakthrough (turn over) occurred
twice at concentrations of 0.25 and 0.75 mole fractions of P A , respectively. When the
mole fractions were 0.25 and 0.75, the mixture of two components behaved as if it was a
single component system as shown in Fig2 (B) and (D). For other azeotropic mixture
systems, the turnover occurred only once. The breakthrough curves for other systems
always showed so-called constant pattern behavior for the whole concentration range.
515
3.2
Adsorption Equilibrium
For binary adsorption equilibrium of PA-TCE -Y-type system, the component that
showed higher amount adsorbed between the two components reversed twice as expected
from the breakthrough curves. For this system, it is reported that the azeotropic point of
vapor-liquid equilibrium is only one, but two azeotropic points were observed in the
adsorption equilibrium. When the saturation vapor pressures of each component were
almost the same, appearance of two azeotropic points were reported for vapor-liquid
equilibrium. It is thought, therefore, that the phenomenon occurred in adsorption
equilibrium for these systems can be ascribed to the fact that the saturation vapor pressure
and the boiling points of each component were almost the same. It seemed the
phenomenon was influenced by experimental temperature and concentration, because the
different result was obtained when different experimental concentration (1000-1 5OOppm,
2000-40OOppm, 5000-S5OOppm) were used. Binary adsorption equilibria for these cases
are shown in Fig.2 in the form of X-Ydiagram. Relation between mole fraction of IPA
and amount of absorbed is shown in Fig.3. (Experiment conditions are the same as the
figure of the center of Fig.2)
Even in these cases, binary adsorption equilibrium could be expressed partly by the
Markham-Benton equation.
516
1.o
3 0.8
0
0.6
3.i
000
0;.
0.2
"."
0.0
0.2
0.4
0.6
0.8
0.0
1.0
0.2
0.4
0.6
0.8
0.0
1.0
0.2
0.4
0.6
0.8
1.0
X (=CO/CO-Total)
X (=CO/CO-Total)
X (=CO/CO-Total)
0.2
0.4
0.6
0.8
1.0
mole fraction of P A
Fig.3 Relation between mole fraction of P A and amount of adsorbed
Molecular Simulation
Fig.4 and Fig.5 show adsorption isothenns for single component systems, obtained
from fixed-bed experiments and molecular simulation, respectively. Adosorption
equilibria were simulated well. Except EtOH system, quantitative order of amount
adsorbed was good agreement with experimental data. As for BEN and TOL systems, the
amount of adsorbed for simulations were lower than experimental data. So it is necessary
to examined van der Waals parameter for benzene ring. Fig.6 and Fig.7 show adsorption
equilibria For binary component systems, obtained from fixed-bed experiments and
molecular simulation, respectively. These are examples, which show azeotropic
adsorption"]. Especially, IPA-TCE, BEN-EtOH systems show two azeotropic points.
Result of simulation shows only one azeotropic point. More investigative is necessary.
517
ECOH
PA
WA
TOL
F a
4
A
TCE
BEN
BEN
01
om1
0 01
01
o.mt omt
0.01
0.1
10
tm
C[mol/m3]
C[mol/m3]
Fixed-bed experimental
1.0
wl
1.o
.i
0.2
0.4
0.6
0.8
1.0
X[=C/CO-totall
0.8 1.0
X[=C/CD-totall
(experimental)
(molecular simulation)
Conclusion
References
1. 1. K. Chihara et al., AIChE, AMU~ Meeting, (1993)
2. 2. K. Chihara et al., AIChE,Annual Meeting, (1995)
3. 3. K. Chihara et a]., Proceeding of the 13'hInternational Zeolite Conf, (2001)
518
Introduction
VOCs emitted from chemical processes need to be treated properly using several kinds of
environmental processes including oxidation, adsorption, and condensation technologies,
etc.[2]. Among these technologies, adsorption process could be the fmt candidate for the
recovery of VOCs since it can enrich VOCs in an effective way. Therefore, adsorption
beds are, in general, incorporated in the VOC recovery systems which also include
distillation towers andor condensation systems andor absorption towers to form hybrid
systems[ I].
In this study, the steam regeneration method widely used for the on-site regeneration
of carbon is not employed to avoid.some negative effects such as fire, side reactions,
fouling and so on. Carbon regeneration by vacuuming or purging has not been
comprehensively used until recently except gasoline recovery systems. Its mainly because
VOCs are strongly adsorbed components onto activated carbons and, so, hardly desorbed
only by lowering total pressure in the beds. Therefore, in order to evaluate the feasibility
of vacuum desorption for the enrichment of VOCs, four-step VSA process, which is
similar to the four-step Skarstrom cycle, had been studied with acetone as a VOC and
Pellet-BG as an adsorbent.
2
VSA processes were simulated using the Aspen ADSIM, a commercial adsorption process
simulator from AspemTech Co.,with the following governing equations:
519
a'Tg
az2
- k g E -+ 3V,p,
aTg
C,
aTg
aV,
+ E -p, -+ P - + HTC * ap(Tg - T,)
y
at
az
where, Ji is an adsorption rate. Along with these equations, The Darcy's law was applied
to describe a momentum balance in a bed. In addition, valve equation was employed to for
the pressure driven model. The dead volume and a knock-out drum were implemented by
void tanks.
Experiments
wi =
IP, * 1 ~ ~ e * ~4"3 ~ ~ a
1+ I P ~* ep6lTn * pi"
In Figure 1, the VSA Pilot is composed of the following four major sections: (1) two
aw. -
A - MTcsi(w,:
-Wi)
at
vertical carbon beds. (diameter: 0.4 m, height : 1.O m); (2) liquid-ring vacuum pump with
a knock-out drum,(3) two Silica-gel dryers; (4) a condensation system incorporating a
chiller. The feed to this pilot plant is the acetone-laden air transmitted from an acetate
production process by a series of two ring blowers with cooling systems. The feed air
contains around 1.2% acetone with a variation of W.596 irregularly.
A VSA cycle was made up of four steps: pressurization, adsorption, vacuum, and
vacuum purge. The step times for the four steps are IOOs, 700-SOOs, ~ O S ,550-65Os,
respectively. As can be seen from step times, the vacuum step time is not long compared
with the vacuum purge step since acetonelcarbon system is not favorable to desorption
only by vacuuming the beds. The pressure during a vacuum purge step was around 150
todabs.), which significantly depends on purge rates.
Water was selected for the sealing liquid for which EG(Ethy1ene Glycol) could be a
candidate. EG shows a very low vapor pressure but too high solubility for acetone. As
acetone is less soluble in water than in EG, in spite of higher vapor pressure, water was
used for sealing liquid and the moisture included in the emitted stream from the pump was
supposed to be captured in dryers.
520
4
4. I
In general, many breakthrough experiments have been done to get some breakthrough
curves under several different conditions for the sake of bulk separation or purification.
However, in the case of VOC abatement or recovery, feed rate might be the only major
operating parameters, having direct relationship with adsorption step time. Feed rate was
set to 80 NCM/hr. At this feed rate, the breakthrough happens at 15 min. after the
beginning of feed injection and the curves have a long tail until saturation, as usually
observed in VOC breakthrough curves[3].
As vacuum swing operation depends largely on the successfbl regeneration, the
performances under some different regeneration conditions were assessed to determine a
regeneration condition. Figure 2 shows that vacuum-only regeneration is not sufficient or
nearly impossible to regenerate the carbon beds, showing lower performance than even
the atmospheric purge. Therefore, it is sure that purging is essential for the regeneration
and too much purging rate deteriorate the regeneration performance because it elevates the
vacuum purge pressure. As an example, when the purge rate of 300 Vmin was employed,
the bed pressure surged to 480 torr. From these basic experiments, the regeneration
performance could be estimated through a regeneration index that shows a magnitude of
driving force for regeneration.
Table 1.
B
C
D
E(base)
300
200
200
100
480
239
760
142
521
0.888
1.188
0.374
1 .ooo
Figure 2. Regeneration curves of a carbon (Pellet BG) bed saturated with feed stream beforehand.
4.2
522
Figure 3. The effects of purge rate on the acetone concentration in the enriched stream and the clean air
Acknowledgements
523
Introduction
Methods
2. I Adsorbents
Two kinds of functional adsorbents are used to which one is for selective adsorption
removal of paraffins and the other for C4 olefins. The former is zeolite A and the latter
524
carbon molecular sieve (CMS) or modified clay. Adsorbents of zeolite A and CMS are
already commercialized and modified clay for olefin selective removal was prepared in
our laboratory. Physical properties of these are summarized in Table 1. Preparation
method of modified clay can be found in other literatures [2,3,4,5].
Average pore
BET surface
Remarks
-10 mesh,
spherical
mes
&t%dA
5.9
463
Commercial
6.0
339
Commercial
120
Prepared
Adsorbent
7
e
area mZ/ *
Zeolite A
CMS
Modified Clay
8 ~ f e ~ ~40~ ~
525
A:feedbuffertank
B:productsurgetank
C:Gfueltank
Results
Adsorption isothenns
526
2.2
_..-..
1.4
zoo
um
goo
...
8 o o i a o o
100
200
-.-A
+,.__.--.a.
__.._I
a00
400
5M)
M)o
100
i
800
Pressure (mmHg)
3.2
Process performances
In the first, zeolite A and CMS adsorbents were loaded in each bed as explained in the
section of purification unit. For a continuous operation at ambient temperature, adsorption
and desorption pressure were allowed to 970mmHg and 25mmHg, respectively. The
duration of a cycle was 600sec. In this case, feed composition was as a follow; methane
0-400ppm, ethane 0-400ppm, propane 0.4-4.3%, 1-butene 200-800ppmv, isobutene
0.07-O.11%, t-2-butene 200ppm, n-butane 2.6-6.7%, and isobutane 92.8-95.6%. By
these conditions, isobutane product purity and recovery were 99.9% and 84%,
respectively, and an isobutane productivity based on total adsorbent amount was
3.1mol/kg/hr. C4olefins in the product could be controlled to less than 100ppm.
In the second, zeolite A and modified clay adsorbents were loaded in each bed as
explained in the section of purification unit. For a continuous operation at ambient
temperature, adsorption and desorption pressure were allowed to 870mmHg and 25mmHg,
respectively. The duration of a cycle was 270sec. In this case, feed composition was as a
follow; ethane 0-OS%, propane 2.5-7.5%, 1-butene 0.05-0.15%, isobutene 0.1-0.25%,
t-2-butene 2OOppm, n-butane 3.5-KO%, and isobutane 86.0-89.0%. By these conditions,
isobutane product purity of over 99.99% (not detectable by gas chromatography) was
obtained with the recovery of 66%. A productivity based on total adsorbent amount was
5.2molkg/hr. The performance of this process is graphically shown in Figure 4. Modified
clay was better than CMS in point of isobutane productivity and removal efficiency of C4
olefms.
527
99.9
99.8
99.7
99.6
88.5
SBM)
css
3800
4otM
4200
4400
4600
Discussion
Acknowledgements
This work was partially supported by the National Research Laboratory (NU)
program,
the Ministry of Science and Technology (MOST).
References
1. Volles W.K. and Cusher N. A., Normal butane hsobutane separation, U.S.Patent No.
460806 1 (1986).
2. Han S.S., Kim J.N., Cho S.H., Choudary N.V., Kumar P. and Bhat S.GT., Adsorbents
for light alkane/alkene separation, The 8th APCChE Congress, Aug. 16-19, Seoul,
Korea (1999) pp. 1777-1780
3. Cho S.H., Han S.S., Kim J.N., Choudary N.V., Kumar P. and Bhat S.GT., Adsorbents,
methods for the preparation and method for the separation of unsaturated
hydrocarbons for mixed gases, US. Patent No. 6315816 B1 (2001).
4. Cho S.H., Han S.S., Kim J.N., Park J.H., Yang J.I. and Beum H.T.,Adsorbent
preparations and applications for C4 olefin separation from mixtures, Korean Patent
Application No. 2001-88953 (2001)
5. Cho S.H, Han S.S., Kim J.N., Park J.H. and Rhee H.K., Adsorptive ethylene recovery
fiom LDPE off-gas, Korean J. Chem. Eng., 19 (2002) pp. 821-826
528
Introduction
Silica membranes have received extensive attention in recent years because of their
excellent chemical and thermal stability, especially in the application of gas separation
and catalytic membrane reactor processes. And the separation of high purity HZfrom the
mixed gas, is very important to convert the chemical energy to the electric energy, such as
fuel cells. The final objective of this study is to understand the adsorption and separation
mechanism in the MTES templating composite silica membrane, which can get high purity
Hzfrom C 0 2 and CH4 mixture.
Experiment
Preparation of membranes
Organic templating membranes were prepared by a dip coating on tubular a-Alz03
support or y-A1203 /a-AIZ03 composite support (outside diameter, 10mm; thickness,
1.Omm, length 1OOmm; and mean pore diameter 0.1pm) by TPABr and MTES sols. After
several times of dip coating, membranes without pinhole products were prepared.
Adsorption Measurement
Due to the adsorption property of top layer on membrane (templating sols; TPABr or
MTES), adsorption experiments should be executed before membrane permeation
experiment. And adsorption experiments were performed at the 293K-3 13K temperature
range and Oatm-O.8atm pressure range for various gases by gravitational method using
electric Cahn balance(Cahn 2000, Cahn instrument, INC). From this experiment,
529
Ceramic membrane is the nanoporous membrane which has the comparatively higher
permeability and lower separation factor. And in the case of mixed gases, separation
mechanism is mainly concerned with the permeate velocity. The velocity properties of gas
flow in nanoporous membranes depend on the ratio of the number of molecule-molecule
collisions to that of the molecule-wall collision. The Knudsen number Kn=h/d, is
characteristic parameter defining different permeate mechanisms. The value of the mean
fiee path depends on the length of the gas molecule and the characteristic pore diameter.
The diffusion of inert and adsorbable gases through porous membrane is concerned with
the contributionsof gas phase diffusion and surface diffusion.
Adopting the dusty gas model(DGM) for the description of gas phase mass transfer and
a Generalized Stefan-Maxwell(GSM) theory to quantiw surface diffusion, a combined
transport model has been applied. The tubular geometry membrane mass balance is given
in equation (1).
Equilibrium flux and kinetics of membrane can be calculatedby equations (1) and (2).
N,o, = --RT
I [Di + $ P + ( l - ~ ) q ,
-1-
bD" ap
I+bP ar
All parameters used in equations (1) and (2) were calculated from single gas adsorption
and membrane permeation experiment. The numerical method for solving above equations
were MOL(Method Of Line). These calculations were executed using LSODE
solver(F0RTRAN code).
530
Figure 2(a) contained the comparison of amount of C02 adsorption between a-A1203
support and CMS(Carbon Molecular Sieve, Takeda Co.) . Owing to larger pore(about
lOOnm) and lower chemical affinity, a-A1203 support has trivial adsorption capacity,
compared with CMS.This result means that surface diffusion caused by adsorption could
be neglected in a-A1203support. Therefore, only Knudsen and viscous difisions were
considered as permeate mechanism of a-AI2O3support. In this paper, single component
adsorption experiments were executed in order to investigate surface diffusion effect of
silica membrane. From the above description, surface diffusion in permeate mechanism
could be neglected due to the non-adsorbable property of a-A1203support. Figure 2(b)
shows equilibrium isotherm curve of MTES templating silica unsupport at 293K.
Langmuir and L-F parameters were obtained from this equilibrium data. Figure 2(c) shows
C02 uptake curve of TPABr at 293K. Diffusional time constants in low pressure range
were calculated from adsorption rate equation using modified Ficks second raw and its
numerical method was presented by Ruthven et a1[6].
From the permeate experiment of membrane, the value of the mean pore radius of
support and other properties can be calculated. The real value of pore radius of a-A1203
support(measured by mercury porosimetry) was near loom, and the calculated value of
mean pore radius from experiment was 101nm(N2)and 1 16nm(C02).These were in a
good agreement with porosimetry measurement and permeate method calculation.[4]
However, in case of light gas, H2, showed some deviation from the theoretical results.
From these data, adsorption data and membrane permeate data, we could analyze
permeate and separation mechanism of organic silica membrane. Figure 3(b) shows
permeate rate in N2/MTES templating silica membrane at 293K. This curve was well
fitted to equation (2). Permeate flux arrived with 40 sec. And Figure 3(c) shows predicted
tans-membrane pressure profile which was calculated by DGM and GSM model with
Langmuir parameters and other membrane parameters.[3,6]
Conclusion
After dip coating on support by organic templating sol, for example TPABr and
MTES, pore size was controlled under lOA . Therefore, it was expected sieving effect or
surface diffusion effect on usupport(t0p layer of membrane) because of its narrow and
small pore. In the mixture of adsorbarblehon-adsorbable molecules, silica membrane was
very selective for adsorbable one, due to its surface diffusion and blocking effects.
Adsorbable molecules, for example C 0 2 and CH4, adhered on surface and surface
diffusion takes place by the hoping of molecules between adsorption sites. And they
blocked the other non-adsorbable molecules, for example COz molecules block H2
molecules. Then other vacant sites were occupied with adsorbable molecules and then
surface concentration of adsorbable molecules became higher and higher. Finally
adsorbable molecules permeated through the membrane and non-adsorbarble molecules
were retentated.
531
Acknowledgements
Reference
Fig. 1. Schematic apparatus for experiment (a) adsorption(ektric cahn balancc)measurcmcntsystem and (b)
membrane transport system
-w
Fig. 2. (a) comparison of C@ gas adsorption equilibrium isotherm curve of a-AIp3 support and CMS at
293& (b) equilibrium isotherm curve of MTES unssuport at 313K (b) CO2 stepwise uptake curve of top layer
of membrane(TPABr sol) at 293K.
532
Fig. 3. (a) permeate flux and separation factor in H d C a mixtute/MTES silica composite membmne system at
293K. (b) peameate rate of Nz in MTES silica composite membrane at 293K (c) predicted pressure profile of
C a on TPABr silica membrane at 4abn
533
Introduction
Fixed-bed adsorption process has been an important unit operation for purification and
bulk separation of gas mixture, especially by pressure swing adsorption (PSA). In recent
years, PSA process has been increasingly commercialized for air drying, hydrogen
purification, air separation, and various other separations [l]. One of the successful
applications of a PSA process is hydrogen recovery because a high-purity H2 product with
high productivity can be obtained from a well-designed PSA.
To design and develop PSA process, detailed analysis of the fixed-bed dynamics
must be preceded, because the key step to developing an optimum PSA process lies in the
design and operation of the adsorption step. Also, on the condition that the theoretical
models of the adsorption breakthrough can predict its experimental results well, it can be
used to investigate the breakthrough dynamics in a bed and predict PSA performance
without any specific experiment.
In this study, breakthrough and desorption experiments were performed in
activated carbon and zeolite 5A beds to study the adsorption characteristics of binary and
ternary hydrogen mixture gas (H2/CH, : 43/57 and H2/CO/C02 : 39.3/35.4/25.3 ~01.96).
The ternary mixture is the pseudo composition of effluent gas from incinerator for
pyrolysis gasification while the binary mixture is the converted mixture gas from LNG by
the cold plasma reaction. The ultimate purpose of this study is to find out the optimum
condition for obtaining high purity hydrogen from H2 mixtures by using PSA process.
The experimental results and dynamics in the bed were analyzed by using a nonisothermal dynamic model incorporating mass, energy, and momentum balances. Although
the temperature increase inside a bed is undesirable, in case of bulk separation, the
534
adsorption dynamics in the bed were investigated according to the relationship between
the concentration and temperature profiles.
Experimental
The binary (H2/C& : 43/57 vol.%) and ternary (H2/CO/COz : 39.3/35.4/25.3 vol.%)
hydrogen mixtures as pseudo composition was used as feed gas. And two kinds of
adsorbents, activated carbon (Calgon Co., PCB,6-16 mesh) and zeolite 5A (W. R. Grace
Co., 4-8 mesh) were used. Prior to each experiment, the adsorbents were regenerated for
more than 12 hours at 423 K and 588 K, respectively.
The schematic diagram of an experimental apparatus is shown in Figure 1. The
adsorption bed was made of stainless steel of 100 cm length and 3.71 cm ID. Effluent
stream was sampled between the back-pressure regulator and the product tank and was
analyzed by using a mass spectrometer (Balzers, QME 200). All the data including
concentration, temperature, pressure and flow rate were saved on the computer.
The breakthrough experiments were performed through the adsorption pressure of
5 to 9 atm, and feed flow rate of 4.5 to 9.1 LSTP/min. And the desorption experiments
were performed through 2 to 4 LSTP/min at constant pressure of 1.5 atm.
The equilibrium parameters used in this study have been taken from independent
single-component experiments using volumetric method at several temperatures.
Adsorption isotherms on each adsorbent are shown in Figures 2 and 3.
3
d2C
duc
d q.
1-&
i=l
535
dqi 2h.
2ei+-+T
d t RE,
- pB
-T,) =o
dTW
dt
4, = n ( ~ &- R ; ~ )
- 2MBoho
(Tw
-Tm
The gPROMS-modeling tool was used to obtain the numerical solution of dynamic
simulation. And the results of simulation were stable for the range of conditions used in
this work.
4
Resultsanddiscussion
As can be seen in Figures 4 and 6, the breakthrough curves had long tail due to
temperature variance in the bed. Therefore, energy balance was considered in simulation
of adsorption dynamics. From the adsorption equilibria of H2, C&, CO, and C02,
temperature dependent isotherm parameters of Langmuir-Freundlich type were obtained.
The experimental values under various operating conditions like adsorption pressure and
feed flow rate were compared with predicted ones using linear driving force model.
In the adsorption experiment of binary mixture (Figure 4), breakthrough time of the
activated carbon bed was longer than the zeolite 5A bed, moreover the zeolite 5A bed had
more tailing effect than the activated carbon bed.
In the desorption experiment (Figure 5), the effect of the feed flow rate had similar
effect with the breakthrough experiment.
Whereas CO was the first breakthrough component followed by C02 at intervals of
hundreds of seconds in the breakthrough experiments of ternary mixture (Figure 6).
Because of the relatively high heat of adsorption of C02 compared with that of CO,
temperature increased at mass transfer zone 0
of C02 noticeably. Especially, CO
showed the rolling-up phenomenon, which is due to the competitive adsorption of more
strongly adsorbed component, C02, and this phenomenon is usually Observed in a multicomponent and an equilibrium control system. As concentration wave fronts of CO and
C02 propagate along the bed, sinusoidal temperature excursion was observed. The first
temperature peak was caused by the adsorption of CO and the latter by that of C02.
Excellent agreement between model predictions and experimental results was
obtained.
5
Conclusions
The adsorption dynamics of binary and ternary hydrogen mixture in activated carbon and
zeolite 5A bed was studied by experimentally and theoretically through breakthrough and
desorption experiments. Energy balance is an essential element for accurate adsorption
process modeling in case of bulk separation. Especially in ternary system, sinusoidal
536
temperature excursions were caused by the large difference of wave velocities of each
component. The roll-up of CO and separation of mass transfer zones behveen CO and COz
led to stepwise breakthrough curve of H2in the activated carbon bed.
Acknowledgements
The financial support of Korea Institute of Environmental Science and Technology (200211105-0004) is gratefully acknowledged.
References
1. R.T. Yang, Gas separation by Adsorption Process, Butterworths, Boston, 1987.
2. D.M. Ruthven, S. Farooq, and K.S.Knaebel, Pressure Swing Adsorption, VCH
publishers, New York, 1994.
3. E.S. Kikkinides and R.T. Yang, Chem. Eng. Sci., 48, (1993) 1545-1555.
4. J. Yang, M.-W. Park,J.-W. Chang, S.-M.
KO,and C.-H. Lee, Korean J. Chem. Eng.,
15, (1998) 211-216.
537
. .
5 1 0 1 5 2 0 2 5 3 0 3 5
Pmwun (am)
:h
o
b H
TmM
Figure 5. Effect of flow rate on zeolite 5A Figure 6. Breakthrough curves under 7 atm
adsorption pressure and 6.8 LSTPImin
bed under 1.5 atm desorption pressure
feed flow rate (ternary mixture).
(binary mixture).
538
Introduction
Technologies have been developed to reduce the hydrocarbon emissions during cold
One of the technologies, the hydrocarbon adsorber [ 1-31 has been most attractive to
automotive makers because it has the advantage in view of cost and performance.
Hydrocarbons of the cold start depend on the condition of a vehicle, fuel and driver.
About 100 hydrocarbon species are present in the exhaust of the cold start. They consist
of about 10% methane, about 30% alkenes such as ethylene or propene, about 30%
alkanes such as pentane or hexane, about 20% aromatics such as toluene or xylene, and
about 10% other species. Therefore, a hydrocarbon adsorber has to show a good
selectivity for the hydrocarbons. In order to remove the adsorbed hydrocarbons effectively,
the hydrocarbon adsorber needs to have an additional function, hydrocarbon conversion.
Until now, in order to select a hydrocarbon adsorber with higher hydrocarbon
trapping and conversion efficiency, experimental tests using vehicle and engine
dynamometer has been employed. A model, Temperature Programmed Adsorption (TPA),
was proposed by Kim, et al. [4-51 to save cost and time. The model has an advantage to
analysis adsorption, desorption and conversion of hydrocarbons simultaneously.
In this study, TPA characteristics of two adsorbers of honeycomb type for various
hydrocarbons were evaluated. Methyl alcohol, acetone, acetaldehyde, 224
trimethylpentane, n-octane and toluene were chosen as the hydrocarbons of cold start. The
effect of the hydrocarbon components and oxygen concentration on TPA behavior was
studied.
start.
Experimental
539
cordierite honeycomb ceramic substrates (cell density of 62 cells/cmz (400 cells/in2), wall
thickness of 0.165 mm, 19mm(D)x30mm(L)).The washcoat was consisted of H-ZSM-5,
--A1203 and base metals (Ba, Ce, Zr)used in a conventional three-way catalysts. The
SVAI ratio of H-ZSM-5 was 150/1. In order to study the effect of the presence of precious
metals on the adsorber, Pd and Rh were used. The first adsorber had the 150/1 WA1 ratio
adsorbent with impregnated Pd/ Rh in a 10/1 ratio, and it was named as HA #l. The
second one had the same SVAl ratio adsorbent without precious metals, and it was named
as HA #2. For adsorbers, washcoat loading amount was same. When impregnating
precious metals, PdClz and RhC13. 3H20 were prepared as the precursors of Pd and Rh.
All samples were dried at 423.15 K for 5 hrs and calcined at 823.15 K for 4 hrs.
The components of hydrocarbons generated from engine during cold start are
dependant on fuels, vehicles and driving conditions. In this study, methyl alcohol
(Aldrich, 99%), acetone (Aldrich, 99%), acetaldehyde (Aldrich, 99%),
224trimethylpentane (Aldrich, 99.8%), n-octane (Aldrich, 99%) and toluene (Aldrich,
99.95%) were chosen as the hydrocarbons of the cold start, and were used without any
treatment.
2.2 TPA
The apparatus for TPA was shown in detail elsewhere. For all experiments the
dimension of a sample (20 mm(D)x30mm(L)) was identical. Before doing TPA
experiment the sample was oxide at 673.15 K for 1 hr in zero air (1 Umin), and then it
was purged with Nz(1 Umin) at 673.15 K for lhr and cooled down to 303.15 K in Nz(1
Vmin). After that, the sample was heated in lo00 ppm hydrocarbon /N2 mixture (1 Vmin)
at 303.15 K to 573.15 K with the ramping rate of 1 Wmin. In addition, to evaluate a
conversion of hydrocarbon, Ozwas supplied with the concentration of 1.47%.
The concentrations of hydrocarbon at the inlet and outlet of the reactor were
measured using Fl'IR (Nicolet) with a mercury-calcium-telluride(MCT) detector, which
was cooled by liquid nitrogen and gas cell (Infrared Analysis), and with 16 scans and a
resolution of 2 cm-'. The concentrations were also checked using GC (Hp589Oplus) with
FID (flame ionization detector) and HP plot column. The vapor pressures of the
hydrocarbons were calculated by using Reid equation [6].
3
Figure 1 shows TPA curves of 224 trimethylpentane, toluene and n-octane on HA #4.
For all cases, the inlet concentration and flow rate was kept to be constant with lo00 ppm
and 1 Vmin under the absence of 0 2 in supply gas. This figure is represented according
to temperature and relative concentration. The relative concentration means the ratio of
outlet concentration (Cout) to inlet concentration (Cin). The value of 1 stands for the full
saturation of a hydrocarbon on the adsorber. The value over 1 represents the sum of
supplied hydrocarbon and desorbed hydrocarbon from the adsorber. The order of
breakthrough appeared to be n-octane, 224 trimethylpentane and toluene. This result may
be attributed to the difference of interaction intensity of the hydrocarons and the adsorber.
Over 330 K all hydrocarbons started to desorb from the adsorber. Although the gas flow
did not contain 02, the value under 1 appeared for all hydrocarbons. The value under 1
appeared around 390 K for toluene, around 500 K for 224 trimethylpentane and nactane.
This result may be attributed to the structure effect of the adsorber and the oxidation
reaction of hydrocarbons and adsorbed oxygen during the pretreatment.
540
540
1.6
500
460
g 0.8
420
-e
380
Y 1*2
0
=
U
(A
0.4
340
0
300
0
40
80
120
160
200
240
Time(min)
Figure 1 TPA curves of 224 trimethylpentane, toluene and n-octane on HA #4 under the absence of 02 in
supply g=
1.6
540
4Acetone
4Methanol
+-Acetaldehyde
500
n
Y
460 w
t3
420
-s!
=a
380
(A
0.4
E"
Q)
c
340
0
300
0
40
80
120
160
200
240
Time(min)
Hgure 2 TPA curves of acetone, methanol and acetaldehydeon HA #4 under the absence of 0 2 in supply gas.
Figure 2 shows TPA curves of acetone, methanol and acetaldehyde on HA #4. The
conditions of the inlet concentration and the flow rate were same as Figure 1. Although
oxygen was not supplied, the relative values of three hydrocarbons moved to "0" with the
increase of the temperature.
541
500
? 1.6
L5
g. 1.2
460
420
Y
g!
0.8
.-2a 0.4
380
+-224TMP
-+Toluene
+Acetaldehyde
0
0
40
80
120
160
200
E"
340
300
240
Time(min)
Figure 3 TPA curves of 224 trimethylpentane, toluene and acetaldehyde on HA #5 under the absence of 02 in
supply gas.
1.6 I
1 540
HA #4
224TMP
-A-0% 02
-E-0.8%02
500
n
460
p!
.
I
-
5 0.8
420
380
E"
$
0
a9
.->
2 0.4
U
340
0
0
40
80
120
160
200
300
240
Time(min)
Figure 4 ' P A curves of 224 trimethylpentane on HA #4 with respect to 0 2 concentration
542
precious metals.
TPA curves of 224 trimethylpentane on HA #4 according to different 02
concentrations are shown in Figure 4. According to the increase of 02 concentration, the
adsorption amount of 224 trimethylpentane was decreased little, but the hydrocarbon
conversion stated at the lower temperature and was advanced over 460 K.
References
1. Williams, J.L., Patil, M.D. and Hertl, W.,By-Pass Hydrocarbon Adsorber System for
ULEV, SAE, paper No. 960343 (1 996).
2. Engler, B. H.,Lindner, D.,Lox, E. S., Ostgathe, K., Schafer-Sindlinger, A. and
543
Introduction
A hydrocarbon adsorber system [l], which has been used for reduction of cold-start
hydrocarbons, adsorbs the hydrocarbons in the initial period of cold-start. Generally, the
adsorber system is consisted of adsorber followed by light off catalyst. As the surface
temperature of the adsorber is heated up, the adsorbed hydrocarbons are released slowly
from the surface, and then converted to inert gases by oxidation reactions on adsorber or
light-off catalyst.
To predict effectively the adsorber system, it is important to understand the behaviors
of hydrocarbons on adsorber and light-off catalyst during cold-start. Kim, et al. [2]
proposed the experimental model, namely TPA (Temperature Programmed Adsorption),
to simulate the behaviors of hydrocarbons on adsorber or light-off catalyst during
cold-start.
In this study, a new mathematical model was developed to predict the experimental
TPA behaviors with reaction, and it was incorporated with additional adsorption model of
extended Langmuir-Freundlich equation (ELF). LDFA approximation and external mass
transfer coefficient proposed by Ullah, ,et. al. were used [3]. Also, rate expression of
power law model was employed [4]. The parameters used in the power model were
obtained directly from the conversion data of hydrocarbons on adsorber or light off
catalyst [5]. In this study, to get numerical solutions for the proposed model, orthogonal
collocation method and DVODE package were employed [6].
2
Experimental
544
Theoretical
Tg =T, =To + a - t
Initial conditions for O<z<L and t=O are as follows
y,
4,
Boundary condition for F O and 0 0 is as follows
=o;
=o
Y , =y/o
Adsorption isotherm of Langmuir-Freundlich for multi-component is defined by
qI =
qm,b,(PY,,,)"I
"
1 + Cb,(FyJ,JJ
RTS
Subscript i refers to hydrocarbons under consideration (224 trimethylpentane,Toluene).
Oxidation scheme of hydrocarbons adapted in this study can be represented as
follows.
C,H, + 9 0 2 + K O 2 + 4 H 2 0
8c02 + 9H2O
CgHl, + 12.502
For rate expression power model was used as follows.
545
Figure 1 shows experimental and predicted TPA results for single component on LOC
#l. Hydrocarbon used was 224 trimethylpentane and toluene. Fluid velocity (7.57E-2 d s )
and concentration of supplied O2 concentration (0.18 Wa) for each hydrocarbon were
same. In the result of adsorption equilibrium, the amount of toluene adsorbed seemed to
be higher than 224 trimethylpentane. As can be expected, toluene was emitted more lately.
However, Toluene was converted more rapidly than toluene over 380 K.
Loc#1
? 1.6
e
3
g 1.2
224TMP
To1
Pre-224 TMP
Pre-To1
---
/1
500
460
g!
E
0
.-W
420
Q)
0.8
380
-2m 0.4
U
c
340
300
0
40
80
120
160
200
240
Time(min)
Figure 1 Experimental and Predicted TPA results of 224 trimethylpentane and toluene on LOC # 1 in presence
of 1.8% 02 ( L = 0.03 m, U = 7.57E-2 ds).
It agreed well with isothermal dynamic adsorption results and conversion results at
steady state. The predicted results by the proposed model described well the experimental
results.
Experimental and Predicted TPA results for binary components, 224 trimethylpentane
and toluene, on HA #4 and LOC #1 were shown in Figure 2 and Figure 3, respectively.
The experimental condition of Figure 2 was identical to that of Figure 3.
546
1.6
0'
540
500
1.2
CI
0"
T
460
420
0.8
e!
a
a,
.-c>
380 a,
340
!-
$ 0.4
0
0
40
80
120 160
Time(min)
200
300
240
Figure 2 Experimental and Predicted "PA results for binary components (224 trimethylpentane / toluene) on
HA #4 in presence of 1.8% 0 2 (-L= 0.03 rn, U = 7.57E-2 ds).
1.6 I
3 540
o
To1
TMP
500
6 1.2
cs
460
Oeci
sE
a
420
0.8
.-a,>
380
340
m 0.4
3
40
80
120 160
Time(min)
200
E
a,
300
240
Figure 3. Experimental and Predicted TPA results for binary components (224 trimethylpentane / toluene) on
LOC#1 in presence of 1.8% 0 2 ( L = 0.03 m, U = 7.578-2 d s ) .
Total concentration of two hydrocarbons in gas phase was 2000 ppm (0.2 kPa). The
mole fiaction of 224 trimethylpentane and toluene was assumed of 0.5 and 0.5,
respectively. The concentration of supplied O2 concentration was 0.18 kPa, and the
velocity was 7.57E-2 d s . In all cases, 224 trimethylpentane was emitted first, but the
reaction was started lately. It matches to the results of adsorption equilibrium and
conversion experiments. The proposed model described the experimental data properly.
547
References
S., Masushita, K., Etoh, S. and Takaya, M., In-Line Hydrocarbon (HC)
Adsorber System for Reducing Cold-Start Emissions. SAE. 2000, paper No.
2000-01-0892.
2. Kim,D.J., J. W.Kim, J. E. Yie and H. Moon, Temperature-ProgrammedAdsorption
and Characteristics of Honeycomb Hydrocarbon Adsorbers. Ind Eng. Chem. Res.,
1. Yamamoto,
2002,41,6589 -6592.
3. Tronconi, E. and Beretta, A., The Role of Inter- and Intra-Phase Mass Transfer in the
SCR-DeNOx Reaction over Catalysts of Different Shapes, Catal. Todqy, 1999, 52,
249-258.
4. Lopez, E., Errazu, A.F., Bono, D.O. and Bucala, V., Altanative Designs for a
Catalytic Converter Operating under Autothermal Conditions, Chem. Eng. Sci, 2000,
55,2143-2150.
5. Kim, D.J. Non-Isothermal Dynamic Ahorption and Reaction in Hydrocarbon
Adrorber Systems. PhD. Thesis, Department of Chemical Engineering, Ajou
University, 2002.
6. Finlyson, B. A. The Method of Weighted Residuals and Variational Principles,
Academic Press, New York, 1972.
548
Introduction
Sorption data for radionuclides in contact with minerals typical of those found in
water-bearing fractures in rock are needed in the safety assessment of deep geological
repositories. Furthermore, an understanding of the factors that influence the sorption
characteristics of the radionuclides is essential when we apply an empirically derived
sorption value outside the range of the experimentalparameters.
The surfaces in old hctures, which have been in contact with moving groundwater,
may have a quite different mineral composition from the surrounding host rock. This
fracture coating material could be the results of weathering and alteration of the rock or
precipitates and crystallization products from the groundwater [l]. It was also reported
that the sorption on natural hcture surfaces is more effective than on fresh core samples,
evidently because of the higher cation exchange capacity of the altered minerals on
fracture surfaces [2].
Most of the sorption experiments for rock materials have been performed using
crushed rocks [3], and only a limited number of sorption studies were performed for rock
coupons or rock cores [4]. The aims of this study are therefore to investigate the kinetics
and reversibility of U(V1) sorption upon the natural fracture surfaces and fresh intact
surfaces of a Korean granite rock, respectively, and to investigate which constituent
mineral of the granite rock contributesto the sorption of U(V1).
Experiment
The granite rock used in the study was sampled from a granite quarry site located at
Dukjeong-myun, Kyongki-do, Korea. Rock samples used in the experiments were sections
of drilling cores containing natural fracture surfaces and machined fresh intact surfaces on
one side. The drill cores were cylindrical, about 10 cm in height and about 10 cm in
diameter. In this study, U(V1) in the nitrate form (U02(N03)2-6H20)
was used as a sorbing
nuclide. The concentration of uranium was measured by ICP-MS (Varian, Ultramass 700).
549
The surface area of the natural fracture surface was measured using a 3dimensional laser
scanner (Inter Tech Co., Ltd). The surface area of the fracture surface was measured as
79.02 cm'. An experimental setup for the surface sorption experiments used in this study
is shown in Fig. 1.
Before granite cores were mounted to the sample holder they were kept in contact
with 0.01 mom NaC10, solution, which is adjusted to a desired pH, for about one month.
Before injecting the uranium tracer solutions, the solutions were adjusted to desired pHs
(i.e., pH 5.5, 7.0 and 8.5) using NaOH or HClO, solutions. The tracer solution was then
pumped to a narrow space between the granite core and the acryl cap at a flow rate of
about 1.0 d m i n . All sorption experiments were performed at about 23&2"C under an
ambient condition. The solution samples for the measurement of uranium concentration
were taken in a kinetic process up to 2 weeks.
3
3.1
where [VJ (moVcm') is the concentration of sorbed uranium per unit surface area of a
granite surface, and [v,] (moVcm3)is the concentration of uranium in the solution phase,
550
50
n
n
U
n
U
$40
+MS-2
(pHz7.0)
2
2
t-MS-3
(pH=8.5)
2 30
$I
4 F S - 1 (pH=5.5)
2 20
-8-FS-2
(pH=7.0)
c.
8
2
10
0
0
10
15
20
Time, days
Figure 2. Kinetic results for U(V1) sorption onto the fresh intact surfaces and the natural fracture surfaces
(MS: fresh intact surfaces, FS: natural fractured surfaces).
The kinetic sorption data can be interpreted based on the assumption that the uranium
sorbs on the surface of granite according to a first-order reaction. The time dependence
can be given as:
pt = P, ( 1-eekt)
and this equation is linearized as:
In( 1 - Pt/Ps) = -k.t
where Pt and P,are the percents of uranium sorbed on the fracture surface at time t and at
steady state, respectively, k (l/day) is a kinetic sorption rate constant, and t is time in days.
The plot of ln(1 PJPs) against t should be linear for a first-order kinetic reaction.
The rate constants are estimated by the slopes of lines fitted by a least squares method
and listed in Table 1. It is concluded that a two-step first-order kinetic behavior dominates
in the surface sorption of U(V1). The relatively slower second-step may be due to such
effects as a diffusion-controlled sorption onto the fracture surface of micropores and a
mineral dissolution of the granite surface [ 191. It is noticed from Table 1 that the reaction
rates do not greatly depend upon pH although the amount of U(V1) sorbed onto the granite
surface is greatly dependent on pH.
551
Table 1. The results of first-order kinetic fitting for the U(U) sorption onto the fresh intact surfaces and the
natural fracture surfaces.
Test
MS- 1
MS-2
MS-3
FS- 1
FS-2
FS-3
3.2
pH
kl (l/d)
k2 (1 /d)
5.5
7.0
8.5
5.5
7.0
8.5
1.015
0.9763
0.6897
0.8888
1.0627
0.863 1
0.3625
0.3662
0.3364
0.2702
0.2878
0.4464
ReversibiIiQ
The results of sorption and desorption of uranium are shown in Table 2. As shown in
Table 2, the desorbed percentages of uranium from the granite surfaces are somewhat
greater than sorbed percentages of uranium on granite surfaces. Thus, the results show that
the sorption process of U(V1) is a little irreversible for the two types of granite surfaces
depending on pH and surface type. This may be due to the fact that small amount of a
mineral such as chlorite mainly contribute to the sorption of uranium and the uranium
sorbed on this mineral is hard to be desorbed from the mineral surface.
Table 2.
Test
pH
Sorptiontype
MS- 1
5.5
Sorption
Desorption
Sorption
Desorption
Sorption
Desorption
Sorption
Desorption
Sorption
Desorption
Sorption
Desorption
MS-2
MS-3
FS-1
FS-2
FS-3
3.3
7*0
8.5
53
70
8.5
Percent of U(V1)
sorbed or desorbed (%)
22.857
14.328
26.555
20.420
17.694
12.190
32.668
25.693
46.586
41.880
24.370
16.050
K*(cm)
1.303
4.190
1.930
8.304
0.775
5.525
2.242
8.95 1
16.233
21.849
1.131
4.688
MineralogicaI eflect
The mineralogical composition of the fracture surface was determined by point counter
methods using electronic microscope and x-ray diffraction. It was observed that the
fracture surface was mainly composed of chlorite, biotite, quartz, and calcite. The fresh
intact granite was mainly composed of quartz, plagioclase, K-feldspar, biotite, hornblende,
and a small amount of sphene and opaque phases. We investigated the distribution of
U(V1) on the surface of granite by x-ray mapping after sorption experiments. For example,
the result of x-ray mapping for the natural hcture surfaces is shown in Fig. 3. It is noticed
lkom the result that chlorite which is present as a minor mineral mainly contributes to the
552
sorption of U(V1) onto the natural hcture surfaces. On the other hand, it is noticed fiom
the x-ray mapping study that U(V1) is preferentially associated with mica on the machined
fiesh surfaces of granite.
Figure 3. The result of X-ray mapping which shows the U(V1) distribution on granite surface. (Ksp:
K-feldspar, PI: Plagioclase, Qz: Quartz, CI: Chlorite)
Acknowledgements
This work was supported by the Ministry of Science and Technology, Korea.
References
Skagius K., Neretnieks I., Porosities and diffisivities of some nonsorbing species in
crystallinerocks, WaterResour. Res. 22 (1 986) pp. 389-398.
2. Muuronen S., Khilrtfinen E. -L., Jaakkola T., Pinnioja S. and Lindberg A., Sorption
and diffusion of radionuclides in rock matrix and natural fi-acture surfaces studied by
autoradiography, Mat. Res. SOC.Symp. Proc. 50 (1985) pp. 747-753.
3. Stenhouse M. J. and Pettinger J., Comparison of sorption databases used in recent
performance assessments involving crystalline host rock, Radiochim. Acta 66/67
(1994) pp. 267-275.
4. Vandergraaf T. T. and Abry D. R. M., Radionuclide sorption on drill core material
fiom the Canadian Shield, Nucl. Technol. 57 (1 982) pp. 399-4 12.
1.
553
Introduction
The hazardous elements such as heavy metal and radionuclide can migrate and enter the
terrestrial and aquatic environments when the wastes are disposed of at an underground
repository. The important phenomenon to limit the migration of the elements in the
geosphere is their adsorption on surrounding solids [l]. The adsorption behavior greatly
depends on the chemical species of the elements as well as the surface property of the
solids [2]. Uranium is a widespread environmental contaminant resulting from mining and
manufacturing activities related to nuclear power. Chemical properties of uranium are
very complex and not clearly known at present. Chemical behaviors of uranium including
precipitation and adsorption are greatly influenced by the conditions of natural aquatic
systems [3]. Underground matrices are mainly composed of rock-forming materials
together with a smaller amount of oxide and clay minerals. Oxide and clay minerals have
larger adsorption potential than rock-forming materials [4]. For this reason, the studies on
the adsorption of heavy metal and radionuclide with oxide and clay minerals have been
identified as one of the important research works associated with waste disposal [5,6].
This study investigated the adsorption behavior of uranium on kaolinite under various
aqueous conditions. The uranium adsorption was studied with particular emphasis on its
chemical speciation and adsorption mechanism. Equilibrium distribution of aqueous and
solid-phase uranium species was predicted by a model calculation using geochemical code.
Experimental investigation of the partitioning of aqueous and solid-phase uranium was
also performed using a precipitation method under different pH and COz partial pressures.
The adsorbed amount of uranium on kaolinite as a function of pH was investigated and the
adsorption mechanism was proposed.
554
2.I
Methods
Modeling of uranium speciation
2.2
555
This solid-phase disappears at pH 7.5 and U species including carbonate is formed above
pH 7. The dominant species in the pH range of 7-9 and above 9 are (UOz)&03(OH)i and
UOZ(CO&~,respectively. The aqueous phases of uranyl ion, uranyl hydroxyl carbonate
and uranyl carbonate are formed as the pHs of solution increase. The solid-phase is uranyl
hydroxide around pH 7. It is found from the equilibrium model calculations that the
dominant species at pHs 5.5 or below is uranyl ion although the COz conditions were
varied. Uranium is precipitated as a hydroxide form of I3 -UOz(OH)z(s)at a neutral pH.
The aqueous phase of uranium hydroxide, hydroxyl carbonate and carbonate are dominant
species at a high pH. These species have anionic charge.
10
PH
Figure 1. Calculated distribution of uranium species in the aqueous and solid-phase of 1x10" M solution
equilibrated under 0%C a condition.
100
80
60
40
20
10
DH
Figure 2. Calculated distribution of uranium species in the aqueous and solid-phase of 1x10" M solution
equilibrated under air condition.
3.2
Precipitation of uranium
556
solid-phase uranium in the UO, solution under 0% C02conditions was less than 30% of
initial amount of U at pHs 5 or below. The amounts of solid U increased rapidly in the
range of pH 5-9. The precipitated U above 70% was maintained in the pH ranges of 7-10.
In the case of air condition, the precipitated U was less than 40% in all pH ranges of 4-1 1
except for 54% of precipitated U at pH 6.8. The amount of solid is relatively small in the
low pH range. The amount of solid-phase increased with the pH of solution and then
decreased rapidly in the high pH range. Comparing these experimental results with the
calculated distribution of U species in Figures 1 and 2, the amounts of precipitated U
agree with the line of solid-phase of D -U02(OH)2(s). The precipitated U increases
rapidly and then decreases with the increment of pH. The precipitated amounts are
relatively small in the low and high pH range. There are maximum percentages in the pH
range of 7-9 and 6.5-7 under 0% C02and air conditions, respectively.
3.3
The adsorbed amounts of U as a function of pH under different COz conditions are also
shown in Figure 3. Under nearly 0% C02 condition, less than 40% of initial U was
adsorbed below pH 5. The adsorbed amount of U increased rapidly as the pH increased.
The adsorbed percentage reached more than 95% of initial U above pH 7 and then the
amount was constant in the pH range fiom 7 to 9.5. But the adsorbed amount began to
decrease above pH 9.5. When the C02 condition is air atmosphere, 28% of initial U was
adsorbed at pH 4.4. The adsorbed amount increased sharply in the pH range of 4-7. The
adsorbed percentage decreased slowly at pH 7 or above.
Adsorption characteristics of metal on mineral can be explained by two parameters
that influence metal behavior. One parameter is the chemical species of that metal and
another is the surface property of mineral. The chemical species of metal varies as the pH
of solution changes [2]. It is known that the progress of adsorption at permanent charge
site is different from that at the edge site of AlOH and SOH structure. Ion-exchange
reaction is a main process at the site of mineral having the permanent charge. This process
occurs at relatively low pH ranges. The adsorbed amount by ion-exchange is not varied
with pH and it is affected by other cations [lo]. Surface complexation occurs mainly at the
edge site and greatly depends on the solution because the surface charge of functional
groups varies with the pH [1 11.
The adsorbed amounts in Figure 3 do not show these phenomena related to
ion-exchange reaction. As shown in the results of Figure 3, the significant increase of
adsorbed amount is found in the pH range of 4-7. This results from the surface
complexation between chemical species of U and hydroxyl groups of mineral surface. As
the pH of the solution increases, functional groups at the edge of kaolinite have negative
charges and surface complexes are then formed by the reaction of anionic surface and
uranium species. The dominant species of U in the pH range of 4-6 is UO, as shown in
Figures 1 and 2. The uranyl cation has a good affinity with anionic surface. In the pH
range of 6-9, the dominant species of U is solid-phase of P-U02(0H)2. Therefore, the
adsorbed amount is mainly contributed with the precipitated uranium. As shown in Figure
3, the adsorbed fraction of U is higher than the precipitated fraction. This excess adsorbed
amount corresponds to the adsorbed amount by surface complexation of uranyl ion or
other uranium species. At higher pH ranges, the adsorbed amount decreased rapidly. This
is explained by anionic species such as U02(0H)3-, (U02)2C03(OH)3-and U02(C03)3, as
shown in Figures 1 and 2, which have no adsorption capacity with mineral surfaces. To
con fm the chemical species of uranium, the aqueous and solid-phase of uranium are to
557
100
.$
a0
3
V
0)
60
40
:g- 20
0)
.
d
!s
a
0
3
PH
References
1. Lieser K. H., Radionuclides in the geosphere: sources, mobility, reactions in natural
waters and interactions with solids, Radiochim. Acta, 70/71 (1995) pp. 355-375.
2. Stumn W., Chemistry of the solid-water interface: processes at the mineral-water and
particle-water interface in natural systems (John wiley & sons, 1992).
3. Kim J. I., Chemical behaviour of transuranic elements in natural aquatic systems,
Handbook on the physics and chemistry of the actinides, Freeman A. J. and Keller C.,
eds. (Elsevier science publishers B. V., 1986).
4. Sposito G., The chemistry of soils (Oxford univ. press, 1989).
5. Payne T. E., Lumpkin, G. R., and Waite T. D., Uranium"' adsorption on model mineral,
Akorption of metals by geomedia (Academic press, 1998).
6. Hyun S. P., Cho Y. H., Hahn P. S., and Kim S. J., Sorption mechnanism of U(1V) on a
reference montmorillonite: binding to the internal and external surfaces, J. Radioanal.
Nucl. Chem. 250(1) (2001) pp. 55-62.
7. Allison J. D., Brown D. S., and Novo-Gradac K. J., MINTEQA2/PRODEFA2, A
geochemical assessment model for environmental systems: version 3.0 user's manual,
EPA/600/3-91/021 (U. S. EPA, 1991).
8. Grenthe I., Chemical thermodynamics of uranium: NEA-TDB (OECD, North-Holland,
1992).
9. Bond K. A., HATCHES: A reference thermodynamic database for chemical
equilibrium studies, Nuex Report NSS/R379 (Nirex, 1997).
10. Dzombak D. A., and Morel F. M. M., Surface complexation modeling: hydrous ferric
oxide (John wiley & sons, 1990).
1 1. Stumn W., Part 1 The solid-solution interface, Aquatic surface chemistry (John wiley
& sons, 1987)
558
Introduction
Methods
The natural kaolin was calcined at 9OOOC and activated kaolinite granules in the 300-400
559
pm size range were obtained for the sorbent materials. CdC12,PbC12and CsCl used in this
study were powdered high-purity chemical reagents (Aldrich Co., >99.9%).The principle
of this experiment is to pass a simulated flue gas, which includes lead or cadmium vapor,
through the high-temperature bed of kaolinite granules.
The experimental system, which is shown in Figure 1, mainly consists of a flue gas
supplying system, a sorption reactor assembly and a metal vapor scrubbing train. All
experiments were performed with a metal vapor-carrier gas of 20 LPM (liter per minute).
The composition of the flue gas entering the sorption bed, which includes metal vapor,
was 8% water, and 16% oxygen by volume, with the remainder consisting of nitrogen.
The metal vapor concentrations were controlled from the knowledge of the averaged
vaporization rates determined by the metal vaporizing thermo-gravimetric furnace
(MAC-QOO,LECO Ltd.) and the flue gas flow rate.
The amount of adsorbed metal was determined by the weight difference of the preand post-sorption sorbent. The structural and morphological change of kaolinite granules
during sorption tests was investigated by the powdered X-ray diffraction (XRD) analysis
(Philips, Xpert MPD) and scanning electron microscopy (SEM) (JEOL, JXA 8600).
1 4 - 1
Figure 1. Experimenta' Set-up of high-temperature metal vapor sorption system: 1. Flow meter 2. Needle
valve 3. N2 4. 0 2 5. Steam generator 6. Gas mixer 7. Valve 8. Thermo gravimetric furnace 9. High
temperature sorption bed 10. Thermocouple 11. Filter 12. Impingers 13. Furnace controller 14.
Silicagel bed 15. Vacuum pump 16. Dry gas-meter
3
3. I
SEM microphotographs of the activated kaolinite granules are shown in Figures 2a. The
activated kaolinite granules include fine metakaolinite grains in the size range of about 2-3
pm, relatively coarse feldspar and muscovite grains. Figure 2a illustrates that the activated
kaolinite granule is an agglomerate of numerous fine metakaolinite grains and thus has a
porous structure. The results of a BET analysis of calcined kaolin agreed with the
microscopic observation. The measured BET surface area of activated kaolinite was 15.5
m2/g. No micro pores were found by BET analysis and the averaged pore diameter is
200.5 A. These results show that the macro pores of calcined kaolin were well developed
by agglomeration of fine metakaolinite grains but metakaolinite grains themselves have no
porous structures. The scanning electron microphotographs of metal-sorbed sorbents are
shown in Figure 2b-d. Adsorbed lead, cadmium and cesium were evenly distributed with
560
the surface and inside the metakaolinite grains in the activated kaolinite granules. The
distribution of cadmium, lead and cesium was similar to the initial distribution of
metakaolinite grains in the activated kaolinite granules.
3.2
Sorption reaction
The changes in the mineral compositions of the sorbent samples by metal sorption are
illustrated in Figure 3a-d. The calcinations of this raw kaolin cause the dehydration
reaction converting kaolinite minerals (AI2O3'2SiO2'xH20) into metakaolinite
(AI2O3'2SiO2).
Figure 3c-d shows that metakaolinite included in the calcined kaolin acts as
a chemical sorbent for lead and cadmium capture. A kind of lead aluminum silicate
(Pb0AI2O3'2SiO2),two kinds of cadmium aluminum silicates (CdO A1203'2Si02and
2Cd0A1203.2Si02),and a kind of cesium aluminum silicate (Cs20A1203'2Si02) were
found in the powdered XRD patterns of each metal-sorbed sorbent grains. Therefore, the
following reaction schemes can be suggested for the high-temperature metal- capturing
mechanisms.
CdO A1203.2Si02+ 2HCl(g)
(1)
AI2O3'2Si02+ CdC12(g)+ H20(g)
Cd0A1203'2Si02+ CdC12(g) + H20(g) --* 2Cd0AI2O3'2Si02+ 2HCl(g) (2)
AI203'2Si02+ PbC12(g)+ H20(g)
Pb0AI2O3,2SiO2
+ 2HCl(g)
(3)
Cs20 A1203'2Si02+ 2HCl(g)
(4)
AI2O3'2SiO2+ 2CsCl(g) + H20(g)
-+
-+
3.3
Metal uptake
561
a) raw kaolin
A
[7
b) activated
kaolinite
0
V
D
a
c) lead-sorbed
kaolinite
OD
Anorthite
Halloysite
Kaolinite
Montmorilonite
Muscovite
Illite
arts
I?
d) cadmium-sorbed
kaolinite
A CdO A1203.2Si02
2Cd0-AIzO3.2SiO2
+
e) cesium-sorbed
kaolinite
10
Figure 3.
15
20
25
30
35
40
45
90
Cd
Pb
cs
Fractional leachability
0.54%
<0.1%
48.6%
562
5 2 . 5 ~ 1 0 L
cs
--d
2 2.0~10
-0E
E
e
1.5~10
1.0~10
L
.
n
a
5.0~10~
c
0.0
20
40
60
80
Time (hr)
Conclusions
Activated kaolinite granules are comprised of 2-3 pm grains separated by large pores,
through which the metal vapors easily diffise. Diffused cadmium and lead chlorides react
with sorbent to form water insoluble metal-mineral complexes. (PbA12Si208,CdA12Si20s
and Cd2AI2Si209).Activated kaolinite grains of 300-400 pm having large pore volumes
and small grains are suited as sorbent for the capture of cadmium and lead vapors from
hot flue gas. Most captured cadmium and lead was present as water-insoluble and
environmentally non-hostile products. Although cesium was more preferentially adsorbed
onto activated kaolinite compared to other two metal vapors, a half of captured cesium
appeared to be water-sorbed cesium compounds, CsCI.
References
1. Agnihotri, R., Chauk, S., Mahuli, S., and Fan, L.S., 1998. Selenium removal using
ca-based sorbents : reaction kinetics. Environ. Sci. Technol., 32, 1841-1846.
2. Barton, R. G., Clark, W. D., and Seeker, W. R., 1990. Fate of metals in waste
combustion systems. Combust. Sci. and Tech., 74,327-342.
3. Ho, T. C.,Tan, L., Chen, C. and Hopper, J. R., 1991. Characteristics of metal capture
during fluidized bed incineration. AZChE Symposium Series, 87, 1 18-126.
4. Linak, W.P. and Wendt, J. 0. L., 1993. Toxic metal emissions from incineration:
mechanisms and control. Progr. Energy Combust. Sci. 19,145-1 85.
5. Mahuli, S., Agnihotri, R., Chauk, S., Ghosh-Dastidar, A. and Fan, L. S., 1997.
Mechanisms of arsenic sorption by hydrated lime. Environ. Sci. Technol., 31,
3226-3231.
6. Sherwood, T. K., Pigford, R. L. and Wilke, C. R., 1975. Mass Transfer, McGraw-Hill
Chemical Engineering Series, 3 19-3 1 1.
7. Uberoi, M. and Shadman, F., 1991a. Sorbents for removal of lead compounds fiom
hot flue gases. AIChE Journal, 36,3226-323 1.
8. U. S. EPA., 1993. Operational Parameters for Hazardous Waste Combustion Devices.
EPA/625R-93/008,62-63.
563
Abstract
The pulse chromatographic technique was used to study low coverage adsorption of linear
and monobranched alkanes in the C5-CS range on two different 10-membered ring
zeolites, ZSM-22 and ZSM-23. Henry adsorption constants, enthalpies of adsorption, preexponential factors of the van't Hoff equation and separation factors were determined. A
detailed interpretation of the experimental data confirmed the previously proposed poremouth adsorption mode for branched alkanes on zeolite ZSM-22, where these molecules
do not have access into the depth of the pores, but rather point their linear part herein.
Zeolite ZSM-23 shows adsorption properties between zeolite ZSM-22 and zeolite ZSM-5,
which is a shape selective zeolite where normal and monobranched molecules have both
access into its pore system.
Introduction
Since their discovery, microporous materials such as zeolites found major application
fields in processes like separation, ion exchange and catalysis. Their uniform pore size
and pore architecture are at the basis of separation processes whereas the chemical
composition of these materials makes them unbeatable candidates to be used as a catalyst
or an ion exchanger. Regardless of which process is used, the molecules engaged are
adsorbed on the surface according to their molecular structure and properties. The
bulkiness of the molecule compared to the pore size of the microporous material decides
if or not the molecule can be trapped in the depth of the porous framework, thus there
exists cases where molecules with larger diameters than the pore size are not able to enter
the pores. This makes the microporous materials acting as a sieve in molecular level and
they are hence referred to as molecular sieves.
564
where A represents mono- (M), di- (D), or tri- (T) valent exchangeable cations, B the
tridimensional framework with an intracrystalline void space consisting of channels and
cages that may sometime be interconnected, and C molecules sorbed in their
intracrystallinevolume which are either water, organic templates used during synthesis,
or sorbed species which can also be reactants, intermediates, and products for catalytic
reaction'. This uniformly defined structure gives zeolites a large versatility in the use of
many reactions. Hydrocracking and hydroconversion are amongst the most important
applications where zeolites with their unique properties are used as host materials. It is
not surprising that zeolites with typical diameters close to those of hydrocarbons exert
shape selective effects. Zeolite Y is perhaps the most extensively zeolite used in
hydrocracking reactions, but it does not exert high selectivity towards a specific
branching due to its large pore system. Ten-ring zeolites with smaller pore structures like
ZSM-5 and ZSM-22 are more suitable for isomerization reactions in the way that they can
exhibit shape selectivity. They possess the optimal pore shape and size to suppress
undesired cracking reactions. Among the 10-membered ring zeolites, ZSM-22 is found to
be the most selective catalyst for the conversion of n-alkanes into 2-methylbranched
isoalkane~~*~.
Different approaches were established to find an unambiguous explanation
for this selectivity including transition state selectivity*,product shape selectivity3and a
pore-mouth, key-lock adsorption-reaction models*6,in which catalytic transformations of
n-alkanes occur specifically in the pore openings, with the molecule only partially inside
the confinement of the pore. The branch is created in the first lobe of the pore. The deeper
the n-alkane penetrates into the pore, the stronger the interaction, explaining the
preference for branching at carbon atoms near the end of the chain. A schematic
representation of pore and pore-mouth adsorption modes is given in Figure 1.
565
The 10-membered ring zeolites (ZSM-22 and ZSM-23) were kindly provided by
Prof. Martens (COK, KULeuven). Both of the zeolites have unidimensional pore
structures without any intersection. The crystals are needle-like shaped for both materials.
Zeolite ZSM-22 (belonging to the TON family) has free pore dimensions of 0.44 X 0.55
nm and zeolite ZSM-23 (MTTfamily) has free pore diameters of 0.45 X 0.42 nm. The
framework structures are sketched in Figure 2. The low coverage adsorption properties
were determined with the pulse chromatographic technique. The details of the
experimental method are discussed elsewhere. The Henry constant was determined fiom
the first moment of the response curve on the TCD detector after injection of an alkane
trace. Adsorption enthalpy and entropy were obtained by fitting the temperature
dependence of the Henry constant to the van? Hoff equation.
Related to their similar pore diameter and pore structure, unsurprisingly the Henry
adsorption constants for linear alkanes are very close to each other on zeolite ZSM-22 and
ZSM-23 (Table 1). Somewhat higher constants are obtained for 2- and 3-methylbranched
alkanes on ZSM-23 compared to zeolite ZSM-22. The adsorption constants of linear
alkanes are obviously higher than branched alkanes on the two cases. The separation
power of a zeolite between a linear and a branched hydrocarbon may be given by the
separation factor (a),which is the ratio of Henry constants of linear and branched
molecules at a certain temperature. a values at 523 K are given for both zeolites in Table
1. For comparison, values for ZSM-5 are also included, which is one of the most popular
shape selective catalyst used in isomerization reactions. From this table it can be seen that
both ZSM-22 and ZSM-23 have higher separation constants compared to ZSM-5. The
zeolites can be listed in the following order with respect to their separation capacity
between linear and 2- and 3-methylbranched alkanes: ZSM-22 > ZSM-23 > ZSM-5. In
narrow pore structures such as zeolites ZSM-22 and ZSM-23 it is very probable that
linear alkanes with smaller kinetic diameters have more access to the available adsorption
sites compared to the more bulky branched molecules. This may be regarded as the first
566
reasoning that explains the large separation factors between those molecules. That the a
values are much higher on ZSM-22 and ZSM-23 than those on zeolite ZSM-5, which
already exerts shape selectivity between linear and branched molecules, may indicate that
different adsorption mechanisms, such as pore mouth adsorption for branched molecules,
may be active on the former two materials.
ZSM-22
ZSM-23
5.6XlO6
5.W106
I ZSM-22
ZSM-23
ZSM-5.
I ZSM-22
63.3
ZSM-23
ZSM-5'
ZSM-22
ZSM-23
61.6
51.1
1.4XlOJ
17.1
13.0
66.8
z.ix10"~1 . 1 ~ 1 0 ' ~ ~
3.W10J
89.4
03.5
19.6
3.?xio-"
7.5X10-'5 4.8X10-'4
8.4X10J
1.1~10'~~
100.6
92.5
90.1
1 . w r o ~ 1.lX1o6
4.4
2.9
1.4
49.3
51.9
56.1
1.5X10'"
2.9X10"'
2.5X106
5.4
3.6
1.7
60.0
61.3
88.8
2.6X10'"
1.9X10-'3
6.1X106
5.3
3.8
1.9
18.1
17.0
18.4
1.5xiO"~ 2.1x10-~~
1.2X10J
6.1
3.3
1.9
81.3
88.8
88.6
2.4X10-"
3.4X10"
4.4X10'"
2.1x104
6.6
4.2
24
59.4
69.2
66.0
2.4X10-"
4.6X106
7.0
4.3
2.0
72.0
79.7
78.0
3.0X10-" 9.8X10-'4
9.9Xl04
2 . 0 ~ 1 0 ~ 0.5
4.1
2.0
84.5
88.8
88.5
3.6X10"'
43x10'"
a. Separalion fadm dculated fmm rehmnce 8 usin0 the van't HM relalion,enthelpiesfw ZSM-5 are fmm reference 8
The adsorption enthalpies were extracted form the slope of the individual van't
Hoff plots. The values obtained are summarized in Table 1. For pentane, almost the same
adsorption enthalpy is measured on ZSM-22 and ZSM-23. For higher n-alkanes, the
difference in adsorption enthalpy seems to become larger. For both zeolites a linear
relationship exists between the number of carbon atoms and the adsorption enthalpy for
both linear and branched hydrocarbons. On ZSM-22 the adsorption enthalpy increases
with about 13 kJ/mol per carbon added regardless the presence and the position of a
branch and this value is about 10 W/mol for zeolite ZSM-23. A further remark is that the
enthalpies of linear alkanes are clearly higher than those of branched molecules on the
two zeolites, where the differences are larger on zeolite ZSM-22 (1 3- 17 kJ/mol for ZSM22 and 3-7 kJ/mol for ZSM-23 - Table 1). On zeolites with well-defined pore diameters
and pore structures the adsorption enthalpy depends on the force field created by the
framework and applied on the guest molecule. These forces are mainly dispersionrepulsion type in the case of apolar hydrocarbons'. Thus, the narrower the diameter of the
pore the higher will be the interaction. In a previous paper' it was shown that this
statement is also confirmed experimentally, where adsorption enthalpies on zeolites with
different pore diameters were compared. It was observed that on zeolite ZSM-22 the
adsorption enthalpies of branched hydrocarbons were significantly lower than on zeolite
ZSM-5 with a slightly larger pore diameter. This was attributed to a different adsorption
mechanism operating on ZSM-22, namely pore-mouth adsorption mode.
The pre-exponential factors on ZSM-22 and ZSM-23 are given in Table 1. Similar
values are obtained for the C5-CS range linear and branched hydrocarbons. Values of
linear alkanes on ZSM-23 are slightly higher than on ZSM-22, and values of branched
molecules are slightly lower. Pre-exponential factors of the isomers are significantly
567
higher than their parent linear alkane on ZSM-22, whereas comparable values are
measured for linear and branched alkanes with the same number of carbon atoms on
zeolite ZSM-23.
Conclusions
Adsorption of linear and branched alkanes in the C5-C8 range was studied on two
Acknowledgements
We are grateful to the IAP program of the Belgian Federal Government for support
in the project 'Supramolecular Chemistry and Catalysis'. J. Denayer is grateful to the
F. W.0.-Vlaanderen, for a fellowship as postdoctoral researcher.
6
References
1. Derouane, E. G.; Proceedings of thefirst Francqui Colloqium, 1996,7
2. Martens, J. A. ; Parton, R. ;Uytterhoeven, L. ; Jacobs, P. A. Appl. Catal. 1991,
76,95
3. Webb Ill, E. B.; Grest, G. S.Catal. Lett., 1998,56,95
4. Maesen, Th. L. M.; Schenk, M.; Vlugt, T. J. H.; de Jonge, J. P.; Smit, B. J.
Catal. 1999, 188,403
5 . Claude, M. C. ;Vanbutsele, G. ;Martens, J. A. J. Catal. 2001,203,213
6. Souverijns, W.; Martens, J. A. ;Uytterhoeven, L. ; Froment, G. F. ;Jacobs, P. A.
Progress in Zeolite and Microporous Materials 1997, 105, 1285
7. Ocakoglu, A. R., Denayer, J. F. M., Marin, G. B., Martens, J. A., Baron, G. V.;
Journal of Physical Chemistry B, 2002 (in press)
8. Denayer, J. F.; Souverijns, W.; Jacobs, P. A.; Martens, J. A.; Baron, G. V. J.
Phys. Chem. B 1998, 102,4588
9. Ruthven, D. M. Principles of adsorption and adsorption processes; John Wiley
and Sons: New York 1984,220
568
PI.
Results
Studies with nitrogen
569
the new facility, for consistency checks, and because this represents a standard procedure.
The reproducibility of the measurements was better than 5% for samples of different
production years and otherwise constant conditions. Comparison of the isotherms
measured with the literature data available for the same material [I, 51 yielded a good
agreement, cf. Fig. 1. A classical type4 behaviour is clearly evident. However, some
differences become obvious by a more in-depth analysis of the data sets, as will be
described below.
The center of Fig. 1 illustrates the Y-functions as proposed by T6th [6,7] for
apparent type4 isotherms. This helps to identie the appropriate isotherm equation. The Y
maximum denotes the completion of monolayer formation, which, however, is not
consistent for the different samples analysed here. More experience with the T6th
approach will be gathered in the ongoing analysis and help gaining a better understanding
of this result.
The differential pore distribution as obtained by the Density Functional Theory is also
shown in Fig. 1 (bottom). Overall distribution for all measurements was found to be in the
range of 6-30 A, with pores above 16 A making up a very small fraction only. A peak
value that is common to all data sets is 12.5 A. Only the NBC samples, although not all of
them, show a second peak at 10.7 A.
2.2
Fig. 2 highlights the isotopic effect for H2and Dz by showing the adsorption isotherms
measured under both sub- and supercritical conditions (T&(Hz)=33.19 K,
T&t(D+38.34K). The lower part illustrates the evaluation of the experimental data
according to the Langmuir equation. It becomes clear that the Langmuir fit works very
well for nitrogen, shows an acceptable performance for the hydrogens, but is not
applicable to helium. The variation of the results is shown in Table 1.
Table 1. Rcsults of the Langmoir plot evaluation at n o d boiling temperature.
GaS
Temp. [K]
V (monolayer) [cd/g]
Surface [m2/g]
Protium
20.4
23.7
77.4
493
519
318
1734
1826
1386
Deuterium
Nitrogen
570
0
120
100
80
A
&
60
40
20
0.2
0.0
0.6
0.4
0.8
1.0
9-
-5
sg
0.12
0.10
0.08
0.04
0.02
0.00
0
10
15
25
20
30
35
40
Figure 1. Comparison of own data measured for NZat 77 K with data by Ldewyckx [5]. The isotherms (top),
the derived T6th Y-function (middle), and the DE;T analysis of these data (bottom)are presented.
571
0.0035
0.003
0.0025
6-
-8
0.002
\
50.0015
n
0.001
0.0005
0
0
0.2
0.4
0.6
0.8
Figure 2. Iuustration of typical measured isotherm curves of Hz and 9(top); intercomparison of different
sorptives by evaluation of experimental data (data For He from 141) at their n o d W i g temperam in a
Langmuir plot, which should yield a straight line when applicable (bottom).
2.3
For comparison, a porous non-evaporable getter alloy material (ZrNalFe, trade name
ST707,SAES Getters) which is commonly used in getter vacuum pumps was investigated
as well. The sample was a typical strip with an active surface of 13.5 c d and a specific
getter mass of 38 mg getter/cm2.The measurements, as shown in Fig. 3, indicate a type-III
sorption behaviour with small amounts adsorbed. However, the relative differences of the
three sorptives are more pronounced on the getter than on charcoal, especially for helium
compared to hydrogen.
572
0.2
0.4
0.6
0.8
RelativePressure (p/pc)
573
Introduction
574
selectivity of specific catalysis and chemical reaction. It can expect very good effect if
condition of most suitable about choice of impregnant and the amount is established.
And it must ponder how expense is cost because impregnated activated carbon fiber is
costlier than activated carbon fiber. When apply in adsorption for specification gas, if
impregnant exists on the surface of activated carbon fiber, removal mechanism by
chemical adsorption that is concerned to chemical reaction/catalysis preferably more than
physical adsorption acts by much bigger factor. Chemical adsorption need activation
process like most chemical reaction, and generate single adsorption. Also, unlike
physical adsorption, as the temperature is higher, endothermic reaction generates and
collision fraction increases. The chemical reaction by lively molecular motion between
impregnant and adsorbate can be generated. Important factor that affect the chemical
property of impregnated activated carbon fiber is interference action between impregnant
and activated carbon fiber. Usually, for other metal or impurities with possibility to be
unrelated chemically with metal substance of surface when activated carbon fiber is
support, their effect to activated carbon fiber is possibility that give toxicity to impregnant.
Therefore, when make impregnated activated carbon fiber, the properties of activated
carbon fiber should be have well-developed pores, high surface area, strong mechanical
strength and no impurities [3,4].
Our study applies an adsorption process using chemically activated carbon fibers
(CACF) to effect NO,, a prevalent atmospheric pollutant difficult to control. A concrete
understanding of adsorption and desorption behavior and surface chemistry on was
progressed.
2
Experimental Methods
575
The results may be deduced that the weight of CACF decreases at a lower temperature
when compared to KOH because the bond energy of KOH is ionized after being
impregnated with ACF. However, the fact that TGA curve showed a similar pattern for
CACF and KOH proves that KOH does not exist in the form of crystal on or inside of
ACF, but has been bonded with ACF physically or chemically, or its electronic property
has been changed due to the movement of its electrons on the surface. This trend may be
seen in DSC, which showed the modified properties of surface. The difference in the
TGA and DSC trends of the three samples are attributable to functional groups and
chemical structures existing on surface, or interaction and physical -and-chemical bonds
between KOH and ACF.
In order to confirm the effect of CACF, compared the breakthrough curve of NO, on
CACF and ACF. The result confirms that CACF shows a good selectivity with NO,, and
it can be determined that KOH provided strong basic functional group to the ACF. And
when adsorbing NOz/Air to CACF as the loading amount of impregnant increases, the
removal efficiency relatively increases because KOH given more selective adsorption site
for NO,. When NO2 was adsorbed on CACF at the temperature 2 IOO'C, the
completely-oxidized KN03, the partially-oxidized KNOz and H20 were produced at the
same time. This indicates that the adsorbent loses its function when selective adsorption
sites are all converted into KN03. However, as for the sample having not reached
saturation points, KOH and KN02 co-exist on CACF at the same time. H20, produced at
the same time, may serve as a side effect to produce HN03or HN02 on the surface. As
the degree of the influence to be exerted by H20 may be dependent on temperature, the
reaction occurs more vigorously when temperature becomes lower.
E,
a
4000
.-0
5c!
2000
u
0
E
o0
100
200
300
Temperature ("C)
400
500
600
100
200
300
Temperalure ( " C )
400
500
600
Figure 1. NO and NO2 concentration profiles obtained from Temperature Programmed Desorption when the
bed depths ofNO, adsorbed CACF are (a) ACF, (b) KOH:ACF=I:9, (c) KOH:ACF=l:4, (d) KOH:ACF=l:3, (e)
KOH:ACF=l:2 and (0 KOH:ACF=l:I.
576
occurred within 20072. As the ratio of KOH increases except for 1:l and 1:2,
concentration of NO and NO2desorbed increases.
Potassium distribution on surface after desorption was analysed by using EPMA. A
previous report concerned the result of the K mapping after production of CACF.
According to the mapping result with magnitude x 3500, the white parts showed
distribution of K. K did not show any difference from the result of the test conducted
after the manufxture of CACF against the sample where NO, was adsorbed and desorbed.
Therefore, Figure 2 was found that NO, only was desorbed fiom the surface with the
crystal, comprised of KNO,(x=2,3) having been created after adsorption, upon desorption
at high temperature 5 600C. The results of ToF-SIMS, stemming from polarity of
positive ions detected through the analysis, were seen in the range of 1-100 m/z, which
provides the data on major peaks. As a result of a qualitative analysis of the spectrum,
K+(m/z-39), KO'(dz=55), K;(m/z=78) and K20+(m/z=94) were observed. Such a
result confirms that a large amount of K existed on the surface after desorption. The
result of surface analysis by EPMA, SEM, and ToF-SIMS confirms that K was distributed
with the level of concentration similar to that of K distributed on the manufactured CACF,
which was not included in the present study though.
Figure 2. The ToF-SIMS positive and negative spectra : C / C d . 9 8 , adsorbed for 2hr with near 5OOppm of
inlet NO, concentration at l o o t , (a)-(b) nonadsorbed on CACF (KOH:ACF=I:3) ; (c)-(d) NO, adsorbed on
CACF (KOH:ACF=l:3).
Reference
1. Lee Y. W., Choi D. K., and Park J. W., Surface chemical characterization using
AES/SAM and ToF-SIMS on KOH-impregnated activated carbon by selective
adsorption of NO, Ind Eng. Chem. Res. 40 (2001) pp. 3337-3345.
2. Mochida I., Kawabuchi Y., Kawano S., Matsumura Y. and Yoshikawa M., High
catalytic activity of pitch-based activated carbon fibers of moderate surface area for
oxidation of NO to NO2 at room temperature. Fuel 76 (1997) pp. 543-548.
3. Illhn-Gom6zM.J., Linares-Solano A., Radovic L. R. and Salinas-Martinez de Lecea
C., NO Reduction by Activated Carbons. 2. Catalytic Effet of Potassium. Energy
577
4. Zhu Z.
578
Introduction
Nitrogen oxides (NOx) is regarded as the most notorious toxic gases emitted into the air in
the process of fossil fuels consumption. However, NOx emission remains difficult
control issues despite decades of research [l-31. NOx is not subdued effectively by
existing granular activated carbons. Over the recent several years, development of
surface modified activated carbon served as a springboard for improving the existing
granular activated carbon (GAC). Such surface modified activated carbon proved to
have far superior adsorption capacity against environment -polluting hazardous
Despite the advantages described as above,
inorganic/organic gases [1,4,5,6,7,8].
surface modified activated carbon still needs to undergo significant improvement via more
systematic and advanced technologies in order to reach perfect process. Adsorption onto
the activated carbon modified chemically with potassium hydroxide (BHAC), in particular,
accompanies not only physical adsorption but also chemical adsorption with adsorbate,
which makes desorption process of BHAC more complicated when compared to GAC.
Desorption requires surface chemical information on molecular ions of adsorbate
distributed on the surface. However, the previous researches lacked study of these aspects.
Therefore, this study investigated a typical behavior that appears when BHAC is used to
examine adsorption at different bed depths at the temperature of 100C and the subsequent
desorption by adjusting the temperature upward. Furthermore, this study analyzed various
surface characteristics in order to collect concrete data concerning surface chemistry after
adsorption and desorption.
579
Methods
BHAC was prepared by impregnating a potassium hydroxide into GAC at 85C for 3h by
wet impregnation method. The fixed-bed column was a 3 16 stainless steel tube, with an
inside diameter of 1.09cm and a length of 40cm. Concentrations of NO and NO2 that
exhausted from the bypass line and adsorption column were analyzed by using a
chemiluminescent NO, analyzer. The first step of adsorption-desorption is a heat
treatment of BHAC to 10-100C in the presence of He. The second step is the NOx
adsorption in the presence of 02. In the third step for cooling down the sample to 10C.
Then, after maintaining to the temperature for 30min, a temperature programmed
desorption(TPD) experiment is done in He at 5"C/rnin up to 600 "C. For surface
characterization, Differential Scanning Calorimetry(DSC), Thermal Gravimetric
Analysis(TGA),
Scanning
Electron
Microscopy(SEM),
Energy
Probe
Micro-Analysis(EPMA) and
Time
of
Flight
Secondary Ion
Mass
Spectroscopy(ToF-SIMS) are applied for the identification of thermal and surface
chemical information.
3
The adsorption experiments, when the bed depth(amount) of BHAC was lcm (0.534g),
2cm (1.067g) and 9cm(4.803g), were tested at 403 K of temperature, 500ppm of NOx
concentration, 30cm/s of linear velocity. The strong basic surface of BHAC gets
oxidized in its adsorptiordreaction with NOx gradually. In this case, the rate, at which
impregnant loses its function after the oxidation of the BHAC surface, mostly depends on
the amounts of impregnant and adsorbent, structure of the activated carbon, concentration,
temperature, and linear velocity. The overall surface oxidation rate decreases when the
amount of NOx adsorbed increases comparatively, i.e. the bed depth gets deeper. The
primary reason of adsorptivity increase is that there are many selective adsorption sites
with the K+ and OH' ions, which can react with NOx. The second reason is deemed to be
related to the re-adsorption of the NO produced [ 1,2,3]. For the bed depth of lcm, 2cm
and 9cm, the each concentration means C/Co of 0.9122, 0.6766 and 0.2828 and the
surface oxidation rate of 91%, 68% and 28%, respectively. This result implies the fact
that fictional loss of the selective adsorption sites is directly related to oxidation of
alkaline surface. When NO2 was adsorbed on BHAC, surface oxidation occurred as seen
in the Eq. (1).
2BHAC
ZNO,
(1)
NO2
(2)
Eq. (2) may occur as a minor side reaction. However, adsorption was not smooth owing
to the boiling point (b.p=2 1.15"C) of NO2 at temperature 2 100C. The adsorption via
chemical reaction, as in Eq. (l), shows high adsorptivity at the temperature range fiom
100C to 150C, which is several times higher than that of adsorption of NOx to GAC
itself in Eq. (2) as reported in the previous papers[2,3]. The chemical modification of
the activated carbon uses chemical substances that have high selectivity against each
580
Figure 1. A. NO and B.NO2 concentration profiles obtained from Temperature Programmed Desorption when
the bed depths of NOx adsorbedBHAC are lcm, 2cm, and 9cm.
(4)
He
(2) Strong bond (SB at 215-350C): potassium nitrite, having been produced on the
surface, seems to depend on decomposition. The sample having not reached complete
saturation / surface oxidation has high intensity. The decomposition of potassium nitrite
also occurs mostly due to production of NO as seen in Eq. (9,
where potassium oxide is
581
adsorbed.
A
2rnO2(4 +
He
OW + 2 W g ) + OAg)
(5)
(3) Very strong bond (VSB at 355-600C): A peak occurs with decomposition of
potassium nitrate, i.e. a more stable substance than potassium nitrite. As NO and NO2 are
produced at the same time, potassium oxide is produced and adsorbed (Eq.(6)).
A
(6)
2 m 0 , (4
+
K 2 0 ( 4 + NO2 ( g )+ N a g ) + 0 2 ( g )
He
B.
A.
C.
Figure 2. SlMS depth profiles of A. NOi, B. NO,and C. OH ions in the non adsorbed BHAC and BHAC after
NOx adsorption and desorption.
Figure 2 A and 2 B shows far larger distribution of NO; and N O to cover 462A on the
surface with 68% oxidation of the surface (bed depth =2cm). The overall distribution of
NO; to reach 1232 A of surface depth, was found to be the highest in NOx ahorbed
>BHAC>after desorption in order. It is deemed that the lower distribution of NO; after
adsorption than BHAC may be attributed to the fact that N hnctional group, having
existed on BHAC, was bonded with surface oxygen and came to be partially desorbed
from the surface when temperature increased. Figure 2 C shows sputter depth profile of
OK. Distribution of OH- is found to be the highest in BHAC. On BHAC, OH- ions
provide selective adsorption sites and react with NO2, as seen in Eq. (l), and evaporate
into H20. Accordingly, after adsorption of NO2, a substantial reduction of O K was
observed regardless of surface depths. However, after desorption, O K ions increased on
the surface which may be explained by two possibilities:
A
KOH(s)
+
K 2 0 ( a )+ H,O(g)
He
(7)
1) As KOH in BHAC, non-reacted selective adsorption sites, was decomposed, as seen Eq.
(7), to produce H20 upon desorption at a high temperature, and H20 evaporated to enable
a hydrogen bond between H with surface oxygen; and 2) H bond was broken away from
some deficient carbon due to a high temperature and H was bonded with surface oxygen.
4
References
1. Lee Y. W., Choi D. K., and Park J. W., Surface chemical characterization using
AES/SAM and ToF-SIMS on KOH-impregnated activated carbon by selective
adsorption of NO, Ind Eng. Chem. Rex 40 (2001) pp. 3337-3345.
2. Lee Y. W., Choi D. K., and Park J. W., Characteristics of NOx adsorption and
582
surface chemistry on impregnated activated carbon, Sep. Sci. Technol. 37 (2002) pp.
937-956.
3. Lee Y. W., Choi D. K., and Park J. W., Performance of fixed-bed KOH impregnated
activated carbon adsorber for NO and NOz removal with oxygen, Carbon 40 (2002)
pp. 1409-1417.
4. Lee Y. W., Choung J. H., Choi D. K., and Park J. W., NOx adsorption on
impregnated activated carbon, Fundamentals of A&orption, IK International Ltd.
(2002) pp. 154-161.
5. Lee Y. W., Park J. W., Choung J. H., and Choi D. K., Adsorption characteristics of
SO2 on activated carbon prepared fkom coconut Shell with potassium hydroxide
activation, Environ. Sci. Technol.36 (2002) pp. 1086-1092.
6. Lee Y.W., Park J. W., Yun J. H., Lee J. H., and Choi D. K., Studies on the surface
chemistry Based on competitive adsorption of NO,-SOz onto a KOH impregnated
activated carbon in excess 02,Environ. Sci. Technol.,36 (2002)pp. 4928-4935.
7. Lee Y.W., Park J. W., Kim H. J., Park J. W., Choi B. U., and Choi D. K.,Adsorption
and reaction behavior for simultaneous adsorption of NOx and SOz over
carbon-supported potassium catalysts, Carbon, in revision.
8. Lee Y. W., Kim H. J., Choi D. K., Yie J. E., and Park J. W., Temperature
programmed reaction and regeneration studies of NOx over potassium
hydroxide-containingactivated carbon, Emiron. Sci. Technol, in revision.
583
Introduction
A strive toward a cleaner environment has led to the global tightening of the sulfur content
in automotive diesel fuel. For example, the sulfur limit of 500ppm has been adopted by
EEC since 1996, and in Japan since 1997[1]. More severe specifications with a sulfur
content of 35Oppm S is now practiced, and a sulfur level as low as 5Oppm or even at least
lOppm is being proposed in Europe for the year 2005[2]. For this reason, there are
considerable efforts being expended to develop new technologies for the production of
clean fuels, like adsorption, extraction, oxidation, alkylation, and bioprocessing[2].
Currently, however, hydrodesulfiuization(HDS) appears to be the technologically
preferred solution.
The most practical method to produce 10 ppm ultra low sulfbr diesel is considered to
be the two-stage HDS process. In this process, the sulfur levels are reduced down to
around 250 ppm in the first stage and are further reduced down, after the hot gas that
contains the inhibiting components are removed, to below 10 ppm in the second stage.
This second stage requires much higher pressure, hydrogen to feed ratio, hydrogen purity
and lower space velocity compared to the conditions used in most of the conventional
HDS processes. It could increase the capital investment[3].
The performance of HDS is lowered by organic hetercompounds and polyaromatic
hydrocarbons, for which the following order of inhibition has been reported Nitrogen
compounds > organic sulfur conpounds > oxygen compounds > monoaromatic
hydrocarbons[4]. SK Corporation in Korea has been developed a unique technology,
called SK HDS Pretreatment Process, to produce the lOppm ultra low sulfur diesel[3].
The technology is based on the adsorption technique, and is designed to remove nitrogen
compounds fiom the feedstock to the HDS process. It improved the performance of
conventional HDS units, by removing effectively the components that inhibit the
desulfiuizationreaction.
The nitrogen compounds have been characterized among the strongest HDS
inhibitors. Many researchers reported a strong inhibiting effect on the thiophene and DBT
HDS reactions[5-8]. It is well known that the basic nitrogen compounds could poison the
584
Experimentals
The nitrogen compound in the light gas oil was classified with basic nitrogen compound
and non-basic compound. For the practical condition,quinoline was used as basic nitrogen
compound and carbazole was as non-basic nitrogen compound. And normal hexane was
selected as model light gas oil. And, silica was used for the adsorbent of nitrogen
compounds.
The model light gas oil was prepared with 300 ppm nitrogen compounds in hexane.
For the adsorption of nitrogen compounds, the adsorbent was immersed in the model light
gas oil for 6 hours. The filtered silica particle was dried in the room temperature for 4
hours.
The 'H M A S NMR was performed on a JNM-ECP300 JEOL spectrometer with a
spinning rates of ca. 5.5 kHz, for the understanding of the local interaction between
nitrogen compound and adsorbent. 1H NMR spectra was carried out at 300.53 MHz using
single-pulse excitation. The d2 pulse width and pulse delay were 4 p and 10s.
Results
Before the adsorption of nitrogen compounds, the silica was exposed in the moistured air
to have different water contents. Figure 1 shows the 'H MAS NMR spectra of silica used
in this study. Figure l(a) is the N M R spectrum of dry silica powder. The narrow peak at 6
= 1.8 ppm is assigned the isolated silanol. It showed general spectrum of dry silica as
reported in many studiesf9-1I]. After the exposure in wet condition, the resonance at 3.5
ppm which means the physically adsorbed water was appeared. The water content of silica
was increased by exposure in wet air up to 0.11 1glg.silica . These dry and wet silica were
used for adsorption of nitrogen compounds.
20
15
10
-6
40
-15
-20
shin (6. m)
Figure 1. 'H MAS N M R spectra of silica (a) before the exposure in moisture and @I) after the'exposure in
mosture.
585
20
15
10
-5
-10
Figure 2. 'HMAS NMR spectra of dry silica (a) before the adsorption of quinolineand (b) after the adsorption
of quinoline.
Quinoline as basic nitrogen compound was adsorbed on dry silica. As shown in figure 2,
the 'H N M R spectrum of the silica with adsorption of quinoline was considerably
changed. The peaks at k 8 . 5 , 7.9 and 7.5 ppm were newly appeared. These peaks could
be assigned to the hydrogen of quinoline. It means that quinoline was adsorbed on the
silica surface. The intensity of peaks was not changed above 130 ppm of quinoline in
hexane. The adsorbed amounts of quinoline was 0.06 g/g.
And, the isolated silanol signal at k1.8 ppm was disappeared and the resonance at k 5 . 0
ppm was highly increased. The broad peak at W . 0 ppm is the hydrogen bonded hydroxyl
proton. With adsorption of quinoline on the silica surface, the hydrogen bonded silanol
was increased. It might be because quinoline could make strong interaction with silica
surface.
20
15
10
.5
-10
Figure 3. 'H MAS NMR spectra of wet silica (a) before the adsorption of quinoline and (b) after the
adsorptionof quinoline.
586
Quinoline was also adsorbed on the wet silica. In the 'H MAS NMR spectra of figure 3,
the originations of peaks are same to dry silica with quinoline in figure 2. The resonance
at k8.5.7.9 and 7.5 ppm could be due to the adsorbed quinoline. And, isolated silanol
group was disappeared. However, the signal at k5.0 ppm which means hydrogen bonded
hydroxyl proton was more increased than that of figure 2(b). The reason why hydrogen
bonding was increased by surface adsorbed water is not obvious. Water might effect on
the interaction between silica surface and quinoline. The detailed analysis is now in
progress.
In the case of carbazole(non-basic nitrogen compounds), there are no characteristic
signal of carbazole. However, the peak of isolated silanol was disappeared and that of
hydrogen bonded hydroxyl proton was highly increased. It could mean that small amount
of carbazole might be adsorbed on the silica. And, carbazole might also strongly interact
with silica surface.
4
Acknowledgements
587
10. Siahkali A. G., Philippou A, Dwyer J. and Anderson M. W., The acidity and catalytic
activity of MCM-41 investigted by MAS NMR FIX2 and catalytic tests, Appl. CuraL
A: Gen. 192 (2000) 57-69.
11. Mariscal R., Lopez-Granados M.,Fierro J. L. G., Sotelo J. L., Martos C. and Van
Grieken R., Morphology and surface properties of titania-silica hydrophobic xerogels,
Langmuir 16 (2000)9460.9467.
588
Adsorption equilibria of VOCs on mesoporous sorbents (MCM-48) synthesized in our laboratory are
measured at several temperaturesusing a quartz spring balance equipped in a high vaccum system.
A new hybrid isotherm model for mesoporous sorbents is proposed by combining both the Langmuir
isotherm at low pressure and the Sips isotherm in multilayer region. Since mesoporous sorbents have
narrow pore size distribution between 20 to 46 A, capillary condensation of VOCs can be observed
at p / po4 . 2 4 3 . Also, the adsorbed amount decreased considerably with increasing pelletizing
pressure. The isosteric heat of adsorption was calculated using experimental data,
Introduction
589
curves of VOCs on MCM-48 without quantitative prediction. A few isotherms have been
developed for the adsorption of condensable vapors and reviewed elsewhere. However,
none of the models yields a complete description of adsorption isotherms over a wide
pressure range with a uniform set of parameter [9,10].
Therefore, in this paper, we used a simple hybrid isotherm for interpreting the
adsorption isotherms of VOCs on MCM-48 (unpressedpressed) as a function of
temperature. The simple isotherm model is constructed by combining both Langmuir
equation at low pressure and Sips equation at regions of multilayer and capillary
condensation. The reason for the selection of Sips equation to explain capillary
condensation is based on an engineering point of view, namely, both flexible fit of
isotherm data and saving calculation time in dynamic simulation although its physical
meaning is somewhat lack. MCM-48 are prepared by conventional hydrothermal
syntheses and characterized by X-ray dihction (XRD) and nitrogen adsorption and
desorption. Also, the isosteric heat of adsorption is calculated using experimental data.
2
2. I
Experimental
To test the adsorption property of MCM-48, the samples were compressed using a
hand-operated press. The pelletized MCM-48 diameter is 10 mm and the external pressure
applied is 0, 50, 100, 200, 300, 400 and 500 kg/cm2. Subsequently, the obtained pellet
was crushed and sieved to obtain pellets with a diameter of 0.1 to 0.2 mm that were used
for adsorption equilibrium and fixed bed studies.
2.3
Characterization
590
Aakorption stu*
The adsorption amounts of VOCs vapor were measured by a quartz spring balance, which
was placed in a closed glass system. A given amount of MCM-48 particles were placed on
the dish, which was attached to the end of quartz spring. This system was vacuumed for
15 hours at 10 Pa and 250C to remove volatile impurities from the mesopoprous
sorbents. The variation of weight was measured by a digital voltmeter that was connected
to the spring sensor. The adsorption equilibrium was usually attained within 30-60min.
Equilibrium experiments were carried out at different temperatures.
Figure 1 presents the nitrogen adsorption and desorption isotherms with BJH pore size
distribution curves for MCM-48. The isotherms are type IV according to the IUPAC
800
E
UJ
9
Is00
0400
-f
s
200
0.0
02
0.4
0.6
0.8
1.o
ppo
classification. Also, the isotherms exhibit sharp steps in the relative pressure P/Po =
which are associated with capillary condensation in channels of MCM-48
structure. The sharpness of the capillary condensation steps indicates uniformity of pore
channels and their narrow size distribution. The isotherm is reversible and does not exhibit
hysteresis between adsorption and desorption. The surface area of MCM-48 was about
1100 m2/g. And the maxima in the pore size distribution curves indicate the uniform
mesopores of approximately 32 A. The BJH data showed approximately20 A distribution
0.2-0.4,
591
from the mean pore diameter for MCM-48, and this matches well with other distribution
curves reported earlier.
Adsorption isotherms play a key role in either the design of the adsorption-based
process for the disposal of wastes containing VOCs or modeling the catalytic oxidation
process. The equilibrium data for mesoporous sorbents are fitted to combined model of
h g m u i r and Sips equations. This hybrid isotherm model with four isotherm parameters
(4,,b, ,b, ,n) is as below:
q=qm
[l+b,P+
blP
1+b2P"
b2P"
4m
bl
b2
n
15
Temperature
303 K
6.260EM0
1.825E-01
9.303E-40
9.848EM 1
Temperature
311 K
6.36084-00
8.592E-02
8.441E-32
4.448E4-01
Temperature
308 K
5.968EMO
1.764E-01
3.297E-25
4.695E4-01
Temperature
323 K
5.978E4-00
7.522E-02
1.993E-49
5.544E4-01
12
10
Pressure, kPa
592
It has been known that condensation pressure depends on the adsorbate, temperature,
pore size, and geometry of sorbent. As increasing temperature, the capillary condensation
pressures is increased and adsorption capacity is decreased. This fact implies that
adsorption and desorption can be easily achieved by only little adjustment of pressure and
temperature. Therefore the effective removal of VOC can be done by pressure swing
adsorption (PSA) or thermal swing adsorption (TSA) processes.
As a useful thermodynamic property, the isosteric heat of adsorption has been
generally applied to characterize the adsorbent surface. The isosteric heat of adsorption is
evaluated simply by applying the Clausius-Clapeyron equation if one has a good set of
adsorption equilibrium data obtained at several temperatures.
where 4,, is the isosteric heat of adsorption, R is the gas constant, and N is the
amount adsorbed.
In Figure 3,, the isosteric heats of adsorption for vapors studied are plotted as a
function of the amount adsorbed. The isosteric heat is approximately 40 kJ/mol between
the adsorption amounts of 0.5 to 2.0 mmol/g, but that is 45 kJ/mol between the adsorption
amount of below 2.0 m o V g and above 8.0 mmoVg. This difference comes from the
capillary condensation. Because of the joint effects of the energetic non-uniformity of the
adsorbent surface and the interaction of adsorbate molecules in the adsorbed film itself,
the heat of adsorption in general varies significantly with the amount adsorbed. The
isosteric heat of adsorption can be divided into two sections, namely, low and capillary
12
0 Pmsun-100
A Pmssure-200
Pmsun-300
0 Pmssunr-400
...-....
10
2
g
2
0
0.0
1.5
3.0
4.6
6.0
7.5
Pressure, kPa
593
I00
200
300
Pressure, kg/cm2
400
500
Acknowledgements
This work was supported by grant No. (R-01-2001-000-00414-0)from the Basic Research
Program of the Korea Science & Engineering Foundation.
References
1. Khan, F.I. and A.K. Ghoshal., Removal of Volatile Organic Compounds from
polluted air. J. Loss. Prevent. Proc. 13 (2000) pp.527-545.
2. Clausse, B.; Garrot, B.; Cornier, C.; Paulin, C.; Simonot-Grange M.-H.; Boutros, F.
Adsorption of Chlorinated Volatile Organic Compounds on Hydrophobic Faujasite:
Correlation between the Thermodynamicand Kinetic Properties and the Prediction of
Air Cleaning. Micro. and Meso Mat 25 (1998) pp.169-177.
3. Kim, D. J., Shim, W.G. and Moon, H., Adsorption Equilibrium of Solvent Vapors on
Activated Carbon. KJChE 18 (2001) pp.518-524.
4. Takeuchi, Y.; Hino M.; Yoshimura, Y.; Otowa, T.; Izuhara H.;Nojima T. Removal of
Single Component Chlorinated Hydrocarbon Vapor by Activated Carbon of Very
High Surface Area. Sep. and Puri! Tech. 15 (1999) pp. 79-90.
5. Chintawar, P. S.; Greene, H. L. Adsorption and Catalytic Destruction of
Trichloroethylene in Hydrophobic Zeolites. AppZ Cat B. 14 (1997) pp. 37-47.
6. Beck, J. S.; Vartuli, J. C.; Roth, W.J.; Leonowicz, M. E.; Kresge, C. T.; Schmitt, K.
D.; Chu, C. T-W.; Olson, D. H.; Sheppard, E. W.; McCullen, S. B.; Higgins, J. B.;
Schlenker, J. L. A New Family of Mesoporous Molecular Sieves Prepared with
Liquid Crystal Templates. J. A n Chem SOC.114 (1992) pp 10834-10843.
7. Zhao, X. S.; Lu, G. Q. Organophilicity of MCM-41 Adsorbents Studied by
Adsorption and Temperature-Programmed Desorption. Colls and SurfA 179 (2001)
pp 26 1-269.
8. Ryoo, R.; Joo, S.H.; Kim, J.M. Energetically Favored Formation of MCM-48 from
Cationic-Neutral SurfactantMixtures. J. Phys. Chem. B 103 (1999) pp 7435-7440.
9. Hartmann, M.and C. Bishof, Mechanical Stability of Mesoporous Molecular Sieve
MCM-48 Studied by Adsorption of Benzene, n-Heptane, and Cyclohexane. J. Phys.
Chem. B. 103 (1999) pp. 6230-6235.
10. Sonwane, C.G. and Bhatia, S.K.Adsorption in mesopores: A molecular-continuum
model with application to MCM-41 Chem Eng Sci 53 (1998) pp. 3143-3156
594
1. Introduction
Molecular simulation has now become powerful tool for the study of adsorbed
molecules in zeolites, and the Grand Canonical Monte Carlo (GCMC) method is
especially useful for predicting adsorption equilibria. However, information on forcefield
parameters and charges are often inadequate, even in systems where the structure is well
known. From the environmental point of view, the adsorption of chlorinated
hydrocarbons by the use of zeolites may have some potential utility in ground water or
soil remediation and other areas. Mellot et al. [3] recently reported new forcefield
parameters and charges for chlorinated hydrocarbons in the faujasite zeolite: NaX, NaY
and siliceous Y. These yield heats of adsorption that are in good agreement with
calorimetric data [2]. In this study, their forcefield was used to simulate adsorption
isotherms and isosteric heats of adsorption for chloroform, trichloroethylene and
tetrachloroethylene in USY-type zeolite, separately. The results were compared with
gravimetric and chromatographic experiments.
2. Experimental
595
adsorption tube (N). The whole apparatus was in a constant temperature air bath. The
temperature range was 303-323 K. The amount adsorbed was measured correspondingto
the pressure of the vapor in the tube. The pressure was measured by pressure sensor (P) at
higher pressure range (2 0.013 atm) and baratron (0)at lower pressure range (<0.013
atm). In this way, adsorption isotherms were obtained (Fig. 5).
2.2 Chromatographic Method [ I ]
h
Al-A4
B
C
D
E
F
G
H
I
J
K
L
M
N
0
: needle valve
: adsorbate-flask
: desplacement meter
: heater
: thermo-controller
: thermo-detector
:quartzbasket
: stertch-detector
: chart recorder
: mass spectrum meter
:quartz basket
: mantle heater
: vacuum pump
: adsorbent tube
: baratron
: pressure sensor
2.3. Simulation
596
0-H
c-c
C-CI
C-H
CIcl
CtH
H-H
x-x
X-H
X-CI
x-c
90.535
25.860
55.650
26.730
119.80
57.530
27.630
0.000
2.698
3.753
3.707
3.358
3.822
3.392
2.%3
0.010
0.000
6.000
6.000
0.010
6.000
O.Ol0
2.3.1 Models
597
~~~
~~
0.001
0.m1
o.woo1
0.m1
0.01
0.1
0.m1 0.001
0.01
0.1
Pressure [am]
Fig3 Comparison between exp. and
simulations for adsorption isotherms of PQUSY-Chloroform system
4 exp. ad. 303K
Baratoron
-exp.
0
303K
chromto.
Pure Siliceous Y
&I
A S i b 1 nest model
0 Acid site model
0 . m 1 0.m1 0.001
0.01
0.1
pressure [atm]
598
4. Conclusions
Equilibrium and isosteric heat of adsorption for the system of chloroform-Y-type zeolite
were studied.
The adsorption equilibria were measured using a gravimetric method and were
expressed as isotherms. A chromatographic method was used to get the initial slope of the
isotherms. In the simulation, GCMC method was used to calculate amounts adsorbed for
various conditions. When the experiment result and simulation result of chloroform are
compared, the simulation for the acid site model was most agreement with
chromatographic data and baratron data. The simulation result of tetrachloroethylene with
three models corresponded mostly for the non-polar molecule, and above all the acid site
model was the closest to the experiment result. Therefore, to get better coincidence
between experimental data and simulation, it was found to be necessary to account for
aluminum rather than silanol nest.
As a conclusion, FF parameters were confidently applied. And modified structure model
are effective for simulation.
Nomenclature
K* :adsorption equilibrium constant [cc/g]
M : molecular weight [glmol]
q : amount adsorbed [g/g]
R :gas constant [JK moll
R-Min
: Bond Length Equilibrium [A]
T :temperature [K]
: potential energy minimum [eV]
Epsilon
K :Boltzmann constant [JK]
References
1. K. Chihara, M. Suzuki, K. Kawazoe, Adsorption rate on Molecular Sieving Carbon
by Chromatography, AIChE J., 24,237 (1978)
2. C. F. Mellot, A. K. Cheetham, S. Harms, S. Savitz, R. J. Gorte, A. L. Myers,
Calorimetric and Computational Studies of Chlorocarbon Adsorption in zeolites, J.
Am. Chem. Soc., 120,5788. (1998a)
3. C. F. Mellot, A. M. Davidson, J. Eckert, Adsorption of Chloroform in NaY Zeolite:
A Computational and Vibrational Spectroscopy Study, J.Phys. Chem. B, 102,2530
(1998b)
599
Introduction
Adsorption equilibria and adsorption dynamics in supercritical fluids have been
reported recently and it will be possible to apply the supercritical fluid to some new
adsorptive separation processes. Fundamental informations on adsorption under
supercritical conditions are necessary to design such processes. Supercritical
chromatography has been used for study on the adsorption equilibria and adsorption
dynamics.Adsorption of organics, i.e., benzene, toluene and m-xylene, respectively, on
MSC under supercritical conditions has already been reported in reference (Chihara,
1995). In the previous study, chromatographic measurements were made for the
adsorption of benzene, toluene and m-xylene on MSC in supercritical COz mixed with
benzene, toluene and m-xylene respectively. Moment analysis of the chromatogram was
carried out. In the study, the organics used in the form of pulse were the same as organics
mixed with supercritical COz. The dependencies of adsorption equilibrium and micropore
diffisivities on the amount adsorbed were obtained.
In the present study, supercritical COz chromatograph packed with MSC was again
used to detect the pulse responses of organics, and the moment analysis technique was
used to analyze. Equilibrium and dynamics were studied for benzene, toluene and mxylene, respectively, -MSC systems in the supercritical COz mixed with organics which
were different fiom that used in the form of pulse. Furthermore, the dependence of
adsorption of the organics on the amount adsorbed of other organics was discussed.
Experimental procedure and conditions
The experimental apparatus (Super 200-type 3; Japan Spectroscopic Co., LTD) was
shown in Fig.1. The carrier fluid of the chromatograph was supercritical COz (critical
temperature 304K, critical pressure 7.3 MPa) and its mixture with the above-stated
600
organics (benzene, toluene or m-xylene) respectively. The adsorbates used in the form of
pulse were different fiom organics mixed with supercriticalC02. For example, in the case
of C02 mixed with benzene, the organic used in the form of pulse was toluene or mxylene. In the previous study, pulse organics were the same as organics in the carrier. The
volumes of the pulse were fixed to be 8 x 10m9m3
as liquid. MSC 5A (Takeda chemicals
Co., HGK882.)was crushed and screened to obtain particle size between 1.49 x lo4 1.77 x. 104m (an average particle radius of 8.12 x. lo- m). 4.82 x 104kg of these
particles were packed into the chromatographic column of 5 x 10-*mlong and 4.6 x lOm
in diameter. The void hction, E, of the bed was determined to be 0.355. The properties of
MSC5A are shown in Table 1 in reference (Chihara, 1978). Flow rate of supercritical C 0 2
was 1.33 x 10-m3/s at 268K and at 15.0,20.0 and 25.OMPa respectively and flow rate of
adsorbate (benzene, toluene or m-xylene) was 1.67 x 10-0m3/s,5.00 x lo- m3/s and 1.00
x
m3/s as liquid at room temperature (298K). The column pressure was kept at 15.0,
20.0 and 25.0 MPa respectively. The pressure drop across the adsorbent bed was
estimated to be about 0.1Mpa and was assumed to be negligible. The experimental
column temperature was kept at 313, 333 and 353 K respectively. Before experimental
runs started, the adsorbent particles were regenerated and stabilized by feeding pure C02
for 2 hours at the experimental pressure and temperature. Pulse responses were detected
using a multi-wave length UV detector (Multi-340; Japan Spectroscopic Co., LTD.) (195350 nm). Response data were processed by a personal computer.
A : Liquid C02 Cylinder
B : Valve
C : Cooler
D1.2: Pump
E : MixingColumn
F : Adsorbate (Liquid)
G : InjectionColumn
H : Six-way Valve
1
: Valve
J
: PackedColumn
K : Valve
L : UV Detecter (MULTI-340)
M : Back Pressure Regulator
N
: PersonalComputer
0 : Fraction Collector
P
: Vent
Fig. 1 Experimentalapparatus
Moment analysis of supercritical fluid chromatogram was tried, and the apparent
adsorption equilibrium constant, K* and time constant of micropore diffusivity, D/a2
obtained from first and second moment of response peak, as in references (Chihara, 1993;
Chihara, 1995).
601
15MPa
20MPa
25MPa
p 1.5
4 1.0
adsorbate : toluene
solute : toluene
a5
~~
Concentration [ml/ma]
20
40
80
toluene
benzene
A m-xylene
y 0.1
1
E
2 0.01
awt
a5
1.0
1.5
temperature :3 13[K]
pressure :2O[MPa]
20
toluene
benzene
in-xylene
temperature : 353[K1
pressure : 20CMPal
0.5
1.a
1.5
2.0
[mol/kd
602
KS
Adsorption state
*"
In the beginning, we will
examine how molecules of
adsorbate is benzene was
used for the adsorbate here. MSC68RC1 model
The results are shown in
Figure 5. We see from Figure
5 that benzene is adsorbing to
the
adsorption
space
reproduced micro pore. Here,
benzene is adsorbed to layer
in parallel in MSC68 model, MSC84RC1 model
on the other hand,
Fig.5 Adsorption state of benzene
It is adsorbed aslant in
0.0025
MSC84 model
01
1
- i
a
Adsorption isotherm
The simulation was carried out
the single component Benzene is
CDO
used for adsorbate. Conditions are
313K and ISOatm. The results are
OMSO68-RC1
shown in Figure 6.
DMSC84-RC1
As for Fig.6, adsorbed amount
for MSC84 model is larger than
06
MSC68 model. The cause of this
0
0.00002 0.00004 0.00006 0.00008
result is that the amount adsorbed is
molar concentration [mol/ni]
dependent on the size of the
Fig.6 Adsorption isotherm of benzene
adsorption space. According to Fig.6,
The amount of adsorption increased with increases of molarity of benzene, and reached to
saturation.
Figure 7 shows comparison of adsorption isotherm for a molecular simulation different
force field and an experiment. Conditions are 313.15K. and ISOatm. The simulation was
carried out the two components system. UNIVERSAL 1.02, London, and DREIDING2.11
were used for the force field, respectively. As for the amount adsorbed, in every figure,
603
Conclusion
Adsorption equilibrium and
adsorption dynamics on MSC were
evaluated for each organics in
supercritical C02 fluid mixed with
adsorbate by chromatographic
measurement. The dependencies of
adsorption equilibrium constants,
K*, and micropore diffiivity, D,
of toluene, benzene and m-xylene,
on molarity of toluene with each
parameters of temperature or
pressure were obtained. It was
found that the values of K* and D
for an organic substance depended
on the amount adsorbed of other
organics strongly. The state of the
molecule could be observed by the
molecular simulation. As for the
amount adsorbed, the simulation is
small, in comparison with the
experiment.
2
e,
3
0.0014
R
C
l-80.0012
I
0 MSC84-RC1
0.001
Y
A
A Exp:
0.0008
0.0006
0.0004
0.0002
0
,M
ij
0.00008
0.0014
0.0012
0 MSC84-RC1
0.001
0.0008
3I 0.0006
1 0.00041
B 0.0002
0'
-"
i:
0.0014
0.0012
0.0008
4- 0.0006
0 MSC84-RC1
0.001
-0
A
~
0.0004
0.0002
0
0
0
v
A Exp.
_
I-I
Londo
Fig.7Comparison with experiment and
molecular simu1ation:Adsorption isotherm
Reference
Chihara, K., Kawazoe, K.,Sumki, M., Seisan Kenkyu, AIChE J, 24,237-246. (1978)
Chihara, K., Aoki, K., AIChE, Annual Meeting, (1993)
Chihara, K., Oomori, K., Kaneko, R., Takeuchi, Y., AIChE, Annual Meeting, (1995)
604
Introduction
Porosity is one of the important factors that influence the chemical reactivity and the
physical interactions of solids with gases and liquids [l]. Physical properties such as
density, surface area and strength are dependent upon the porosity and the pore structure
of a solid. Especially for industrial applications, the control of porosity with well-ordered
structural pore networks is of great importance, for example, in the design of catalysts,
adsorbents, membranes, structural materials and ceramics. Researches on uniform pore
structure of nanometer to micrometer dimensions have been progressed with great interest
due to a variety of possible application in catalysis, molecular separation, membranes,
structural materials and adsorbent [2]. Recently, ordered inorganic structures with
macropore have been prepared using physical templating method [3], latex sphere and
emulsion droplets, or chemical templating method [4] by post-hydrothermal treatment and
primary particle seeding. Micro- and mesopores provide size or shape selectivity for guest
molecule, while additional macropores can reduce transport limitations and enhance the
accessibility to the active sites [5]. As theoretically proven by Levenspiel, the bimodal
catalyst can guarantee high diffusion efficiency [6]. For example, cobalt catalysts
supported on bimodal silicas show remarkably high activity in liquid-phase
Fischer-Tropsch synthesis [7].
Relatively few studies on the synthesis of mesoporous alumina have been reported to
date [8]. One of the limitations of the reported synthetic strategies is that the rate of
hydrolysis (and condensation) reaction of aluminum alkoxide are much faster than that of
silicon alkoxide. In this study, we proposed a novel method to prepare bimodal porous
aluminas with meso- and macropores with narrow pore size distribution and well-defined
pore channels. The b e w o r k of the porous alumina is prepared via a chemical
ternplating method using a w l carboxylates. Here, self-assemblied micelles of wboxylic
acid were used as a chemical template. Mesoporous aluminas were prepared through
careful control of the reactants pH, while the procedures are reported elsewhere [9].
605
Experimental
Polystyrene beads (PS) are employed as physical templates for macropore. The
emulsifier-fiee emulsion polymerization method used here allows for the synthesise of
nearly monodisperse latex beads of PS in the size of ca. 100 nm [101. PS beads were
prepared using 700 ml degassed water, 54 ml styrene monomer, 0.65 g potassium
persulfate as initiator, and 20 ml divinylbenzene as cross-linking agent. PS beads were
obtained at 7OoC and 350 rpm, and dried under ambient condition.Aluminum
sec-butoxide and stearic acid were separately dissolved in parent alcohol, sec-butyl
alcohol, at room tempature, and then the two solutions were mixed. Appropriate amount
of HN03 solution was dropped into the mixture at a rate of I mVmin to acidify and
hydrolyze the aluminum precursor. PS beads were added into aluminum hydroxide
solution after stirring for 10 h. The fmal pH of the reactant was approximately 7. Organic
templates, both stearic acid and PS bead, were easily removed fiom dried aluminum
hydroxide by calcination. The overall synthetic procedure is as shown in Fig. 1.
An adsorption test for dye was performed using model solution, which was prepared
with acid red 44 (crystal scarlet, Aldrich). Prepared aluminas (P2and P4)were added into
2%polydiallyldimethylammonium chloride (PDDA, Aldrich) solution, and stirred for 3 hr.
0.1 g of PDDA treated aluminas were stirred with 10 ml of dye solution (50 ppm).
Depletion of dye was determined by UV (510 nm) spectrometry (HP8453, Hewlett
Packard).
*!
Stearic acid
-b
___,
calcination
macropore
Figure 1. Schematics for the synthesis of porous alumina with bimodal pore size distribution. Templates
removal steps are followed by dotted-arrow for polystyrene beads and solid-arrow for silica gels as physical
templates.
3
3. I
606
TEM result that less ordered worm-like pore distribution was formed in mesoscale (Fig.
3b).
Table 1. Characteristics of bimodal porous aluminas
Pore size [nm]
V [cm3g-']
SA[m2g-l]
Damla1
DBni M
DWB-FHH
Icl
PI
4.2
0.15
149
0.53
485
P2
6.8
3.4
51
0.24
216
P3
6.4
P4
6.2
3.5
50
0.35
239
[a] Gurvitsch (4VIA) model. [b]BJH model on the desorption. [c] BdB-FHH spherical model on the desorption.
Sample
Important trends in N2isotherm when the PS beads are used as a physical template
are shown in Table 1 and Fig. 2. In Table 1, PI is the alumina prepared without any
templates, P2 is prepared without physical template (PS bead), P3 is prepared without
chemical template (stearic acid), and P4 is prepared with all templates. For above 10 nm
of pore size and spherical pore system, the Barrett-Joyner-Halenda (BJH) method
underestimates the characteristics for spherical pores, while the Broekhoff-de
Boer-Fre~el-Halsey-Hill(Bdl3-FHH) model is more accurate than the BJH model at the
range 10-100 nm [13]. Therefore, the pore size distribution between 1 and 10 nm and
between 10 and 100 nm obtained fiom the BJH model and BdB-FHH model on the
desorption branch of nitrogen isotherm, respectively. N2isotherm of P2 has typical type
IV and hysteresis loop, while that of P3 shows reduced hysteresis loop at P/Po cu. 0.5 and
sharp lifting-up hysteresis loop at P/Po> 0.8.This sharp inflection implies a change in the
texture, namely, textural macro-porosity [4,14]. It should be noted that P3 shows only
macropore due to the PS bead-fiee fiom alumina h e w o r k .
--Pz
0.0
0.2
0.4
0.6
0.8
P3
P4
1.0
PPO
Figure 2. Nitrogen adsorption-desorption isotherms of the porous alumina prepared using stearic acid and/or
PS bead as a template (curve are shifted for clarity). The inset shows the corresponding pore size distribution
from the desorption branch.
When neither chemical nor physical template is used in preparation of alumina, PI,
the resulting material shows less ordered pore size distribution, while P4 shows bimodal
pore systems with both mesopore (3.5 MI)and macropore (50 nm) after thermal treatment.
607
As shown in Fig. 3% the size of PS bead is approximately 100 nm, and dried PS beads
show an aggregate form. However, the pore sizes of calcined P4 and P3 are
approximately 50 nm. Calcination resulted in polymer-he metal oxide strucures, with
spherical voids smaller than the PS bead diameter, by 50%. This contraction phenomenon
is obviously related to the reorganizaiton of the surrounding walls during the calcination
process as evidenced in Fig. 3c and Fig. 3d. The part of the wall retracts by the burning
PS bead [I I]. This thermal treatment causes the link of metal oxide in the structure (Fig.
3d), and it is also affected by the calcination temperature.
Figure 3. E M micrographs of (a) colloidal PS bead and (b) calcined Pt,and SEM images of (c) as-made P4
and (d) calcined P4.
608
1.2,
1.0 0.8 .
0.6 -
0.4
0.0 J
20
40
BO
80
time (nin)
References
1. U. Schubert, N. Husing, Synthesis of Inorganic Materials, Wiley-VCH, 2000.
2. A. Stein, B. J. Melde ,R. C . Schroden, A h . Muter. 2000, 12, 1403; B. Lee, Y. Kim,
H. Lee, J. Yi, Micropor. Mesopor. Mat. 2001,50,77.
3. B. Lebeau, C. E. Fowler, S. Mann, C. Farcet, B. Charleux, C. Sanchez, J. Mater.
Chem. 2000, 10, 2105; C. F. Blanford, H.Yan, R. C. Schroden, M. Al-Daous, A.
Stein, Adv. Muter. 2001,13,401.
4. X. Wang, T. Dou, Y. Xiao, Chem. Commun. 1998, 1035; J. Sun, Z. Shan, T.
Maschmeyer, J. A. Moulijn, M.-0. Coppens, Chem. Commun.2001,2670.
5 . - M.-0. Coppens, J. Sun,T. Maschmeyer, Catal. Today, 2001,69,331; Y. S. Cho, J. C.
Park,W. Y. Lee, J. Yi, Catai. Lett. In press, 2002.
6. 0. Levenspiel, Chemical Reaction Engineering, 3rd Ed. John Wiley & Sons, 1999.
7. N. Ysubaki, Y. Zhang, S. Sun, H. Mori, Y.Yoneyama, X. Li, K. Fujimoto, Catal.
Commun.2001,2,3 1 1.
8. F. Vaudry, S. Khodabandeh, M. E. Davis, Chem. Muter. 1996,8, 1451; S . Cabrera, J.
El Haskouri, J. Alamo, A. Beltran, S. Mendioroz, M. D. Marcos, P. Amoros, Adv.
Muter. 1999, 11,379.
9. Y. Kim, B. Lee, J. Yi, The Korean J. of Chem. Eng. 2002, 19(5).
10. S. Vaudreuil, M. Bousmina, S. Kaliaguine, L. Bonneviot, A h . Muter. 2001, 13,
1310.
11. S. Valange, J.-L. Cuth, F. Kolenda, S. Lacombe, Z. Gabelica, Micropor. Mesopor.
Mat. 2000,35-36,597.
12. C. J. Brinker, G. W. Scherer, Sol-Gel Sience, Academic press, 1990.
13. M. Kruk, M. Jaroniec, Langmuir 1997, 13, 6267; W. W. Lukens, P. S. Winkel, D.
Zhao, J. Feng, G. D.Stucky, Langmuir 1999,15,5403.
14. W. Lin, J. Chen, Y. Sun, W. Pang, J. Chem. SOC.Chem. Commun. 1995,2367; K. R.
Kloetstra, H. W. Zandbergen, J. C. Jansen, H. B. Bekkum, Microporous Muter. 1996,
6,287.
15. Y. Wang, J. Banziger, P. L. Dubin, G. Filippelli, N. Nuraje, Environ, Sci. Technol.
2001,35,2608.
609
Introduction
Although carbon nanotubes (CNTs) have been recently discovered [9], they have been
attracting a great deal of scientific interest due to their potential application in areas such
as adsorbents and composite materials. CNTs have the number of graphite sheets in tube
walls can vary fkom 1 for single-walled nanotubes (SWNTs) to over 50 for multi-walled
nanotubes (MWNTs), and inner diameter raging from Inm to 5nm with a definite
diameter [ 1,3]. The possibility of controllable pore size and distribution suggests that
CNTs might be used applications such as gas storage and selective separations from gas
mixtures.
Up to now, numerous studies have been conducted on their synthesis [9,10],
treatment [5,13] and physical properties [4]. However only limited number of studies has
been carried out on the adsorption of gas in CNTs, including experimental works [8,1 I ]
and molecular simulations [3,7,14-151. Adsorption behavior depends strongly on the
microporous structure of the particular adsorbent. In this work the effect of pore size on
the adsorption behavior is of interest. The adsorption equilibria of methane, ethane and
their mixture into SWNTs were studied by using a Grand Canonical Monte Carlo
(GCMC) method. We reported equilibrium isotherms of methane and ethane, and the
selectivity from their equimolar mixture.
2
CNTs are cylindrical structures and retain their cylindrical shape when their internal
diameters are less than lnm. CNTs flatten to form a honeycomb structure when the
610
internal diameters exceed 2 . 5 ~ 1[12]. Although the nanotubes typically have their ends
capped, selective oxidation can remove their end caps and reveal their hollow central
cavities [5,13]. A high-resolution transmission electron microscope (TEM) image of
SWNTs (manufactured by Iljin Nanotec, Korea) is shown in Figure I (a).
(4
Figure 1. A high-resolution TEM image(a) and a segment of an armchair mode of single-walled carbon
nanotubes(b).
There are two modes of rolling graphite sheet, which give rise to the armchair and
saw-tooth configurations. We construct SWNTs according to the armchair mode of
rolling. SWNTs constructed in this manner have only certain allowed diameters. SWNTs
at different allowed diameters can be produced by the saw-tooth mode of rolling. Figure 1
(b) illustrates a segment of an armchair SWNT of diameter D=l.496nm. D is the centerto-center distance of two diametrically opposite carbon atoms on the nanotubes walls. The
boundary condition of axial direction was applied. We used a length of 7.87nm for all
simulationsreported in this work. The C-C bond length of 0.142nm corresponding to that
of graphite was used.
The intermolecular interactions between two molecules and fluid-wall interactions in
SWNTs were given by a 12-6 Lennard-Jones (LJ) potential. Methane was modeled as a
spherical LJ molecule and ethane as two LJ sites with the unified methyl group. The
interactions were cut at 2.286nm which corresponding to 5 times the methane o parameter.
In each step, one of these was chosen with equal probability at random. For each
point on the isotherm, the system was allowed to equilibrate for 5 ~ 1 steps
0 ~ before
collecting data. After equilibration, the simulation continued for 2 ~ 1 steps
0 ~ in order to
calculate the average values of the extent of adsorption. Further details of the simulations
are given elsewhere[2,6].
3
611
. .-
10
x(2.035~11
t
0.678~11
0.950~11
0.814nm
5
0
10
20
30
40
Prrasurc [bar]
10
20
30
40
Pressure [bar]
Figure 2. Simulated isotherms for methane and ethane adsorption in single-walled carbon nanotubes of different
diameters.
The most important parameter from the point of view of mixture separation is the
selectivity. Figure 3 shows the binary selectivity at 298.2K with a 50% methane, 50%
ethane bulk-gas mixture over a range of pressures and pore diameters. The curves show
behavior with an initial increase in selectivity due to cooperative interactions between the
ethane molecules as the pressure is increased. As pressure increases further the adsorbate
densifies, which imposes an ordering of the adsorbate. The selectivity is a strong function
of pressure and pore width. The most commonly used approach to predict
multicomponent adsorption is Ideal Adsorbed Solution Theory (IAST) based on a
classical thermodynamic analysis. This approach requires pure component adsorption
isotherms, at the proposed temperature of operations of the adsorption unit, for all of the
components in the mixture. The pure-component isotherms form the inputs to IAST, and
the binary predictions are plotted in Figure 3. The binary simulation results by GCMC are
in good agreement with IAST.
612
GCMC
80
lAST
A - 9 .
D[m]
1.628
2.035
2.713
20
0
Figure 3. Comparison of GCMC simulation and IAST predictions of selectivity derived from simulated single
component isotherms.
Conclusions
The grand canonical Monte Car10 (GCMC) method was applied to calculate adsorption
equilibria of methane, ethane and their mixture. At low pressure small pores filled rapidly
due to strong wall potentials. The selectivity strongly depended on pressure and pore
width.
Acknowledgments
References
1. Ajayan P. M., Stephan O., Colliex C. and Trauth D., Aligned carbon nanotubes
arrays formed by cutting a polymer resin-nanotube composite. Science 265 (1994)
pp. 1212-1214.
2. Allen M. P. and Tildesley D. J., Computer simulation of liquids (Clarendon, Oxford,
England, 1987).
3. Ayappa K. G., Simulation of binary mixture adsorption in carbon nanotubes:
Transitions in adsorbed fluid composition. Lungmuir 14 (1998) pp. 880-890.
4. Dujardin E. Ebbesen T. W., Hiura H. and Tanigaki K., Capillarity and wetting of
carbon nanotubes. Science 265 (1 994) pp. 1850-1 852.
5. Ebbesen T. W., Ajayan P. M., Hiura H. and Tanigaki K., Purification of nanotubes.
Nature 367 (1994) p. 5 19.
6. Frenkel D. and Smit B., Understanding molecular simulation from algorithms to
applications(Academic Press, San diego, 1996).
613
7. Gu C., Gao G. H., Yu Y. X.and Nitta T., Simulation for separation of hydrogen and
carbon monoxide by adsorption on single-walled carbon nanotubes. Fluid Phase
Equilibria 194-197 (2002) pp. 297-303.
8. Hilding J., Grulke E. A., Sinnott S. B., Qian D., Andrews R. and Jagtoyen M.,
Sorption of butane on carbon multiwall nanotubes at room temperature. Langmuir 17
(2000) pp. 7540-7544.
9. Iijima S.,Helical microtubulesof graphitic carbon. Nature 354 (1991) pp. 56-58.
10. Iijima S. and Ichihashi T., Single-shell carbon nanotubes of 1-nm diameter. Nature
363 (1993) pp. 603-605.
11. Mackie E. B., Wolfson R. A., Arnold L. M., Lafdi K. and Migone, Adsorption
studies of methane films on catalytic carbon nanotubes and on carbon filaments,
Langmuir 13 (1997) pp. 7 197-7201.
12. Tersoff J. and Ruoff R. S.,Structure properties of a carbon-nanotube crystal. Phys.
Rev.Lett. 73 (1994) pp. 676-679.
13. Tsang S. C., Chen Y. K., Harris P. J. F. and Green M. L. H., A simple chemical
method of opening and filling carbon nanotubes, Nature 372 (1994) pp. 159-162.
14. Yin Y.F., Mays T. and McEnaney B., Molecular simulations of hydrogen storage in
carbon nanotubes arrays. Langmuir 16 (2000) pp. 10521-10527.
15. Zhang X. and Wang W., Methane adsorption in single-walled carbon nanotubes
arrays by molecular simulation and density functional theory. Fluid Phase Equilibria
194-197 (2002) pp 289-295.
614
J.I.YANG,M.H.JUNG,S.H.CHOANDJ.N.KIM
Separation Process Research Center, Korea Institute of Energy Research,
71-2, Jang-don, Yusung-gu,Taejeon, 305343, Korea
E-mail:yangji@kier.re.kr
Carbon dioxide adsorbing capacity was investigated using hydrotalcites as high temperahue
adsorbents. A gravimetric method was used to determine the Co2 adsorbing capacities of the
hydrotalcites, and the temperature was 450 "C. Hydrotalcite took higher adsorbing capacity
compared to other basic materials such as MgO, Alza. To increase the Co2 adsorbing capacity of
the hydrotalcite, MglAl ratios, preparation methods, and K2C03 impregnation were. checked. As a
result, the hydrotalcite prepared by high supersaturationwith MglAl=2 showed desirable adsorptiondesorption pattern and a higher C@ adsorbing capacity. Furthermore, KzC03 impregnation on the
hydrotalcite increased the C a adsorbing amount and the optimum value of &Ca impregnation
was 20 wt%. The hydrotalcite prepared by high supersaturation with Mg/Al=2 and 20 wt% K z C a
impregnation took the highest C@ adsorbing capacity of 0.77 mrnol/g at 450 "C and 800 mmHg.
Introduction
PI.
Hydrotalcite is a double-layered material that is composed of a positively charged
brucite-like layer and a negatively charged interlayer. Hytrotalcites are represented by the
wherein, M(II)=Mg, Cu,
general molecular formula, [M(II)I.xM(III)x(OH)~"'A~n~yH~O
Ni, Co, Zn; M(III)=Al, Fe, Cr,V; A" is any interlayer anion such as CG", Cl-, NO',
S
O
:
- and x=0.1-0.33 [3]. The basicity of hydrotalcite depends on chemical composition
(type of cation, ratio of Mz'/Mh, type of anion existing in the interlayer) and activation
conditions. For example, calcination of the hydrotalcite above 450 "C results in mixed
metal oxides with strong basicity and high surface area. Thus, they can be used as base
catalysts or catalyst supports. In this research we prepared several hydrotalcites with
different preparation methods, varying Mg/Al ratios and adding different amounts of
K2C03for the purpose of using them as high temperature COzadsorbents.
615
2.1
Methods
Preparation of hydrotalcites.
Two different processes were used for preparing hydrotalcites; low supersaturation and
high supersaturationaccording to the methods described in the literature [4].
2.2
A gravimetric method was used to determine the C02adsorbing capacities of the prepared
hydrotalcites. The amount of sample loaded into the TGA unit (C-1100,CAHN
INSTRUMENTS.INC.)was 65 mg. The sample was pretreated in flowing He at 500 "C
for 3 h. After the temperature was lowered to 450 "C,C02 was introduced to the balance
and the weight change was measured. The range of adsorption pressure was between 0 to
lo00 mmHg.
3
3.I
Results
Comparison of hydrotalcite with other C02 adsorbentsat high temperature.
C02 adsorbing capacities of a pure MgO, a pure A1203 and a hydrotalcite (Mg/Al=2,
prepared by high supersaturationmethod) were measured at 450 "C,and their adsorptive
isotherms are shown in Figure 1. Both of individual components of hydrotalcite, MgO and
Al2O3, showed appreciable C02 adsorbing abilities even at high temperatures due to their
basicity. However, the hydrotalcite adsorbed the significantly more amount of C02than
MgO and A 1 2 0 3
3.2
3.3
Hydrotalcites were prepared by two different methods of the differing precipitation rate
during the preparation of hydrotalcite precursor. Although both hydrotalcites showed
almost same adsorbed amount of C02, the hydrotalcite prepared by the high
supersaturation nethod had the higher desorption capacity. The hydrotalcite of high
supersaturation is known to have a low crystallinity, many crystalline nuclei and high
surface area due to its small particle size. And the higher surface area of hydrotalcites
616
prepared by the high supersaturation method may yield the desirable adsorptiondesorption behavior.
0.50,
..
.
0
100
2w
300
4M)
800
6w
7w
800
ow
1000 1100
Peq. mmHg
0.30
.
2
0
0.25
0.20
5 0.15
3 0.10
' 0.05
d
U
0.09
10
MglA ratio
Figure 2. Adsorbed amount of COz on hydrotalcites with varying ratios of Mg/Al (T=450
"C,prepared by low supersaturation method).
3.4
Hoffman et al. [5] reported that the COz adsorbing capacity of the hydrotalcite could be
increased by KzCO3 impregnation in the presence of steam according to the reaction
(K2C03+COz+HzO=2KHC03).Furthermore, the increased basicity due to the
impregnated alkali metal carbonate may provide positive effect of adsorbing more COz to
the hydrotalcite even without steam. Based on that assumption, different amounts of
KzCO3 were impregnated on the hydrotalcite and their COZ adsorbing capacities were
617
investigated. It should be pointed out that COPadsorptionsin this experiment were carried
out without s t e m
l'O
0.1
02t
0.0 I
0 5 1 0 1 5 2 0 2 5 r ) 3 5 4 0 4 5 !
h C 0 , loading amount, wt %
Figure 3. Effect of
Conclusion
The hydrotalcite with the composition of Mg/Al=2 was a suitable COZadsorbent at high
temperature, viz. 450 "C, and its C02 adsorbing capacity was 0.28 mmoVg. A high
supersaturation method for making a hydrotalcite was desirable because the structure of
the hydrotalcite prepared by the method was proper for regeneration by pressure swing
operation. The KzC03 impregnation on the hydrotalcite was favorable to COz adsorbing
capacity because it made chemical properties of the hydrotalcite more basic than that of
the hydrotalcite without KzC03 impregnation. The 20 wt% K2CO3 impregnation in the
hydrotalcite (Mg/Al=2, high supersaturation) took the highest COZadsorbing capacity of
618
0.77 mmoVg at 450 "C and 800 d g . Above the amount of K2Ca impregnation, the
1. Hufton J. R., Mayorga S. and Sircar S., Sorption-enhanced reaction process for
hydrogen production. AIChE J. 45 (1999)pp. 248-256.
2. Yong Z.,Meta V. and Rodrigues A. E., Adsorption of carbon dioxide onto
hydrotalcite-like compounds (HTls) at high temperatures. I n d Eng. Chem Res. 40
(2001)pp. 204-209.
3. Mckenzie A. L., Fishel C. T. and Davis R. J., Investigation of the surface structure
and basic properties of calcined hydrotalcites. J. Cutul. 138 (1992)pp. 547-561.
4. Narayann S.and Krishna K..Hydrotalcite-supportedpalladium catalysts. Appl. Cutul.
A 174 (1998)pp. 221-229.
5. Hoffman J. S. and Pennline H. W., Investigation of C02 capture using regenerable
sorbents. Proc. of the I ThAnnual Intemutional Pittsburgh Coal Conference. 2000.
619
1. Introduction
Recent years, the pollution of volatile organic compounds (VOCs) has attracted
much attention. The VOCs have become important pollutants of air"]. The leakage of the
VOCs from chemical and pharmaceutical manufacturing, printing processes, paint and
adhesive manufacturing and applications, composites and fiberglass molding etc. is the
source of the pollutants. A number of adsorbents are capable of capturing a wide range of
VOCs. However, the conventional process of regenerating the adsorbents by using
organic solvents or thermal fluid still poses a major challenge in this field, notably
because of the high expense or secondary pollution. Thermal regeneration involves
higher temperature, which results in excessive burnout of the carbon (Grant 1990) It].
Chemical regeneration usually requires the use of organic solvent and involves inevitably
a secondary separation or pollution. Recently, some efforts, including supercritical
regeneration 13], ultrasound regeneration [4751 and bioregeneration of an adsorbent, have
been underway. During the 1980s a number of researchers investigated the otential for
using microwave heating to regenerate adsorbents. Burkholder (1986) [6 found that
applying microwave energy enhanced the desorption of ethanol without heating silicalite
because it selectively heated the ethanol without heating adsorbent. Schmidt (1993) ['I
used microwave to desorb water from activated alumina and from Type 4A and 13X
zeolites, molecular sieves, as well as methanol from 13X zeolite. Initial results indicated
that for particular adsorbentladsorbate systems, microwave heating could dramatically
reduce re eneration time. Further, heating was uniform within a fixed bed. Opperman and
Brown
(1999) firstly compared the microwave regeneration and the thermal
regeneration of activated carbons. Their experimental results showed that the temperature
required to regenerate completely the activated carbon when the microwave method was
used was much lower than that when the thermal regeneration method. Turner (2000)
proved that the use of microwave can make the adsorbate with the greater microwave
absorptivity be desorbed selectively, and the surface and adsorbed species can be heated
selectively. The objective of this work is to use microwave energy to regenerate
polymeric adsorbents saturated with benzene and toluene respectively.
620
converting into heat. The property that describes how well a material or an adsorbate
adsorbs microwave energy and convert into heat is the effective dielectric loss factor
(c> ). Generally, the heat -up rate of an actuating medium in an applied electric field is
in proportion to its dielectric loss fator, and the frequency and the intensity of the
electric field, and on the other hand, its heating rate under microwave field is in inverse
proportion to its density and its specific heat capacity, as indicated in equation (1) [91.
Where M is mass of the substance or actuating medium, c i is an effective
dielectric loss factor of the actuating medium under microwave field, P is density of the
actuating medium, C, is specific heat capacity of the actuating medium, f is fiequency of
microwave, and E is intensity of the electric field. It means that the smaller the
dielectric loss factor of the actuating medium, the less the amount of microwave energy
adsorbed by the medium is, and thus the slower the its heating rate is.
t
If the dielectric loss factor c> of a material is equal to zero or very small, then the
material is transparent or semi-transparent to microwave, which means that microwave
can easily penetrate through the material without being adsorbed. For the fixed bed in
which the adsorbent has saturated with the adsorbate, when the use of microwave heats or
regenerates it, if the effective dielectric loss factor of the adsorbate is much larger than
that of the adsorbent, the adsorbate would be rapidly and selectively heated and then
desorbed, while the main body of the fixed bed, the adsorbent, would not be obviously
heated. It implies that in this case the most of microwave energy is used to heat the
adsorbate instead of the adsorbent It not only gets high efficiency of regeneration but also
decreases consume of the energy required to regenerate the adsorbent. As a result, it is an
important advantage of the application of microwave to regenerate the fixed bed.
Usually, the dielectric loss factors of polymeric adsorbents are relative small, i.e. the
polymeric adsorbents are transparent or semi-transparent to microwave. So they are
suitable to be used to adsorb VOCs and then be regenerated by microwave.
3. Experimental section
3.1. Reagent and Materials
Benzene (AR), Toluene (AR), N2 (purity: 99.5%). Polymeric resins: NKA 11 resin (a
polar resin), AB-8 (a weak polar resin) and D4006 (a non-polar resin), which were
purchased fiom Nankai Chemicals plant, Tianjin. Diameter of the resins ranged from
0 . 3 m to 1.0mm.
3.2. Device Instrument
WD8OO microwave oven whose power intensity was 0.734W/cm2, which was made
in Tianjin; FNJA electronic scale with 0.0001g of accuracy, which was made in Shanghai;
Adsorption column made of Teflon, which was 7cm long, and 1.3cm in diameter.
3.3. Adsorption of VOC on Polymeric Resins
Firstly, the resin was filled in the adsorption column, and then was dried by N2 under
microwave field for 10-15 minutes. Secondly, gassy mixture of dried air and VOC was
introduced into the column at constant flow rate 0.16 m3/h until the resin packed in the
621
column was saturatedby the VOC.The adsorption column was put on the electronic scale
with 0.0001g of accuracy. Its weight increased gradually as the VOC adsorbed on the
resin, and then got constant when the resin was saturated. The weights of the column
before and after the adsorption of the VOC can be measured using the electronic scale.
Finally, knowing the weights as well as the weight of the resin packed in the column,
ones can calculate the amount adsorbed on the resin, qo(g/g).
60-70%.
Table 1 showed the time dependence of temperatures, Tb, of three kinds of the fixed
beds respectively packing with the NKA I1 resin, the AB-8 resin and the D4006 resin. It
can be seen that the temperatures of the fixed beds when using the microwave
regeneration were relative low in comparison with the temperature (90%) of the fixed
bed when using the thermal regeneration. A interesting result was that not only the
622
temperatures of the fixed beds when using the microwave regeneration were much lower
than that when using the heat regeneration, but also the regeneration rate of the polymeric
adsorbents obtained by using the microwave regeneration were much higher than that by
using the heat regeneration method. It implied that these polymeric adsorbents were
semi-transparent to microwaves, allowing the microwave energy to be applied efficiently
throughout the adsorbent bed, and meanwhile, under the microwave field the activated
energy of desorption of these organic compounds from the resins became decreased,
which made the regeneration of the adsorbents easy in comparison with the heat
regeneration.
50
On the other hand, it should be noted that, the temperature of the fixed bed packing
with the D4006 resin was the lowest one, while the temperature of the fixed bed packing
with the NKA I1 resin was in the highest one. That is to say, the weaker the polarity of the
polymeric resin was, the lower the temperature of the fixed bed corresponding to the
resin was. It meant that the dielectric loss factor of the polymeric resin was in proportion
to its polarity. It should be mentioned that since a thermocouple or thermometer can not
be used to measure directly the temperature of the fixed bed under microwave field. The
temperatures of the fixed beds was measured by means of a special thermometer and
Microwave workstation Mar5 purchased from CEM company, US.
Table 1 Temperature Variance of the Fixed Beds Packed with Different Resins under Microwave Field
Microwave radiation time (s)
60
240
300
400
28
31.5
37
38
40.5
28
41
55
58
61
28
40
69
75
80.3
623
efficiency of the AB-8 resin was intervenient. It implied that adsorption affinity between
these VOCs and the polymeric adsorbents decreased with the decrease of adsorbent
polarity. The weaker the polarity of the adsorbent, the lower the corresponding desorption
activated energy of the VOCs on the adsorbent was, which would make the VOCs more
easier to desorb from the adsorbent. For example, compared with the regeneration
efficiency of the NKA I1 resin, not only the regeneration efficiency of the D4005 and the
AD-8 resin was more than 90%, but also the regeneration rates were higher.
100-
80
2obdsp/
-0-Adsorbent:
D4000
-A- Adsorbent: AB-0
-0Adsorbent: NKA-II
--
--o-Adsorben(:
D4000
-0-Adsorbent: AB-0
4
Adsorbent: NKA-II
100
200
300
400
500
t (S)
5. Conclusion
The application of microwave to regenerate the polymeric adsorbents can not only get
higher regeneration efficiency in comparison with the use of conventional heat
regeneration, but also make the temperatures of the fixed beds be much lower than that
when using the heat regeneration. The weaker the polarity of a polymeric adsorbent, the
easier its regeneration was.
Acknowledgements
This work was supported by the National Natural Science Foundation of China (No.
29936100) and the Natural Science Foundation of Guangdong Province.
References
1. Opperman S.H. and Brown R. C., Pollution Engineering, 3 l(1) (1999) p58
2. Grant T. M. and King C. J., Ind. Eng. Chem. Res., 29 (1 990) p264
3. Xie Lanying, Xi Hongxia, LI Xiangbin, Li Zhong, Ion Exchange and Adsorption,
16(5) (2000) p413
4. Rege S.U. Yang R.T. and Cai C.A., Desorption by Ultrasound: Phenol on Activated
Carbon and Polymeric Resin, AIChE Journal, 44(7) (1998), pp1519-1528
5. LI Zhong, LI Xiangbin, XI Hongxia, Effects of Ultrasound on Adsorption
equilibrium of Phenol on Polymeric Resin, Chemical Engineering Journal, Vo1.86
(2002) pp375-379.
6. Burkholder H. R., Fanslow G. E., and Bluhm D. D., Ind. Eng. Chem. Fund , 25:
(1986) p414
7. Schmidt Philip S. and James R. Fair, Waste Management, 13(5-7) (1993) p25
8. Turner Michael D., Laurence R. L. and Yngvesson K. S., AIChE Journal, 46(4)
(2000) p758
9. JIN Qinhan, Microwave Chemistry, Beijing: Science Press, 1999
624
Adsorption of binary gas mixtures in the presence of ad-ad interactions is studied through grand
canonical Monte Carlo simulation in the framework of the lattice-gas model. The disordered surface
has been characterized by patches of shallow and deep sites, arranged in a chessboard-like topography.
The adsorption process is monitored through partial and total isotherms, and differential heats of
adsorption. Interesting behaviors have been observed depending on ad-ad interactions and energetic
disorder.
Introduction
The substrate has been represented by a square lattice of M=LxL adsorbing sites with
periodical boundary conditions. The heterogeneityhas been introduced by considering the
two referred kinds of sites. This is a so-called bivariate surface, in equal concentration,
forming hd patches distributed in a chessboard-likeordered topography.
Let us introduce the site occupation variable ci: ci=O if the site i is empty, and ~ = - l
[%=I] if the site i is occupied by a B[A]-atom. The variable a labels the different kind of
625
sites; a 4 [a=1] represents a shallow [deep] site. Each component occupies only one
adsorption site. The energies involved in the process are:
[EBD]: adsorption energy for an A p]particle on a deep site.
[EM]:adsorption energy for an A [B] particle on a shallow site.
W M [WBB] nearest neighbor (NN) energy interaction between an ad-pair AA [BB].
WAB, NN energy interaction between an ad-pair AB (or BA).
&AD
EAS
where 6 is the Kronecker delta function, pA [ p ~ is] the chemical potential of specie A [B],
and I",i means that for a given site i, the sum runs over its four NN sites.
The binary mixture adsorption is simulated by assuming an ideal AB-gas at fixed T, pA
and p ~In. equilibriumthere are two ways to perform a change of the system state: adsorbing
(desorbing) one molecule onto (fiom) the surfkce.
For a given topography, an elementary MC simulation step (MCS) is as follows:
1) Set PA, p ~T,
, and an initial state by placing randomly N molecules on the lattice.
2) Choose randomly one of the components of the mixture -*X ( X=A or B).
3) Choose randomly one of the M sites 4 i; generate a random number 5 E [0,1]:
i) if the site i is empty, and 5 5 W,, ,then an X particle is adsorbed on i. Otherwise,
the transition is rejected. Wadsis the transition probability fiom a state with N
particles to a new state with N+1 particles
ii) if the site i is occupied by an X particle, and 5 S wd, , then the X particle is
desorbed fiom i. Otherwise, the transition is rejected. wda is the transition
probability fiom a state with N particles to a new state with N-1 particles.
4) Repeat fiom step 2)M times.
W* and Wda were obtained in the Metropolis scheme [5]. Then, the total and partial
isotherms are obtained as simple averages over m successive configurations: @LA,~B)=
=(N)/M, eA(pA,pB)=(NA)/M, and ~PA,CIB)=(NB)/M,where (...) means the time average
throughout the simulation, and Nx (X=A or B) is the number of adsorbed X-particles
(N=NA+NB).The differentialheat of adsorption qi for the i-specie is [6]:
626
boundary conditions. Finite size effects are negligible. The first mo=2x105MCS were
discarded to allow equilibrium. The next m=2x105 MCS were used to compute averages.
The chemical potential of one of the components is fixed through the process, p~=0,while
the other one is variable.
3
Figure 1 shows the effect of WBB on adsorption isotherms and differential heats of
adsorption, for a strongly heterogeneous substrate (A.EA=EAD-EAS=-32hT) and repulsive
and
T WAB=O. For pA+ -00 (being p~=0),0 ~ and
4 0~ is a function of
interactions W M ~ C B
WBB. 8B(pA+ -00 ,p~=o)
diminishes with WBB, since the B species behaves as a repulsive
single gas on an homogeneous system. In fact, the range of variation of 8B(pA+ -00 ,pB=O)
lies between 0.5 and 0.226, for WBB=O and WBB + 00, respectively.
40
30
4,
20
10
0
-10
-4.00
*.
-20
-40
-20
0
P A
Figure I: W
M ~ WA&
,
-40
-20
0
P A
20 0.0
I ,O
0.5
QA
In order to analyze the effect of the A-B interaction, Fig. 2 shows the behavior of
~ different WABS. As
isothermsand differential heats of adsorption for wM=4kBT,W B B and
pA+ -00, the surface is half covered by B particles, distributed at random. With increasing
PA, NA increases, which produces a decreasing h 6 B owing to the WAB repulsions. In fact,
the probability of fmding a pair AB (or BA) adsorbed on NN sites diminishes with wAB.In
the limit wAB+ w every A particle on the lattice excludes five sites for the adsorption of B
particles (the occupied site plus its four NN sites).
For 0<0~<0.25, the A species is adsorbed on deep patches;
[OBI increases
[decreases]. During this regime the number of desorbed particles is greater than the number
627
40
qd
20
-20
-40
-20
0
F A
Figure f:W
M ~ ,w
20
-20
20 0.0
FA
s d and different WM'S. a) total and b) partial isotherms;c) differential heats of adsorption.
[OBI increases
For 0.25<0A<0.5,the A particles fill border sites of deep patches.
[decreases] resulting in a decreasing of the total coverage 0 [see Fig. 2 (a)-(b)]. This
adsorption regime is observed until eBm0.06 where half of the inner shallow sites are
occupied (A particles adsorbed on border shallow sites would increase the energy of the
system due to the A-B interactions). The adsorption process follows until the deep patches
become completely covered (0,,=0.5); in this limit, the A isotherm exhibits the well known
plateau due to the surface heterogeneity, which induces a plateau in the B isotherm.
For increasing pA,beyond 0,=0.5, the A particles cover the shallow patches giving
place to the formation of ordered structures inside them while the B particles are desorbed
due to the repulsions. This behavior appears as a fast drop to zero in 0 ~while
,
0~ and 0
increase The total coverage climbs from 0.5 to 1 with an intermediate plateau at 0 m0.75
because of the A-A repulsions.
Figure 2 (c) shows q ~ ( 0and
~ )@A)
for the same cases depicted in Fig. 2 (a)-(b). The
influence of WAB on the differential heats of adsorption can be easily understood by
following the same reasoning like for the corresponding adsorption isotherms. For
0<0~<0.25,48'0, even for ~ ~ 3because
0 , A and B particles are adsorbed avoiding A-B
repulsions. In this regime, q A measures the adsorption energy of deep sites. For
0.25<0A<0.5, q ~ = 0while q A shows an abrupt jump due to the formation of ordered
structures in the adsorbate. In O.5GA<0.75,qAand q B slowly diminish with eA;finally, for
eA>O.75, both of them remain constant.
In Figure 3 we have plotted the results corresponding to W M = W A B ~ CAQ=
B T ,-32k~T,
and different values of wBB. Isotherms and differential heats of adsorption can be
understood by following the analysis of Figs. 1-2, because the behavior observed in Fig. 3 is
the superpositionof those effects.
In summary, when B-Brepulsions are introduced the initial coverage decreases. In this
case, both total and B isotherms are strongly dependent on wBB, unlike the A isotherm which
do not depend on wBB; for wBB+ 00 there exists a limit curve for QA)
and %(PA). On the
628
other hand, a novel behavior is evidenced in the total isotherm at low coverage when A-B
interactions are considered. During this regime the number of desorbed particles is greater
than the number of adsorbed particles which results in a decrease of 0, which shows a
minimum at OA=O.2S.
40
qd
20
-20
1
-40
-20
FA
-40
-20
20 0,O
0.5
1 ,O
FA
OA
a) total and b) partial isotherms; c) differential heats of adsorption.
Figure 3: W M ~ WA&
,
and differentWBB'S.
Solid circles represent the case W M ~ ~ B
WT
- B, ~
References
1. Ruthven D., Principles of Adsorption and Adsorption Processes (Wiley, N.Y. 1984).
2. Rudzinski W., Steele W. A. and Zgrablich G., Equilibria and Dynamics of Gas
Adsorption on Heterogenous Solid Surfaces (Elsevier, Amsterdam 1997).
3. Bulnes F., Ramirez-Pastor A. J., Riccardo J. L. and Pereyra V., Adsorption of Binary
Mixtures on Heterogeneous Surfaces. In Adrorption Science and Technology ed. By
Do D. D. (Word1 Scientific Publishing, Singapore2000) pp. 5 17-52 1.
4. Bulnes F., Ramirez-Pastor A. and Pereyra V.,Study of Adsorption of Binary Mixtu-res
on Disordered Substrates. J. of Mol. Cat. A: Chem 167 (2001) pp. 129-139.
5. Nicholson D. and Parsonage N. D., Computer Simulation and the Statistical Mechanics
of Adsorption (Academic Press, London 1982).
6. Bakaev V. A. and Steele W. A., Grand Canonical Ensemble Computer Simulation of
Adsorption of Argon on a Heterogeneous Surface. Langmuir 8 (1992) 148.
629
Introduction
The role of the adsorptive surface characteristicsin many processes of practical importance
is a topic of increasing interest in surface science [ 11. The energetictopography can strongly
affect some phenomena related to the solid-gas interface, like surface diffusion, reactions,
reconstruction, etc. It is well known that in the case of adsorption, lateral interactions
usually compete with topography and obscure its effects on adsorption isotherm, entropy,
adsorption heats, etc 121. However, much less attention has been paid to analyze the
dependence on heterogeneity of the thermodynamic factor. To study the effects of energy
correlationsand energy interactions on the thermodynamic factor is of central importance in
order to analyze the behavior of the chemical diffusion coefficient of adsorbed species by
using the Kubo-Green approximation [3].
We have performed Monte Carlo simulations of adsorption on heterogeneous surfaces,
in the context of the lattice-gas model [4], where the energetic topography has been
generated from the Dual Site-Bond Model (DSBM) [5]. The process is monitored through
adsorption isotherms and coverage fluctuations [3]. Our scope here is to discuss how energy
correlations and lateral ad-ad interactions affect the main characteristics of adsorption
properties, particularly the coverage fluctuations which appears as very sensitive to both
disorder and interactions.
To model the substrate we have used the Dual Site-Bond Model (DSBM) [ 5 ] , which has
proved to be useful to analyze topography effects on several molecular processes on
heterogeneous surfaces. DSBM provide a statistical description of the disordered media
based on two elements: sites, and the corresponding saddle points (bonds); the adsorptive
energy surface is described by site and bond probability density functions Fs(Es) and
FB(EB).The distribution hnctions Sand B associated to Fsand FBare defined by
630
ES
S(E,)= IF,(E)dE
B(E,) = JFB(E)dE
0.
(1 1
The joint probability density function of finding a connected pair of a site with energy
ES and a bond with energy Esis given by
The correlation function 4 carries information on how sites and bonds are assigned to
each other. The simplest picture is to consider the maximum randomness allowed by the
Construction Principle (the energy of a site cannot be less than the energies of the
connected bonds). Finally Fs(Es) and FB(EB) are, in general, arbitrary functions fulfilling
the condition B Q S(0,which ensures that there will be sufficient amount of bonds to be
connected to sites with sizes equal or smaller than E. The overlapping degree f2,defmed as
the intersection area under Fs and FB is a natural measure of site-bond correlation.
Non-overlapping distributions represent a completely random heterogeneous surface with
zero correlation length, and increasing overlapping generates random patches topographies
of increasing sizes (or correlationlengths). Intermediate values of represent more realistic
situations where correlations between neighboring entities are neither null nor infinitely
extended but rather short ranged. The greater CI the larger the correlation Cdr)between two
elements separated by a distancer. Cdr) has an exponential decay for intermediate and high
values of f2, Cdr) oc exp[-r/ro] where ro is a typical correlation length depending on n:ro
=2f22/(1-n)2 [5].
Different kinds of heterogeneous surfaces can be generated by choosing adequate site
and bond distributions. The procedure by which correlated heterogeneous topographies are
simulated in the DSBM is described in detail elsewhere [6].
3
In the m e w o r k ofthe lattice gas model, the adsorption process is simulated by assuming a
square lattice ofM=LxL adsorption sites, with periodic boundary conditions, in equilibrium
with an ideal gas characterizedby chemical potential ,uand temperature T. The surface as
well as the adsorbate are inert upon adsorption. Then, for a given configuration of
adparticles, the hamiltonian H of the system is given by
M
H = W C c i c j +cC,Ei - p C c i
2 1i.j)
i=l
i=1
(4)
where w is the nearest neighbor (NN) interaction constant, { i j )denote pairs of NN sites,
and Eiis the adsorption energy of the site i. The spin variable cj take the value c f l [ ~ i l if]
the site i is empty [occupied] (multiple site occupation is excluded).
At a fvted T and for a given value of f i the adsorption process has been simulated by
using the grand canonicalMonte Carlo method [5]. At any elementary step, a site chosen at
random is tested to change its occupancy state according to the Metropolis scheme of
probabilities: W(XpX,)=min{ 1,exp[-(Hf-Hi)/kBTI},where Hf and Hi are the hamiltonians
of the final (X,)and initial states (Xi), and RB the BoltPnann constant. A Monte Carlo Step
(MCs) consist of testing at random Msites to change its occupancy state. Then, mean values
of thermodynamic quantities are obtained by simple averages over m succesive
configurations, like the surface coverage, 8, and the internal energy of the system, U,given
631
Without loss of generality, we can consider that all energies are measured in units of kBT.
Then, all results will be independent of the temperature.
We used the Monte Car10 method described in [5,6] for generating heterogeneous
substrates fiom DSBM. We have considered uniform distributions for sites and bonds
(A&=MB=1) with mean site energy Eh=2.5; the site distribution is fixed while the bond
distribution is shifted toward lower energies to increase the correlation degree. We used
square lattices of size LxL, with L=400 [L=700] sites for fk0.5 [R20.5]. The
approximation to thermodynamic equilibrium usually required -10 MCs. Then, the next
4x10 MCs were used to evaluate the equilibrium properties.
Fig. 1 shows the MC results for the coverage fluctuationsf(f=Ti) correspondingto
the random topography (W),
and for different values of the NN interaction, w. As it was
expected, the adsorption process is qualitatively similar to the corresponding to the
homogeneous substrate. For w=O, f exhibits the linear dependencef+l-O); in this case,
particles occupy firstly the strongest sites, which are distributed at random on the surface
and the process follows with the filling of weaker and weaker sites.
For the repulsive case (w>o), and for low values of w, f monotonically decrease with 8
while for a fixed value of efdecreases with w, because for a given value of pthe number of
adparticles N decreases with w. The minimum infat M . 5 for large values of w indicates
the tendency to ordered structures in the adsorbate, since the particles adsorb avoiding NN
interactions. in this case, lateral interactions become more important than heterogeneity
(wc=1.763668, 8,=0.5 are the critical values for a orderdisorder transition on an
homogeneous substrate [3,7]). In this conditions fluctuations will strongly promote the
collective diffusion in the adlayer. Contrarily attractive interactions inhibit the collective
diffusionas f increases with w for all 8 (fig. 1(b)).
The effect of the energy correlations onffor repulsive and attractive interactions, is
shown in figs. 2 and 3, respectively.
In the case of repulsive interactions, neither for R+O (random heterogeneous
substrate) nor Q+ 1 (strongly correlated patches of sites) the energy correlation influences
importantly the thermodynamicfactor (and accordingly the collective diffusion).
As shown in fig. 2 the adsorption isotherms are poorly sensitiveto the correlations. The
adsorption proceeds in such a way to avoid the occupation of NN sites, because NN
repulsions would increase the energy of the system.
The effects of the energy correlation on adsorption isotherms and coverage fluctuations
in the presence of attractive interactions is shown in Fig.3. For k-0, there exists a
competence between the convenience of occupying strong adsorbingsites and the attractive
interactions. Thus, the adsorption is more favorable at intermediate 8, and Q) increases
632
faster with 0 at 830.5. Accordingly f reaches a maximum around half coverage. For
increasing a,the topography of quasi-homotaticpatches favors an increase in the number of
adparticles at low f i Then, the slope of)@t
increases more rapidly with Q at low pressure,
and the maximum offshifts to lower values of coverage. At intermediate 0, the slope of the
isotherm changes due to the strong adsorptive patches are almost completely covered,
producing a remarkable drop in$ At high coverage, f develops another local maximum
owing to the adsorption occurs on less adsorptive patches, and for increasingp, the lateral
interactionsenhances the isotherm slope. The local maximum off (at 8 0 . 5 ) which shifts to
higher 8 with a.
1,o
~=-0.25
0,8
0,6
f0,4
OS
02
0,o
0,O
0,2
0,4
0,6
0,8
1,0
0,2
0,4
0,6
0,8
0,o
1,0
Figure 1: coverage fluctuations for M.(a) repulsive interactions; (b) attractive interactions.
1,o
1.o
03
0,6
f0,4
-&-&2=0.75
4 = 0 . 8 5
0,2
lines: Q=0.85
0,o
0,O
0,2
0,4
e 0,6
0,8
1,0
12
Figure 2: (a) coverage fluctuations, and (b) adsorption isotherms for w>o and different values of n.
Unlike the repulsive case, this important dependence off on the energy correlation for
attractive interactions is also expected to affect the collective diffiion coefficient. It is
worth noting that diffusion will be significantly inhibited at low and high coverage except at
intermediate 8.
In summary, within the thanework of a general model of heterogeneous substrates with
energy correlations we have shown, through the analysis of the thermodynamicfactor, that
633
f
4
-0,O
0,2
0,6
0,4
0,8
1,0
-1
0,o
Figure 3: (a) coverage fluctuations, and (b) adsorption isotherms, for 1 6 0and different values of n.
References
1. W. Rudzinski and D. Everett, Adsorption of gases on heterogeneous surfaces, Acad.
Press, N. York (1992); W. Rudziisb, W. Steele and G. Zgrablich, Equilibria and
dynamics of gas adsorption on heterogeneous surfaces. Elsevier,Amsterdam (1996)
2. G. Zgrablich, C. Zuppa, M. Ciacera, J.L. Riccardo and W. Steele, The effect of
energetic topography on the structure of the adsorbate. Surface Sci. 356 (1996).
634
Introduction
Model
635
potential p Particles can be adsorbed with the restriction of at most one adsorbed particle
per site and we consider a nearest neighbor (NN) repulsive interaction energy w among
them. Then the adsorbed phase is characterized by the hamiltonian:
where t?h9,+& is the total s h c e coverage (summing the coverage on weak and strong
if empty or =I if occupied) and the sum runs
sites), ni is the site occupation number (4
over all pairs of NN sites (ij9. Without loss of generality, we can consider that all energies
are measured in units of b T , and that sI=O and s2=sI+AE,
in such a way that the
adsorptive energy is characterizedby the single parameter AE.
The adsorption process is simulated through a Grand Canonical Ensemble Monte
Carlo (GCEMC) method [5]. Given T and p, an initial configuration with N=M/2 adparticles at random positions is generated. Then an adsorption-desorption process is
started, where a site is chosen at random and an attempt is made to change its occupancy
state with probability given by the Metropolis rule -in{
1,exp[-AWkBT]},where AH=
=Hf-Hi is the difference between the hamiltonians of the final and initial states. A Monte
Carlo Step (MCS) is achieved when M sites have been tested to change its occupancy
state. The approximation to thermodynamic equilibrium is monitored through the
fluctuations in the number N of adsorbed particles; this is usually reached in -I05MCS.
After that, mean values of thermodynamic quantities, like the coverage 0 and the internal
energy U,are obtained by simple averages over M configurations: &(N)/M and U=(H)-p
(N) where the brackets denote averages over uncorrelated configurations.
By changing the value of p, the adsorption isotherm at a given temperature can be
obtained. Furthermore, from the simulation results, the differential heat of adsorption qd as
a function of the coverage is calculated as qd@=[a(U)/iWJ~.
We have used M=104 and w 1 0 5 .With this size of the lattice (L=lOO,in such a.way2
that it is a multiple of r) we verified that finite size effects, which affect the isotherms in
the case of repulsive interactionsat much smaller sizes, are negligible.
3
It is known that, at low temperatures and depending on w/AE, the adsorption process
follows two different regimes [4].
For w/AE I1/4, which corresponds to the so-called Regime 1 : i ) strong patches are
filled first up to W . 2 5 , where a 42x2) structure is formed on them; ii) the filling of
strong patches is completed up to e0.5. Processes corresponding to the regions
0.5-0.75
and 0.75-1,
respectively, are equivalent to processes i ) and ii) for weak
patches.
For w/AE 2 1/3, denoted as Regime I1 : 11 the strong patches are filled until the
42x2) phase is formed on them; ii) idem i) for the weak patches; iii) the filling of the
strong patches is completed; iv) the filling of the weak patches is completed. These
characteristics can be easily followed through the behavior of the differential heat of
adsorption. Regimes I and I1 are disconnected; in between (1/4< w/AE<1/3), the system
behaves in a mixed transition regime changing continuously from one to another.
Figures 1 and 2 show the behavior of adsorption isotherms, (a), and 4d@, (b), for
different topographies in regimes I and 11, respectively. We have identified the different
636
topographies as: 1, [l,] for chessboard [random] patches of size 1, and bp for the case of a
surface with two big patches. It can be seen that all curves are contained between two
limit ones: the one corresponding to lc and the one corresponding to bp. The fact that
both adsorption isotherm and heat of adsorption curves for different topographies,
characterized by a length scale 1, vary between two extreme cwes, suggests that we
should search for some appropriate quantity to measure the deviation among these curves
and study the behavior of such quantity as the length scale is varied. The quantity we
found most suitable is the area between a given curve and a reference curve. For
adsorption isotherms, this quantity, ;~b,is defined as
where @@) is the reference adsorption isotherm. A similar quantity, x,,, can be defined
for the heat of adsorption curves. By taking as a reference curve the one corresponding to
the bp topography, we obtain Figure 3 (a), where we can see that x,, behaves as a power
law in 1 with two different values of a, for regime I, and regime 11. Exactly the same
behavior is also found for n.
1 .o
0.2
L
-30
-20
-10
I0
20
0,O
0,2
0,4
0,6
0,s
11-20
I,O
Figure 1: Adsorption isotherm (a), and differential heat of adsorption (b) correspondingto regime 1.
-20
-10
10
20 0,O
0,2
0,6
0,4
0,s
I,O
For a given regime, a is the same for chessboard and random topographies. This
reinforce the idea that a random topography characterized by a scale length I behaves like
a chessboard topography with a larger scale length. In ref. [4] we have demonstrated that
637
chessboard and random topography curves for x (either xa or a)should become the same
curve as a h c t i o n of an effective length scale (representing an effective patch size), I,,
given by Ic-s.~, where s=l [s=2] for a chessboard [random] topography. MC results are
in agreement with this theoretical prediction (see Fig. 3).
, .
-1
I
REGIME1
AE=4w
(b)
0,l
10
,\
0,2
i REGIME11
AE=3w
, //,
0,4
0,3
,
0,5
--7
A
w/AE
kn
a=a,=-1.952f0.053; f o r w l A E 1 1 1 4
a = a 2=-3.049&0.065; forwIAE2113
a =az+ [12(113 - w l hE)lS(a,
- a , ) ; for 1 / 4 5 w l hE 1113; p = 0.42 f 0.04
(5)
Then, we can establish with great generality that x (mo or a),calculated by using any
suitable reference curve, behaves as a power law in the effective length scale le
Inx =consr-aInf,rr
(6)
where the exponent a has a universal behavior given by equation (5). We stress that the
same universal behavior is obtained by using as a reference isotherm a suitable theoretical
approximation, for example, mean field.
Even if the scaling law, eq. (6), is valid in general, the values of the exponent given in
eq. (5) are valid only for b T = l . For different temperatures, we fmd the following results:
1) the value of a for regime I, al,
does not change with T [hollow squares in Fig. 4 (a)];
2) the value of a for regime 11, a2,increases steadily as T increases approaching
asymptotically the value of al[hollow circles in Fig. 4 (a)]. The full line represents a
fitting curve to the Monte Carlo results. When the same variation is applied to the
transition region, the general behavior represented in Fig. 4 (b) is obtained.
4
Conclusions
The results suggest a method to solve the problem of the characterization of the
energetic topography of heterogeneous substrates which can be approximated by bivariate
638
-1-
kT-2
AE=4w
0,l
0,2
AE=3w
0,3
0,4
0,5
-4,O
w/AE
Figure 4: Variation of universal exponent a with T. (a) Hollow squares, al(T) at fixed d E l 2 and w=2
(regime 1); hollow circles, e ( T ) at fixed e l 2 and w=5 (regime 11); full line fitting to the later. (b) General
diagram showing the behavior of exponent a for different regimes and different temperatures.
4.Bulnes F., Ramirez-Pastor A.J. and Zgrablich G., Scaling Behavior in Adsorption on
Bivariate Surfaces and the Determination of Energetic Topography. J. Chem. Phys.
115 (2001) 1513; Power Laws in Adsorption and the Characterization of
Heterogeneous Substrates. Acisorprion Sci. and Tech. 19 (2001) 229; Scaling Laws in
Adsorption on Bivariate Surfaces P&s. Rev. E, 65 (2002) 3 1603.
5. Nicholson D. and Parsonage N. D., Computer Simulation and the Statistical
Mechanics of Adsorption (Academic Press, London, 1982).
639
Introduction
A major bottleneck in dealing with lattice gases of polyatomic species within the frame
work of classical statistical mechanics is to properly calculate the configurational entropic
contributions to the thermodynamic potential; this means the degeneracy of the energy
spectrum compatible with given number of particles and adsorption sites. In single-site
adsorption, this is usually done through the mean-field assuming that the particles are
distributed randomly over the sites regardless their mutual interactions. However, the
entropic effects in multisite-occupancy adsorption are by no means negligible. For
instance, the coverage dependence of configurational entropy of linear k-mers in one
dimension is strongly dependent on k [l] even for noninteracting particles. It is the fact
that a polyatomic particle excludes more that one state of the states available to the
remaining particles upon adsorption that makes the problem extremely difficult the
counting of number of configurations.
Quantum Fractional Statistics (QFS, also called General Exclusion Statistics)
initiated by Haldane [2], based upon a generalization of the Paulis exclusion principle
(generalized exclusion principle), has recently deserved much attention in quantum
systems since particle interactions can be regarded as statistical interactions
characterized by a parameter g which essentially accounts for the number of states (out of
the states available to a single particle) that a particle excludes when added to the system.
Fermions, bosons, and particles with fractional statistics correspond to g=1, g=O and
O<g<l, respectively.
In the present work we propose the extension of these ideas to classical polyatomic
lattice gases as to describe the thermodynamic properties of multisite adsorption and show
that its treatment can be significantly oversimplified from this perspective. In this case will
be shown that g lies in the range g>l. It is also shown that the adsorption isotherm of kmers on a one-dimensional lattice (recently presented in [3]) can be rigorously obtained if
the statistical parameter g equals the k-mers size (g=k). Application to adsorption of kmers of various geometries on two-dimensional lattices is carried out and compared with
MC simulations (adsorption isotherm and entropy). Results show that the approach
appears as a promising way of gaining insight into the thermodynamics of multisiteoccupancy adsorption and in the determination of gas-solid potential and the configuration
of adsorbed polyatomics from adsorption experiments.
640
Quantum Fractional Statistics relies on the fundamental assumption [2] that AdP-gAN,
where Ad is the change in the Hilbert-space dimension of a single particle when a number
AN of particles is added to the system confined into a finite region of the space, and g
(exclusion statistical parameter1 accounts for the number of states excluded by a single
particle added to the system. If 6 denotes the total number of states available to a single
I
particle, then,
d=G-g(N- 1)
(1)
where d is the number of remaining states available to a single particle when N-1 particles
have been added (adsorbed) to the system (adlayer).
It is assumed here that g is not density-dependent. Although this is arbitrary, it is
necessary to make the problem analytically handable hereafter.
The grand partition function of identical polyatomic molecules is
where
and
(d+N-l)! - [G+l)W-l)]!
w(N)=
N!(d-N)! N![D-g(N-l>l]
(4)
E,(N) = &,N
(5)
where E, denotes the adsorption energy per molecule, the distribution which maximizes eq.
(1) constrained to the above condition is [4]
641
representing the adsorption isotherm of linear rigid species on a square lattice, where g
has been let as force parameter. In order to account for lateral interactions present in
experiments, we can, in first approximation, include them through a mean-field
contribution. Hence
The adsorption process is simulated through a Grand Canonical Ensemble Monte Carlo
(GCEMC) method [4]. For a given value of the temperature T and chemical potential p,
an initial configuration with N dimers adsorbed at random positions (on 2N sites) is
generated. Then an adsorption-desorption process is started, where a pair of nearest
neighbor sites is chosen at random and an attempt is made to change its occupancy state
with probability:
(9)
where AH=&-Hi is the difference between the Hamiltonians of the final and initial states.
A Monte Carlo Step (MCS) is achieved when M pair of sites have been tested to change
its occupancy state. The equilibrium state can be well reproduced after discarding the first
rn'=105-106MCS. Then, averages are taken over m=l@-106configurations.
Thermodynamic quantities, such as mean coverage 8 and average internal energy U
are obtained as simple averages:
where <N> is the mean number of adsorbed particles, and <...> means the time average
over the Monte Carlo simulation runs.
The computational simulations have been developed for square and honeycomb LxL
lattices, with L = 144 and periodic boundary conditions. With this lattice size we verified
that finite-sizeeffects are negligible.
4
Monte Carlo isotherms of interacting and noninteracting dimers on a square lattice have
been interpreted in terms of the new isotherm proposed in eq. (8). w and g were assumed
as fitting parameters of our analysis; and k=2 since data correspond to dimer adsorption.
642
1.0-
0.8-
0.6-
1 ' *''
k
p
'
k ," .
.'
fa /
* ' .
j *!
..!// U
0.40.2-
Attractive Dimers -
MC Simulation
w/kj=0.00
w/k B T = -0.50
A w/k B T = -1.02
QF Statistics
T A AA -I- A A*>-
o 1 1-(-AA1
1'
j
n n . ..->'
n ^ 7*> 1^ ft ftl
10
-5
Figure 1. Adsorption isotherms for homonuclear dimers adsorbed on a square lattice with attractive nearest
neighbor interactions. The symbols represent the results from MC simulations and the lines represent the results
from QF Statistics.
Figure 1 and 2 correspond to attractive and repulsive dimers respectively. For the
attractive case, which is the most interesting for experimental systems, it is observed that
the value of g obtained comes very close to 4, and w agrees very well with the one set in
the computer experiment, within a small statistical uncertainty, g = 4 is also consistent
with the number of states that an isolated dimer on a square lattice excludes to others.
1.00.8-
.'A
'
fi
0.6-
Repulsive
Dimers
MC Simulation
w/k B T = 0
0.4-
w/k B T = 2
w/k B T = 4
QF Statistics
0.20.0
10
20
30
40
643
With regards to the repulsive case, the model adsorption isotherm reproduces the MC
data fairly well for w / k ~ T d The
. discrepancy in the case w/kT=4 links to the orderdisorder phase transitions that dimers develop on a square lattice at w k T , ' d , 8,'=1/2
and w/k~T:nr5, l:=20 (see ref. [5]). These transitions can not be reproduced by the
approximation (mean field) used in eq. (8). As it is clear from Figure 2, the simulated
isotherm for w/k~T=4display a plateau (characteristicof an ordered phase) at l=1/2 since
w/k~T,'<rl. However, only a knee around 8-20 is visible at this temperature because
w/k~T,34.A deeper discussion of the referred phase transitions can be found in ref. [ 5 ] .
The fact that the values of g and W ~ Bobtained
T
from fitting of isotherms match very
well the theoretical values used in the simulations of the strong repulsive cases is
attributed to compensation effects and should not be considered as having much physical
meaning, provided the theoretical isotherm differs significantly from the MC one.
In summary, we have presented a new theoretical perspective of adsorption of
polyatomics. The approach simplifies the inherent complexity of this kind of adsorption
systems in a statistical exclusion parameter which hass a physical meaning traced to the
adsorption configuration on the lattice sites.
In addition, mean field approximation works unuasully well in the frame of the
present model, at least for the case of small polyatomics. Both adsorption configuration
and ad-ad interactions could be better known from the present theory.
Future studies already in progress address the analysis of experimental results and the
relationship between g and the configuration of the adsorbed particle on lattice sites.
References
I . Ramirez-Pastor A. J., Eggarter T. P., Pereyra V. and Riccardo J. L., Statistical Thermodynamics and Transport of Linear Adsorbates. Phys. Rev.B, 59 (1999) pp. 1 10271 1036.
2. Haldane F.D.M., Fractional Statistics in Arbitrary Dimensions: A Generalization of
the Pauli Principle. Phys. Rev. Lett, 67 (1991) pp. 937-940.
3. Ramirez-Pastor A. J., Rom6 F., Aligia A. and Riccardo J. L., Multisite-occupancy
adsorption and surface diffusion of linear adsorbates in low dimensions: rigurous
results for a lattice gas model. Lungmuir, 16, (2000) pp.5100-5105; Rom6 F.,
Ramuez-Pastor A. J. and Riccardo J. L., Configurational Entropy in k-mer
Adsorption. Lungmuir, 16 (2000) pp. 9406-9409; Romh F., Ramirez-Pastor A. J. and
Riccardo J. L., Configurational Entropy for Adsorbed Linear Species (k-men). J.
Chem. Phys,114 (2001) pp. 10932.
4. Wu Y. S., Phys. Rev. Lett, 13 (1994) pp. 922.
5 . Ramirez-Pastor A. J., Riccardo J. L. and Pereyra V. D., Monte Carlo study of dimer
adsorption at monolayer on square lattices. Surjiuce Science, 41 1, (1 998) pp.294-302.
644
new formalism, which provides the isotherm of multilayer adsorption from the adsorption isotherm
at monolayer. The validity of the approach is tested by comparison with Monte Carlo simulations.
Introduction
Among the various theories and models that have been proposed to describe multilayer
adsorption in equilibrium, the ones of Brunauer-Emmet-Teller (BET) [l] is the most
widely used and practically applicable. The great popularity of the BET equation in
experimental studies of adsorption led some authors to extend the original theory of
multilayer adsorption. Thus, numerous generalizations of the BET model have been
reported in the literature, including surface heterogeneity, lateral interaction between the
admolecules, differences between the adsorption energy and structure between the first
and upper layers, etc, [2,3].These leading models, along with much recent contributions,
have played a central role in the characterization of solid surfaces by means of gas
adsorption [4]. One fundamental feature of BETS model is preserved in all these theories.
This is the assumption that an adsorbed molecule occupies one adsorption site. In a recent
work [ 5 ] , an improved solution for multilayer adsorption with multisite-occupancy on
one-dimensional substrates was presented. The particular case of multilayer dimer
adsorption was dealt with in detail and a new adsorption isotherm was obtained for
determining of surface area and adsorption energy from experiments.
In the present paper, the calculations have been extended to k-mers in one and twodimensional surfaces, based upon the Occupation Balance Approximation [6]. The
theoretical results are compared with simulated data. The proposed model is simple, easy
to apply in practice, and leads to new values of surface area and adsorption heats.
Physically, these advantages are a consequence of properly considering the
configurational entropy of the adsorbate.
2
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functions in the first and higher layers. The fact that k-mers can arrange in the first layer
leaving sequences of 1 empty sites with l<k, where no fiuther adsorption of a k-mer can
occur in such a configuration, makes the calculation of entropy much elaborated than the
one for monomer adsorption.
For a lattice having M adsorption sites, the maximum number of columns that can be
grown up onto it is n-=M/k. The grand partition function, &,, of the multilayer in
equilibrium with a gas phase at chemical potential p and temperature T,is given by
n =O
{=Cq,q'-'&
i=l
=cCqi'L
cR,q
=-=-
i=l
l-',q
cx
I-x
n=O
in this case, n represents the number of k-mers and X1 is the monolayer fugacity.
The substitution (=Ilshows that Z,,, can be transformed to El, then
From the condition in eq. (4), we can write the monolayer coverage, el,as
where T and fi are the temperature and the mean number of k-mers (columns) at
monolayer (multilayer), respectively. From eq. (2) and (9,the total coverage, 8, results
646
Following this scheme, the exact solution for multilayer adsorption of k-mers on a
lattice in 1-D can be obtained. We start h m the equation
k-1
Po
ck(l-Bl)k + B l [ I - ( ~ ) B 1 ]
The eqs. (6) and (8) represent the exact solution describing the adsorption of k-mers
at multilayer regime on a homogeneous surface in I -D. In the case of monomer adsorption
(when k=l), the equations (6) and (8) reduce to the well-known BET isotherm [l]. For
k=2, the dimer isotherm can be written in a simple form:
647
averages were taken over lo4 MCS succesive configurations. The total coverage was
obtained as simple averages, B=k(N)/M, where (N) is the mean number of adsorbed
particles, and (...)means the time average over the Monte Carlo simulation runs.
4
0.005- Arlnonporocuskka(77K)
c (23.4t)1.6
0.0
0.2
0.4
0.6
0.8
1.0
nO.OO0,
0.00
,
0.05
,
0.10
,
0.15
,
0.20
P 1 Po
P 1 Po
Figure 1. a) Adsorption isotherms for k-mers adsorbed on I-D with different values of the parameter c. Lines
correspond to exact theoretical results and symbols represent data from Monte Carlo simlation. b) Fitting of
experimental adsorption isotherms of At, Nz / nonporous silica, through the linearized dimer isotherm equation
(9). The resulting values of the parameter c and the monolayer volume v, are shown in the figure.
Although a detailed analysis of experimental data is out of the scope of the present
work, fitting of standard data for the systems Ar,N2 / nonporous silica is shown in figure 1
b). We have adjusted the values of the parameter c and the monolayer volume v, (being
k v / v m )from the proposed adsorption isotherm for dimers, which differ appreciably from
the BET values (namely, ~ 1 3 5 . 2 v,=37.7
;
for N2 and ~ 4 1 . 5 v,=32.5
;
for Ar). The
larger values obtained for c in the BET case trace to the compensation arising in the BET
(monomer) model because of its larger entropy with respect to the dimer (k-mer) case.
The larger values of v, arising from the dimer case may appear more controversial,
although it results straightforwardlyfrom the model.
Regarding with k-mer multilayer adsorption in two dimension, we propose an
approximation to the adsorption isotherm based on the recently developed Occupation
Balance approach (OB) [6].In the simplest case of k=2, the monolayer isotherm for noninteracting dimers adsorbed on a square lattice can be written as,
2;'
4
9
3 2
=-7+ - 8, + -6,
el
Analogous adsorption isotherms result for honeycomb and triangular lattices. The relative
pressure for the square lattice is obtained inserting eq. (1 0) into eq. (4).
648
(1 1)
-=
P
48,
Po
16c+(4-28~)8,+9c@ +3c@
The eq. (1 1) and similar for other connectivities provide a theoretical solution to
multilayer of dimers on lattices in 2-D. This treatment, in which the entropic effects of the
adsorbate size are accounted for, bears theoretical interest because it represents a
qualitative advance with respect to the existing models of multilayer adsorption.
As shown in figure 2 the lattice geometry affects appreciably the multilayer regime
for weakly adsorbing surfaces (-1, 10). It is expected that the effect increases with the
adsorbate size. Additionally, MC simulation agrees very well in the whole pressure range
with the proposed approximation.
0.0
0.1
0.2
1rIanp-r
0.3
0.4
0.0
PIPo
0.1
0.2
0.3
0.4
0.5
0.6
PIPo
Figure 2. Adsorption isotherms for dimers adsorbed on two-dimensional lattices with different values of the
parameter c. The theoreticai results for different connectivities are shown at left. A comparison between
theoretical (lines) and simulated (symbols) results for dimers adsorbed on square lattices is presented at right.
649