Chemical Engineering Journal 253 (2014) 305315

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Modeling and simulation of the adsorption of biogas hydrogen sulde on

treated sewagesludge
F.J. Gutirrez Ortiz , P.G. Aguilera, P. Ollero
Departamento de Ingeniera Qumica y Ambiental, Universidad de Sevilla, Camino de los Descubrimientos, s/n, 41092 Sevilla, Spain

h i g h l i g h t s

 The dynamic behavior of a xed bed with treated sewagesludge for H2S removal is modeled.
 The Bohart and Adams model does not predict suitably the complete breakthrough curves.
 The Klinkenberg solution implies a linear isotherm, and the prediction is not good enough.
 The LDF model with a non-linear isotherm provides a good approach of the adsorption process.
 As an application, a scale-up of the lab scale to a larger one was performed and assessed.

a r t i c l e i n f o a b s t r a c t

Article history: For the design of a xed-bed adsorber, it is essential to know the prediction of the column breakthrough.
Received 4 April 2014 This paper compares two modeling approaches of the dynamic behavior of a xed bed that contains trea-
Accepted 30 April 2014 ted sewagesludge for biogas desulfurization. The rst approach is based on the simple model by Bohart
Available online 21 May 2014
and Adams, which has been widely used to describe the adsorption dynamics when chemical reaction
takes place, and the second one uses the linear driving force model (LDF), solving it analytically by Klin-
Keywords: kenberg equation and numerically with the aid of Aspen Adsorption. While the BohartAdams model
Biogas
uses rectangular isotherm to describe the equilibrium, the LDF model is solved with a more realistic
Hydrogen sulde
Sewagesludge
and suitable isotherm. The Klinkenberg solution implies a linear isotherm, and the prediction is not good
Simulation enough, although better than that of the approach of BohartAdams. The trouble is that the linear iso-
Adsorption therm used in the analytical solution is not realistic and a nonlinear isotherm is required. This paper pre-
Modeling sents a methodology to estimate the overall mass transfer coefcient dynamically as well as the isotherm
that best ts. Thus, the LDF model with the Freundlich isotherm provide a breakthrough curve that match
the experimental results much better than the BohartAdams approach. In order to apply the prediction
obtained, a scaling up of the lab scale was performed, discussed and assessed.
2014 Elsevier B.V. All rights reserved.

1. Introduction different processes for removal of hydrogen sulde from landll

Landll biogas is a product of anaerobic degradation of organic
substrates, and conversion of the chemical energy contained in
biogas, which is rich in CH4, into electricity is possible through
combustion in internal combustion engines [1]. These units can
be seriously damaged by the hydrogen sulde (H2S), because it
can cause corrosion. Therefore, the removal of H2S from the biogas
is particularly crucial in order to use it as fuel for engine.
Desulfurization of gaseous fuel can be done on various adsor-
bents depending on the temperature of the feed gas. There are
Corresponding author. Tel.: +34 95 448 72 68.
E-mail address: frajagutor@etsi.us.es (F.J. Gutirrez Ortiz).
biogas, but activated carbon adsorption process has been mainly
studied by researchers in recent years, because their large surface
area and surface functional groups [2].
Although sewagesludge surface is smaller than that of acti-
vated carbons, they can remove hydrogen sulde, once suitably
treated, and they are much cheaper than activated carbons. Thus,
a xed-bed of treated sewagesludge may be an interesting option
for the biogas purication process.
An experimental characterization of several treated sewage
sludge was previously carried out, and as a relevant result, the
adsorbent obtained by calcination at 700 C of one of the three
kinds of sludge (coded as LG700PA) showed an adsorption capacity
twice of that of a commercial activated carbon without impregna-
tion [3].

http://dx.doi.org/10.1016/j.cej.2014.04.114
1385-8947/ 2014 Elsevier B.V. All rights reserved.
306 F.J. Gutirrez Ortiz et al. / Chemical Engineering Journal 253 (2014) 305315

Nomenclature

C H2S concentration in gas phase KF coefcient of the Freundlich isotherm

C0 H2S feed concentration L total bed depth
Cb H2S breakthrough concentration q concentration of H2S (or load) in solid phase
dp mean particle diameter qe value of q in equilibrium with C
dpore mean pore diameter qs saturation value of q
De effective diffusivity t time
Di internal diameter of the bed tb breakthrough time
DK Knudsen diffusivity u gas interstitial velocity
Dm molecular diffusivity z distance from the bed entrance
ftor tortuosity factor
kBA BohartAdams rate constant Greek
kext external mass transfer coefcient e bed void fraction
Ka overall mass transfer coefcient ep particle porosity
Ke equilibrium constant of a linear adsorption isotherm q gas density
KL equilibrium constant of Langmuir l gas viscosity

A continuous xed-bed adsorber does not run under equilib-
rium conditions, so the ow conditions and mass-transfer aspects
throughout the column affect the performance [4]. The dynamic
behavior of a xed bed column is described in terms of the efuent
concentrationtime prole, i.e., the breakthrough curve, which is
essential in the evaluation of the efcacy of an adsorber. The shape
of the equilibrium isotherm (graphical representation of the gas
uptake quantity as a function of pressure at a constant tempera-
ture) determines the shape of the breakthrough curve, which is
also affected by both inter- and intra-particle transfer processes
in the column and adsorbent [5]. Therefore, accurate measurement
of the isotherm and mass transfer phenomena are fundamental.
This paper compares two modeling approaches of the dynamic
behavior of a xed bed that contains thermally treated sewage
sludge for biogas desulfurization. Experimental results obtained
in a previous work [3] were use in the comparison of the two mod-
eling approaches. The data and methodology given in this paper
provide a basis for a dynamic adsorption model that could be used
to design and evaluate an adsorber on a larger scale. As an applica-
tion of that, a scale-up of the lab scale to a larger one with a biogas
ow-rate about 150 times higher was performed, discussed and
assessed.
2. Modeling
Mathematical models are useful to understand the behavior of
xed-bed columns as well as to design and to optimize this process
unit. To predict the dynamics of the hydrogen sulde adsorption on
carbonaceous material, such as activated carbon or sewagesludge,
the mathematical model must include the adsorption isotherm, the
massenergy balance inside the adsorbent particle and the mass
energy balance of the gaseous phase in the bed [6], as well as mass
transfer phenomena (an equation for the mass ux).
In the xed-bed columns, the concentrations in gas phase
change through the time and space. As the process is unsteady,
the development of a model that describes the concentration pro-
le in the bed with the time is quite complex. Comprehensive
xed-bed models that take into account the nonlinear equilibrium
behavior as well as axial dispersion, resistance to mass transfer,
and sorption kinetics are described in terms of partial differential
equations, which generally involve a very difcult numerical solu-
tion [7]. Consequently, simplied or shortcut methods for correlat-
ing the breakthrough curves of adsorbents columns are extensively
used for the initial design and analysis of xed-bed columns [8],
and frequently, they provide a straightforward and helpful
approach.
In this paper, different adsorption models are proposed to
describe the breakthrough curves that were experimentally
obtained in a previous work [3]. Thus, the pioneer model by Bohart
and Adams was selected to compare it to the linear-driving-force
(LDF) approximation, solved analytically by the Klinkenberg equa-
tion and numerically with the aid of Aspen Adsorption, depending
on the adsorption isotherm. Likewise, the results of these
approaches were compared to experimental data. For the valida-
tion of the models, some of the experimental points of each break-
through test were reserved to compare their results with those
obtained using the model proposed. Additionally, in some cases,
replicates could be carried out and they were also compared to
the models. Finally, it was assumed that only the hydrogen sulde
was adsorbed although both the carbon dioxide and the methane
could compete for the active adsorbent centers, being thus also
adsorbed along with the H2S. Therefore, a very high selectivity of
the adsorbent to the hydrogen sulde was assumed. From the com-
parison of modeling results and the experiment, this assumption
was quite right.
2.1. Breakthrough curve
By assuming isothermal conditions and plug ow of gas through
the xed bed (zero axial dispersion), and taking into account that
changes in uid velocity are negligible because this is a trace sys-
tem, i.e., the adsorbable component (H2S) concentration is low
(<2000 ppm), the Eqs. (1) and (2) describe the dynamics of adsorp-
tion [6,8]:
Mass differential balance equation for xed-bed:
@C @C 1  e @q
u 0 1
@t @z e @t
@q
f q; C 2
@t
where C is the H2S concentration in gas phase, u is the gas intersti-
tial velocity, e is the bed void fraction, q is the concentration of H2S
(or load) in solid phase, t is the time and z is the distance from the
bed entrance.
The initial and boundary conditions are the following:
t 0 : Cz 0; qz 0 z  0
z 0 : Ct; z C 0 t  0
where C0 is the concentration at the inlet of the bed.
For Eq. (2), the idealized equilibrium model (instantaneous
equilibrium is assumed at all points in the column and there are
 F.J. Gutirrez Ortiz et al. / Chemical Engineering Journal 253 (2014) 305315 307

no mass transfer resistances) is seldom accurate in predicting the 2.4. Linear-driving-force approximation
breakthrough behavior [6]. Thus, a nonequilibrium model is
needed to obtain a realistic dynamic response of the bed. The BohartAdams model and the Thomas model are based on
the assumption that the rate of adsorption is controlled by the sur-
2.2. The approach of Bohart and Adams face reaction. However, external and internal diffusion limitations
are not absent in the overall process. Moreover, adsorption may
Bohart and Adams [9] proposed a model for the adsorption of not be limited by kinetics of chemical reaction, but controlled by
one component that has been widely used to describe adsorption external and/or internal mass transfer. Thus, an alternative
dynamics when chemical reaction takes place, because they approach is to consider both inter- and intra-particle mass transfer
described the adsorption by a quasi-chemical rate equation. In to control the adsorption process.
this approach, the diffusion steps (in both lm and pore) are The linear-driving-force (LDF) approximation takes this
assumed to be very fast, and the surface step is rate-controlling. approach in such a way that a lumped overall resistance describes
The adsorption or surface rate (quasi-chemical rate law) is the mass transfer, and where the adsorbent particle is treated as a
following: homogeneous phase in which diffusion takes place with a constant
effective diffusivity; the reaction kinetics is assumed to be much
@q faster than the mass transport. Thus, the mass transfer rate is rep-
kBA Cqe  q 3
@t resented as proportional to the deviation from equilibrium:
where qe is the value of q in equilibrium with C, and kBA is the @q
BohartAdams rate constant. Now, q is the volume-average H2S K a qe  q 7
@t
concentration in solid surface. The model incorporates a rectangular
where Ka is the overall effective mass transfer coefcient.
adsorption isotherm, i.e., irreversible (the H2S adsorbed onto the
adsorbent surface cannot be desorbed), such that qe = qs (saturation
2.4.1. Analytical solution
value) for C > 0 and qe = 0 for C = 0.
If the equilibrium isotherm is linear (qe = KeC), an analytic
Thus, Eq. (1) can be analytically solved and written in a simpli-
expression can be derived, such as Klinkenberg did [13] using
ed linear form (Eq. (4)) [8]:
dimensionless equations as follows:
 
C0 kBA NL 1e @/ @ u
ln 1  kBA C 0 t b ; with N qs 4 Mass balance in the bed : 0 8
Cb u e @n @ s
where L is the total bed depth, Cb is the breakthrough concen-
tration and tb is the breakthrough time. The parameters N and @u
Adsorption velocity : /u 9
kBA can be obtained by linear regression from the slope and inter- @s
cept, respectively, of a linear plot of ln (C0/Cb  1) versus tb, if C0, L where:
and u are known.   
C q KeKaz 1  e z
Eq. (4) allows determining the breakthrough time under differ- / ; u ; n ; s Ka t 
ent experimental conditions as well as predicting the behavior at C0 qs u e u
different bed heights and hydrogen sulde concentrations. There- Thus, using the above mentioned initial and boundary condi-
fore, it could be a useful tool for design and scaling. tions, the analytical solution is:
  
C 1 p p 1 1
2.3. Adsorption isotherms  1 erf s  n p p 10
C0 2 8 s 8 n
The main difference between the BohartAdams model and where erf(x) is the error function of Gauss, dened by Eq. (11).
others similar models lies in the form of the isotherm assumed. Z x
2 2
Thus, for instance, the Thomas model [10] assumes a Langmuir iso- erf x p et dt 11
therm. The nonlinear isotherm of Langmuir has the following form: p 0

The coefcient of overall mass transfer (which includes both the

qe KLC
5 external and internal mass transfer) was determined as follows:
qs 1 K L C
2
1 dp dp
where KL is the equilibrium constant of Langmuir. When the 12
isotherm is highly favorable for adsorption, both models will give K e K a 6kext 60De
similar results [5]. Nevertheless, other possibilities for a better The external mass transfer coefcient (kext) was calculated by
description of the adsorption dynamics of H2S on thermally treated the RanzMarshall correlation (Eq. (13)) [14]:
sewagesludge consist of using other isotherms. This way, some
experiments were carried out to t Langmuir and Freundlich Sh 2:0 1:8Re1=2 Sc1=3 ; Sc < 400; 1 < Re < 70; 000 13
isotherms. where:
The experimental Freundlich isotherm is displayed as follows:
kext dp ue dp q l
qe K F C n 6 Sh ; Re ; Sc
Dm l qDm
where KF is a coefcient that mainly depends on the tempera- Dm, dp, q and l are the molecular diffusivity, particle diameter,
ture and the specic surface area of adsorbent. The exponent n also gas density and gas viscosity, respectively. Dm was calculated by
depends on the temperature. the FullerSchettlerGridding correlation (Eq. (14)) [15]:
Freundlich equation is more used in chemisorption than the  0:5
Langmuir equation due to its better t to the experimental results 1 1
103 T 1:75 Mgas MH2 S
[11]. This is because the Freundlich isotherm is more realistic con- Dm  2 14
P 1=3
sidering an energetically nonuniform surface instead of a uniform V 1=3
gas V H2 S
surface as in the Langmuir isotherm [12].
308 F.J. Gutirrez Ortiz et al. / Chemical Engineering Journal 253 (2014) 305315
with Dm in cm2/s T in K, P in atm, M is molecular weight, and V is the
diffusion volume.
De is effective diffusivity, which may be calculated by the
Bosanquet equation (Eq. (15)):
 1
ep 1 1
De
ftor Dm DK
ep is the particle porosity and ftor is the tortuosity factor.
Finally, DK is the Knudsen diffusivity, which is calculated by Eq.
(16):
 1=2
T carried out by inductively coupled plasma atomic emission spec-
DK 4850dpore
M H2 S
where dpore is the mean pore diameter.
The model was solved with the aid of Matlab R2010b
(Mathworks).
2.4.2. Numerical solution
The dynamic model (Eq. (1)) with the LDF approach (Eq. (7))
and a non-linear isotherm can be solved only by using a numerical
method. Thus, they were implemented in and solved using the
commercial software package Aspen Adsorption V7.1 [16], in
which a bed of spherical particles with constant diameter equal
to 2 mm (average size of the experimental particle size range)
was specied.
The methodology requires performing two steps. First, the iso-
therm parameters of the H2S adsorption onto the adsorbent must
be tted using the adsorption capacity of the adsorbent at different
H2S feed concentrations. The second stage consists of estimating
the overall mass transfer coefcient from the experimental break-
through curve obtained in the laboratory. This can be carried out at
a given H2S feed concentration or using different values of concen-
trations. The isotherm was tted by the nonlinear least-squares
method called NL2SOL [17], which minimizes the nonlinear sum
of squares using analytic Jacobian. To estimate the overall mass
transfer coefcient, the Upwind Differencing Scheme (UDS1) was
selected as discretization method (nite volume scheme) for solv-
ing the Eq. (1) with Eq. (7), which leads to an hyperbolic partial dif-
ferential equation, because UDS1 is an unconditional stable
method that reaches the convergence very quickly against other
schemes with the same number of nodes.
3. Experimental
A high number of adsorption tests were carried out using a
xed-bed cylindrical column (30-mm ID) where the adsorbent
5
4
Ln( (Co/C)-1)
0
20
Fig. 1. Experimental tting to the BA model for the adsorbent LL900A at a bed height of 70 mm and H2S inlet concentration of 2036 ppm.
was disposed. A simulated biogas composed by a mixture of CH4
(60 vol.%), H2S (2000 ppm) and CO2 (balance) entered the bed, with
a supercial velocity at room temperature (25 C) of 2.6 cm/s.
Three types of thermally treated sewagesludge were used as
adsorbents. The thermal treatment was performed in a tubular fur-
nace with different nal temperatures (500, 700 or 900 C), using a
15
holding time of 30 min and a heating rate of 5 C/min. In addition,
two activated carbons, one fresh and the other chemically impreg-
nated with NaOH, were used to establish a suitable comparison
framework.
Physical and chemical characterization of the adsorbents was
16 troscopy (ICP-OES), X-ray Diffraction (XRD), X-ray Photoelectron
Spectroscopy (XPS), Scanning Electronic Microscopy (SEM), physi-
sorption determination and mercury porosimetry. A detailed
description of the experimental apparatus, methods of investiga-
tion and results can be found elsewhere [3].
In addition, the H2S adsorption isotherms of one of the adsor-
bents (LG700PA) was obtained at room temperature (25 C), using
a bed height of 100 mm. H2S concentrations tested were 1980,
1065, 570 and 162 ppm, using nitrogen for diluting the mixture
coming from the bottle with 2200 ppm of H2S. The ow rate of
the gas mixture was always 1.1 L/min. Likewise, the amount of
adsorbent disposed inside the bed was 34 g in each test. To
enhance the ow distribution of gases at the adsorbent bed inlet,
an inert bed of 50 mm height with glass spheres of 6 mm diameter
was located at the bottom of the adsorbent bed.
4. Results and discussion
Some of the tests performed in the previous experimental study
[3] were used to t the parameters of the models and then a com-
parison between experimental and simulation results for both the
BohartAdams (BA) model and the LDF model was made.
4.1. Results of the BohartAdams approach
Fig. 1 shows ln (C0/Cb  1) were plotted versus time using exper-
imental data with one of the adsorbents selected (LL900A), at a bed
height of 70 mm and an H2S inlet concentration of 2036 ppm. By
regression analysis, the slope and the origin ordinate were equal
to 0.207 and 9.874, respectively. The simple determination coef-
cient (r2) was 0.95. The model parameters tted were 67.10 m3/
kg-min and 3.27 kg/m3 for the BohartAdams (BA) rate constant
(kBA) and the adsorption capacity of the sorbent per volume unit
of the bed (N), respectively. With these parameters, the break-
through curves were simulated for different cases. Fig. 2 depicts
Ln( (C o/C )-1) = -0,2074t + 9,8741
25 30 35 40 45 50
Time (min)
 F.J. Gutirrez Ortiz et al. / Chemical Engineering Journal 253 (2014) 305315 309

500 L:7 cm; experimental for

fitting (Co=2036 ppm)

H2S outlet concentration (ppm)

L:7 cm; simulated by B-A
400 model

L:7 cm; experimental for

validation (Co=2036 ppm)
300
L:11 cm; simulated by B-A
model

200 L: 11cm; experimental

(Co=2036 ppm)

L:13cm; simulated by B-A

model
100
L:13cm; experimental
(Co=2274 ppm)

0
0 20 40 60 80 100 120
Time (min)

Fig. 2. Experimental and simulated breakthrough curves for the adsorbent LL900A, using the BH model at three bed-heights and two H2S feed concentrations.

Table 1
Experimental and simulated breakthrough time for the adsorbent LL900A.
Breakthrough L = 70 mm
C0 = 2036 ppm
t200 Experimental (min) 35.8
t200 Simulated (min) 37.0
the experimental breakthrough curves for the adsorbent LL900A
and those obtained using the BA model for different bed heights
(70, 110 and 130 mm) and two inlet concentrations (2036 ppm
for the two rst bed heights and 2274 ppm when the bed height
used was of 130 mm). The model was only tted from the experi-
mental data obtained at a bed height of 70 mm. Afterwards, the
model was used for the other two bed heights, which matched well
the experimental data. Furthermore, replicates were performed at
a bed height of 70 mm, and it can be observed that the experimen-
tal points are close to the model results. Therefore, the BA model
suitably ts the breakthrough curves, providing breakthrough
times similar to those experimentally obtained. Table 1 shows
the experimental and model-based breakthrough times, using a
breakthrough concentration of 200 ppm.
The same procedure was applied to other adsorbent (LF900A),
rst computing the parameters at a 70 mm bed height, and then
obtaining the simulated breakthrough curve at a bed height of
L = 110 mm L = 130 mm
C0 = 2036 ppm C0 = 2274 ppm
110 mm, using an H2S concentration of 2274 ppm. In this case,
the calculated N and kBA values were equal to 3.27 kg/m3 and
64.0 69.4
64.7 69.1
79.96 m3/kg min, respectively. Fig. 3 shows all the experimental
and model-based curves tested. The experimental and the simula-
tion results match quite well, especially in the steepest part of the
concentration breakthrough wavefront. However, the model does
not work well in the initial zone of breakthrough curve, at concen-
trations lower than 50 ppm, where the values of ln ((C0/Cb)  1)
does not t to a straight line.
Additionally, Fig. 4 depicts the breakthrough data for a third
adsorbent (LG700 PA), at a bed height of 100 mm and an initial
H2S concentration of 1980 ppm. In this case, the calculated N and
kBA values were equal to 5.58 kg/m3 and 10.18 m3/kg min, respec-
tively. However, the simple determination coefcient (r2) was only
0.66, so the tting is worse regarding the other adsorbents. Now,
the tting was extended beyond 500 ppm (upper limit in Figs. 2
and 3), covering thus the complete range of concentrations up to
1980 ppm (it must be taken into account that performing the t-
ting to 500 ppm, r2 increased to 0.92). In addition, with the esti-
mated parameters, the breakthrough curve was simulated by

500
L:7 cm; experimental for
fitting
H2S outlet concentration (ppm)

400 L: 7 cm; simulated by B-A

model

L:7 cm; experimental for

validation - 1
300
L:7 cm; experimental for
validation - 2

200 L:11 cm; simulated by B-

A model

L:11 cm; experimental

100

0
0 10 20 30 40 50 60 70 80 90 100
Time (min)

Fig. 3. Comparison between experimental and simulated breakthrough curves for the adsorbent LF900A at two bed-heights (H2S feed concentration of 2274 ppm).
310 F.J. Gutirrez Ortiz et al. / Chemical Engineering Journal 253 (2014) 305315

2000

Co=1980 ppm; for ng

1800
Co=1980 ppm; simulated by B-A model
Co=1980 ppm; for validaon
1600

H2S outlet concentration (ppm)

Co=1065 ppm; simulated by B-A model
Co=1065 ppm; experimental
1400
Co=570 ppm; simulated by B-A model
Co=570 ppm; experimental
1200

1000

800

600

400

200

0
0 50 100 150 200 250 300 350 400 450 500
Time (min)

Fig. 4. Experimental and simulated breakthrough curves for the adsorbent LG700PA with the BH model at a bed height of 100 mm and three H2S feed concentrations.

changing the H2S feed concentration (1065 ppm and 570 ppm), Table 2
and simulated curves did not match well the experimental curves. Parameters used in the Klinkenberg analytical solution.
Thus, e.g., at 570 ppm of inlet H2S concentration, for a break-
Parameter Value Unit
through concentration of 200 ppm, the BohartAdams equation
Particle density 2505.4 kg/m3
predicts a breakthrough time of 374 min. From the breakthrough
Bulk density 481.0 kg/m3
curve it is seen that the corresponding experimental breakthrough Bed void fraction 0.808
time is approximately 151 min. The predicted breakthrough time is Particle porosity 0.21
thus much greater than the observed breakthrough time. In this Bed length 0.10 m
case, in which the H2S feed concentration is changed, the model Bed diameter 0.03 m
Feed gas ow-rate 1.83E05 m3/s
still ts worse, as explained next. Indeed, the breakthrough curve
Particle diameter 0.002 m
is smoother at low concentrations than at high concentrations. This Pore diameter 6.52E09 m
is coherent with the assumption of a rectangular isotherm, which Tortuosity factor 3
may be a satisfactory approach for relatively large concentrations Gas density 1.1012 kg/m3
Gas viscosity 1.32E05 kg/m s
of strongly adsorbed H2S, such as was found in the previous exper-
imental study [3].

4.2. Results of the Klinkenberg analytical solution includes the parameters used. The value of tortuosity factor is
based on [18], and the rest of parameters were obtained from the
Fig. 5 shows the experimental and the theoretical breakthrough previous study [3] and from [19]. The equilibrium constants (Ke)
curves, using the analytical solution by Klinkenberg. Table 2 were computed by tting the experimental results of adsorption

2000
Co = 1980 ppm; Simulated
1800 by Klinkenberg Eq.

Co = 1980 ppm;
1600
H2S outlet concentration (ppm)

experimental

1400 Co = 1065 ppm; Simulated

by Klinkenberg Eq.

1200 Co = 1065 ppm;

experimental

1000
Co = 570 ppm; Simulated
by Klinkenberg Eq.
800
Co = 570 ppm;
experimental
600
Co = 162 ppm; Simulated
400 by Klinkenberg Eq.

Co = 162 ppm;
200 experimental

0
0 50 100 150 200 250 300 350
Time (min)

Fig. 5. Experimental and simulated breakthrough curves for the adsorbent LG700PA with the Klinkenberg solution at a bed height of 100 mm and four H2S feed
concentrations.
 F.J. Gutirrez Ortiz et al. / Chemical Engineering Journal 253 (2014) 305315
1,2
1
0,8
Log qe
0,6
0,4
0,2
0
1 1,5
Fig. 6. Fit of the experimental data to a Freundlich isotherm for the adsorbent LG700PA.
isotherm to the linear isotherm: 8262.4, 11245.9, 13726.2 and
22721.4 m3 gas/m3 ads corresponding to a H2S feed concentration
of 1980, 1065, 570 and 162 ppm, respectively, at which the overall
mass transfer coefcient was 5.55  103, 4.08  103,
3.34  103, 2.02  103 s1. The external mass transfer coefcient
was 4.81  102 m/s.
In Fig. 5, it can be observed that the shapes of the H2S concen-
tration breakthrough front at different H2S feed concentration are
not very similar with those of experimental breakthrough curves.
The larger slope in the beginning of the real breakthrough curves
suggests a higher mass-transfer rate than that in the end, where
the small slope indicates that adsorption rate becomes very small
when adsorbent approaching to equilibrium. In fact, the break-
through curve prediction from Klinkenberg model is symmetrical,
and this approach cannot give a good t at different H2S feed con-
centrations, especially at high concentrations.
4.3. Fitting of the adsorption isotherms
The aim of measuring the adsorption isotherm was to simulate
the system tested in the laboratory more accurately in a nonequi-
librium model that includes mass transfer resistances.
To t the Freundlich equation, the natural logarithm of the
adsorption capacity was graphically represented versus the natural
logarithm of concentration, and by linear regression analysis, the
isotherm parameters were obtained (Fig. 6). The adsorption capac-
ity obtained from the experimental breakthrough curves for the
adsorbent LG700PA was 9.91, 7.26, 4.74 and 2.23 mg H2S/g adsor-
bent at 1980, 1065, 570 and 162 ppm of H2S feed concentration,
respectively. The isotherm equation for the adsorbent LG700PA is
the following:
qe 0:1039 C 0:6036
As a rst step to apply and solve the Eqs. (1) and (7) with the
adsorption isotherm, these parameters were used as inputs in
Aspen Adsorption, in suitable units (Table 3). The two parameters
to be entered were 0.0835 m3/kg and 0.6036.
Table 3
Adsorption capacities for the adsorbent LG700PA at different H2S feed concentrations.
Concentration (mol H2S/m3) Adsorption capacity (mol/kg)
8.8393  102 0.2915
4.7545  102 0.2134
2.5446  102 0.1394
7.2321  103 0.0656
311
Log (q e ) = 0,6036 Log( C ) - 0,9834
2
R = 0,9983
2 2,5 3 3,5
Log C
Additionally, it was carried out an experimental data tting
using the Langmuir isotherm (Fig. 7), but it was worse than that
for Freundlich. The parameters entered the simulator were
4.41E04 kmol/kg and 20825.09 m3/kmol.
By selecting the Freundlich isotherm, the parameters above
mentioned were further tted using the experimental data. The
nal values of the two parameters were 0.0688 m3/kg and
0.5841, respectively, with a tolerance of 106. Fig. 8 shows the
experimental isotherm and the isotherm obtained with the param-
eters calculated by regression and computed by simulation.
4.4. Dynamic estimation of the overall mass transfer coefcient
The overall mass transfer coefcient was estimated with the
experimental conditions for the adsorbent LG700PA, i.e., a biogas
ow-rate of 1.1 L/min, a xed bed of 30 mm diameter and
100 mm height, a bed void fraction of 0.808 and an apparent den-
sity of 481 kg/m3. The H2S feed concentration was equal to the
experimental values used for obtaining the breakthrough curve.
Results from the different estimates of the mass transfer coef-
cient (Ka) from experimental breakthrough fronts at several con-
centrations are shown in Table 4. These coefcients were
included in the LDF model (Eq. (7)) that, along with Eq. (1) and
the tted Freundlich isotherm, allowed calculating the travelling
front or wavefront.
It should be noted that the overall mass transfer coefcient (Ka)
increases as the H2S feed concentration increases, which at rst
may seem strange. However, previous researchers [20,21] pro-
posed a correlation for the prediction of the overall LDF rate con-
stant considering the value of q at equilibrium (qs) with feed
concentration (C0), so Ka would be multiplied by the ratio C0/qs,
approximately. Using the Freundlich isotherm, this implies an
17
increase in Ka when increasing the H2S feed concentration, as
aforementioned.
The predicted curves are close to those experimentally
obtained, except at 1065 ppm of H2S feed concentration, which
may be due to experimental errors, since a value of Ka higher than
the obtained was expected, following the same trend as for other
concentrations.
Additionally, Fig. 9 illustrates the breakthrough curves in rela-
tive terms (outlet concentration-to-inlet concentration ratio versus
the treated biogas volume) to better observe that the adsorbent
can treat a smaller volume of biogas as the feed concentration
increases. This is because the overall driving-force increases as
the H2S feed concentration increases. A higher pore and/or external
312 F.J. Gutirrez Ortiz et al. / Chemical Engineering Journal 253 (2014) 305315

250
C /q e = 0,0668 C + 71,817
2
R = 0,9715
200

150

C/qe
100

50

0
0 500 1000 1500 2000 2500
C

Fig. 7. Fit of the experimental data to a Langmuir isotherm for the adsorbent LG700PA.

3,5E-04

3,0E-04
Adsorption capacity (kmol/kg)

2,5E-04

2,0E-04
Experimental

1,5E-04 Calculated

Simulated
1,0E-04

5,0E-05

0,0E+00
0,E+00 2,E-05 4,E-05 6,E-05 8,E-05 1,E-04
Concentration (kmol/m3)

Fig. 8. Experimental isotherm and Freundlich isotherm (computed and simulated) for the adsorbent LG700PA.

Table 4
Mass transfer coefcients estimates for the adsorbent LG700PA at different H2S feed
concentrations by Aspen Adsorption.
Concentration (ppm)
1980
1065
570
162
lm diffusion rate will result in a steeper concentration wavefront,
which can be observed in the breakthrough curves.
4.5. Results of the LDF model with a non-linear isotherm
Fig. 10 illustrates the simulated breakthrough curves and those
experimentally obtained, at four inlet concentrations. Only 20
nodes were used in the discretization, since more nodes gave the
same result. Additionally, the t was performed using the same
overall mass transfer coefcient for all the curves (that obtained
at 570 ppm and coded by adding r1 in Fig. 10), i.e., a value of
the mass transfer coefcient was tted from a breakthrough curve,
Mass transfer coefcient (s1) and the simulated wavefronts barely changed. Probably, this is
1.92  103 because the internal mass-transfer is the controlling step (using
1.17  103 the Klinkenberg equation, the ratio between the internal and the
1.58  103 external mass-transfer resistances is about 3). It is observed that
1.15  103 the predictions matches well the experimental data, although the
nal slight curvature exhibited in the experimental breakthrough
deviates from the prediction, which may suggest that a more rigor-
ous model than the LDF approximation should be taken into
account to fully describe the dynamics of adsorption. However, it
can be concluded that the LDF model with a single lumped mass
transfer coefcient accounting for the non-linearity of the isotherm
provides an adequate approximation of the adsorption process.
These results give lower values of Ka as compared to those obtained
using the Klinkenberg solution and, however, the curves analyti-
cally predicted (Fig. 5) seems to require a still higher value for Ka
in order to make steeper them. This is not realistic, and it is prob-
ably due to the use of the linear isotherm.
 F.J. Gutirrez Ortiz et al. / Chemical Engineering Journal 253 (2014) 305315 313

0,9

0,8

0,7

0,6

C/Co
0,5

0,4
Co= 1980 ppm
0,3
Co=1065 ppm
0,2 Co=570 ppm

0,1 Co=162 ppm

0
0 50 100 150 200 250 300 350 400

Treated volume (L)

Fig. 9. Experimental breakthrough curves in relative terms for the adsorbent LG700PA at four H2S feed concentrations.

2000

1800
Co=1980 ppm;
Aspen simulated

1600 Co=1980 ppm;

H2S outlet concentration (ppm)

Aspen simulated_r1
Co=1980 ppm; for
validation
1400
Co=1065 ppm;
Aspen simulated
1200 Co=1065 ppm;
Aspen simulated_r1
Co=1065 ppm; for
1000 validation
Co=570 ppm; Aspen
simulated_r1
800 Co=570 ppm; for
validation
Co=162 ppm; Aspen
600 simulated
Co=162 ppm; Aspen
simulated_r1
400 Co=162 ppm; for
validation

200

0
0 50 100 150 200 250 300 350 400
Time (min)

Fig. 10. Experimental and Aspen-Adsorption-simulated breakthrough curves for the adsorbent LG700PA at four H2S feed concentrations.

Against the BohartAdams model that uses a rectangular iso-
therm and assumes the surface-rate as limiting step, simulations
were carried out using the linear driving force (LDF) model which
take into account the experimental adsorption isotherm (Freund-
lich equation, in this case) and mass transfer process to control
the adsorption process. It can be concluded that the tting was
much better using the LDF model, with the aid of Aspen Adsorp-
tion, as shown in Figs. 4 and 10, where the experimental break-
through curves are compared to the simulations performed using
both the BohartAdams method and the LDF model, respectively,
at different H2S feed concentrations. Therefore, the LDF model that
includes the effects of mass transfer rate with a nonlinear isotherm
results in a theoretical representation that more closely approxi-
mates the adsorption process studied in this paper.
4.6. Scale-up assessment
Finally, in order to apply the prediction of the breakthrough
curve by the LDF model with the Freundlich isotherm, a scale-up
was performed and assessed. In xed beds, the critical parameters
are the residence time (L/u) and particle size (dp). This latter is the
same as in the lab scale, i.e., 2 mm on average. A higher residence
time may be achieved by increasing the height of the column,
while keeping the supercial velocity through the column. This
way, the overall mass transfer coefcient should be the same in
both scales, although the supercial velocity is not too relevant
since the main resistance to mass transfer is due to the internal
solid diffusion. Thus, the supercial velocity through the bed depth
was chosen according to the lab results (0.026 m/s). Moreover,
the Reynolds number is low (Re < 40) so the viscous term of
the Erguns law is dominant to compute the pressure drop in the
bed. Besides, to have near plug ow in the lab bed, the particle
Peclet number (related to the ratio L/dp) should be high enough
to cause a high bed Peclet number (related to the ratio L/Di),
whereas in a larger scale unit the particle Peclet number is of min-
imal importance, since dp is the same but both L and Di are much
greater, and thus the bed Peclet number is expected to be high
enough. However, since a scaling up is being performing, disper-
sion effects might have to be considered in the lab scale modeling,
and this is a point for a future work.
314
2000
1800
H2S outlet concentration (ppm)
1600
1400
1200
1000
800
600
400
200
0
0 10
Fig. 11. Simulated breakthrough curves for scaling-up assessment for the adsorbent LG700PA at four H2S feed concentrations.
A scale up to 10 m3/h was established, which involves an inter-
nal diameter (Di) of 0.37 m. Additionally, a bed depth (H) of 3.0 m
was chosen. Fig. 11 illustrates the breakthrough curve at two H2S
feed concentrations for this case using the lab scale supercial
velocity (0.026 m/s). Moreover, it was also scaled up using a higher
supercial velocity (0.26 m/s), keeping in mind to reduce the unit
size and, hence, the space needed. Although, this higher velocity
implies an internal diameter of 0.117 m, with this option, the mass
is also reduced to the tenth part (using the same bed depth), so it is
expectable that the lifetime of the bed is equally reduced, as shown
in Fig. 11. The number of beds and the space required would have
to be larger, and the pressure drop would be quite higher (about
120 Pa), so the use of a high velocity is not recommendable.
By specifying a breakthrough concentration of 200 ppm, the bed
lifetime (breakthrough time) would be 45 and 60 h at 1980 and
1065 ppm, respectively. The lifetime of the adsorbent increases
as the H2S feed concentration decreases. The pressure drop is lower
than 10 Pa, computed by using the Ergun equation, so the power
consumption would not be signicant. However, the adsorbent
load is 155 kg. If the estimated cost due to dehydration and ther-
mal drying of the sewagesludge was assumed to be of the same
magnitude order of that computed for the thermal treatment from
the data obtained in the previous work [3], which was 0.27 /kg of
fresh sludge, using an electricity cost of 0.12 /kWh [22], the total
cost of the adsorbent would be somewhat lower than 0.60 /kg,
ve times cheaper than activated carbon on average. However,
due to its short lifetime predicted in the scale up, and in order to
apply it in a full scale, the need of adsorbent would be huge so a
regeneration method should be studied to enlarge the use of the
adsorbent. This is currently under study and it will be included
in a future paper.
5. Conclusions
For the design of a xed-bed adsorber, a dynamic model of
adsorption helps to calculate the height required, operating life-
time and adsorption capacity of the bed. This paper analyses the
dynamic response of different adsorbents, but especially one of
them (coded as LG700PA), with a relatively high adsorbent capac-
ity based on a previous experimental study [3]. The breakthrough
curve was steeper at higher H2S feed concentrations, but its shape
barely changed with bed height and it was moved almost parallel,
which is reasonable since the mass of adsorbent varied proportion-
ally, and hence, the residence time.
F.J. Gutirrez Ortiz et al. / Chemical Engineering Journal 253 (2014) 305315
Co:1065 ppm; D:0.37m; H:3m; v:0.026m/s Co:1065 ppm; D:0.117m; H:3m; v:0.26m/s
Co:1980 ppm; D:0.37m; H:3m; v:0.026m/s Co:1980 ppm; D:0.117m; H:3m; v:0.26m/s
20 30 40 50 60 70 80 90
Time (h)
The BohartAdams model could be used as an acceptable
approach to determine the breakthrough time, if the breakthrough
concentration is within the sharper zone of the breakthrough
curve. However, at the initial and nal zones of this curve, the
curve is less steep and the extrapolation to other heights does
not work. Additionally, when varying the H2S concentration at
the xed-bed inlet, this method no longer give a good estimate
of the breakthrough curves, due to the simplication of considering
a rectangular isotherm (irreversible). Therefore, the use of this
model must be taken with care.
Beyond the relatively simple modeling, such as the Bohart
Adams approach (or the Thomas model), it is necessary to obtain
better solutions for the breakthrough curves by the rigorous model
equations that take into account an isotherm and mass transfer
resistances. The LDF model is perhaps the simplest concept to
describe mass transfer while maintaining a sensible physical basis.
The analytical solution requires a linear isotherm that is not realis-
tic and then the breakthrough curves obtained deviate from the
experimental, especially at higher H2S feed concentrations. Thus,
dynamic simulation of the adsorption process was carried out with
the aid of Aspen Adsorption V7.1, which makes it possible to esti-
mate the overall mass transfer coefcient numerically and solve
the LDF model when using a nonlinear adsorption isotherm. The
Freundlich isotherm tted quite well to the experimental data. This
way, this modeling can provide a reasonable prediction of the
breakthrough curves, and hence, be used for scaling up. A scale-
up assessment from lab scale to a larger scale with a ow rate
about 150 times higher was performed, and it was veried that a
regeneration of the adsorbent is required.
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