Separation and Purification Technology 24 (2001) 173 188

www.elsevier.com/locate/seppur

Oxygen separation from air by PSA: modelling and

experimental results
Part I: isothermal operation
Adelio M.M. Mendes a, Carlos A.V. Costa a,*, Alrio E. Rodrigues b
a
LEPAE Department of Chemical Engineering, Faculty of Engineering, Uni6ersity of Porto, 4200 -465 Porto, Portugal
b
LSRE Department of Chemical Engineering, Faculty of Engineering, Uni6ersity of Porto, 4200 -465 Porto, Portugal

Received 20 May 2000; received in revised form 5 November 2000; accepted 24 November 2000

Abstract

This work presents an experimental and simulation study of a pressure swing adsorption (PSA) unit running a
traditional Skarstrom cycle and a Skarstrom cycle with co-current equalisation for the oxygen separation from air
using a 5A zeolite. The effects of production pressure, purge and product flowrates, and production step duration on
the product purity and recovery are studied for both cycles and compared. The Skarstrom cycle with co-current
equalisation proved to perform better than the traditional Skarstrom cycle, e.g. for the same operating conditions it
gives better product purities and recoveries. Nevertheless, both cycles present the same general trend as a function of
the operating conditions. The PSA/LDF-DG model is employed to simulate both PSA cycles. This model considers
a linear driving force representation of the dusty gas intraparticle mass transport model. Within the range of tested
conditions, it was found that the model can predict reasonably well the product concentration time evolution for the
cyclic steady state and for the unsteady state, for both cycles. 2001 Elsevier Science B.V. All rights reserved.

Keywords: Adsorption; Mathematical modelling; Zeolites; Pressure swing adsorption; Oxygen separation

Nomenclature
Bo adsorbent permeability (m2)
B eo adsorbent effective permeability (B eo = mpBo/~t) (m2)
Di i-solute Knudsen diffusivity (m2/s)
D ei i-solute Knudsen effective diffusivity (D ei = mpDi /~t) (m2/s)
Dij molecular diffusivity (m2/s)
D eij effective molecular diffusivity (D eij = mpDij /~t) (m2/s)
D oij D oij =D eijPref (m2/s/Pa)
Dax axial dispersion (m2/s)

* Corresponding author.
E-mail address: ccosta@fe.up.pt (C.A.V. Costa).

1383-5866/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S 1 3 8 3 - 5 8 6 6 ( 0 0 ) 0 0 2 2 7 - 6
174 A.M.M. Mendes et al. / Separation/Purification Technology 24 (2001) 173188

Fprod product flowrate (m3N/s)

Fpurge purge flowrate (m3N/s)
k Li i-solute Langmuir constant (Pa 1)
L column length (m)
pi i-solute interparticle partial pressure (p*= i pi /Pref) (Pa)
psi i-solute intraparticle volume averaged partial pressure (p*si = psi /Pref) (Pa)
P interparticle total pressure (Pa)
Pref reference pressure (Pa)
Pe Peclet number (Pe= urefL/Dax)
q ref reference concentration for normalisation (qref = mpPref/zRT) (mol/kg)
qi i-solute particle averaged adsorbed concentration (q*= i qi /qref) (mol/kg)
Qi i-solute Langmuir isotherm constant (mol/kg)
ro particle radius (m)
R* pipe dimensionless mass transport parameter
Rbp ratio between bed and particle time constants (Rbp = ~b/~p)
Rgk ratio between component B molecular and Knudsen diffusion time constants (Rgk = ~g /
~k N )
2
Rgv ratio between component B molecular diffusion and intraparticle viscous flow time con-
stants (Rgv =~g /~v )
Rkk ratio between components A and B Knudsen diffusion time constants (Rkk = ~k O /~k N )
i = zRTQi k i /mp and
2 L 2
RQ k
i , Ri dimensionless parameters for the bicomponent Langmuir isotherm (R Q
k L
R i =k i Pref)
R perfect gas constant (Pa m3/mol/K)
t time (s)
T absolute temperature (K)
u* interstitial velocity (u* =u/uref)
upurge interstitial velocity during the purge step (m/s)
uref reference interstitial velocity (interstitial velocity at the columns outlet during the produc-
tion step) (m/s)
yi product i-solute mole fraction (m)
z* normalised axial co-ordinate (z* =z/L)

Greek letters
h parameter (h =mp(1 m)/m)
m bed porosity
mp adsorbent porosity
vM average viscosity (kg/m/s)
q dimensionless time (q =t/~b)
qcycle dimensionless cycle time
qpress dimensionless pressurisation time
qprod dimensionless production time
z pellet density (kg/m3)
~b bed time constant (~b =L/uref) (s)
~g molecular diffusion time constant (~g =Prefr 2o/D oij) (s)
~ki i-solute Knudsen diffusion time constant (~ki = r 2o/D ei ) (s)
~p particle time constant (~p =mp~g) (s)
~t tortuosity
~v intraparticle viscous flow time constant (~v = r 2ovM/B eoPref) (s)
Vi LDF-DG model parameter, related with the diffusion mass transport
i LDF-DG model parameter related with intraparticle viscous flow
 A.M.M. Mendes et al. / Separation/Purification Technology 24 (2001) 173188
Superscripts
* dimensionless variable
N normal conditions (0C and 1 atm)
1. Introduction
Pressure swing adsorption (PSA) became a
commercial separation process with the patents by
Guerin de Montgareuil (French Patent No.
1,233,261) and Skarstrom (US Patent No.
2,944,627) in 1957 and 1960, respectively. In 1964,
PSA technology was for the first time used to
separate oxygen from air [1]. Since then, PSA has
gained an important share of the oxygen produc-
tion market, competing with cryogenic distillation
for low concentrations (the conventional PSA
technology can only produce oxygen at 95%
mixed with 5% argon) and flowrates. In 1977, Air
Products patented a PSA unit for the simulta-
neous production of oxygen and nitrogen from air
[2]. Hayashi et al., in 1985 (U.S. Patent No.
4,529,412), patented a combined PSA system for
the production of high-purity oxygen from air.
This system is made of two PSA units in series:
the first using a zeolite to remove nitrogen, and
the second a carbon molecular sieve to remove
argon. More recently, Tsuru and Hwang [3] pro-
posed a combined PSA plus membrane technol-
ogy to produce argon-free oxygen.
Few authors studied the equilibrium-based PSA
units for oxygen production from air. Fernandez
and Kenney [4] proposed two equilibrium models,
one using linear isotherms and another using a
linear isotherm for oxygen and a Langmuir
isotherm for nitrogen, to model an experimental
three-step PSA unit for oxygen production using
a 5A zeolite. They studied the effects of produc-
tion pressure (2.35 P 55.7 atm) and cycle dura-
tion (305 tcycle 5127 s) on product purity,
concluding that the interparticle concentration at
the production end of the column is lower in
oxygen for low production pressures and large
cycle times.
Farooq et al. [5] and Ruthven and Farooq [6]
used a 5A zeolite, to separate oxygen from air in
a PSA unit performing the Skarstrom cycle. These
175
authors modelled the experimental system using a
linear driving force (LDF) approximation for in-
traparticle mass transfer and a bicomponent
Langmuir isotherm. They also assumed isother-
mal behaviour, negligible pressure drop, linear
pressurisation and blowdown, and axial dispersed
plug flow. They studied the effects of cycle time
(1005 tcycle 5 250 s), production pressure (1.755
Pprod 5 3.25 atm) and product flowrate (interstitial
product velocity at normal conditions, 0.355
uN 5 1.41 m/s) on product purity and recovery.
Within their operating conditions, they concluded
that product purity presents a maximum as a
function of cycle time, increases with production
pressure and then becomes independent, and is
independent of product flowrate. They conducted
a similar study for the recovery concluding that it
goes through a maximum as a function of cycle
time, decreases when the production pressure in-
creases, and increases with the product flowrate.
Kayser and Knaebel [7] modelled the oxygen
separation from air in a 13X zeolite using an
equilibrium model with a linear isotherm for oxy-
gen and a polynomial isotherm for nitrogen.
These authors studied the effects of pressure ratio
and the purge and production pressure on recov-
ery. They concluded that the recovery has a max-
imum as a function of the production pressure for
non-zero purge pressure.
Liow and Kenney [8] studied the backfill step in
a PSA cycle for oxygen separation from air. They
used 5A zeolite particles with especially large
pores (average pore size, 800 nm), 2.8 4 mm
diameter. These authors studied the effect of pres-
surisation rate, product flowrate, backfill flowrate
and particle size on product purity. They pro-
posed two models; one model for the isobaric
steps, and another for the non-isobaric steps. For
both models, they assumed that total pressure
inside and outside the adsorbent were the same as
all the interparticle assumptions already made by
Farooq et al. [5] and Ruthven and Farooq [6].
176 A.M.M. Mendes et al. / Separation/Purification Technology 24 (2001) 173188
During isobaric steps, interparticle transport was
modelled using the StefanMaxwell representation
for diffusion in mesopores and a LDF approxima-
tion for diffusion in crystallites. During non-iso-
baric steps, the mass transport inside the zeolite was
modelled assuming instantaneous diffusion in the
mesopores and the same LDF approximation for
the crystallites, where the mass transport coefficient
was obtained experimentally. These authors con-
cluded that their model successfully predicts their
experimental results and studied the influence of
various operating conditions for their special PSA
cycle.
The present work studies the oxygen separation
from air in a commercial 5A zeolite, from Laporte,
using a traditional Skarstrom cycle and a
Skarstrom cycle with co-current equalisation. The
main objectives of this work are as follows.
To compare a more complex model including a
LDF approximation of the dusty gas model,
with experimental results, including the cyclic
steady and unsteady states.
To extend the work carried out by Farooq et
al. [5] and Ruthven and Farooq [6] on the
influence of cycle time, production pressure,
product and purge flowrates, on product purity
and recovery.
To compare a six-step PSA cycle (Skarstrom
plus co-current equalisation) with the tradi-
tional four-step cycle.
2. Experimental
A two-bed PSA unit was assembled to perform
the traditional Skarstrom cycle and the Skarstrom
cycle with co-current equalisation, as sketched in
Fig. 1a,b.
The stainless steel columns are 84 cm long filled
with 5A zeolite beads from Laporte regenerated at
370C during about 24 h. The bed and zeolite
characteristics are presented in Table 1. Concentra-
tions, flowrates and pressures were respectively
measured using a quadropole mass spectrometer
(Spectramass Dataquad V3.29, UK), five mass
flowmeters (Bronkhorst, Hi-Tec, The Netherlands)
and two 0 10 bar pressure transducers (Lucas-
Schaevitz P741-0022, USA) (Fig. 1c). This experi-
mental set-up was controlled using a computer that
reads every second a value from each sensor. The
air was supplied by an oil-less compressor and
dehumidified in a mechanical dehumidifier, and in
a pre-column filled with 5A zeolite and silica gel.
The compressor has an on/off pressure control and
therefore the output stream has a cyclic small
pressure variation of about 0.2 bar. Also, for all
experiments, we started the PSA by filling the
system with air (78% N2, 22% O2 + Ar) at ambient
pressure and then initiated the pressurisation step.
The blowdown was carried out at ambient pressure.
For each experimental run, and after the cyclic
steady state had been reached, a set of ten cycles
was recorded and averaged, and a 95% confidence
interval calculated for each measured variable.
The maximum measured pressure drop during
the pressurisation step was 0.08 bar. This pressure
drop was considered sufficiently small to be ne-
glected. Temperature excursions were less than 5C
and thus the system behaves almost isothermally
[9].
3. Mathematical model
The PSA/LDF-DG (linear driving force approx-
imation to the dusty gas model) mathematical
model used in this work was proposed by Mendes
et al. [10] and is based on the following main
assumptions: (i) the flow pattern is described by the
axially dispersed plug flow model, (ii) the intra-
particle mass transfer is described by the LDF-DG
model [11] and the intracrystallite mass transfer
resistance is considered negligible [12], (iii) isother-
mal operation, (iv) equilibrium represented by a
bicomponent Langmuir isotherm, (v) negligible
axial pressure drop, (vi) perfect gas behaviour, and
(vii) variable interparticle velocity.
For the O2/N2 system, the model equations are
as follows.
Interparticle oxygen balance:
((u*p*O2 ) 1 ( 2p*O2 (p*O2 (p*sO2 (q*O2
+ +h +
(z* Pe (z* 2
(q (q (q
=0 (1)
 A.M.M. Mendes et al. / Separation/Purification Technology 24 (2001) 173188 177

 
Interparticle global mass balance: Equilibrium equations:
(u* dP* (p* (q* RQ i p
*si
P* + +h % si +% i =0 (2) q *= where i =O2, N2
(z* dq i (q i (q
i
1+R kO2p *sO + R kN2p *sN
2 2
(4)
Intraparticle component mass balances:
The concentration profiles at the beginning of
(p*si (q*i each new step are taken to be the same as those at
! "
+ =
(q (q the end of the previous step. The boundary condi-
p* p*si
Rbp V( i + c( i Rgv P*(P*
i tions for the traditional Skarstrom cycle are pre-
i p*sO p*sN )
Ei 2 2
sented in Table 2. The Skarstrom cycle with
(3) co-current equalisation has two more steps. For
these steps, we considered that, when we link the
where EO2 =(Rkk /Rgk ) + Rkkp*sO +p*sN , EN2 =(1/ columns, the component mole fractions at the
2
Rgk ) + [(Rkkp*sO + p*sN )/Rkk ] and P* =2 (P/Pref) = inlet of the pressurising column are the same as
i p*.
i
2 2
those at outlet of the blowing down column (as

Fig. 1. PSA cycles: (a) Skarstrom cycle, (b) Skarstrom cycle with equalisation. (c) Schematic diagram of the two-bed PSA
experimental unit.
178 A.M.M. Mendes et al. / Separation/Purification Technology 24 (2001) 173188

Table 1 monocomponent data measured by Sorial et al.

Bed and 5A zeolite characteristics and bicomponent Langmuir
[13] up to 5 bar and at 293.15 K.
parameters for oxygen and nitrogen at 293.15 K
Axial dispersion was estimated using the corre-
Adsorption bed lation presented by Langer and co-workers (cited
Internal column diameter 25.0 mm by Ruthven [14]) for packed beds. The values
External column diameter 28.2 mm obtained for the Peclet number for various oper-
Mass of zeolite in each column 0.3085 kg ating conditions were over 500. For Pe\ 200, the
Bed porosity, m 0.36a
PSA/LDF-DG gives almost the same results and
Adsorbent particles therefore we used Pe=500 for all the simulations.
Average diameter 1.70 9 0.02 mm
Farooq et al. [5] used the same correlation to
Density (apparent) 1160 kg/m3b
Porosity, mp 0.31b obtain the Peclet number and the same value of
Average pore diameter 20 nmb Pe =500.
Bicomponent Langmuir adsorption
Molecular and Knudsen diffusivities and per-
parameters meability were estimated using respectively the
Oxygen ChapmanEnskog correlation (see, for example,
Q (mol/kg) 3.342 Ref. [15]), the Knudsen correlation (see, for exam-
k L (bar1) 0.03494 ple, Ref. [16]) and the Poiseuille equation for
Nitrogen
Q (mol/kg) 1.880
k L (bar1) 0.2025
Table 2
a Boundary conditions for the traditional Skarstrom cycle
Obtained from the apparent density, the bed volume and
the mass of zeolite.
b z* = 0 z* =1
Measured using mercury porosimetry.
Pressurisation, P*(q) (p*O2 /(z*=0
we usually do for the case of production/purge), q  [0,qpress]
=P*pressurisation (q)
and that total pressures at the connecting pipe p*O2 (q) u*(q) =0
ends are related by the Poiseuille equation.
=p*O2pressurisation (q)
Production, q P*(q) (p*O2 /(z*=0
 [qpress,qpress
4. Results and discussion =P*production
+qprod]
p*O2 (q) u*(q) = u*production
Several experiments were performed with the
=p*O2production
traditional Skarstrom cycle and with the
Blowdown, (p*O2 /(z*=0 (p*O2 /(z*=0
Skarstrom cycle with co-current equalisation. The q  [qpress
experimental conditions are presented in Table 3,
+qprod,2qpres
where the flowrate is presented in litres per minute s+qprod]
(at 0C and 1 atm). P*(q) u*(q)=0
The PSA performance was studied as a func-
=P*blowdown (q)
tion of the production pressure, purge flowrate, Purge, (p*O2 /(z*=0 P*= P*purge
product flowrate, production time and equalisa- q  [2qpress
tion extension. In order to be able to use the +qprod,qcycle]
PSA/LDF-DG model to simulate all the experi-
ments, we need to calculate the model parameters. p*O2 (q)/P*purge
The oxygen and nitrogen bicomponent Lang- =p*O2 (z*
muir parameters, presented in Table 1, were esti-
= 1, q, other column)/
mated by fitting the Langmuir equation (Eq. (4)) P*production
to the bicomponent isotherms predicted using the u*(q)= u*purge
ideal adsorption solution theory applied to the
 A.M.M. Mendes et al. / Separation/Purification Technology 24 (2001) 173188 179

Table 3
PSA experimental operating conditions

Experiment Pproduction (bar) Cycle time, tcycle Press. step Prod. Flowrate Purge flowrate Equalisation
(s) duration, tpress (s) (LN/min) (LN/min)

A.1 4.2 180 40 0.10 1.15 No

A.2 4.2 180 40 0.55 1.15 No
A.3 4.2 180 40 1.05 1.15 No
A.4 4.2 180 40 0.10 1.50 No
A.5 4.2 180 40 0.10 0.50 No
A.6 4.2 60 10 0.10 1.15 No
A.7 4.2 240 40 0.10 1.15 No
A.8 4.2 180 40 0.25 1.15 No
A.9 3.0 180 40 0.10 1.15 No
A.10 5.1 180 40 0.10 1.15 No
A.11 7.1 180 40 0.10 1.15 No
A.12 6.8 180 40 0.10 1.10 No
B.1 4.2 180 40 0.10 1.15 Yes
B.2 4.2 180 40 0.55 1.15 Yes
B.3 4.2 180 40 1.05 1.15 Yes
B.4 4.2 180 40 0.10 1.50 Yes
B.5 4.2 180 40 0.15 0.50 Yes
B.6 4.2 60 10 0.10 1.15 Yes
B.7 4.2 240 40 0.10 1.15 Yes
B.8 4.2 180 40 0.25 1.15 Yes
B.9 3.1 180 40 0.10 1.15 Yes
B.10 5.2 180 40 0.10 1.15 Yes
B.11 7.1 180 40 0.10 1.15 Yes

circular cross-section pores (see, for example, Ref.
[16]). The average viscosity was computed using a
correlation by Wilke (see, for example, Ref. [15]).
In order to calculate some of the model
parameters, we need a value for the tortuosity.
This was estimated by fitting the model to the
experimental results of runs A.1, A.2, A.3, A.5
and A.11. The value obtained for the tortuosity
was ~t = 3.6, which is inside the range suggested
by Yang [17] for commercial zeolites (1.75 ~t 5
4.5).
The equilibrium parameters at 293.15 K are:
RQ Q L
O2 =10.9, R N2 =31.8, R O2 =0.0354 and R N2 =
L
cles, once the cyclic steady state was reached. Fig.
2 illustrates the experimental and fitted values for
the pressure history during a cycle and for the
purge flowrate for run A.1. Table 4 presents the
values for parameter Rbp, the ratio between bed
and particle time constants, indicating operation
more or less close to equilibrium, as well as
forP*(t),
n the dimensionless total pressure at the
boundary conditions (n), according to the
schemes in Fig. 3.
4.1. Traditional Skarstrom cycle

0.157, and the transport parameters at 293.15 K
and 1 bar are: Rgk =0.323, Rkk =1.07 and Rgv =
1.38 10 2.
Purge and product flowrates and total pressures
were considered constant. Total pressure time
evolution during pressurisation and blowdown
were represented by a multi-linear relationship.
All these variables were calculated by fitting the
average value obtained from ten experimental cy-
Twelve experiments were performed with the
traditional Skarstrom cycle. The operating condi-
tions are summarised in Tables 3 and 4. As an
illustration of the general experimental and simu-
lation behaviour, Fig. 4 shows the time evolution
of feed flowrate and Fig. 5 shows the history of
product purity (oxygen plus argon mole fraction)
at cyclic steady state and during start-up. The
shaded areas in Fig. 5a correspond to the non-
180 A.M.M. Mendes et al. / Separation/Purification Technology 24 (2001) 173188

productive steps where concentration was not Table 4

Pressurisation and blowdown pressure histories and parameter
recorded. Tables 5 and 6 show the average exper- Rbp (see Fig. 3 for the dimensionless pressure indices)
imental and simulated values of oxygen mole
fraction in product, feed flowrate and recovery Experiment Rbp Pressurisation Blowdown
(ratio between oxygen in product stream and oxy-
gen fed to the PSA unit during one cycle). P*1 P*2 P*1 P*2
It is apparent from Figs. 4 and 5 that the model
A.1 69.3 2.2 3.4 2.2
is able to reproduce not only the experimental A.2 50.9 2.2 3.4 2.2
averaged values shown in Tables 5 and 6, but also A.3 39.4 2.2 3.4 2.2
the cyclic steady state histories of feed flowrate A.4 54.1 2.2 3.4 2.2
and product purity as well as product purity A.5 144.3 2.2 3.4 2.2
A.6 69.3 2.2 3.4 2.2
during the cyclic unsteady state.
A.7 69.3 2.2 3.4 2.2
In general, we can say that the PSA/LDF-DG A.8 61.9 2.2 3.4 2.2
model is able to represent the experimental system A.9 49.5 1.8 2.5 1.8
quite reasonably. A.10 83.3 2.5 4.4 2.5
A.11 117.1 3.3 6.4 3.3
A.12 112.2 2.2 5.3 1.6
B.1 69.3 1.33 1.65 3.70 3.40
B.2 50.9 1.33 1.65 3.70 3.40
B.3 39.4 1.33 1.65 3.70 3.40
B.4 54.1 1.33 1.65 3.70 3.40
B.5 133.2 1.33 1.65 3.70 3.40
B.6 69.3 1.33 1.65 3.70 3.40
B.7 69.3 1.33 1.65 3.70 3.40
B.8 61.9 1.33 1.65 3.70 3.40
B.9 51.1 1.23 1.45 2.90 2.70
B.10 85.8 1.45 1.90 4.70 4.20
B.11 117.1 1.65 2.30 6.30 5.50

4.2. Effects of the production pressure

The study of production pressure influence on

Fig. 2. Experimental and fitted cyclic steady-state histories: (a)
total pressure (measured the columns inlet) and (b) purge
flowrate.
product purity and recovery was achieved by
varying the production pressure in experiments
A.9 (P*=3.0), A.1 (P*= 4.2), A.10 (P*= 5.1),
A.12 (P*= 6.8) and A.11 (P*= 7.1).
The general conclusion is that, within our ex-
perimental range, product purity and recovery
decrease when production pressure increases (see
Tables 5 and 6).
The higher purity observed in experiment A.9 is
due to abnormal behaviour of the mass spectrom-
eter. Also, the lower purity observed in run A.11
can be explained by the feed pressure oscillation
due to the compressor that is operating close to its
maximum pressure.
Farooq et al. [5] and Ruthven and Farooq [6],
observed the same trends. They also remarked
that the purity goes through a maximum for a
 A.M.M. Mendes et al. / Separation/Purification Technology 24 (2001) 173188
Fig. 3. Multilinear fitting model for the total pressure evolu-
tion during: (a) pressurisation, (b) blowdown and (c) blow-
down/equalisation.
181
certain production pressure. We did not observe
this maximum because we always worked at
higher production pressures.
4.3. Effects of the purge flowrate
The study of purge flowrate effect on product
purity and recovery was carried out by varying
the purge flowrate in experiments A.5 (Fpurge =
0.50 LN/min), A.1 (Fpurge = 1.15 LN/min) and
A.4 (Fpurge = 1.50 LN/min).
We can conclude that, within the range of our
experimental operating conditions, as purge
flowrate increases, product purity goes through
a plateau and then decreases and recovery de-
creases (see Tables 5 and 6 and Fig. 6a).
For low purge volumes, as in run experiment
A.5, the system is particularly sensitive to small
perturbations, like oscillations in pressure at the
compressors outlet or in product and purge
flowrates. Because the regeneration of the pro-
duction column is incomplete for low purge vol-
umes, the nitrogen wave front eventually breaks
through, leading to a decrease of the average
product concentration. This can explain the dis-
crepancy between model prediction and experi-
mental results in run A.5.
The purge step was first introduced to in-
crease the PSA performance. A fraction of the
product of one column is fed to the other
column counter-currently to decrease the nitro-
gen partial pressure and increase regeneration,
improving the separation capacity. Increasing
the purge volume also means that some product
is lost. The combined effect on the PSA is an
increase in product purity with purge flow rate,
up to a threshold value, above which the
product purity decreases, as noted by, for exam-
ple, Yang and Doong, [18]. Fernandez and Ken-
ney [4] used a three-step PSA for oxygen
separation that is equivalent to a four-step PSA
with no purge (Fpurge = 0 LN/min). The obtained
product purity was in the order of 38%. Again,
we did not observe that maximum because we
have always worked with a range of purge
flowrates such that a high oxygen concentration
in the product could be obtained.
182 A.M.M. Mendes et al. / Separation/Purification Technology 24 (2001) 173188

production step duration increases (see Tables 5

Fig. 4. Experimental and simulated feed flowrate history at
cyclic steady state.
and 6 and Fig. 8a).
Farooq et al. [5] and Ruthven and Farooq [6]
observed about the same trend for the product
purity but they recorded a different behaviour for
the recovery. The experimental results obtained
by these researchers indicate the existence of a
maximum recovery, although the production pres-
sure was not kept constant and the purge flowrate
was not measured.
Fig. 9 shows the cyclic steady-state product
purity history of experiment A.7. This experiment
has a particularly long production step. It is possi-
ble to see that after 60 s of production time
(t= 100 s in the figure), both the experimental and

4.4. Effects of the product flowrate

The study of product flowrate influence on

product purity and recovery was conducted by
varying the product flowrate in experiments A.1
(Fprod =0.10 LN/min), A.8 (Fprod =0.25 LN/min),
A.2 (Fprod =0.55 LN/min) and A.3 (Fprod =1.05
LN/min).
We verified that, within our experimental range,
product purity decreases and recovery increases
when product flowrate increases (see Tables 5 and
6 and Fig. 7a).
Farooq et al. [5] observed the same trend for
the recovery but not for the product purity. In
that case, they found no dependence on the
product flowrate, but stated that over a threshold
value for product flowrate the product purity
should decrease, as we observed.

4.5. Effects of the production step duration

The study of production step duration influence

on product purity and recovery was performed by
varying the production step duration in experi-
ments A.6 (tproduction =20 s), A.1 (tproduction =50 s)
and A.7 (tproduction = 80 s).
We observed that, within our experimental Fig. 5. Experimental and simulated evolution of product pu-
rity for the Skarstrom cycle: (a) at cyclic steady state and (b)
range, product purity presents a plateau and then during cyclic unsteady state. The two spikes (t : 60 and t :
decreases and recovery always increases when 810 s) are due to a mass spectrometer gain change.
 A.M.M. Mendes et al. / Separation/Purification Technology 24 (2001) 173188 183

Table 5
Experimental and simulated oxygen+argon mole fraction in the product at the cyclic steady state

Experiment yO2+Ar (%) Equalisation

Column 1 Column 2 Average Simulation

A.1 96.6 9 0.3 96.7 9 0.3 96.6 90.3 96.1 No

A.2 75.19 2.1 75.192.2 75.1 92.1 81.6 No
A.3 59.59 2.2 59.69 2.3 59.5 92.3 64.1 No
A.4 94.19 2.3 92.69 0.4 93.3 91.3 92.9 No
A.5 89.1 9 0.7 90.2 9 0.4 89.6 90.6 96.6 No
A.6 95.39 0.4 95.190.8 95.2 90.6 96.3 No
A.7 90.79 1.9 92.59 2.0 91.6 92.0 88.9 No
A.8 82.693.7 84.99 3.7 83.7 93.7 92.8 No
A.9 99.39 0.2 99.49 0.1 99.4 9 0.1 96.4 No
A.10 93.292.2 94.79 0.4 93.9 91.3 94.8 No
A.11 87.490.7 86.79 0.7 87.0 9 0.7 91.8 No
A.12 93.790.6 93.89 0.6 93.7 90.6 95.3 No
B.1 98.69 0.2 98.7 9 0.2 98.7 90.2 98.7 Yes
B.2 87.792.5 85.892.5 86.8 92.5 89.3 Yes
B.3 66.692.3 66.69 2.4 66.6 92.3 66.7 Yes
B.4 99.290.1 99.29 0.2 99.2 90.2 98.1 Yes
B.5 89.393.0 92.09 0.4 90.6 9 1.7 97.4 Yes
B.6 91.590.6 91.69 0.9 91.6 90.7 96.5 Yes
B.7 99.190.5 98.99 0.9 99.0 9 0.7 90.2 Yes
B.8 94.390.4 94.69 0.3 94.4 90.4 97.5 Yes
B.9 98.6 9 0.2 98.99 0.2 98.8 9 0.2 98.8 Yes
B.10 97.990.2 97.99 0.2 97.6 90.2 99.0 Yes
B.11 96.290.2 96.0 90.3 96.1 90.3 99.0 Yes

simulated purity fall down very quickly, indicat- mental averaged values shown in Tables 5 and 6,
ing that the saturation of the column has been but also with the experimental cyclic steady-state
attained. history for product purity.

4.6. Skarstrom cycle with equalisation 4.7. Effects of production pressure

Eleven experiments were performed using the
Skarstrom cycle with co-current equalisation. The
equalisation time was set to 2 s for all the experi-
ments, and it is included into the pressurisation
and blowdown step durations. The system
achieves about 50% of complete equalisation. The
other operating conditions are summarised in Ta-
bles 3 and 4.
As an illustration of the general experimental
and simulation behaviour, Fig. 10 shows the ex-
perimental (run B.1) and simulated product purity
time evolution at cyclic steady state. The model
predicts reasonably well not only with the experi-
The study of production pressure influence on
product purity and recovery was carried out by
varying the production pressure in experiments
B.9 (P*=3.1), B.1 (P*= 4.2), B.10 (P*= 5.2)
and B.11 (P*= 7.1).
The general conclusion is that, within our ex-
perimental range, product purity exhibits a
plateau and the recovery decreases when produc-
tion pressure increases (see Tables 5 and 6 and
Fig. 11). In these experiments, we do not observe
a decrease in product purity when production
pressure increases, as was the case when using the
184 A.M.M. Mendes et al. / Separation/Purification Technology 24 (2001) 173188

traditional Skarstrom cycle. This behaviour can
be explained by the partial compensations due to
pressure rising rate during pressurisation and
equilibrium effects when pressurising with a
system richer in oxygen than the feed gas.
4.8. Effects of purge flowrate
The study of purge flowrate effect on product
purity and recovery was conducted by varying the
purge flowrate in experiments B.5 (Fpurge =0.50
LN/min), B.1 (Fpurge =1.15 LN/min) and B.4
(Fpurge = 1.50 LN/min).
Within our experimental range, product purity is
almost constant, and recovery decreases when
purge flowrate increases (see Tables 5 and 6 and
Fig. 6b).
The abnormal results observed with run B.5 have
the same explanation as that given for run A.5.
If we consider to the simulation results, we can
see that product purity should go through a max-
imum and at the same point recovery begins to
decrease less. So, from the point of view of purge
flowrate effects, both cycles have the same
behaviour.
4.9. Effects of product flowrate
The study of product flowrate influence on
product purity and recovery was carried out by
varying the product flowrate in experiments B.1
(Fprod = 0.10 LN/min), B.8 (Fprod = 0.25 LN/min),
B.2 (Fprod = 0.55 LN/min) and B.3 (Fprod = 1.05
LN/min).
Here we observed essentially the same behaviour
as where using the traditional Skarstrom cycle (see
Tables 5 and 6 and Fig. 7b).

Table 6
Cyclic steady-state experimental and simulated recovery and feed volume per cycle (1 bar and 293.15 K)

Experiment Experimental Simulated Equalisation

Fpurg Ffeed Fprod Recovery (%) Ffeed Recovery (%)

(LN/cycle) (LN/cycle) (LN/cycle) (LN/cycle)

A.1 2.04 90.12 12.09 0.2 0.18 90.04 6.6 91.5 12.6 6.3 No
A.2 2.02 90.09 12.3 90.2 0.93 9 0.11 25.9 93.2 13.3 27.8 No
A.3 2.12 9 0.12 12.990.4 1.79 9 0.15 37.8 93.7 14.2 39.3 No
A.4 2.75 90.11 12.7 90.2 0.219 0.04 7.1 91.3 13.6 5.7 No
A.5 0.92 90.09 10.1 90.2 0.199 0.05 7.7 92.0 10.2 7.8 No
A.6 0.77 90.22 9.4190.2 0.07 9 0.02 3.2 90.9 10.3 3.1 No
A.7 3.28 90.15 13.9 9 0.3 0.30 90.04 9.0 91.2 14.0 8.4 No
A.8 2.01 90.10 12.2 90.3 0.46 9 0.07 14.2 92.3 12.6 15.2 No
A.9 2.04 90.09 9.1390.3 0.18 9 0.04 8.9 92.0 9.82 8.1 No
A.10 2.02 90.15 13.7 9 0.3 0.18 9 0.04 5.8 91.3 14.3 5.5 No
A.11 2.10 90.34 17.8 90.5 0.179 0.03 3.7 90.7 17.9 4.2 No
A.12 1.99 90.22 21.0 90.4 0.18 9 0.03 3.6 90.6 16.6 4.8 No
B.1 2.01 90.11 11.0 90.2 0.19 9 0.05 7.6 92.0 10.9 7.5 Yes
B.2 1.97 90.11 11.89 0.3 0.899 0.12 29.8 9 4.2 11.8 34.4 Yes
B.3 2.08 90.10 12.4 9 0.2 1.83 90.13 44.5 93.6 12.5 46.4 Yes
B.4 2.77 90.13 11.8 90.3 0.199 0.04 7.3 91.5 11.9 6.8 Yes
B.5 0.94 90.10 9.6 90.2 0.189 0.04 7.8 91.7 8.6 9.3 Yes
B.6 0.75 90.22 8.5 90.2 0.07 9 0.02 3.4 9 1.0 8.4 3.8 Yes
B.7 3.25 90.13 13.59 0.3 0.29 90.04 9.7 9 1.4 12.9 9.2 Yes
B.8 1.98 90.11 11.4 9 0.2 0.45 9 0.07 16.8 92.7 11.1 18.1 Yes
B.9 2.00 90.08 8.890.3 0.18 9 0.04 9.2 9 2.1 8.9 9.2 Yes
B.10 1.99 90.15 13.59 0.2 0.18 90.03 5.9 9 1.0 12.3 6.6 Yes
B.11 2.03 90.22 17.1 90.3 0.189 0.04 4.6 91.0 14.8 5.5 Yes
 A.M.M. Mendes et al. / Separation/Purification Technology 24 (2001) 173188 185

has a slightly different behaviour. The experimen-

tal product purity increases first and then presents
a plateau, while the simulated results present a
maximum. This should be the correct behaviour
because increasing production duration is equiva-
lent to increasing production per cycle.
Model predictions in terms of product purity
for runs B.6 and B.7 are quite far from the
experimental results. The low value obtained for
product purity in run B.6 can be explained by
stability problems due to a low purge volume. The
solenoid valves are controlled within 1 s error.

Fig. 6. Experimental and simulated product purity and recov-

ery as a function of the purge flowrate: (a) Skarstrom cycle
(runs A.5, A.1 and A.4), and (b) Skarstrom cycle with equali-
sation (runs B.5, B.1 and B.4).

4.10. Production step duration

The study of production step duration influence

on product purity and recovery was performed by
varying the production step duration in experi-
ments B.6 (tproduction =20 s), B.1 (tproduction =50 s)
and B.7 (tproduction = 80 s).
For our experimental range, the recovery al-
ways increases when production step duration Fig. 7. Experimental and simulated product purity and recov-
increases (see Tables 5 and 6 and Fig. 8b). ery as a function of product flowrate: (a) Skarstrom cycle
The experimental and simulated product purity (runs A.1, A.8, A.2 and A.3), and (b) Skarstrom cycle with
equalisation (runs B.1, B.8, B.2 and B.3).
186 A.M.M. Mendes et al. / Separation/Purification Technology 24 (2001) 173188

Fig. 9. Experimental and simulated evolution of product pu-

rity at cyclic steady state (A.7).

rity and recovery are higher for the Skarstrom

Fig. 8. Experimental and simulated product purity and recov-
ery as a function of the production time: (a) Skarstrom cycle
(runs A.6, A.1 and A.7), and (b) Skarstrom cycle with equali-
sation (runs B.6, B.1 and B.7).
cycle with equalisation. Also, product purity and
recovery change more for intermediate values of
product flowrate (experiments A.8 and B.8, A.2
and B.2) and production pressure (experiments
A.11 and B.11).
The simulated results are generally closer to
the experimental ones for the six-step PSA cycle.
This can be explained in terms of a better re-
generation, which overcomes the perturbations
introduced by the equalisation control.

For short pressurisation/blowdown times, any

variation from cycle to cycle and dead volumes
have a large impact in the obtained product pu-
rity. On the other hand, the high value obtained
in run B.7 cannot be explained except by an
abnormal behaviour of the detection system.

4.11. Comparing the Skarstrom traditional cycle

with the Skarstrom cycle with co-current
equalisation

The experimental and simulated relative dif-

ferences on product purity and recovery between Fig. 10. Experimental and simulated evolution of product
the two cycles for equivalent experiments are purity at cyclic steady state (B.1) for the Skarstrom cycle with
presented in Table 7. As expected, product pu- co-current equalisation.
 A.M.M. Mendes et al. / Separation/Purification Technology 24 (2001) 173188 187

covery were studied in a range that is complemen-

Fig. 11. Experimental and simulated product purity and recov-
ery as a function of the production pressure (runs B.9, B.1,
B.10 and B.11).
5. Conclusions
Several experiments and respective simulations
using the PSA/LDF-DG model were performed
using the traditional Skarstrom cycle and the
Skarstrom cycle with co-current equalisation.
The PSA/LDF-DG model follows quite closely
the experimental results both for the cyclic steady
state and for the unsteady state. The PSA/LDF-
DG model does not take longer to solve numeri-
cally than any other LDF-based PSA model.
The effects of cycle time, production pressure
and product flowrate on product purity and re-
tary to the work carried out by Farooq et al. [5]
and Ruthven and Farooq [6], respectively: 605
tcycle 5 240 s, 3.05 Pprod 5 7.1 bar and 0.0575
uN 5 9.90 m/s. The conclusions are as follows.
1. Production pressure: product purity and re-
covery decrease when the production pressure
increases in agreement with the results pre-
sented by Farooq et al. [5] and Ruthven and
Farooq [6].
2. Product flowrate: product purity decreases and
recovery increases when product flowrate in-
creases. The product purity results are compli-
mentary of those presented by Farooq et al.
[5], whereas recovery results agree with the
same work.
3. Production step duration: product purity de-
creases and recovery increases when produc-
tion step duration increases. The results
obtained for product purity agree with those
presented by Farooq et al. [5] and Ruthven
and Farooq [6], whereas the results for recov-
ery show a different trend.
We also studied the influence of purge flowrate,
and concluded that product purity and recovery
decrease when purge flowrate increases.
The influence of the same operating conditions
was studied for the six-step PSA cycle. The ob-
served trends are the same as those already de-

Table 7
Comparison of the experimental and simulated product purity and recovery for the Skarstrom cycle and the Skarstrom cycle with
equalisationa

Skarstrom cycle Experimental Simulated Skarstrom cycle with equalisation

DRec.% DyO2+Ar% DRec.% DyO2+Ar%

A.1 15 1 19 3 B.1
A.2 16 17 31 16 B.2
A.3 18 11 18 4 B.3
A.4 2 6 19 6 B.4
A.5 1 0 19 1 B.5
A.6 6 4 19 0 B.6
A.7 8 8 9 2 B.7
A.8 18 13 28 5 B.8
A.9 3 1 14 3 B.9
A.10 2 4 14 4 B.10
A.11 24 11 31 8 B.11

a
DRec.= [Recwith-equal-Recwithout-eual]/Recwithout-equal; Dy=[ywith-equal-ywithout-equal]/ywithout-equal.
188 A.M.M. Mendes et al. / Separation/Purification Technology 24 (2001) 173188
scribed for the four-step PSA cycle. Nevertheless,
a general increase on product purity and recovery
is observed for the same operating conditions,
especially for intermediate values of product
flowrate and production pressure.
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