Separation and Purification Technology 33 (2003) 25
/43

www.elsevier.com/locate/seppur

Heuristic design of pressure swing adsorption: a preliminary

study
S. Jain a, A.S. Moharir a, P. Li b,*, G. Wozny b
a
Department of Chemical Engineering, Indian Institute of Technology, Bombay 400 076, India
b
Institut fur Prozess und Anlagentechnik, Technische Universitat Berlin, KWT9, 10623 Berlin, Germany

Received 29 November 2001; received in revised form 15 November 2002; accepted 4 December 2002

Abstract

Due to its complicated nature and multiple decision parameters including plant dimensionality and operation
condition, the design of pressure swing adsorption (PSA) processes is not a trivial task. Most previous studies on PSA
design have been made through rigorous modeling and experimental investigation for specific separation tasks. General
heuristics for a preliminary design of PSA processes are necessary but not well investigated so far. In this paper, we
attempt to develop easy-to-use rules for PSA process design, based on analysis of the inherent properties of adsorbate
/
adsorbent systems (i.e. equilibrium isotherm, adsorption kinetics, shape of breakthrough curves, etc.) and simulation
results. These rules include the selection of adsorbent, particle size, bed size, bed configuration, purge volume, pressure
equalization and vacuum swing adsorption. Results of two case studies are presented to verify the rules proposed in this
preliminary study.
# 2002 Elsevier Science B.V. All rights reserved.

Keywords: Pressure swing adsorption; Simulation; Design and operation; Heuristics

1. Introduction Since the development of PSA, many improve-

Because pressure swing adsorption (PSA) has
the properties of high selectivity, high throughput
and high energy efficiency, more and more PSA
processes are designed and operated to carry out
gas bulk separation and purification tasks in the
chemical industry. In a PSA process, the adsorbent
adsorbs the preferential species of a gas mixture,
which is then desorbed by reduction in pressure.
* Corresponding author. Fax: /49-30-314-26915.
E-mail address: li@dynamik.fb10.tu-berlin.de (P. Li).
1383-5866/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
doi:10.1016/S1383-5866(02)00208-3
ments in the process have been done to make it
more efficient. The most previous studies on PSA
design have been made through rigorous modeling
and experimental investigation for specific purifi-
cation tasks. Since a PSA process is quite compli-
cated and there are many parameters to be
decided, there have been no general easy-to-use
design rules so far. Because a pilot plant study of
PSA is costly compared with computational study,
simulation has become a viable alternative to pilot
plant experiments. Based on basic kinetics and
equilibrium data as well as operation parameters,
simulation provides a method of predicting outlet
26 S. Jain et al. / Separation and Purification Technology 33 (2003) 25
/43

Nomenclature
b Langmuir constant (atm 1)
C concentration in gas phase (mole per m3 of fluid)
D intracrystalline diffusivity (cm2 s 1)
dp diameter of particle (cm)
G purge/feed volume ratio
K Henrys Law constant
k overall mass transfer coefficient (s1)
L total height of the column (m)
N total number of components
P pressure (atm)
Q molar flow rate
q adsorbed phase concentration (mole per m3 of solids)
q* equilibrium concentration of adsorbed phase (mole per m3 of solids)
qs Langmuir constant (mol cm 3)
R universal gas constant
T temperature (K)
t time (s)
v superficial velocity (m s1)
W power (kW)
x adsorbed phase composition
y gas phase composition
z height of the bed ( /0 at feed end, /L at product end) (m)
Greek symbols
a separation factor (dimension less)
o bed Porosity
f factor defined in (Eq. (19))
g ratio of specific heats in gas phase
h mechanical efficiency
r density (kg m 3)
m gas viscosity (Cp)
t residence time (s)
Subscripts
0 initial
1, 2 components
act actual
ads adsorption
blow blowdown step
f feed
g gas phase
H high pressure step
I component
L low pressure step
min minimum value
pres pressurization step
prod product
purg purge step
s solid phase
 S. Jain et al. / Separation and Purification Technology 33 (2003) 25
/43
concentrations and the dynamic capacity of PSA,
without recourse to experimentation. To this end,
a comprehensive model and a numerical solution
method are required [1,2].
Cen and Yang [3] showed that due to its
simplicity, the equilibrium model can be widely
used for PSA simulation. Alpay and Scott [4] used
the linear driving force (LDF) model to describe
the adsorption and desorption kinetics in spherical
particles. Raghavan and Ruthven [5] presented
numerical simulation of PSA in the recovery of
trace adsorbable from an inert carrier using the
linear equilibrium and linear rate expressions.
They also assumed that during pressure changes
(blowdown and pressurization) there was no mass
transfer between the fluid and adsorbent. Ragha-
van and Ruthven [6] discussed numerical simula-
tion for a simple two bed PSA process in which
effects of kinetics and changes in flow rate due to
adsorption are significant. They showed that when
the above effects are significant, adsorption equili-
brium and constant velocity assumptions are no
longer valid.
Chahbani and Tondeur [7] discussed the mass
transfer kinetics in PSA. They showed that the
choice of the pore diffusion model plays a key role
for obtaining reliable simulations. They compared
their results with other models like LDF and
equilibrium model. Kvamsdal and Hertzberg [8]
showed the effect of mass transfer during the
blowdown step. According to their results, the
frozen solid assumption is valid only in certain
cases, and taking into account the mass transfer
during the blowdown step gives a better overall
model performance in the studied cases. A series
modeling and simulation studies have been done
aiming at finding proper PSA design and opera-
tion such as the particle size and pressure ratio [9
/
12].
These previous works mainly focused on mod-
eling and simulation of PSA. From these studies, it
is found that for design and operation of PSA, one
has to go for a rigorous simulation. Modeling PSA
leads to a nonlinear dynamic partial differential
equation system, which is difficult to solve. The
parameters in PSA models affecting the behavior
of the process are highly coupled to each other.
Studies on the sensitivities of these parameters
27
through rigorous modeling and simulation are
quite expensive. Therefore, it is necessary to
develop heuristic rules with which design and
operation of PSA processes can be made without
doing more rigorous simulation.
Heuristic rules (or rules of thumb) simplify the
design and/or operating options and shortlist a few
options which could be probed further. They thus
reduce the dimensionality of an otherwise combi-
natorial design problem. Heuristics has found wide
applications in process design (usually a prelimin-
ary design). Potential designs from heuristic rules
can then be fine tuned using rigorous simulation, if
necessary.
The number of decision parameters, including
plant dimensionality and operation condition, is
quite large in the design of PSA. More and more
adsorbents are being developed, but adsorbent
/
adsorbate system characteristics themselves are
not fully understood. The accumulated experiences
with adsorptive separations are also insignificant
compared with those in the cases of thermal
distillation and chemical reaction.
This work attempts to develop a set of heuristic
rules for the design of PSA systems. A model of
adsorptive separation is used to generate case
studies. Based on the properties of adsorbate
/
adsorbent systems (i.e. equilibrium isotherm, ad-
sorption kinetics, shape of break through curves
etc.), systematic knowledge of the input/output
relations thus gained is extracted out to evolve
some simple rules for design. Product purity and
recovery are the performance factors studied to
derive the rules for various decision steps in design
of PSA. They include decisions on size of particles,
pressure levels, configuration of PSA cycle, resi-
dence time in PSA bed, design of PSA bed, choice
for pressure equalization step and choice for VSA
process.
2. Modeling PSA processes
Fig. 1 shows a typical PSA process. The process
consists of two fixed-bed adsorbers undergoing a
cyclic operation of four steps: (1) adsorption, (2)
blowdown, (3) purge, and (4) pressurization. By
employing a sufficiently large number of beds and
28 S. Jain et al. / Separation and Purification Technology 33 (2003) 25
/43

@Ci @vCi (1  o) @qi

  0; i 1 and 2 (1)
@t @z o @t
The last term in Eq. (1) is the mass transfer term
between solid and gas, where qi is the concentra-
tion of component i in the solid. For pressure
changing steps (pressurization and depressuriza-
tion) this term is zero due to assumption (2).
Summation of Eq. (1) for all the components leads
to the total mass balance equation. For constant
pressure steps (adsorption and purge) the total
concentration of the fluid remains constant in the
bed, thus the total mass balance will be

@v (1  o) X @qi
N
C  0 (2)
@z o i1 @t

while for pressure changing steps the total mass

balance is
Fig. 1. Basic two-bed PSA process.
@v 1 @P
using more complicated procedures in changing  0 (3)
@z P @t
bed pressure, PSA may be carried out as a
continuous process. Additional steps such as co- where it is assumed that the pressure drop in the
current depressurization and pressure equalization bed is negligible. Eqs. (1)
/(3) are applied for the
have been added to improve the purity and flow from z/ 0 to L . If the flow is reverse, the
recovery of products as well as to make the process term @/@z will be negative. The mass transfer
more energy-efficient. A common feature of all kinetics is modeled using the LDF approximation,
PSA processes is that they are dynamic, i.e. they based on the simplification of Ficks second law of
have no steady state. After a sufficiently large diffusion
number of cycles, each bed in the process reaches a @qi
cyclic steady state (CSS), in which the conditions ki (qiqi ) (4)
in the bed at the end of a cycle are approximately @t
the same as those at the beginning of the next where qi denotes the equilibrium concentration of
cycle. component i. It is calculated using either extended
In the present work, the following assumptions Langmuir isotherm,
are made to model a PSA process: (1) the system is
isothermal with negligible pressure drop through qi bi pi
 (5a)
the adsorbent beds; (2) the pressure change in the qSi X
jn

steps of pressurization and blowdown is so rapid 1 bj pj

j1
that no significant exchange between adsorbed
phase and gas phase occurs. This is also called the or using Henrys law,
frozen solid assumption; (3) Langmuir isotherm is
qK
i i Ci (5b)
valid for the system; (4) the mass transfer rate is
represented by a linear driving force expression; The following boundary conditions are consid-
(5) the ideal gas law is applicable and (6) plug flow ered for Eqs. (1)
/(3). For the adsorption and
is assumed, i.e. there is no axial or radial disper- pressurization steps, the concentration of fluid at
sion. The component balance for species i in the the inlet is assumed to be equal to the feed
bed is [1,2]: condition, since axial and radial dispersion is
 S. Jain et al. / Separation and Purification Technology 33 (2003) 25
/43 29

neglected, namely Ci (z; 0)C0 ; qi (z; 0)qi (13)

Ci jz0 Cfi (6) The above set of equations is discretized by
for the purge step it is using finite difference and then solved by the
Newton
/Raphson algorithm.
PL The performance of a PSA process is measured
Ci zL  (Ci zL )ads (7)
PH on the basis of product purity and product
recovery. Product purity of the desired component
and for the depressurization step
2 is defined as its average composition in the
@Ci adsorption step
jz0 0 (8)
@z tads

The velocity boundary condition for the pres-

surization and adsorption step is
g
0
y2;prod (t)dt
y2;prod  (14)
vz0  vf (9) tads

where vf is the superficial velocity of feed at z /0. while product recovery is defined as

 
amount of component 2 obtained during adsorption step
amount of component 2 used in purge step
Reco   
amount of component 2 used during adsorption step in feed
amount of component 2 fed during pressurization step
y2;prod (PH vf tads  PL Gvf tpurg )
 (15)
y2;f (PH vf tads  (PH  PL =2)vf tpres )

(Velocity need not be constant with time during
pressurization step unless specifically controlled.
Normally, controllers are not used in PSA. Above
could be seen as a simplifying assumption.) For
the purge step the velocity boundary condition is
vzL  Gvf
where G is the purge-to-feed velocity ratio. For the
blowdown step the velocity boundary condition is
vzL  0
In the cyclic operation, the initial condition in
the bed is the condition at the end of the previous
step. For startup, either a clean bed or a saturated
bed can be used. For a clean bed the initial
conditions are
Ci (z; 0) 0; qi (z; 0)0
and for a saturated bed they are
Eq. (15) is valid only for a PSA process having
re-pressurization step with feed.
3. Heuristics for PSA process
(10)
When an adsorption for separating a gas
mixture is determined, a logical sequence of
decision steps in design of a PSA process is as
(11) follows:
1) Selection of a proper adsorbent based on its
equilibrium and kinetic characteristics.
2) Selection of particle size distribution and
particle shape.
3) Selection of operating pressure levels for a
(12) PSA system.
4) PSA cycle configuration and duration of each
individual steps.
30 S. Jain et al. / Separation and Purification Technology 33 (2003) 25
/43

5) PSA bed dimensions. the adsorbent particle depends on the diffusivity of

6) Inclusion/exclusion of pressure equalization adsorbing molecules. For short time intervals this
step. dependency can be approximated by [1]:
7) Vacuum swing adsorption (VSA) as an alter- p
qt 8 D (18)
native.
Thus the separation factor for kinetically con-
Based on the model described in the last section, trolled process is calculated by
simulation studies were carried out to analyze the s
performances of PSA and to develop heuristics for D1
the decision steps indicated above. The systems a12  (19)
D2
considered for the simulation, as given in Appen-
dix A, cover a wide range of adsorbate
/adsorbent It is always useful that the separation factor is
alternatives. The resultant heuristic rules are pre- calculated by considering both equilibrium and
sented in the following. kinetic effect. Thus the separation factor can be
defined as
s
3.1. Selection of adsorbent K1 D1
a12  (20)
K2 D2
Adsorption is achieved due to the interaction
forces between the adsorbing molecules and the In this study, Eq. (20) is used to calculate the
adsorption surface. Different substances are ad- separation factor for all cases considered. Table 1
sorbed with different affinities. It is this selectiv- shows some simulation results. Adsorbents with
ity that provides the basis for adsorption different selectivities are used to separate a two-
separation processes. The task of adsorbent is to component fluid mixture (such as say air with 20%
provide the surface area required for selective oxygen and 80% nitrogen) with a mole-fraction of
adsorption of the preferentially adsorbed species. 0.2 for the highly adsorbed species (species 1).
A high selectivity is of users interest. The separa- While doing simulation the other parameters are
tion factor (a ) can be used as a measure of kept constant. Fig. 2 shows a graphical represen-
selectivity. The separation factor of an absorbent tation of these results. From Table 1 and Fig. 2, it
is defined as [1]: can be seen that the product purity will be
increased, if a higher separation factor is selected.
x1 =x2 Thus a high separation factor is a key for a quick
a12  (16)
y1 =y2 screening of various adsorbents.
where x1 and y1 are, respectively, the mole fraction
Table 1
of component 1 in adsorbed phase and fluid phase. Comparison of adsorbents based upon separation factor
The separation factor depends on the adsorption p
property, either adsorption kinetics or adsorption K1/K2 / D1 =D2 a Product purity of component B
equilibrium, or both. In an equilibrium controlled 1 0.68 0.68 0.78
adsorption process, it is simply the ratio of the 1 2.14 2.14 0.821
equilibrium constants. For an extended Langmuir 1 6.76 6.76 0.952
isotherm and a linear isotherm, this separation 1 21.4 21.4 0.999
factor is the ratio of Henrys constants 0.11 6.76 0.75 0.787
2.5 6.76 17.1 0.993
K1 10 6.76 67.6 0.999
a12  (17) 2.14 1 2.14 0.812
K2 7 1 7 0.942
10 1 10 0.954
In a kinetically controlled adsorption, the selec-
tivity depends on the difference of kinetic para- The conditions for the simulation are given in the caption of
meters. The time-dependent concentration within Fig. 2.
 S. Jain et al. / Separation and Purification Technology 33 (2003) 25
/43
Fig. 2. Effect of separation factor on product purity (PH /3
atm, PL /1 atm, tads /tpurg /40 s, tpres /tblow /5 s, o /0.4,
vf /0.007 m s 1, purge/feed/2, L /0.65 m).
3.2. Size distribution and shape of particles
In adsorption processes, the particle size dis-
tribution and particle shape decide the bed poros-
ity. Porosity affects bed performance in two ways.
If other parameters remain constant, a lower
porosity leads to a higher bed pressure drop. On
the other hand, a lower porosity means a higher
adsorbent content of the bed and hence a higher
adsorption capacity. Moreover, a lower porosity
means less loss of the adsorbable component
during the blowdown step and less requirement
of product gas for an effective extraction during
the purge step. Both of these properties increase
the product recovery.
Bed porosity can be varied using different
shapes and sizes of adsorbent particles and to
some extent packing techniques. Simulation stu-
dies are made using various values of bed porosity.
The results are shown in Fig. 3. The effect of bed
porosity on product purity is significant for both
bulk separation and purification processes. The
effect on product recovery is significant only in
bulk separation cases. Fig. 3a
/d show that as
porosity increases both the product purity and
recovery will decrease. From Fig. 3e, it can be seen
that as the porosity increases, product recovery
remains almost constant for purification processes
(where the highly adsorbing species is in very low
concentration, e.g. air containing moisture).
On the other hand, the porosity of a bed also
affects the bed pressure drop. In a packed bed the
pressure drop can be calculated from Blake
/
Kozeny equation
31
@P 180mv (1  o)2
  ; z  [0; L] (21)
@z dp2 o3
From Eq. (21), as the porosity increases the bed
pressure drop will decrease. Fig. 4 shows the
pressure drop versus the bed porosity. For a given
system, Eq. (21) can be rewritten as
@P (1  o)2
 f (22)
@z o3
where f is given as
180mv
f (23)
dp2
There are two opposite effects of porosity: high
product purity requires low porosity and a low
pressure drop is achieved with high porosity. From
Fig. 4, it can be seen that for bed porosity lower
than 0.3, the pressure drop increases rapidly. Thus
this should be the lower limit of porosity (which
can be achieved for most practical particle shapes
and sizes). For bed porosity higher than 0.5, the
change in pressure drop becomes moderate, thus
this can be considered as the upper limit. Similarly,
the effect of the porosity on the product purity, as
shown in Fig. 3a
/e, indicates that when bed
porosity is higher than 0.5, the purity will decrease
significantly, thus confirming the use of 0.5 as the
upper limit of the bed porosity.
3.3. Selection of adsorption pressure
Selection of the adsorption pressure is based on
the equilibrium relationship of the system. An
isotherm describes the equilibrium loading of a
species, which is dependent on the partial pressure
of the species in an adsorption process. As the
adsorption pressure increases, the amount of fluid
adsorbed on the adsorbent will increase. To
determine the pressure level for adsorption, one
should keep in mind that the larger the difference
between the capacities of the competing adsor-
bates, the purer the raffinate will be. The selectiv-
ity of an extended Langmuir isotherm and a linear
isotherm is constant [1,2]. These isotherms are,
therefore, called constant selectivity isotherm.
For constant selectivity systems, if the pressure is
32 S. Jain et al. / Separation and Purification Technology 33 (2003) 25
/43

Fig. 3. Effect of porosity on bed performance (a): Bed porosity vs. product purity. (b): Bed porosity vs. product recovery. (c): Product
recovery for system 3. (d): Product purity for systems 4 and 5 (purification process). (e): Product recovery for systems 4 and 5
(purification process).

increased, which causes more adsorption of the
highly adsorbed species, the product purity will be
increased. The less favorable species is also ad-
Fig. 4. Effect of bed porosity on bed pressure drop.
sorbed more, but in comparison to the more
favorable species it is always less, as long as the
more adsorbing species is present in significant
quantities in the bulk phase. Therefore, for such
systems a higher pressure always leads to a purer
product.
Besides this advantage of high pressure for
constant selectivity systems, there is one disadvan-
tage too, that is energy loss. A higher pressure level
leads to higher compression costs and a higher loss
of energy in the blowdown step. If an adiabatic
compression is assumed, the power requirement
can be approximated as [1]:
 S. Jain et al. / Separation and Purification Technology 33 (2003) 25
/43 33

where PH and PL are high and low pressure levels,

respectively, Q is the volumetric flow rate, and T is
the operating temperature. Simulation results of
extended Langmuir and linear isotherms are given
in Fig. 5a
/c for various adsorption pressure levels.
It can be seen that as the pressure increases, the
product purity will be increased. At the same time
the power required for compression also rises. If a
high purity product is desired, the adsorption
pressure should be as high as possible. Fig. 6
shows that the power requirement increases with
the increase of the adsorption and the desorption
pressure ratio. Considering the trade-off between
product quality and power requirement, the ad-
sorption pressure should be taken as the value at
which the change of the adsorbed phase concen-
tration with pressure becomes moderate.
If the selectivity varies with the operating
pressure, the adsorption pressure should be that
at which the selectivity is maximum. To study the
effect of pressure for varying selectivity systems,
two hypothetical systems (with imputed isotherm
constants) are taken and simulated. The simula-
tion results are shown in Fig. 7a and b. It is

Fig. 5. Effect of adsorption pressure on product purity with

yf /(0.99, 0.01). (a) System 1 and 2. (b): System 3. (c): Systems
4 and 5 (purification process).

 (g1)=g 
g QRT PH
W  1 (24)
g1 h PL

Fig. 7. Effect of pressure on bed performance for varying

Fig. 6. Effect of pressure ratio on power requirement.
selectivity. System A: Having same properties as system 2 of
Fig. 6 except equilibrium selectivity. System B: Having same
properties as system 2 of Fig. 6 except equilibrium selectivi-
tyand kinetic selectivity. The kinetic data are: k1 /0.002 s 1,
k2 /0.00018 s 1. (a): Selectivity. (b): Product purity.
34 S. Jain et al. / Separation and Purification Technology 33 (2003) 25
/43

illustrated that the product purity is maximum at

the pressure where the selectivity is also maximum.

3.4. Selection of adsorption time

In a PSA process, the duration of the adsorption

step is determined by studying the breakthrough
curve. The term breakthrough curve refers to the
response of the initially clean bed to an influent
with a constant composition. It can be seen by
monitoring the concentration of the effluent.
Breakthrough occurs when the effluent concentra-
tion reaches a specific value. The adsorbate con-
centration in the flow at any given point in a bed is
a function of time, resulting from the movement of
concentration front in the bed. The breakthrough
curve for a gas containing a single adsorbate can
be obtained by the solution of the mass balance Fig. 9. Effect of distribution of total adsorption time on bed
performance. (a): Product purity. (b): Product recovery.
equations for both the bed and adsorbent parti-
cles, along with the equilibrium isotherm.
The duration of the adsorption step is the time
period needed for breakthrough to occur. After
this time the product purity will decline, and
before this time the full bed capacity will not be
employed. Thus the adsorption time should be
near the breakthrough time. This time depends
upon isotherm, diffusivity and residence time of
the feed in the bed.
From simulation studies, it can be observed that
beyond a certain value of the adsorption time, the
change in product purity becomes insignificant.
The product purity decreases as the adsorption of
less adsorbable species increases. Fig. 8 shows how
the change in the adsorption time affects the
product purity. It can be seen that the time of

Fig. 10. Effect of distribution of total adsorption time on bed

Fig. 8. Effect of adsorption time on product purity. (System 2: performance for purification process (a): Product purity. (b):
PH /4 atm, PL /1 atm, purge/feed/2). Product recovery.
 S. Jain et al. / Separation and Purification Technology 33 (2003) 25
/43 35

the adsorption step should be where the product

purity is maximum. This is the time when break-
through occurs.

3.5. Effect of distribution of adsorption time

In a two-bed, four-step PSA system, adsorption

takes place in both the pressurization and adsorp-
tion steps. The apportion of the total adsorption
time to these two steps affects the performance of
PSA. Figs. 9 and 10 show the simulation results
corresponding to different time allocations to these
two steps. In Fig. 10, where the results shown are
those of purification processes, it can be seen that
as the ratio of the pressurization time and the
adsorption time increases, the product recovery
will decrease, but its purity will increase. With a
higher time ratio, less product will be obtained. At
the same time, higher time ratio improves product
quality. Moreover, it can be seen from the simula-
tion results that the rate of the decrease of product
recovery is much greater than the rate of the
increase of product purity. Thus, the change in
recovery is a dominating factor to determine the
Fig. 11. Effect of purge/feed ratio on bed performance (a):
adsorption time apportion. Having these two
Product purity. (b): Product recovery.
opposite effects and taking the fact that the
recovery effect is more dominant, the ratio of the
saturated, thus more purging is necessary. At the
pressurization time to the adsorption time should
same time, since purging is done by utilizing the
be low. The upper limit should be 0.2, according to
product, increase in the purge volume decreases
the simulation results.
the product recovery. Generally, the purge volume
specification for PSA is given by the purge-to-feed
3.6. Effect of purge-to-feed ratio
volume ratio.
The purge step in PSA is a desorption step that Simulation was made with different values of
regenerates adsorbents by desorbing the adsorbed the purge-to-feed volume ratio. The results are
species. In a PSA process, saturated adsorbents are presented in Fig. 11. The effect of this ratio on
regenerated by lower pressure, thus a low pressure product purity and recovery is shown for two
purge step is required. Generally, from the product cases. It can be seen that as this ratio increases, the
vessel with the raffinate at a high pressure, a product purity increases as well, but the recovery
fraction of the product stream is withdrawn to decreases. The rate of the increase in purity is
purge the bed and expended to a low pressure. The much slower than the rate of the decrease in
volume required in the purge step affects the recovery. From these results, one may infer that
product quality as well as its recovery. As the the purge-to-feed ratio should be neither too low
purge volume increases, purging becomes more nor too high. A guideline regarding this ratio from
effective, providing a regenerated bed with adsor- the simulation results is that it should be between
bents of less loading and leading to an increased 1.0 and 2.0, if purging is done by product. These
product purity. In principal, the bed should be are volumetric ratios. It should be noted that,
fully regenerated with adsorbents completely un- although the volume of purge used is more than
36 S. Jain et al. / Separation and Purification Technology 33 (2003) 25
/43
the volume of feed, the mass of purge is less than
the mass of feed or product, since the pressure of
purging is much lower than the feed pressure.
3.7. Residence time determination
The residence time of species in a bed is the ratio
of the bed holdup to the volumetric feed rate.
Sufficient residence time should be provided, so
that the desired product purity can be achieved.
For species with lower diffusivities, greater resi-
dence time is required. The choice of residence
time is critical in adsorption, since if the residence
time is too short, there will be no significant
adsorption. Increase in residence time can be
made by reducing the feed rate or by increasing
the bed volume. Since the feed rate is decided by
the desired capacity of the unit, required residence
can be achieved by changing the bed volume.
However, in an existing unit, residence time can be
altered only by adjusting feed rate or feed pressure
or both.
Fig. 12. Effect of residence time and feed composition on
product purity. System 2: PH /3 atm, PL /1 atm, tads /
tpurg /40 s, tpres /tblow /5 s, L/0.65 m. (a): Effect of
residence time. (b): Effect of feed composition.
Simulations were made to study the effect of
residence time on bed performances. Fig. 12 shows
the effect of residence time and feed composition
on the product purity for system 2 (refer Appendix
A). Similar profiles can be obtained for other
systems too. For different systems, the shape of
profiles remains the same. The main features of
these plots are that, at low residence time, no high
product purity can be obtained, and the relation-
ship between feed composition and product com-
position is linear. When keeping the feed
composition constant, product purity can be
increased by increasing residence time. If the feed
composition of the desired species is high, product
purity will increase linearly with residence time.
Fig. 13 shows the effect of the decrease in
diffusivity with a factor of 0.1 for the highly
adsorbing species. Comparing Fig. 13 with Fig.
12, it can be observed that for the same residence
time, a decrease in diffusivity leads to a decrease in
product purity. This means that for the same
product purity, more residence time is needed for
systems with lower diffusivity. To calculate the
residence time for a given system and a given
product purity, the concept of the minimum
residence time is introduced in the following.
3.7.1. The minimum residence time
A PSA process reaches its cyclic steady state
after a certain number of cycles of operation. A
steady state PSA model can be developed using the
same assumptions as stated before. The governing
equations may be obtained as follows. First, by
combining Eqs. (1) and (4) and letting the time-
differential terms be zero, the following equation
can be gained
Fig. 13. Effect of residence time and feed composition on
product purity for system 2 by decreasing diffusivity of the
highly adsorbing species with a factor of 0.1.
 S. Jain et al. / Separation and Purification Technology 33 (2003) 25
/43 37

o dCi dz
  (25)
(1  o) ki (qi qi ) v

If the maximum driving force is applied, i.e. by

taking qi / 0 in the above equation, one has

o dCi dz
  (26)
(1  o) ki q
i v
Fig. 15. Effect of kinetic separation factor on the ratio of
actual-to-minimum residence time for system 2. PH /4 atm,
The boundary condition for this equation is the
PL /1 atm, tads /tpurg /40 s, tpres /tblow /5 s, vf /0.007 m
same as given in Eq. (6). It is easy to solve this s 1, L /0.65 m.
equation, and the solution for the highly adsorbed
component will give the residence time for a
system under the conditions of a constant velocity
and the maximum driving force. Therefore, the
solution of Eq. (26) gives the minimum residence
time for a given feed and desired product compo-
sition. Initially, one may expect the existence of
certain relationship between the ratio of the actual
and the minimum residence time, with the kinetic
parameters and separation factor. These relations
are shown in Figs. 14 and 15. Fig. 14 gives the Fig. 16. Effect of summation of mass transfer coefficients on
relationship between the separation factor and the the ratio of actual-to-minimum residence time. PH /4 atm,
time ratio. As the separation factor increases, the PL /1 atm, tads /tpurg /40 s, tpres /tblow /5 s, vf /0.007 m
s 1, L /0.65 m, feed composition (0.21, 0.79).
required ratio of actual-to-minimum residence
time also increases. The results of actual-to-mini-
mum residence time versus the mass transfer residence time. The difference arises due to the
coefficient ratio are shown in Fig. 15. But this difference in driving force, which is the adsorbed
relation is less clear. As an explanation, one may phase concentration in a practical cycle. The
argue that the ratio of actual-to-minimum resi- concentration in the adsorbed phase depends on
dence time depends on the total amount of gas the mass transfer of each component, which relies
adsorption, rather than the kinetic selectivity (the on the individual mass transfer coefficient. In this
ratio of diffusivities). Basis for this argument is way, the total effect on the adsorbed phase
that in the calculation of the minimum residence concentration depends on the sum of the mass
time, the maximum driving force is considered transfer coefficient, rather than the kinetic selec-
(taking qi /0), but this is not the case of the actual tivity. To test this argument, in Fig. 16, the time
ratio is plotted against the sum of the mass

Fig. 14. Effect of adsorption separation factor on the ratio of

actual-to-minimum residence time for k1/k2 /0.0055 in sys-
tem 2. PH /4 atm, PL /1 atm, tads /tpurg /40 s, tpres / Fig. 17. Relation between (k1/k2)(K1/K2) and the ratio of
tblow /5 s, vf /0.007 m s 1, L/0.65 m. actual-to-minimum residence time.
38 S. Jain et al. / Separation and Purification Technology 33 (2003) 25
/43
transfer coefficients. A more obvious relationship
between these two quantities can be seen.
In Fig. 17 an attempt is made to combine the
relations of Figs. 14 and 16, from which the
relation between (K1/K2)(k1/k2) and the ratio of
actual-to-minimum residence time can be ob-
served. It should be noted that this ratio also
depends on the feed composition, but this relation
is not so clear. This is because in calculation of the
minimum residence time, the assumption of a
constant velocity is taken, which is invalid if the
concentration of the highly adsorbing species is
high in the feed. If the concentration of the highly
adsorbing species in the feed increases, the product
flow rate will be low as compared with the feed
flow rate, and the minimum residence time will be
much less than the actual residence time. Thus the
ratio of actual-to-minimum residence time will
also depend on feed composition. This relation is
illustrated in Fig. 18, in which various cases
(including systems 1, 2 and 3) are tested. It is
seen that all these data fit a straight line, which can
be approximated with the following relation
 
tact K
1100(k1 k2 ) 1 yf1 (27)
tmin K2
Most of the systems have (k1/k2)(K1/K2)yf1 B/
0.015, where the value of the time ratio is in
between 1 and 2. From this result, a quick
estimation of the bed size can be made.
The bed volume is determined based on the
required residence time. To specify the bed size, i.e.
the bed diameter and bed height, some criteria
should be kept in mind. The choice of the bed
diameter depends on the fluidizing velocity, which
Fig. 18. Relation between (k1/k2)(K1/K2)yf1 and the ratio of
actual-to-minimum residence time.
is the minimum velocity required to fluidize a bed.
The maximum velocity in the bed should not
exceed 70% of the minimum fluidizing velocity
[9]. For velocities greater than this value, entrain-
ment of adsorbents in effluent stream may occur
and also the pressure drop in the bed would be
very high. After determining the fluidizing velo-
city, the bed diameter can be calculated. Another
important criterion for bed specifications is the
crushing strength of the solids. The height should
be such that no crushing occurs in the bed.
3.8. Pressure equalization
The first improvement over Skarstroms cycle is
the introduction of a pressure equalization step, as
shown in Fig. 19. After the first bed has been
purged and the second bed has completed its high-
pressure adsorption step, instead of blowing down
the second bed directly, the two beds may be
connected to each other through their product
ends in order to equalize their pressures. The first
bed is thus partially pressurized with gas from the
outlet region of the second bed. After the pressure
equalization, the two beds are disconnected and
the first bed is pressurized with feed gas while the
second bed is vented to complete the blowdown.
The pressure equalization step conserves energy,
because the compressed gas from the high-pressure
bed is used to partially pressurize the low-pressure
bed. Since this gas is partially depleted of the
strongly adsorbed species, the degree of separation
is conserved and the blowdown losses are reduced.
Based on these considerations, a pressure equal-
Fig. 19. Pressure equalization step in a PSA process.
 S. Jain et al. / Separation and Purification Technology 33 (2003) 25
/43 39

Table 2 3.8.1. Selection of the intermediate pressure

Comparison of PSA process with and without pressure equal- The intermediate pressure is the pressure after
ization step for air separation on CMS the pressure equalization step. As the intermediate
Product Recovery without pres- Recovery with pressure pressure increases, the degree of saturation of the
purity sure equalization equalization highly adsorbed species increases in the bed, which
is unfavorable. If it is higher than a certain value,
0.914 0.418 0.532
0.945 0.374 0.51
this saturation causes decrease in product purity
0.96 0.348 0.488 and recovery. Simulation results for different
0.972 0.325 0.469 intermediate pressures are shown in Fig. 20. It
can be seen that once the intermediate pressure is
increased beyond a threshold value, both the
ization step is often incorporated in the PSA product recovery and purity are adversely affected.
process. This means that the intermediate pressure should
Simulation results are presented in Table 2 be below this threshold value. If the intermediate
indicating the PSA performance with and without pressure is denoted as PI, then the following
a pressure equalization step. It can be seen that a relation holds approximately
pressure equalization step favors product recovery. PI PH
But if the pressure swing is sufficiently low, the (0:5 to 0:8) (28)
PL PL
inclusion of a pressure equalization step may be
impractical. Otherwise, the pressure equalization
step should always be incorporated in the PSA
process.
3.9. Vacuum swing adsorption

Vacuum swing adsorption (VSA) is also a

Skarstrom cycle in which the low-pressure purge
step is replaced by a vacuum desorption. The
product end of the bed is kept closed and the
vacuum is applied through the feed end, as shown
in Fig. 21. In a VSA process, using the same high
operation pressure as a Skarstrom cycle and for
the same product purity, the loss of the less
favorably adsorbed species in the evacuation step
is normally less than the corresponding loss in the
purge. The gain in raffinate recovery is achieved at
the expense of the additional mechanical energy
required for the evacuation step. A significant

Fig. 20. Effect of intermediate pressure (after purge) on

product purity and product recovery (a):System 1: Feed
composition: (0.4, 0.6), PH /5 atm, vf /0.007 m/s, L/0.6
m, purge/feed/1.5. (b): System 2. Feed composition: (0.21,
0.79), PH /5 atm, vf /0.007 m/s, L/0.65 m, purge/feed/1.5. Fig. 21. The sequence of VSA cycle (only one bed is shown).
40 S. Jain et al. / Separation and Purification Technology 33 (2003) 25
/43
amount of energy can be saved, if the adsorption
takes place slightly above the atmospheric pressure
and the desorption is done at a very low pressure.
A VSA cycle will, therefore, be advantageous over
a normal Skarstrom cycle, if a low-pressure
product is acceptable.
In kinetically controlled separation, a major
disadvantage using a normal Skarstrom cycle is
that the slowly diffusing raffinate product would
be continuously adsorbed during the purge step.
This problem can be avoided by using VSA. In
kinetically controlled processes there is a little
difference in isotherms of feed components (e.g.
nitrogen separation from air using zeolite 4A) but
a large difference in diffusivity. In such a system,
purging with the product to remove the highly
diffusing species from the bed is undesirable. This
is so because apart from wasting product (a certain
fraction of nitrogen), the raffinate gas will be
adsorbed during this step, thereby reducing the
capacity for oxygen during the next adsorption
step. For such type of systems a VSA process is
worth considering.
Simulation is performed for the nitrogen separa-
tion from air using carbon molecular sieve (CMS).
The results are shown in Table 3, which illustrate
that the recovery of nitrogen is greater in a VSA
process than in an ordinary Skarstrom cycle. From
the results and the above explanation, it can be
concluded that for kinetically controlled processes,
VSA is a better choice over a normal Skarstrom
cycle.
4. Two case studies
Heuristics developed in the previous section
have been tested using two case studies. Rajasree
and Moharir [16] discussed simulation based
synthesis, design and optimization of PSA pro-
cesses. The system used was air separation using
Zeolite 5A. The data are given in Table A1 in the
Appendix A with system 6. Table 4 compares the
results in [16] with the results obtained using our
heuristic rules. In [16] the pressure equalization
step was used for some cases. They showed that
product (oxygen) recovery increases from 28.5 to
32.8% when pressure equalization step is included.
According to the proposed heuristics, recovery
increases if pressure equalization is considered.
Air separation using CMS was considered by
Nilchan [15]. The author discussed optimization
approach for PSA processes. The objective func-
tion used in the case study is minimizing the power
requirement. The data are given in Table A1 in the
Appendix A with system 2. Table 5 compares the
results in [15] using optimization study with the
results obtained using the heuristic rules proposed
in this study.
Both the case studies show that the results
obtained using the heuristics are close to the
results obtained using optimization. It demon-
strates that heuristics based synthesis is useful for
preliminary design and screening of PSA pro-
cesses. In addition, in both case studies the flow
to be separated is air, but the adsorbent is different
(in case 1 Zeolite 5A, and in case 2 CMS), due to
different product requirement. In the first case
oxygen is the desired component, and in the
second case nitrogen is the desired component.
The separation factor for nitrogen in the second
case is 41, while in the first case it is 0.16. If
nitrogen is the desired component from air, CMS
adsorbent should be used rather than Zeolite 5A.
The heuristic rule proposed for this case also
suggests using the adsorbent with a higher separa-
tion factor.
Table 3
Performance comparison of VSA cycle with ordinary Skar-
strom cycle
Product purity % Recovery of nitro- % Recovery of ni-
for nitrogen in % gen in Skarstrom cycle trogen in VSA cycle
89.5 56.4 88.3
92.5 53.7 83.3
94.2 49.7 77.6
95.1 42.1 72.5
98.2 21.6 60.1
The blowdown pressure used is 1 atm and the vacuum
pressure used is 0.25 atm.
 S. Jain et al. / Separation and Purification Technology 33 (2003) 25
/43 41

Table 4
Comparison of results by the heuristic rules and optimization (Case Study 1)

Purity of oxygen 87.8% and From Rajasree and Using heuristic rules proposed
recovery is 36.8% Moharir [16]

o 0.376 0.3
/0.5

PH (atm) 6 Heuristic suggests to use high pressure to obtain higher purity
P /F 6.125 1.0
/2.0
tads 65 Both are equal
tdes (s) 65
tpress/tads 0.077 0.0
/0.2
tmin (s) 104.00 104.00
tactual (s) 270.0 316.0

5. Conclusions Rule 3 (b): For systems with pressure dependent

In PSA design and operation, heuristics devel-
oped in this study may be summarized as follows:
Rule 1 : Adsorbent, which gives the largest
separation factor, should be used.
Rule 2 : Bed porosity should be in the range
0.3
/0.5. Particle size distribution and shape
should be such that bed porosity is within these
limits.
Rule 3 (a ): For systems whose isotherms are
given either by the Henrys Law or by the
extended Langmuir isotherm expression, the
adsorption pressure should be as high as
possible, subjected to the power requirement
constraint.
selectivity, adsorption pressure should be the
pressure, which gives maximum selectivity.
Rule 4 (a ): The adsorption time should be near
the adsorption breakthrough time.
Rule 4 (b): For a two bed PSA process, the
adsorption and desorption time should be
equal.
Rule 5: The maximum limit for the ratio of the
pressurization time to the adsorption time
should be 0.2.
Rule 6 : The ratio of purge-to-feed volume
should be in the range 1.0
/2.
Rule 7 (a): The bed diameter should be such
that the velocity within the bed does not exceed
70% of the minimum fluidizing velocity.
Rule 7 (b ): Bed height should not cross the
crushing strength of adsorbent particles.

Table 5
Comparison of results by the heuristic rules and optimization (Case Study 2)

Purity of nitrogen 87.1% and From Nilchan [15] Using heuristic rules proposed
recovery is 67.6%

o 0.4 0.3
/0.5

PH (atm) 2.36 Power requirement decides the adsorption pressure
P /F Purging was not Zero purge results in high impurity in the product. As in the case study,
considered without purge consideration high impurity (12.89%) was achieved
tpress/tads 0.086 0.0
/0.2
tmin (s) 18.2 18.2 (solution of Eq. (26))
tactual (s) 21.2 19.3
42 S. Jain et al. / Separation and Purification Technology 33 (2003) 25
/43

Rule 7 (c ): The Ratio of actual-to-minimum Table A2: Purification systems

residence time should be in the range 1
/2. Eq.
(27) may be used to calculate the ratio.
Rule 8 (a ): For processes with high swing in Number 4 5
pressure, a pressure equalization step should be System CO2 /He /Silica H2O /Air /Alu-
included. Gel [13] mina [13]
Rule 8 (b ): The ratio of intermediate pressure to Component CO2 1% H2O 1%
the low pressure should be in the range 0.5
/0.8 1
of the ratio of the high pressure to the low Component He 99% Air 99%
pressure. 2
Rule 9 : For a kinetically controlled process, K1 9084 52.7
VSA should be considered. k1 (s1) 2.583 e-4 4.67 e-2
The work for developing heuristics for PSA has
been initiated in this paper. Some rules could
appear obvious or trivial, considering the accumu-
lated knowledge on PSA at this stage. More
detailed models and more extensive simulation
References
studies in future would help modify the rules
proposed here and develop more elaborate heur- [1] D.M. Ruthven, S. Farooq, K.S. Knaebel, Pressure Swing
istics. Moreover, the study of interactions between Adsorption, VCH Publishers, New York, 1994.
individual decision parameters is also part of the [2] R.T. Yang, Gas Separation by Adsorption Processes,
further work. Butterworth Publishers, Boston, 1987.
[3] P.L. Cen, R.T. Yang, AIChE Symposium Series 80 (1985)
68.
[4] E. Alpay, D.M. Scott, Chemical Engineering Science 47
Appendix A: Systems considered in the simulation (1992) 499.
[5] N.S. Raghavan, D.M. Ruthven, The American Institute of
studies Chemical Engineers Journal 31 (1985) 385.
[6] N.S. Raghavan, D.M. Ruthven, The American Institute of
Chemical Engineers Journal 31 (1985) 2017.

Table A1: Bulk separation systems

Number 1 2 3 6

System CH4 /N2 /CMS Air separation
/CMS Hypothetical Air separation
/Zeolite
[14] [15] system 5A [16]
Composition of compo- N2 40% O2 21% 40% N2 79%
nent 1
Composition of compo- CH4 60% N2 79% 60% O2 21%
nent 2
qs1 (mol cm3) 0.00182 0.00264 0.0033 0.0258
qs2 (mol cm3) 0.00255 0.00264 0.00065 0.00344
b1 (atm 1) 0.26 0.14 0.161 0.0155
b2 (atm 1) 0.62 0.154 0.164 0.057
k1 (s 1) 9.99 e-4 2.7 e-3 0.002 0.0098
k2 (s 1) 4.82 e-6 5.9 e-5 0.0018 0.0032
 S. Jain et al. / Separation and Purification Technology 33 (2003) 25
/43
[7] M.H. Chahbani, D. Tondeur, Separation and Purification
Technology 20 (2000) 185.
[8] H.M. Kvamsdal, T. Hertzberg, Chemical Engineering
Science 50 (1995) 1203.
[9] Z.P. Lu, J.M. Loureiro, M.D. LeVan, A.E. Rodrigues, The
American Institute of Chemical Engineers Journal 38
(1992) 857.
[10] Z.P. Lu, J.M. Loureiro, M.D. LeVan, A.E. Rodrigues,
Gas Separation and Purification 6 (1992) 15.
[11] Z.P. Lu, J.M. Loureiro, M.D. LeVan, A.E. Rodrigues,
Industrial Engineering and Chemical Research 32 (1993)
2740.
43
[12] Z.P. Lu, J.M. Loureiro, A.E. Rodrigues, M.D. LeVan,
Chemical Engineering Science 48 (1993) 1699.
[13] W.L. McCabe, J.C. Smith, Unit Operations of Chemical
Engineering, fifth ed., McGraw-Hill, New York, 1993.
[14] A.I. Fatehi, K.F. Loughlin, M.M. Hassan, Gas Separation
and Purification 9 (1995) 199.
[15] S. Nilchan, The optimization of periodic adsorption
processes, Ph.D. Thesis, Department of Chem. Tech.,
Imperial College of Science, Technology and Medicine,
London, 1997.
[16] R. Rajasree, A.S. Moharir, Computers and Chemical
Engineering 24 (2000) 2493.