Chmrieol En@new~ Scie,,ce. Vol. 41. No. 5. pp. 1333-1343, 1986. ooo9-2509/86 53.00+0.

00
Printed in Great Britain. 0 1986. Pergamon Preos Ltd.

AIR SEPARATION BY PRESSURE SWING ADSORPTION ON

A CARBON MOLECULAR SIEVE

M. M. HASSAN and D. M. RUTHVEN

Departmentof Chemical Engineering,Universityof New Brunswick,Fredericton,N.B., Canada E3B 5A3

and

N. S. RAGHAVAN
Alcan InternationalLimited, Kingston Laboratories,Kingston, Ontario, Canada K7L 424

(Received 5 February 198% in revised fomt 28 August 1985)

Abstract-A simplitied dynamic model for a PSA air separationprocessis developedbased on linearized
mass transfer rate expressionsand binary Langmuir equilibrium. Constant pressure is assumed during
adsorption and desorption steps but the variation in flow rate through the column due to adsorption is
aeeounted for. The model predictions,using independentlymeasured kinetic and equilibriumdata are
comparedwith experimentalresultsobtainedin a simpletwo-bed air separationPSA systempackedwith a
carbon molecular sieve adsorbent. The model is shown to provide a good representation of the
experimentally observed behaviour over a wide range of conditions.

Pressure swing adsorption (PSA) processes, first de-
veloped by Skarstrom (1959,1960,1972), in the form of
the heatless drier have found widespread application
in hydrogen purification and air separation, as well as
in air drying. The rational design and optimization of
such processes requires a detailed mathematical model
since the effects of the process variables (flow rates of
purge and feed, cycle time, bed length and pressure
ratio) are strongly coupled, making it difficult to arrive
at an optimal combination purely by empiricism
and intuition. The earlier mathematical models
(Shendalman and Mitchell, 1972; Chan et al. 1981;
Knaebel and Hill, 1982) were based on equilibrium
theory and the effects of mass transfer resistance were
ignored. The validity of such an approximation has
been confirmed experimentally for air separation on a
5A zeolite adsorbent by Flores-Femandez and
Kenney, 1983. However, for adsorption of CO2 on
silica gel (Mitchell and Shendahnan, 1973) and C2HL
on both 4A and 5A zeolites (Hassan et al., 1985)
experimental PSA studies reveal rather large devi-
ations from the equilibrium theory predictions, sug-
gesting that, at least for these systems, kinetic effects
are probably important. Although equilibrium theory
can provide valuable guidance as to the range of
acceptable operating conditions and the limits of
performance, the quantitative value of such models is
therefore limited. Furthermore, the equilibrium theory
approach is obviously restricted to systems in which
the adsorptive selectivity depends on a difference in
equilibrium and it is clearly not applicable to systems,
such as air separation on a carbon sieve. The adsorp-
tion equilibrium isotherms for oxygen and nitrogen on
carbon molecular sieves are almost identical and the
preferential sorption of oxygen in these adsorbents is
of kinetic origin, resulting from the higher micropore
diffusivity of that species.
The alternative approach which requires developing
a suitable dynamic model to account for the mass
transfer kinetics has been adopted by Mitchell and
Shendalman (1973), Chihara and Suzuki (1983),
Raghavan et al. (1985) and Carter and Wyszynski
(1983). However, in all these models the adsorbable
species was assumed to be present only at low concen-
tration in an inert carrier so that the gas velocity could
be regarded as constant along the length of the column.
Such an assumption is obviously not valid for air
separation since, even on a carbon sieve where oxygen
is the preferentially adsorbed species, the variation in
fluid velocity due to adsorption will be significant. In
the present paper we report the development of a
simple dynamic model for a bulk separation involving
the competitive adsorption of two components and
allowing for the variation in fluid velocity through the
column. Experimental data are presented for PSA air
separation on a carbon molecular sieve and it is shown
that the model, with independently measured kinetic
and equilibrium parameters, provides a good predic-
tion of the behaviour of the system.
THEORETICAL MODEL
The simple two-bed PSA cycle involves four steps as
shown in Fig. 1. During step 1, a high pressure feed is
supplied continuously to bed 2, in which preferential
adsorption of the faster diffusing oxygen occurs. The
relatively slowly diffusing nitrogen is removed as pure
raffinate product. A small fraction of this stream is
expanded to low pressure and used to purge bed 1. In
step 2, bed 1 is pressurized with feed while bed 2 is
blown down in the reverse flow direction. The same
cycle is repeated in steps 3 and 4 with high pressure
flow and adsorption occuring in bed 1, and purging
occuring in bed 2. In order to develop a mathematical

1333
1334 M. M. HASSANet al.
Adding eqs (1) and (2) and considering eq. (3),

av2 I--EiYqm l--E %2

(4)
cnp az + -at+--=oO.
& E at

I--Product

Da
Solid phase in bed 2.
k2
COI. 2 -
at
= k,(qz2 - 4a2) (3

0
Purge Roprossurbotlon ah2
at = k, Mu-qm) (6)
F**d Blowdown -
I I

0
I
0.4
11
.l
I
0.5 ml
I
a9-?
r
I I
I
I
I,
1
where

= 1 + b,C,, + b,C,

Fig. 1. Schematic diagram of the PSA cycle. bB9,Citz (7)

4*e2= 1+ b,CA2 + b&,2
Boundary conditions:
model for this system the following assumptions are
introduced:

(1) The system is isothermal with total pressure re-

- vOH
(, Iz-o- - CA2Iz-o+>
c.42 (8)

maining constant throughout the high pressure ac,, - 0. (9)

and low pressure operations (steps 1 and 3). az Z-L

(2) The fluid velocity within the bed during adsorption

and desorption varies along the length of the ExternaijZuid in bed 1.
column, as determined by the mass balance.
(3) The flow pattern is described by the axial dispersed --
=*I D
plug flow model. at
(4) The equilibrium relationships for both oxygen and
nitrogen are represented by the binary Langmuir
isotherm.
(5) The mass transfer rates are represented by linear acBl
--
driving force rate expressions and the rate coef- at
ficients are taken to be the same for both high
pressure (adsorption) and low pressure (desorp- + --=O
i--6 aqBl (11)
tion) steps. This is a reasonable assumption when & at
the mass transfer rate is controlled by micropore CA1+ cm1 = cLp (constant). (12)
diffision and the curvature of the isotherm is
modest (see Hassan et al., 1985). Adding eqs (10) and (1 I) and considering eq. (12),

Subject to these assumptions, the dynamic be- (13)

haviour of the system may be described by the
following set of equations (A = 0,; B = Nf ):

Solid phase in bed 1.

Step 1. High pressure flow in bed 2 and low pressure
a9,,
(purge) pow in bed 1
-=
at k, k:, - qad (14)
External fluid phase in bed 2.
aqBl k, (4:t - 4Bl) (15)
--
=A2 a%~ ac,, +c,z dr-
-+v*-
at D, a22 aZ where
b,q,C,t
4:t =
+
(-)-=oat
l---E
E
%A2
(1) 1+ b,CA,, + b&et
hh&et (16)
4+el=
1+ bACAl+ b&m

+
(--
l-& aqB2E(-J
>at
&
(2)

tThc notation z = O+ and Z =O- is used to denote

CA2 + C,, = C,, (constant). (3) positions just inside and just outside the column inlet.
 Air separation
Boundary Conditions:
where
CA, = CA2
IZ-O- I Z-l_P-P,
The valid initial conditions for the start-up of the
cyclic operation with two clean beds are the following
two sets of equations:
4A2(Z. t = 0) = 0; qe2 (Z, t = O).= 0
c,, (z, t = 0) = 0; c,l (z, t = 0) = 0;
qAl (z, t = 0) = 0; q#,, (z, t = 0) = 0.
Step 2. Blowdown of bed 2 and pressurization of bed 1
For blowdown, the following approximations are
introduced:
(1) The gas phase mole fractions at the end of
blowdown step remain the same at each and every
position in the bed as was prevailing at the end of
the preceding high pressure flow adsorption step
but the total pressure is reduced instantaneously
from the high pressure P, to the purge pressure
p,*
(2) The solid phase concentrations are assumed to
remain frozen during this step.
For pressurization, the following two
mations are introduced:
(1) During pressurization by feed air, the fluid phase
O2 and Nt remaining in the bed from the preced-
ing low pressure purge flow operation are pushed
in plug flow towards the closed end of the bed
through a distance given by (1- PL/PH) from the
feed inlet. Thus for example, if the pressure ratio,
PJP, is 0.33, then the concentrationo of O3 and
N1 at the end of pressurization are the average of
the respective concentrations that existed through
the entire length of the bed at the end of the
preceding low pressure purge flow. These average
concentrations, however, exist only through a
dimensionless length of 0.33 from the closed end of
the bed, the remainder being filled with the
pressurizing feed air. The existence of a plateau
region after (1 - PJP,)
distance was observed in
the pressurization studies for the system air in SA
zeolite by Flares-Femandez and ICenney (1983).
(2) The solid phase concentrations of O1 and N2
remain unchanged at the values prevailing at the
end of the preceding low pressure purge flow.
Steps 3 and 4 are essentially the same as steps 1 and 2
by pressureswing adsorption 1335
respectively with the exception that the flow directions
are reversed.
The above equations were written in dimensionless
form and solved by the method of orthogonal collo-
cation (Villadsen, 1970) to give the gas and solid phase
concentration of Oz and N1 as a function of dimen-
sionless bed distance (Z/L) for various values of time.
Brief details are given in the Appendix.
(18)
The effective sorption rate constant is related to the
diffusional time constant by k - ZLD/r where, follow-
ing Glue&auf and Coates (1947) the value of D is
(19) commonly taken as 15. However, Nakao and Suzuki
(1983) showed recently that, for a cyclic adsorption
process such as PSA, the proportionality constant n is
in fact dependent on cycle time. The relationship was
established by comparing the results of simulations
using the full diffusion equation and the linearized rate
expression. In the present simulation we have therefore
used the (cycle time dependent) values of Q recom-
(20) mended by Nakao and Suzuki (1983).
PSA EXPERIMENTS
A schematic diagram of the apparatus is shown in
Fig. 2. The two columns, each of stainless steel (length
35 cm, i.d. 3.5 cm) were packed with carbon molecular
sieve. Details are given in Table 1. In accordance with
the usual PSA cycle, fzed was introduced into one
column while the other column was desorbed by
blowdown and purging with a small fraction of the
purified product stream at atmospheric pressure. The
sequence of valve switching was controlled by a
Xanadu Universal Programmable timer. The flow
rates of feed air, purge and product streams were
controlled and measured by Matheson flow con-
trollers. The oxygen concentration in the product
approxi- stream was monitored continuously by a servomex
0A137 paramagnetic oxygen analyser. The outputs
from the pressure transducers, the oxygen analyser, the
flowmeters were monitored continuously on a multiple
channel strip chart recorder.
RESULTS AND DISCUSSION
Experimental results
Efficient separation of Oz and Nz can be achieved,
over a fairly wide range of conditions, to yield a high
pressure (raffinate) product containing 1-2 y0 residual
Oz. The approach to the cyclic steady state is quite
slow and generally requires 25-30 half cycles, as may
be seen from Figs 3-7. Most of the runs were started
with both beds initially free of both N2 and Oa (purged
with He prior to the ruti) but in Run 14, bed 1 was
initially equilibrated with air at atmospheric pressure
while bed 2 was equilibrated with air at the high
pressure (3 atmospheres). Comparison of the data
from Runs 7 and 14 (Fig. 3), in which flow rates and
cycle times are the same, confirms that the same cyclic
steady is eventually approached regardless of the initial
state of the beds.
The effects of varying the flow rate, purge/f& ratio
1336 M. M. HASsw et fzi.

Reference Gas

4
TCD TCD
Ertr. Roff.

PSA PSA
COi. Cal.
1 2

350mm 350mm
FM1 X X FM2
35mm 35mm
v V
-

0
PC2

I
IT,
Feed RV4

Fig. 2. Schematic diagram of small pressure swing adsorber. FC, Flow controller; FM, flow meter; PC,
pressure gauge; PT, pressure transducer; T, thermocouple; PRV, pressure relief valve; RV. regulating valve;
SV, solenoid valve; V, shut-off valve; TCD, thermal conductivity detector.

Table 1. Experimental conditions and parameters used in calculation of

theoretical curves

Feed gas composition 21% Or. 79% N,

Feed pressure 3 atm
Purge pressure 1 atm
Column length 35cm
Cross-sectional area 9.62 cm2
Bed voidage 0.40
Temperature 25C (ambient)
Adsorbent Carbon molecular sieve
(Bergbau Forschung)
Particle size l/8 pellets
Particle density 019877 gm/cm
Equilibrium Constant for 02 (KA)t 9.25
Equilibrium Constant for Ns (Ka)+ 8.90
Saturation constant for Qz and N2 (qs) 264 x lob3 mole/cm3
Diffusional time constant for Ot (o/rs)* 3.73 x lo-ss-
Diffusional time constant for Nz (D/r)t 1.17 x lo-4s-

tIndependently measured values (see Ruthven et ai., 1986).

and cycle time were investigated and the results are pressurization times were taken as 25 % of the adsorp-
summarized in Figs 3-10 and in Tables 1 and 2. tion or desorption times. In Run 13 the adsorp-
For all runs except Run 13, the blowdown or tion/desorption time was 90 s while the blow-
 Air separation by pressure swing adsorption

10

Fig. 5. Etkct of varying pm&feed ratio on approach to

cyclic steady state (from initially clean beds). x ,. Run 3, u
=1.65;0,Run7,or=1.Q[3,Run11,a=O.S.Forallruns
L/v = 25, cycle time = 150 s. Theoretical curves calculated
using the parameters given in Table 2 are shown as wntinu-
ous lines.
Fig. 3. Approach of residual oxygen wncentration in product
to cyclic steady state showing cffbct of diffbrent initial bed
conditions. 0, Run M-both beds initially equilibrated with
air (bed 1 at atmospheric pressure, bed 2 at 3 atmospheres
pressure); x , Run 7-both beds initially clean (purged with
He). For both runs L/v = 25, purge/feed ratio = 1.0, cycle
time = 150 8. Theoretical curves predicted with parameters
given in Table 2 are shown as continuous lines.

cl x
c
ooooooo
3 00 000000
0000000
s
.I
.
5
I= Fig. 6. Effect of varying length/velocity ratio on approach to
m cyclic steady state (from initially clean beds). x , Run 8, L/o
z =30;0.Run7.L/v=25;O.Run6,L/v=2O.Forahrunsa
= 1.0, cycle time = 150s.
lo+1
0
*
5
.
10

15
.
20
*
25
J
Holf Cycle Number-

10-l

t <b>
. . I

10-l0 . 1
5
. 1
10
. 1
15
. 1
20
. 1
25
J
Half Cycle tkmbm-
Fig. 7. Effect of varying cycle time on approach to cyclic
Fig. 4. Approach of residual oxygen wncentration in product steady state (from initially clean beds). x , Run 9, Steps 1 or 3
to cyclic steady state value (beds initially clean). (a) Feed =!3O~Step2or4= 22_5s;O,RunlO,Stepslor3=40s,
=air(Runn(b) feed= 15%01inHecarrier(Run152For StepsZor4= 10s;O.Ruu3,Steps1or3=6Os,Steps2or4
both runs L/v = 25, purge/feed ratio = 1-0. cycle time E 15s;a,Run13,S~lor3=90qSteps2or4= lOs.For
= 150 s. Theoretical curves are shown as wminuous lines. all runs a = 1.65, L/v = 25.
 M. M.
0
0 be true in the xeolite based air separation process
.\,,
Fig. 8. Variation of residual oxygen (at steady state) with
purgc/fatd ratio (L/v = 25, cycle time 1500). Tlleoretlcal
curve calculatedwith parametersgiven in Table 2,-.
Fig. 9. Variation of residualoxygen concentration(at steady
state)with L/v ratio (a = 1.0,cycletime = 150s). Theoretical
curve, ealeulatedwith parametersgiven in Table 2,-.
1 Fig. 7. The residual oxygen concentration was found to
Fig. 10. Variation of residual oxygeu concentration (at steady
state) with cycle time (L/v - 25, Q = 1.65). Theoretical
curve calculatedtaking account of variation of SJwith cycle
time-; Theoretical curve calculated assuming n =
15,-L -- - - The corresponding curves for O2 tquilibrium
during blowdown with variable R (----) and with R = 15
(- -) are also shown. Parameters are given in Table 2.
Hw.er al.
down/pressurization time was reduced to 10 s as
compared with Run 9 where times were 90s
and 22.5 s respectively. It is evident that the
blowdown/repressurization times do not have any
significant effect for this system. However, this may not
where mass transfer rates are much higher.
It was observed that in all experiments with air as
feed, starting with clean beds, the oxygen concen-
tration in the high pressure product passes through a
maximum. and then declines somewhat as the cyclic
steady state is .approached. This overshoot was not
observed in Run 14, starting from pre-saturated beds,
and appears to be due to competitive adsorption of O2
and N2. Initially, when the beds are clean, both
components are adsorbed with very little competition.
As the adsorbed phase concentration builds up, the
adsorption becomes more competitive and the faster
diffusing oxygen may then displace some nitrogen
during the later portions of the adsorption step, thus
reducing somewhat the oxygen concentration in the
high pressure product stream. In order to confirm this
hypothesis another experiment was performed, with
initially clean beds, using a feed containing 15 o/0O2 in
He with no Nz. The results are shown in Fig. 4 from
which it may be seen that in the absence of N2 the
overshoot no longer occurs.
The effect of varying the purge/feed ratio is shown in
Fig. 5. It is apparent that product purity increases with
purge/feed ratio but, on the other hand, an increase in
this ratio implies a lower recovery of nitrogen and a
higher power cost. In practice there is therefore a limit
beyond which increasing the purge rate is uneconomic.
The effect of varying the length/velocity ratio is
illustrated in Fig. 6. It may be seen that a low residual
oxygen concentration is favoured by a large Ljv ratio
but the effect of this variable is less pronounced than
the effect of purge/feed ratio.
The effect of varying the cycle time is illustrated in
pass through a minimum value of about 1.5 y0at a cycle
time of 150 s (60 s adsorption/desorption
pressurixation/blowdown).
and 15 s
Comparison with theoretical predictions
In order to predict the behaviour of the system from
the mathematical model, values of the equilibrium
parameter K,, K,, qs and the diffusional time con-
stants DA/r and D# are required. These were
determined experimentally by standard chromato-
graphic and gravimetric methods. The results of this
study are reported in detail elsewhere (Ruthven et al.,
1986); the relevant parameters are summarized in
Table 1.
The residual oxygen concentrations in the nitrogen
product, at cyclic steady state, for all experimental runs
are summa&cd in Table 2 together with the values
predicted theoretically from the numerical simulation.
Comparisons between the theoretically predicted and
 Table 2. Summaryof experimentalconditions and residual oxygenin product at cyclicsteady state

Constant

Run Feed Purge Purge to W Time for Time for 02 N2 Product cont. at
No. rate rate feed lIlti0 Step 1 or 3 Step 2 or 4 steady state % 0, #
(SLPM) (SLPM) ratio (s) 9
(Q n, L.k f), flak, Expt. Theory
v * v
j
2 0.90 0.28 0.93 21 60 15 2.25 =.
0
3 0.96 0.551 1.65 25 60 15 12 1.1178 65 0.1904 1.50 1.48 u
5 1.21 0.644 1.60 20 60 15 12 0.8946 65 0.1523 2.55 2.91 yb
6 1.20 0.405 1.0 20 60 15 12 0.8940 65 0.1523 4.20 4.49 s
8
7 0.81
0.96 0.27
0.32 1.0
1.0 30
25 60 15
15 12
12 1.341
1.1178 65
65 0.2284
0.1904 2.45
2.95 2.01
2.70 1
9 0.96 0.551 1.65 25 !!I 22.5 11 1.0247 49.5 a1449 2.15 230
10 0.96 0.551 1.65 25 40 10 14 1.3048 73 0.2138 2.09 ::Z a
11 0.96 0.16 0.50 25 60 12 1.1178 65 0.1904 6.80 k!

12
13 0.96
0.96 0.551
0.551 1.65
1.65 25
25 90
90 ::.5
10 11
11 1.0247
1.0247 49.5
49.5 0.1449
0.1449 2.60
2.53 2.30
2.30 i
14+ 0.96 0.32 1.0 25 60 15 12 1.1178 65 0.1904 3.00 295 a
154 0.96 0.32 1.0 25 60 15 12 1.1178 6.28 5.21 f
16 0.96 0.32 1.0 25 90 22.5 11 1.0247 49.5 0.1449 4.70 3.90
Theoretical 0.96 0.551 1.65 25 25 6.25 16 1.4912 92.5 0.2709 - 221

+Initial condition for this run was saturated beds.

~Feedforthisrunwas15%02inHe.

_.__-._.. -I -_._ __ .-- .--

__._ -__-_ -..
_. __.- ._-_--.
_ _ _. _ _. .- _ . - -. -
1340 M. M. %hSSAN et al.
experimentally observed trends of residual oxygen
concentration with purge/feed ratio, Ljv ratio and Ax (i,i)
cycle time are shown in Figs 8-10. It is evident that the
agreement between theory and experiment is generally
bA
good and the observed trends are correctly predicted.
The importance of taking account of the variation of Q b,
with cycle time is clearly illustrated in Fig. 10. If this
effect is neglected the model predicts a monotonic Bx (i,j)
decrease with increasing cycle time, rather than the
minimum which is observed experimentally. chi
The assumption that the adsorbed phase concen-
tration remains frozen during blowdown is probably a CBi
good approximation for the slowly diffusing nitrogen
but may not be valid for the more rapidly diffusing C HP
oxygen. For a sufficiently rapidly diffusing sorbate
equilibrium would be approached during blowdown CL,
and the real situation must lie somewhat between the
two extremes of the frozen bed and equilibrium
models. We therefore undertook a brief investigation
in which we examined the effect of assuming that
during blowdown the oxygen maintains equilibrium DB
between adsorbed and gas phases while the nitrogen
concentration in the adsorbed phase remains frozen. D Ll
The results are summarized in Fig. 10. The equilibrium
blowdown assumption leads to the same qualitative D L2
pattern of variation of residual oxygen concentration
with cycle time as the frozen bed model (i.e. the oxygen G purge to feed velocity ratio, voL/vOH
concentration passes through a minimum, as observed KA
experimentally) and this was found to be true both
when n was assumed constant and when Q was KEi
allowed to vary with cycle time. However, the level of
residual oxygen predicted by the equilibrium model is kA
considerably lower than the experimental values and
the frozen bed assumption evidently provides a better k,
representation of the observed behaviour.
A more detailed comparison between theory and L length of adsorption bed, cm
experiment is shown in Figs 3-5 in which the observed PeH
and predicted bchaviour during the approach to cyclic,
steady state conditions are compared. For Run 14 in PeL
which the beds were initially equilibrated with air, the
model provides a very good prediction of the transient qAi
behaviour as well as the final steady state. However, the
predictions of the transient behaviour is less satisfac- 4Bi
tory for the runs starting from clean bed conditions
since the experimentally observed overshoot in the qAs
oxygen concentration is not predicted by the model.
However, in view of the obvious approximations in the 4Bs
model, the agreement between theory and experiment
* *
appears very satisfactory, particularly regarding pre- qAir
diction of the residual oxygen at cyclic steady state. The
model should thkrefore prove useful for optimization
of the process cycle and for guidance in the choice of
operating conditions for existing units. In the present
study the model has been applied specifically to air
separation on a carbon molecular sieve adsorbent but
with suitable changes in the parameter values the same Vl
model is, in principle applicable to the equilibrium 02
based zeolite air separation process or indeed to any VOH
system involving two adsorbable components for
which the equilibrium isotherm can be represented by
the binary Langmuir equation. VOL
NOTATION
collocation coefficient for the gradient,
external fluid phase
Langmuir isotherm constant for com-
ponent A, cm3/g mole
Langmuir isotherm constant for com-
ponent B, cm3/g mole
collocation coefficient for the Laplacian,
external fluid phase
adsorbate concentration of component A
in fluid phase for bed i, g mole/cm
adsorbate concentration of component B
in fluid phase for bed i, g mole/cm3
total concentration of fluid correspond-
ing to pressure P,, g mole/cm
total concentration of fluid correspond-
ing to pressure P,, g mole/cm3
micropore diffusivity, cm* /s
micropore diffusivity of component A,
cm2 /s
micropore diffusivity of component B,
cm/s
axial dispersion coefficient for flow in bed
1 during step 1, cm/s
axial dispersion coefficient for flow in bed
2 during step 1, cm/s
adsorption equilibrium constant for com-
ponent A, (-)
adsorption equilibrium constant for com-
ponent B, (-)
overall mass transfer coefficient for com-
ponent A, s-l
overall mass transfer coefficient for com-
ponent B, s-r
Peclet number for high pressure flow in
bed 2 during step 1, Lv,,/D,
Peclet number for low pressure flow in
bed 1 during step 1, LvoH/D,,
adsorbate concentration of component A
in solid phase for bed i, g mole/cm3
adsorbate concentration of component B
in solid phase for bed i, g mole/cm3
saturation concentration of component A
in solid, g mole/cm3
saturation concentration of component B
in solid, g mole/cm3
qBi defined by eqs (7) and (16) for i = 2 and
i = 1 respectively, g mole/cm3
time, s
= v1 /v,,, interstitial fluid velocity in bed
19 (-)
= v2/voH, interstitial fluid velocity in bed
2, (-)
interstitial fluid velocity, in bed 1, cm/s
interstitial fluid velocity, in bed 2, cm/s
interstitial fluid velocity at the inlet of the
bed in which high pressure flow adsorp-
tion is carried out, cm/s
interstitial flow velocity at the inlet of the
 Air separation by pressure swing adsorption 1341

bed in which low pressure flow desorp- on the front boundary of chromatograms and on the
tion is carried out, cm/s effectiveness of separation. J. &em. Sot. 1315.
Hassan, M. M., Raghavan, N. S., Ruthven, D. M. and
xAi C,,/C,, or CAi/C,, depending on Boniface. H. A., 1985, Pressure swing adsorption-II.
whether high pressure flow adsorption or A.I.Ch.E. J. 31, 2008-2016.
low pressure flow desorption occurs in the Knaebel, K. S. and Hill. F. B., 1982, Analysis of gas
ith bed, (-) purification by heatless adsorption. Paper No. 91d, Annual
A.1.Ch.E. meeting, Los Angeles, California.
XBi GJCHP or C,,/C,, depending on
Mitchell, J. E. and Shendalman. L. H., 1973, Study of heatless
whether high pressure flow adsorption or adsorption in the model system CO2 in He: part II.
low pressure flow description occurs in A.1.Ch.E. Symp. Ser. 69, No. 134, 25.
the ith bed, (-). Also equal to (I- XAi) Nakao, S. and Suzuki, M., 1983, Mass transfer coefficient in
X dimensionless distance, Z/L cyclic adsorption and desorption. J. &em. Engng Japan 16,
114.
yAi qAi/qhs. adsorbate concentration of com-
Raghavan. N. S., Hassan, M. M. and Ruthven. D. M., 1985,
ponent A in solid phase in bed i, (-) Numerical simulation of a PSA system-I. Isothermal
YBi q&q%, adsorbate concentration of com- trace component system with linear equilibrium and finite
ponent B in solid phase in bed i, (-) mass transfer resistance. A.1.Ch.E. J. 31, 385392.
Ruthven, D. M., Raghaven, N. S. and Hassan, M. M., 1986,
Z axial distance coordinate, cm
Absorption and diffusion of nitrogen and oxygen in a
t-1 dimensionless quantity carbon molecular sieve. Chem. Engng Sci. 41, 1325-1332.
Shendalman. L. H. and Mitchell, J. E., 1972, A study of
Greek letters heatless adsorption in the model system CO1 in He: part 1.
Chem. Engng Sci. 27, 1449.
= -
Lk Ai dimensionless parameter for Skarstrom, C. W., 1959, Use of adsorption phenomena in
QAi
V OH automatic plant-type gas analyzers. Ann. N.Y. Acad. Sci. 72,
component in bed i, (-) 751.
Skarstrom, C. W., 1960, U.S. patent 2,444,627 (to ESSO
Lk, Research and Engng Co.).
= - dimensionless parameter for Skarstrom, C. W., 1972, Heatless fractionation of gases over
V OH
solid adsorbents, in Recent Developments in Separation
component B in bed i, (-) Science, Vol. 2. CRC Press, Cleveland, Ohio.
dimensionless parameter for Villadsen, J. V.. 1970. Selected Approximation Methods for
BAl = b,G,,, Chemical Engineering Problems. Denmarks tekniske hoj-
component A in bed 1, (-) skile. Lyngsby.
B61 = b,C,,, dimensionless parameter for
component B in bed 1, (-) APPENDIX
BA2 = b,C,,, dimensionless parameter for When we consider the high pressure flow in bed 2 and the
component A in bed 2, {-) low pressure flow in bed 1 as the operations during step 1, the
equations to be considered for bed 2 are, eqs (1). (4)-(9), and
B B2 = b&HP, dimensionless parameter for
the equations which describe the operation in bed 1 are, eqs
component B in bed 2, (-)
(1% (13~(19).
E bed porosity, (-) Since steps 1 and 3 are identical except for the direction
Y = qBS/qAS, (-1 of flow, it is sufficient to consider the equations relevant to
step 1.
l--E qAS
*I =-*-, dimensionless parameter Equations (l), (4k(7) combined and written in dimension-
& CL, less form become:
for bed 1, (-) 1 a2xA2 - axA2
ax,2
-=-. - - v,*---
ar PeH dx ax
f--e qAS
dimensionless parameter
=-C

for ;d 2, (-;

-yA2 +YXA2aB2
>

>I (21)
REFERENCES
flB2 (I - xA2)
Carter, J. W. and Wyszynski, M. L., 1983, The pressure swing -yB2 .
x 1 +fiA2XA2+flB2 c1 -xA2)
adsorption drying of compressed air. C&m. Engng Sci. 38,
1093. Equations (5), (6) and (7) when combined give,
Chan, Y. N., Hill, F. B. and Wong, Y. W., 1981, Equilibrium
theory of a pressure swing adsorption process. Chem. ayAZ flAzXA2
dr = (IA2 - yA2 (22)
Engng Sci. 36,243. 1 + flA2xA2 + bB2 t1 - XA2) 3
Chihara, K. and Suzuki, M., 1983. Simulation of non-
ayB2 bB2 t1 - xA2)
isothermal pressure swing adsorption. J. &em. Engng -YB2 . c3)
Japan 16, 53. ~ a7 = 0LB2 1 + bA2XA2 + flB2 (I - xA2) >
Fiores-Fernandez, G. and Kenney, C. N., 1983, Modelling of The relevant boundary conditions, eqs (8) and (9) in dimen-
the pressure swing air separation process. Chem. Engng Sci. sionless form lead to
38, 827.
Forsim, 1976, A Fortran package for the automated solution ax,
of coupled partial and/or ordinary differential equation
systems. Atomic Energy of Canada Limited.
-I
ax r=O= *=0-
- xA2 (24)

Glueckauf, E. and Coates, J. J., 1947. Theory of chromato-

graphy, Part IV. The influence of incomplete equilibrium -Iax *=, =
aXA2
0. (25)
1342 M. M. HASZUN et af.

Equations (4~(7) when combined in dimensionless form yield

av,
..-----=- 92 [aA2
{ BA2X.42
- YA2
+A,-P+-x,,2

- vz (j)*Ax
Ix-o-
(j, 1))
-(P-Bx (j, 1)

dx 1+ BA2XA2 + BB2 u - X,2) >

+yaB2 1 +BA*X&+&zff
fiBZ t1 - xA2)
-X,)
-yB2
>I. (26) -A,+PeHXAZ

- p2 (/).Ax
I.X-0-
(j. M+2))+F1
-(P*Bx(j,M+2)

(j, (35)
Similarly, for bed 1 the following dimensionless equations
are arrived at. based on (lo), (13)-(19): where

Fz 0) = kz
(x, (i) - lb,,

x
1 +BalXal +BBI (~--AI)

&,I t1 - xA,) + YxA2 (/).a82

+YXA1aB1
i 1+/3~lX~l +#~l (1 - XA,)
- yBl

(27)

ayAl BAL~AI
-yAl j=)
-= az A1
{ 1 +BAIXAI+BBI (1 --AI) I
ayBl ,%l (I- XAI)
7 = aBl - yBl (2% Equations (22) and (23) now become:
1+ BA~XAI + Be1 (I- XAI)

ayA2 (i) fiAZX,U(j)

axAl Fg- = OrA
ax .X=0 XX1orbedt
-xAl 1+BAZXA2(j)+~B2.(1_XA2(j))

w-0
(36)
(31)
ayB2 ti, 8B2 l1 -x, th)

aa,
-=
ax
- +l [aAl (
f +BAlx~l
BA~XAI

+fia2 (1~-XAI)
TsaB2
I 1+bB2XA2(/)+f?B2-(1-XA2(/))

-yB2(i) .
*I
&,l c1 - xAl)
+ YaBl (32) The expression for velocity is given by a set of algebraic
1 +BA~XAI+BB~ (~-XAI)
equation as follows:

1V2
(0
Equation (20) which is a valid condition for the startup of Ax (M + 2, i), Ax (j, M + 2) -
the cyclic operation with two clean beds, leads to the Ti2[-4x(X
i)-
Ax (M+2,M+2)
following two sets of dimensionless equations:
XA2 (x, r = 0) = 0; x,, (x, * = 0) = 0; = Fs(j)- Ax (j, 1)
YA2 (x, T = 0) = 0; Y, (x, r = 0) = 0 (33)
- Ax(M+2,1),Ax(j,M+2) _
Vz (1) (38)
x,, (x, r = 0) = 0: x,, (x, r = 0) = 0;
Ax(M+2,M+2) >
YA1 (X, z = 0) = 0, Y,, (x, z = 0) = 0. (34)
Note: ~~(l)=l.Oaud~(M+2)=0;/=2,M+l.
When eqs (21), (24) and (25) are combined and written in
collocation form based on a Legendre type polynomial to
represent the trial function, the following set of ordinary In eqs (35~(37)
differential equation results for the high pressure flow step in l/(Ax(l,M+2)-((Al-Ax(M+2,M+2)))
AI -
bed 2 (step 1):
M+l A,=Ax(M+~,M+~)/(Ax(I,M+~)-(As.Ax(M
~ = ,zz (P.Bx(j, i)- vz (j)Ax(j. i)) +2*M+2)))
A, = (Ax (1.1) - Pe&Ax (M + 2,l)
-(A~.(P.BxO. 1)
hl+1 A., = l/Ax (M + 2,1)
-F-~(/)*Ax(j,l))- c Ax(M+2,i))
As =Al*A4
i-2

-(A,-(P-Bx(j, 1) P = l/Pe,
M-F1 M = number of collocation points.
-Vz((/)-Ax&I))* C (A,~Ax(M+2,i)
i-2

-AxU,i))) F,U) = -J/z

ay, m ya5, w
-+-.
+(A,-(P~Bx(j,M++)-v~(j)-Ax(j,M
a7 a7 >
M+l
Equations (27x (30) and (31), combined and transformed into
+2))- I: (As-Ax(M+2,i) ODJ% by the collocation method lead to:
i=z
A4+1
axA, (i)
-Ax (1, 9)) . x,,(i) ___ = ,g2 (Q.Bx (/,i)- PI (i).Ax(i,Of
at
>
 Air separationby pressure swing adsorption 1343

-(B,.(Q-Bx(j. 1) ayEi (i) IPBl.XAI ti>

hf+1 - 8% = aBI
1 +flAl-xAl (j)+bBlo(l-XAl (j))
- U, (j).Ax (j, 1)). C Ax W+Z 0)
1-2
-yBl ti) - (41)
-(&.(Q.Bx(j;U >
M+I The expression for velocity is given by a set of algebraic
- P,(j).Ax (j, 1)). c (&-Ax.(M+2,i) equations which is:
I-2

1VI
(i)
-Ax (LO)) Ax(M+2,i)*Ax(j,M+2) -
Ax(M+2,M+2)
+(B,-(QmBx(j,M+2)-VI(jj.Ax(j,M
Al+1
+2)). 1 (Bs-Ax (M+2,1) Ax (M+2,1)Ax (j,M+2)
i=1
Ax(M+2,M+2) >
--Ax (1.0)) -X,, 60 PI (1) J = 2, M + 1. (42)
>

+B,*PeL.G*XM _
j_M+2(Q.Will dPI (M+2) o
Note: PI (1) - G and
dX =
-VI (/).Ax(i,
1))
In eqs (39)-(42)
-B,.PeL*G-Xu (Q*Bx(j,M++)
I j-M+2 B, - l/(Ax(l,M+2)-((BB-Ax(M+2.M+2)))

-PI (/).Ax(j,M+2))fF1 (j) (39) B2 = Ax (M+Z, M+2)/(Ax (1, M+2)-(B,-Ax (M

where +2.M+2)))
B, = (Ax (1.1) - Pe,)/Ax (M + 2, 1)
F, Ci)= tii CX,,, (i) - l)a,,
C BA== l/Ax(M+2,1)
BAIXAI ti) Bs = B,*B,
- -YA, ti1
x { 1 +BAl+x*I (i)+Bm (1 -X**(i)) > Q = l/PeL.
+~XAI (/)-aBl

-31
The dimensionless partial differential equations for the
-yBl(si) . high pressure tlow in bed 1 (Step 3) and the low pressure flow
in bed 2 (Step 3), were similarly written and reduced to sets of
Equations (28) and (29) can be written as: ODEs and algebraic equations by the orthogonal collocation
method. The resulting algebraic equations were solved by
~YAI ti) BAI. x,1 (3 using standard subroutine for solving system of equations,
a+ = KAI
{ 1 +8Al*XAl (i)+hm(l -xAl (i)) while the resulting ODEs were solved using Adams variable
step integration algorithm as provided in the Forsim package
- YAI ti) W)
of the Atomic Energy of .Canada Ltd. (Forsim. 1976).
> simultaneously.