Chemical Engineering Science, Vol. 44. No. I, pp. 1-8, 1989. @m-2509/89 $3.00 + 0.

00
Printed in Gnat Britain. 0 1989 Pergamon Press plc

PRESSURE SWING ADSORPTION: DEVELOPMENT OF AN

EQUILIBRIUM THEORY FOR BINARY GAS MIXTURES
WITH NONLINEAR ISOTHERMS

JOHN C. KAYSER and KENT S. KNAEBEL’

Department of Chemical Engineering, The Ohio State University, Columbus, Ohio 43210, U.S.A.

(First received 27 October 1987; accepted in revisedform 11 July 1988)

Abstract-A conventional pressure swing adsorption cycle is analyzed for an arbitrary feed composition of a
binary mixture where both components may have nonlinear equilibrium isotherms. The method of
characteristics is used to solve the equilibrium-based continuity relationships resulting in an algebraic
expression for the recovery of the less strongly adsorbed component.. For the case of linear isotherms, the
nonlinear expression reduces properly to the previbusly developed and experimentally verified binary linear
isotherm theory. A case study examines the separation of oxygen from air at 0.0-C and pressures up to
6.0atm on zeolite 13X. At these conditions, the oxygen isotherm is essentially linear, but nitrogen has a
concave downward equilibrium isotherm. That curvature reduces recovery compared with that expected
based on purely linear isotherms, which are approached at low absolute pressures. Specifically, for constant
pressure ratios the recovery decreases as either the purge pressure or feed pressure increases. Conversely,
operation in the linear isotherm domain yields no indep+dent effect of those pressures (i.e. only the pressure
ratio is of consequence). In addition, when the purge pressure is fixed, there exists an intermediate pressure
ratio at which maximum rkcovery is achieved. In contrast, recovery increases monotonically with pressure
ratio in the linear isotherm region.

1. INTRODUCTION The analysis presented here identifies conditions that

1.1. Background directly influence process performance and therefore
The recent development of equilibrium-based adsorp- facilitates cycle modifications that may significantly
tion models has provided considerable insight to the improve separation performance. In addition, the
parameters that affect the performance of pressure effects of curved isotherms 011 product recovery are
swing adsorption (PSA) processes. In some cases (i.e. explored using actual nonlinear isotherm data in a
given certain assumptions and constraints) those case study.
models have yielded analytical solutions to the con- The solution is limited to constant pressure feed and
tinuity equations. Such results are appealing because purge steps, in which complete bed utilization occurs
they allow simple examination of general performance (i.e. the composition fronts reach the end of the bed at
trends over broad ranges of operating conditions. In the end of the respective steps). Likewise, it is pre-
cases where the assumptions and constraints of the sumed that pure product is recovered, and that a
analytical model are closely approximated, the equa- portion is used for pressurization as well as purge.
tions may be used quite accurately to predict cycle
times and product recovery for a given adsorber 1.3. Prior work
design and operating conditions. In addition, the Equilibrium-based theories of PSA have evolved
theoretical framework of equilibrium-based models towards applicability in increasingly general situ-
has proven to be a useful basis for conducting exper- ations. Early theories were limited to the purification
imental research. of binary mixtures in which the more strongly ad-
sorbed component was present at trace impurity levels
1.2. Object and approach of this work (Shendalman and Mitchell, 1972; Chan et al., 1981).
This paper presents an analytical solution to the Other work extended the applicability to arbitrary
continuity equations applied to a specific PSA cycle feed compositions of a binary mixture but resorted to
for the case of a binary mixture that exhibits nonlinear numerical integration of some of the relevant equa-
adsorption isotherm behavior for one or both ad- tions (Flores Fernandez and Kenney, 1983). Analyti-
sorbing species. The inclusion of nonlinear isotherm cal solutions to the equations governing PSA pro-
relationships in the governing equations is needed cesses for an arbitrary feed composition were sub-
since many actual (and potential) industrial PSA sequently developed (Knaebel and Hill, 1985). That
cycles operate under conditions in which the analysis applied for linear isotherms, constant press-
components exhibit nonlinear adsorption equilibria. ure feed and purge steps, and for either pressurization
with feed or with product. The theory was validated in
bench-scale air separation experiments (Kayser and
Knaebel, 1986) and is referred to here as the binary
‘Author to whom correspondence should be addressed. linear isotherm, or BLI, theory.
1
2 JOHN C. KAYSER and KENT S. KNAEBEL

An extension of the BLI theory relaxed the con- STEP

straint of constant pressure during the feed step 0 a 0 @
(Kayser and Knaebel, 1988). Cycles that allow press-
ure to vary during the feed step were predicted to have Feed Blowdown Vent
significantly different, and under certain conditions NW YF la FL
YW
top,
superior, separation performance than those having a
constant pressure feed step. Following in that vein, the
r=L
case of a varying pressure feed step with nonlinear

1
isotherms is a logical extension of this work and will be
the subject of a future report.
Zf
Prior developments of equilibrium-based theories
for PSA with nonlinear isotherms have been reported
by Flores Fernandez and Kenney (1983), Doong and z=o r
Yang (1986) and Underwood (1986). In each case the
governing equations were integrated numerically,
T
hence little advantage was gained over comparable Pressurization
with Product
simulations that incorporated dissipative effects. NPR
Mathematical models of PSA for several classes of
Fig. 1. Basic steps in the pressure swing adsorption cycle,
effects have been fully reviewed by Wankat (1986) and
flow orientation convention, and molar flows that are per-
Yang (1987). tinent to the process performance.
The equations derived in the subsequent section are
applicable, in general, to isothermal sorption steps and
are not restricted to PSA cycles. In that vein, the
current development resembles the recent work on
equilibrium sorption processes by Basmadjian and
Coroyannakis (1987) and Davis and LeVan (1987).
Both employ hodograph transformations for adsorp-
tion step and cycle analysis. In the former, a non-
adsorbing carrier bearing two solutes is treated. That
permits veloeity variation to be neglected, whereas it is
taken into account in the present work. Furthermore,
accumulation of material in the interstitial fluid is
neglected in the former, while it is included here. That
term is not negligible when adsorbent selectivity is low
to moderate, as in separation of oxygen from air with
zeolite 13X, which is considered as a case study later in
Step
this paper. Finally, Davis and LeVan (1987) have
examined gas separations by thermal swing cycles Fig. 2. Pressureswing patternduring a typical cycle: 1 refers
comprised of adsorption, heating and (optionally) to the pressurizationstep, 2 refersto the feed step, 3 refersto
-cooling steps. Their analysis of adiabatic cycles in- the blowdown step, and 4 refersto the purge step (cf. Fig. 1).
corporated wave phenomena that were discerned by
mapping between hodograph and physical planes.
That approach may improve PSA simulations when The assumptions and constraints of the theory are
both thermal effects and nonlinear isotherms are listed below.
relevant.
(1) Two component, ideal gas mixture.
(2) Local equilibrium between the gas and solid
2. DEVELOPMENT OF THE BINARY NONLINEAR
phases.
ISOTHERM THEORY
(3) Uncoupled adsorption equilibrium isotherms.
2.1. Basic concepts (4) Negligible axial dispersion.
The underlying principles of the present devel- (5) Negligible axial pressure gradients.
opment are virtually identical to those presented in the (6) Constant pressure during feed and purge steps.
earlier papers (Knaebel and Hill, 1985; Kayser and (7) Isothermal operation.
Knaebel, 1988). Consequently, the similar details are (8) No radial dependence of velocity or composition.
only summarized here, but the distinctions are empha-
sized in the subsequent derivation of the working 2.2. Material balance relationships
equations. The analysis begins with the following component
The basic steps of the PSA cycle studied in this molar balances:
paper as well as conventions of position and direction
+RT(l-E)+
are shown in Fig. 1. The pressures during the respect-
ive steps are shown in Fig. 2. (
&--
3PYA
at +
d@Y*
dz >
(1)
 Pressure swing adsorption 3

am, + auph readily recast as two ordinary differential equations

+RT(l-s)fg=O. (2)
E-
( at __
az > (which must be simultaneously satisfied) by the
method of characteristics. The technique involves the
The first simplification of the balance equations is to elimination of ay,/dt and ay,/az using the total
substitute adsorption relationships for each differential of y,:
component. For generality, independent but arbitrary
functions will be assumed as: dY,=$$dt+gdz. (11)

(3) Solving eqs (10) and (11) simultaneously leads to

certain relationships between the terms, viz.

dz BAU
-= (12)
dt Cl +(P- I)Y,I
There are, of course, physical constraints on these and
functions. For example, as the adsorbate approaches
zero coverage, the relationship must follow Henry’s dy, (B- l)(l -YY,)Y,
(13)
law. By convention, the more strongly adsorbed df’ C~+~P-~)YAIP'
component is identified as component A. At fixed The former yields characteristic trajectories in the z, t-
temperature, the partial derivatives with time of eqs (3) plane. The latter dictates the interdependence of com-
and (4) are of the form: position and pressure along those characteristics. It is
clear from eq. (13) that, when pressure is constant,
composition is also constant along each characteristic.
Although eqs (6j(13) are identical in form to those
Therefore, substitution of eqs (3) and (4) into eqs (1) in the BLI theory, the present relations are inherently
and (2), respectively, yields: more complicated because of the composition (and
pressure) dependence of p. Furthermore, at constant
apYA
-+pa-= aupy, o
pressure it is possible to rearrange eq. (9) to evaluate
at az the composition dependence of the velocity which is
and valid when y, and u are continuous differentiable
functions of t and z. The result is simply
aph aupyl3 = o

-+A- 1-B
at aZ dy, . (14)
1 +(B- l)YA
Analytic integrals of the right-hand-side exist only for
some rather simple isotherm forms. A subsequent
the componentpartial pressure. Note that in the BLI
relation is valid when discontinuities are present.
theory this parameter was constant, while here it is
defined locally. 2.3. Wave phenomena
The remaining derivation revolves around ma-
Before proceeding with analysis of the steps in a
nipulation of eqs (6) and (7). First of all, adding eqs (6)
PSA cycle, it is essential to establish the basis by which
and (7) generates:
the more subtle steps can be understood. Specifically,
the feed step and purge step are critical to the analysis
Pg+(I-B)f$+8*$=0 (8) because of their impact on performance. Furthermore,
it has been learned that the wave phenomena associ-
where P = PA l&3, which is also locally defined. ated with these steps provide keys to experimental
dPY* evaluation and operation of PSA systems (Kayser and
Eliminating - between eqs (6) and (8) gives
at. Knaebel, 1986; Matz and Knaebel, 1987).
Rhee et al. (1986) have discussed wave phenomena
aupyA aup
;g+tB-l)-+l
B
=o (9)
at length. The only drawback is that, in their examples
that focus on chromatographic applications, velocity
is presumed to be independent of composition, which
which will be of considerable use later. In addition, eqs
is not the case here. Despite that, the elementary
au
(6)and (8) may also be combined by eliminating -: concepts that are employed here are explained more
aZ fully there.
W- l)(l -YA)YA 1 dp Formation and propagation of a composition
aYA BAU aYA
shock wave dominates the feed step. The condition
at+[l+(,?-l)~Al az 1 +(B-- l)y, P dt
necessary for this occurrence is that the feed be
(10)
enriched in the more strongly adsorbed component as
Equilibrium-based theories have been successful compared with the initial column contents. For sys-
and facile because eq. (10) is of a form that can be tems described by linear isotherms, the analysis is
4 JOHN C. KAYSER and KENT S. KNAEBW

simple: eq. (1) or (2) is solved in difference form by When the influent contains more of the less strongly
exploiting the nil accumulation at the shock front. adsorbed component than ir$tial contents of the
For systems that have nonlinear isotherms, how- column, as occurs during the purge step, character-
ever, a balance of component A around the shock istics that describe the respective composition paths
front yields a more involved expression for the velocity diverge, as given by eq. (12). This also results in a so-
called simple wave, comprised of material having
compositions between those of the initial column
contents and the influent. The characteristics of the
influent, having constant composition, are parallel. As
where a result, imminent breakthrough of the influent de-
pends only on its composition and velocity, not on the
initial column contents.

and the subscripts 1 and 2 refer to the leading and 3. STEPWISE CYCLE ANALYSIS-
trailing edges of the shock front, respectively, and
The performance of the cycle illustrated in Figs 1 and 2
&, =L(PYA,/RV, as specified by eq (3).
involves, principally, eqs (8), (12), (13) and (15). Gen-
Similarly, in such systems the compositions that
erally, these equations are manipulated to obtain
bound the shock front are subject to a uniqueness
expressions for the numbers of moles of influent
condition. Uniqueness must be determined because of
and/or efRuent during each step. The following devel-
the multiplicity of solutions that could arise from the
opment presumes complete bed utilization and that
nonlinear equations. One that is useful for the gas
the cycle is started at cyclic steady state, which always
adsorption applications described here is the gen-
connotes production of the pure, less strongly adsorb-
eralized entropy condition suggested by Oleinik
ed component during the feed step.
(1963). That condition is expressed as the following
inequalities based on eq. (10):
3.1. Pressurization
ti YA\I (16)
Since the influent during this step has the same
y~,-y..+, - YA, -YA, - J’&-yAa composition as that used to purge the bed, viz. yAl. = 0
where YAW ) eq. (13) becomes trivial. Thus, despite the
Gessure change, composition remains constant, and

J/Y-4, =
s
Y%

0
BAU
l+(b-l)YA

in which j = 1, 2, or i, and y,, is within the closed

dYA (17)
eq. (8) can be integrated to determine the influent
interstitial velocity
L dP
UPlt =B,Pz. (1%
interval of y,, to yA2. Actually, the lower limit of
integratidn in eq. (17) is arbitrary and should not affect As a result, the number of moles of recycled product
the result. Note that the integrand is merely the required for pressurization is
characteristic velocity defined by eq. (12). For the
simple case in which material at y,, is fed to an
NF% =
initially clean column (yA, = 0), both inequalities yield
the same results, viz.
= A..~(~(~-~)+~l--d(ls~-~~)) (20)
W3)
YAz
where& is to be stipulated in a form given by eq. (4)
Thus, yAZ = yA, only if J/,, increases monotonically and the subscripts H and L refer to the high and low
between yA = 0 and yAF. Otherwise, yA2 becomes an pressure states, respectively.
intermediate mole fraction, corresponding to that
having the maximum characteristic velocity [as given 3.2. High pressure feed
by eq. (12)]. In that case, the material having compo- As explained in Section 2.3, this step is dominated
sition between yAl and y,, forms a so-called simple by the propagation of a composition shock wave
wave. As a result, the bed cannot be completely through the adsorbent bed. The velocity of that wave,
saturated with feed prior to imminent breakthrough of which is given by eq. (15), depends on the interstitial
the shock wave. fluid velocities at the leading and trailing edges of the
When the curvature of the isotherms is not severe, wave. These may in turn be interrelated by equating
i.e. at low partial pressures, the uniqueness condition the shock wave velocities determined from eq. (15) and
will be automatically satisfied, and the shock velocity its counterpart based on component B to get
predicted by eq. (15) will be valid for yA2 = y,, . At ut 1 +te- l)YA,
partial pressures sufficiently large for isotherm curva- -=
(21)
Ul 1 + ce - lb,,
ture to be significant, however, eq. (16) must be
considered. where 8 = 8,/e, and
 Pressure swing adsorption

1.
5

&Yi2
--Yil
pEl
1-a A,-..& RT
where&=1 l+----

Note thatxj =A(P,yiJ /RT), as given by eq. (3) or (4),

for any state j. The parameter 8, is evaluated at a
specific (local) composition by the tangent to the
respective isotherm. In contrast, the parameter Qi is
evaluated at a jump discontinuity by the chord of the
respective isotherm. For certain simple isotherm
forms, there are also simple analytical relationships
between & and pi and between 8 and /3. In fact, for
linear isotherms these terms are identical. Conversely,
under conditions in which isotherm curvature is
significant (i.e. yAI # y,,,,) eq. (21) cannot relate the
influent velocity to that of the product because the
composition profile is no longer represented by an
ordinary jump condition. In that case, eq. (14) can
relate ur and u2. Fig. 3. Graphical interpretation of the isotherm tangent and
The material balance equation for the feed step is chords that affect the material balance of a PSA cycle.

based on the time, t,, required for the shock wave to

traverse the length of the adsorber.

complete the entire cycle balance. For the nonlinear

isotherm case, analysis of partial purge will require a
rather involved numerical approach.
where, according to Fig. 1, the velocity is inherently
Some of the important terms from the material
negative. Consequently, when isotherm curvature is
balance equations are shown graphically in Fig. 3.
slight (i.e. yal =yAF) and when yA, = 0, the product
Slope m, is equal to filyA= o, slope mp is equal to
moles are
f*(PH~AFIRT)I(PW~*FIRT), and slope m3 equals
N,,=N,Cl+(e--l)~,,rl. (23) fB (P,y,,,lRT) -fB ‘PH yBF lR T’ For the linear iso_

r*)-(!&) .
3.3. Low pressure purge
During the constant pressure purge step, eq. (13) them case: m1 = m2 = K,, while m3 = KB.
indicates that y, is constant along each characteristic.
The characteristic velocity, given by eq. (12) is mini- 3.4. Product recovery
mized when yA1 = 0 so that other characteristics The most significant scale of performance of a PSA
diverge from those of the influent. Therefore, a simple system is the recovery of the less strongly adsorbed
wave is formed, as discussed earlier, and the analysis of component. Notwithstanding, the purity of that prod-
the purge step involves the integration of eq. (12) to uct is also significant, along with the productivity (i.e.
obtain the purge step duration: the flow rate per unit mass of adsorbent). These,
however, depend heavily on dissipative effects that
t,= WAoUL (24) may influence the separation, e.g. at high flow rates or
and subsequently the number of moles required: short cycle times. Therefore, the latter scales of per-
formance must generally be evaluated experimentally.
N,=
s
where PA0= PAlyA= o.
1L

0
PL
.z A,,uLFTdt = ~
~4s PL
BAA RT
(25)
The pure component B recovery is:

R=
N HP-NL-NPR

c1 -YYAF)NH -
Note that the purge requirement is dictated by the
Henry’s law slope of the isotherm of the more strongly For conditions in which isotherm curvature is slight, it
adsorbed component. For many adsorbates (e.g. those is possible to combine eqs (20), (22), (23), (25) and (26)
represented by Freundlich isotherms) this term can be to get an explicit expression for product recovery. For
extremely large and may be sufficient to preclude linear isotherms, those equations reduce to the exper-
complete purging. In fact, a shift to a higher tempera- imentally verified recovery equation of the BLI theory
ture may then be necessary, leading to a combined that applies for pressurization with product.
temperature and pressure swing cycle.
As implied earlier, the analysis of the purge step is 4. CASE STUDYl SEPARATION OF OXYGEN FROM AIR
independent of the initial column contents as long as 4.1. Basis and approach
y, > 0 at the purge inlet prior to purge. Consequently, To gain insight into the properties of eq. (26), the
detailed analysis of the depressurization step is not system of nitrogen (A) and oxygen (B) on zeolite 13X at
needed. If partial purge is desired, however, analysis of O.O”C is considered. For simplicity, the feed is assumed
the depressurization step may be needed in order to to be free of argon and other minor components. As a
6 JOHN
result, the feed is comprised of 79 mole% nitrogen and
21 mole% oxygen.
Both isotherms have been measured using a mano-
metric technique and are presented in Fig. 4. The
nitrogen isotherm data were correlated with a second
order polynomial that satisfies Henry’s law at the
origin and fits the data well over the entire range of
measurement (i.e. up to about 6 atm). The oxygen
isotherm data were fitted to a linear equation. Neither
equation should be extrapolated much beyond the
region of measurement since neither exhibits the satu-
ration plateau known to exist for these gases on
zeolites. The isotherm relationships are:
PYB
nB = KB=
with Tin K, P in atm, R = 82.057 mol cm3/atm K, and
ni has units of mol/cm3 (solid). At O.O”C, we have found
K, = 15.013, Ke = 4.7542 and M, = - 2.457
x lo4 cm3/mol. In addition, to obtain the values of
K*, K, and M,, a particle density of 1.50 g/cm” (solid)
and a bulk density of 0.780 g/cm” were used. Conse-
quently, the bed voidage used in the calculations was
0.480, consistent with the particle and bulk densities.
Note that the bed voidage incorporates the interstitial
voids and at least some of the intraparticle pores. It
can be shown that, when consistent values of particle
density and porosity are employed in the material
balance equations and in evaluating the isotherm
parameters, these individual values have no ultimate
effect on the results. Only the value of bulk density,
which is easily measured, affects the outcome.
It should be noted that previous experimental
studies have shown that the equilibrium theory ap-
pears to be valid for low to moderate interstitial
P (atm)
0.0 I. 12 2.24 3.36 4.48
0.003
x BLI
E P
s
4 0.002
;;
9
i=
e
$ 0.001
i*
0.000
0.0000 0.0001 0.0002
P vi/ R T [mcl/cucm(s))
Fig. 4. Isotherm data and correlations for oxygen and
nitrogen on zeolite 13X at O.O”C.
CKAYSER and KENT SKNAEBEL
velocities. Specifically, Kayser and Knaebel(l986) and
Matz and Knaebel (1988) found close agreement for
separation of oxygen from air with zeolite 5A. They
used adsorbent productvities of up to about 0.04 m3
(0, at STP)/kg (adsorbent) h and column L/d ratios of
about 25 to 1.
Before estimating the product recovery, it is necess-
ary to ensure that yAF = 0.79 = yAL2and yA,_ = 0 = yAl
satisfy eq. (16) or (18). Based on eqs. (9), (12), (27) and
(28), it is possible to evaluate the mole fraction, yX , at
which the characteristic velocity is maximized.
yx = f (K.;K;)RT+ 1
(30)
[. A 1
(27) If the maximum allowable pressure is 6.0 atm due to
limited equilibrium data, then yX = 0.854 which is
greater than yAF = 0.79. A pressure of 6.84 atm is
necessary to maximize the characteristic velocity for
yX = 0.79. Therefore, pressures below 6.84 atm (with
y,, = 0.79) satisfy the restriction of moderate non-
linearity for these components, and uniqueness of the
shock wave is assured.
In this case study both the purge step pressure, P,,
and the feed step pressure, P,, have been varied
systematically in order to examine their effect on
recovery. As either P, or P, decreases, the operation
moves toward the linear region of the isotherms and
the recovery approaches the limit given by the BLI
theory. Consequently, recovery based on BLI theory
for the Henry’s law slopes of the isotherms is also
considered. The calculated recoveries as a function of
pressure ratio are presented in Figs 5 and 6.
4.2. Discussion of case study results
The effects of curvature of the nitrogen isotherm
have been examined for the PSA cycle described in
Figs 1 and 2. Since the nitrogen adsorption isotherm
exhibits significant nonlinearity under these con-
ditions, the effects on the performance of the PSA
I-O
1
5.60 6.72
THEORY
H
0.6
1.0
101 lo2 1
0.0003 P = P” / PL
Fig. 5. Recovery of oxygen from air at O.O”C as a function of
pressure ratio for various values of Pa, with P, approaching
zero as a limit.
 Pressureswing adsorption 7

maximum recoveries are obtained at an infinite press-

ure ratio (i.e. P, = 0), but the maxima decrease as P,
increases.
An analytical tool has been developed for under-
standing simple PSA cycles with nonlinear isotherms.
The insight gained may substantially affect the way
the cycles are designed and operated. Notwith-
standing, the case study is based on a simple PSA cycle
that is probably not the optimum for product re-
covery. It is recognized, therefore, that the obser-
vations derived from the case study cannot be directly
0.2
transferred to other PSA cycles incorporating more
complicated steps (e.g. partial purge and/or varying
0.0 pressure during the feed step), or to applications with
10° lOI lo2 lo3 significantly different adsorbent/adsorbate interac-
P - PH / PL tions. Despite that, it is hoped that the methods and
approach will be applicable in diverse conditions and
Fig. 6. Recovery of oxygen from air at O.O”Cas a function of
pressureratio for various values of P,, with P, up to 6.8 atm. adaptable to even more complex situations.

process are dramatic. Based on the resvlts shown in NOTATION

Figs 5 and 6, several observations are made that are in -43 cross-sectional area of bed, cm’
contrast to observations based on linear isotherms: x function of concentration of species i, mol/cm3
(solid)
(4 At a fixed pressure ratio, recovery of light product fi” first derivative of J with respect to concen-
invariably decreases as either the purge step press- tration of species i
ure or the feed step pressure is increased, whereas 9 pertains to gas phase
for linear isotherms recovery remains constant. Ki slope of equilibrium isotherm of component i in
(b) Larger pressure ratios are required to ensure net Henry’s Law region
positive recovery as the feed step pressure is L length of packed bed, cm
increased, while for linear isotherms the minimum MA second order coefficient for equilibrium iso-
pressure ratio that yields positive recovery is therm of component A, cm3/mol
constant. ni moles of component i adsorbed per volume of
w The maximum recovery obtained as P, ap- solid, mol/cm3 (solid)
proaches 0 decreases with increasing feed step moles of gas in stream j during a step
Nj
pressure, though for linear isotherms it is constant. P pressure, atm
(d) There is a maximum purge step pressure beyond PH pressure of feed step, atm
which positive recovery is impossible, regardless PL pressure of purge step, atm
of the pressure ratio. R gas constant, 82.057 mol cm3/atm K
(e) For a low to moderate purge step pressure, there is R recovery of light product, ratio of moles of B
a pressure ratio at which recovery is maximized produced to moles of B fed
that corresponds to a feed step pressure well below S pertains to solid phase
the saturation limit. t time, s
T temperature, K
5. CONCLUSIONS IL interstitial velocity, cm/s
The effects of isotherm nonlinearity in an equilib- uj
interstitial velocity at location j, cm/s
rium-based model of a specific PSA cycle have been shock-front velocity, cm/s
examined. The resultant theoretical equations are Yi mole fraction of component i
algebraic and explicit. In addition, the equations Yij mole fraction of component i at location j
reduce to the experimentally verified equations of the Y.2 mole fraction of gas with maximum character-
binary linear isotherm theory (Knaebel and Hill, 1985; istic velocity
Kayser and Knaebel, 1986). Z axial position within adsorbent bed, cm
The theory is applied in a case study to the separ-
ation of oxygen from air with zeolite 13X at O.O”C. The Greek letters
structure of Figs 5 and 6 demonstrates that the farther B separation factor based on tangents of iso-
the purge step pressure (PL) or the feed step pressure therms, flA/BB
(P,) is removed from the linear region, the lower the Bi column isotherm parameter of component i, E/(E
recovery for a given pressure ratio. Moreover, when +(I --E)fi)
P, is fixed there is a pressure ratio that maximizes & void fraction of adsorbent bed
recovery. Conversely, when P, is fixed, higher press- e separation factor based on chords of isotherms,
ure ratios are required to obtain positive recovery, and 8, iea
8 JOHN C. KAYSER and KENT S. KNAEBEL

1
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