Computers them. Engng Vol. 22, Suppl., pp.

S633-S636, 1998
0 1998 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: SOO98-1354(98)00112-4 0098-1354/98 $19.00 + 0.00

Optimal Operation of Rapid Pressure Swing

Adsorption with Slop Recycling
B.H.L. Betlem*, R. W.M. Gotink, and H. Bosch

Department of Chemical Engineering, University of Twente, The Netherlands

Abstract
Rapid pressure swing adsorption (RPSA) is a cyclic process operating, basically, in three phases: a pressurization, a
delay, and a depressurization phase. A new, modified operation is suggested by the addition of either a raffinate
recycle phase or an extract recycle phase, during which raffmate respectively extract is returned to the feed tank.
This feasibility study focuses on design based on the optimal process operation. The degree of difficulty of
separation is used as an independent variable to indicate under what condition slop recycle is useful.
Slop recycle proves to increase the recovery and in some case the productivity. The addition of a rafftnate recycle
phase is only profitable for difficult separations, when the composition profile is inclined towards a concave shape.
The addition of an extract recycle is nearly always profitable as during the depressurization phase over some period
the product fraction in the exhaust exceeds the fraction in the feed. For high degrees of difficulty the improvement in
the recovery is over 1000/o,and for easy separations this is still about 40%. All simulations are carried out for a
hypothetical binary mixture, a product purity of 90%, a cyclic stationary state, and optimized switching times.
0 1998 Elsevier Science Ltd. All rights reserved.

Keywora5: rapid pressure swing adsorption, optimal control, recovery, productivity, slop recycling.
Rapid Pressure Swing Adsorption
Rapid pressure swing adsorption is a cyclic gas
separation process based on the difference in
adsorption rate or adsorption equilibrium of the
different gas components for a solid adsorbent
(Ruthven 1994). RPSA involves two principle steps:
(1) adsorption at a relative high pressure, during which
the specific components get attached to the adsorbent,
and (2) desorption, during which these components are
removed by pressure reduction.
Figure 1. RPSA process with either extract or raffmate
recycle. The optional slop recycle flows are indicated
by dashed lines.
?? Correspondence: B.H.L.Betlem@ct.utwente.nl
RPSA utilizes a single adsorber (see Figure 1). At one
side of the adsorber bed, alternately, during
pressurization feed is supplied and during
depressurization exhaust containing the relatively
easily adsorbing compounds is removed (see Figure 5).
The inlet pressure swing results in a composition front
moving slightly forward and backward through the
bed. Usually, between the pressurization and the
depressurization, an extra phase is inserted during
which feeding is ceased. This period, called the delay
phase, causes the pressure front to penetrate further
into the bed. The product flow containing the relatively
poor adsorbing compounds is nearly constant. This
operation requires high pressure differences (1 to 3
bar) through the bed and a short cycle time (5 to 20 s).
The large pressure gradients can be realized by using
adsorbents with very small particle sizes (100-500
urn). The cycle times of RPSA are rather short
compared to the conventional pressure swing
adsorption (PSA).
The advantages of RPSA compared to PSA are:
. By using reduced particle size and short cycle
times, the adsorbent productivity is much larger at
equal recovery and product purity. Therefore
RPSA plants are more compact.
?? The process requires only one bed to realize a
constant product flow, whereas PSA needs at least
two adsorbers to ensure a constant flow. This
offers substantial capital cost savings.
?? No purge flow is required to remove the
components during desorption.

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S634 European Symposium on Computer Aided Process Engineering-8
. Due to the short cycle times the adsorption process
is nearly isotherm.
The main disadvantage compared to PSA is:
?? the energy demand is much larger by the large
pressure difference.
Problem Definition
For a multi-component gas mixture the separation
performance of RPSA is characterized by three
parameters: enrichment, recovery and productivity:
enrichmen, = PI inproduct
[P] in feed
product amount P
I-1
recoveV = feed amount P ’
adsorbent productivity =
product amount P
bed amount sot-bent * production time
kh)]
In above definitions P stands for the main product
compound, which belongs to the group of least
adsorbed compounds.
The goal of this study is to examine the feasibility of
slop recycling to improve the process performance,
especially the product recovery. Not a specific case is
studied, but rather a series of hypothetical binary
separations with increasing difftculty of separation. For
binary gas separations an independent variable, y, can
be defined:
Henry’s constant of Q , , cycles, as a part of the raftinate or extract is added to
’ = Henry’s constant of P
In the binary mixture P is the product compound and Q
the compound which has to be extracted. This variable,
y, will be referred further as the “relative adsorbility”.
It is a measure for the degree of separation difftculty.
Model and Simulation
The dynamics of the process are rather complex due to
the existence of short cycle times and large pressure
gradients in the bed. For the simulations the following
simplifications and assumptions have been made:
ideal gas behavior,
the gas viscosity is taken to be composition
invariant,
the gas concentration has plug flow behavior with
axial dispersion,
the gas flow is described by the Ergun equation,
radial gradients are neglected,
the process operation is isotherm,
the adsorption (or desorption) isotherms are linear
(according to Henry’s law),
the adsorption (or desorption) mass transfer is
linear with the driving force, which is the
difference between the equilibrium amount and the
adsorbed amount.
The simulations are performed with the simulation
package gPROMS, developed by Imperial College,
London UK. This package can handle mathematical
dynamic modeling and simulation of arbitrarily
complex unit operations distributed over rectangular
domains, described in terms of mixed systems of
integrals, partial and ordinary differential and algebraic
equations. GPROMS solves the set of relevant
equations simultaneously. Discrete events, such as
phase transitions, can be scheduled.
Within gPROMS about six discretization methods are
available. For problems involving flow reversal the
gPROMS provider advises the orthogonal collocation
method on finite elements. The discretization of a
distributed variable using an orthogonal collocation
method of order M using N finite elements generates
M * N + 1 discrete variables. In our simulations,
usually, M = 2 and N = 7. Two problems concerning
discretization should be mentioned. The switching
moments, which are the optimization degrees of
freedom, are restricted to the discretization points in
time. Therefore, the time discretization determines the
optimization accuracy. Secondly, the maximal possible
number of discretization intervals is strongly limited
due to singularity problems. In the simulations the
length to time ratio is kept constant conform the gas
velocity in the bed.
The successive cycles of RPSA without slop recycling
have an interaction by the state of the bed at the end of
the cycle which is passed on to the next cycle.
However, the addition of slop recycling creates an
extra dependency between the successive separation
the feed of a subsequent cycle. The performances of
the simulations with and without slop recycle are
compared at cyclic stationary state. In practice, this
state will occur after a number of separations, the feed
amount and feed composition remaining constant.
During all simulations the product purity was kept,
arbitrarily, at 90%.
RPSA behavior
Figure 2 shows the composition profiles for different
relative adsorbilities. Throughout a cycle the profile
does not change much. During the feed phase the bed
is enriched with least adsorbed compound, during the
delay phase the enriched mixture moves further into
the bed, whereas in the exhaust phase the least
adsorbed compound distribute to both bed ends.
The mean composition profiles are similar to those of
other separation processes, such as composition
profiles in batch distillation columns. When the
separation is difficult the profile is slightly concave
and at the raffinate exit the gradient is rather large. The
“composition front” lays at the end of the bed. As a
consequence the bed is very sensitive to feed
composition and flow changes. When the separation
has a moderate difftculty the profile is S-curve shaped
and the composition front lays in the second bed half.
Flow changes shift the curve through the bed evolving
a relatively large component movement. For easy
 European Symposium on Computer Aided Process Engineering-8
separations the profile is convex. The composition
front lays in the first half of the bed and operation
changes have a small influence on the product purity.
Although, a large part of the bed seems to make no
contribution to the separation, still its length is
necessary to realize the pressure profiles in the bed.
length [m]
length [m]
0 0 length [ml
Figure 2. Composition profile during a cycle for three
different degrees of separation difficulty: y = 1.15
(high difficulty), y = 1.5 (medium difficulty), y = 7.0
(easy), at xF = 0.2 1, xp = 0.9. Switching times: 0 s =
pressurization, 1.86 s = delay,
3.71 s = depressurization, 13 s = next cycle.
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Optimal operation
The switching times are taken as the degrees of
freedom of the optimization of the RPSA operation.
The feed pressure is remained constant and the output
flow is adapted to meet the product purity requirement.
As the recovery for RPSA is rather low, this variable
has been chosen for optimization. But there is a strong
relation between both. As indicated in Figure 3 and
Figure 4, at optimal recovery, the recovery as well as
the productivity increase with increasing relative
adsorbility.
The recovery appears to be linearly dependent on a
function of the relative adsorbility and on the inverse
product composition (Figure 3). In the next section this
relation log(y)/xp will be used as a degree of difficulty
of separation to describe the performance of the slop
recycles. The bed length and feed purity have no
influence on the recovery. In the relative adsorbility
range investigated, for different bed length the product
flow at optimal recovery is identical. Only in case of
low relative adsorbility (y < 1.5), then a larger length
will increase the product flow and the recovery. But in
absolute sense this increase has no meaning (at y = 1.2
for L = 1 m the recovery is 0.26 % and for L = 1.5 the
recovery is 0.37%). For a lower product purity, the
smaller contents of the least adsorbed compound are
fully compensated by a larger product flow.
ox d.
004 020 0 40 060 080 loo 1 20
hlw 1XP
Figure 3. At optimal recovery the recovery is linear
related to a function of y and xp. (7 = 1.2,2.1,4, 7).
Standard: xF = 0.21, xp = 0.9, L = 1 m.
ow OM 1.00 1.5n zw
XF 1(~.(I -xF)). (y/L)
Figure 4. At optimal recovery adsorbent productivity is
Linearrelated to a mnction of y, xr, xp, and L.
(r = 1.2,2.1,4,7).
Standard: xF = 0.21, xp = 0.9, L = 1 m
S636 European Symposium on Computer Aided Process Engineering-8
In contradiction to the recovery, the adsorbent
productivity appears to depend on the bed length as
well as on the feed and product purity. For higher feed
purity, lower product purity, and smaller bed length the
productivity will increase (Figure 4).
Addition of recycles
optionalptwJes
Figure 5. An optional product or exhaust recycle phase
added to the common RPSA cycle phases.
As mentioned before, conventional RPSA includes
three production phases: pressurization, delay, and
depressurization (see Figure 5). Sometimes, after
depressurization a second delay phase is added. During
009 0 20 0.40 0.00 0.80 100 1 20 1 40
Wd 1XP
Figure 6. Recovery of RPSA process with raffinate or
extract recycle related to the difficulty of separation
(y = 1.2,2.1,7,25; xF = 0.21, xp = 0.9).
Figure 7. Productivity of RPSA process with raffinate
or extract recycle related to the difficulty of separation
(u = 1.2,2.1, 7,25; XF= 0.21, Xp= 0.9).
all the three phases product is delivered. Therefore,
principally, raffkate recycling can be inserted in all the
three phases or added as a fourth phase. Extract
recycling can be incorporated at any time during the
exhaust phase or also added as a fourth phase. This
results in many possibilities for slop-recycling to
investigate. A number of possibilities is studied, but
only the addition of a fourth phase for rafflnate or for
extract recycling proved to be useful. During the
simulations the optimum appeared to be rather
insensitive for changes in the switching times.
Figure 6 and Figure 7 show the recovery and the
adsorbent productivity improvement related to the
separation difficulty when extract and raffmate
recycles are introduced. The results are obtained for
optimized recovery. Because for diffkult as well as for
easy separations, during depressurization the extract
purity is temporarily higher than the feed purity
(Figure 2), extract recycling is always profitable. The
extract can be used to increase the feed purity. For
relatively difficult separations the improvement lies
above the 100%. Also raffinate recycling improves the
recovery. But only for difficult separations this will not
be at the expense of the productivity. By increasing the
gas velocity the “composition front” threats to come
out of the bed temporarily. With this raffinate which
has a purity below the product requirement, the feed
can be enriched so that the separation becomes less
difficult.
Conclusions
Raftinate recycling becomes profitable when the
composition profile in the bed is slightly concave. This
only happens for rather diffkult separations (log(y)/xp
5 0.4) at the end of the exhaustion phase. Then the
higher gas velocity combined with the enrichment of
the feed counterbalances the reduction of the
production time. The rafflnate recycling has a positive
i
1 60 effect on the product recovery as well as on the
production rate.
Extract recycling is always profitable, especially for
relatively easy separations (log(y)/xp 2 0.4). At the end
of the exhaustion period the exhaust purity (of the
product component x) in the is always over the feed
purity. Recycling of this part to the feed will lead to a
higher recovery. Then the production will also
increase. At log(y)lxp = 0.4 the recovery improvement
amounts to a 100%.
Symbols
L adsorbent bed length [rn]
x mole fraction of least adsorbed component
XF mole fraction x in feed
XP mole fraction x in product
Y ratio of Henry constants in binary mixture
References
Ruthven, D.M., Farooq, S., Knaebel, K.S., (1994),
Pressure Swing Adsorption, VCH Publisher