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Ind. Eng. Chem. Res.

2005, 44, 8815-8829 8815

SEPARATIONS

Propane/Propylene Separation by Pressure Swing Adsorption Using


Zeolite 4A
Carlos A. Grande and Alı́rio E. Rodrigues*
Laboratory of Separation and Reaction Engineering (LSRE), Department of Chemical Engineering,
Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias s/n, 4200-465, Porto, Portugal

In this work we have studied Pressure Swing Adsorption (PSA) process for separation of propane/
propylene mixtures using zeolite 4A extrudates (CECA) as an alternative to distillation. Purified
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propylene is withdrawn in the blowdown step at 10 kPa because is the most adsorbed compound.
The cycle used comprises five steps: pressurization, feed, purge with product, depressurization
to intermediate pressure and counter-current blowdown for propylene recovery. Two mixtures
with different propylene/propane ratios (54-46 and 85-15 diluted to 50% with nitrogen)
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corresponding to different sources of propylene production (steam cracking and Fluid Catalytic
Cracking) were studied. The effects of the different step times in the performance of the PSA
unit were evaluated. PSA performance was also studied using different operating conditions:
process temperature and feed pressure. Also, the removal of inert from the process was studied.
The simulation of the PSA unit was performed in gPROMS using a bi-LDF approximation for
mass transfer. Experimental purities of propylene around 99.0% were obtained. The recovery
of propylene in some of the runs reached values higher than 85% which is much higher than
30% obtained in previous studies. The best performance was obtained at 408 K where simulated
purity was 99.43% with a recovery of 84.3% and a unit productivity of 2.57 mol/h.kg of zeolite.

1. Introduction that, with purity higher than 99%, propylene recovery


was always smaller than 30%.
The separation of propane/propylene streams is the In a previous paper, we have reported experimental
most intensive separation carried out in petrochemical data of adsorption equilibrium of propane in zeolite 4A20
industry; the polymer-grade propylene requires a purity much higher than that previously reported in the
> 99.5%. Adsorption-based processes may enhance the literature.12,15,16 Even though a very large difference in
selectivity of the separation requiring less energy. Such the crystal diffusivity of both gases was observed, it is
processes have been explored in the last years to carry the reason that kinetic separation can still be success-
out the olefin/paraffin separations as an alternative to fully performed using this adsorbent.
the traditional distillation.1 To use an adsorption tech- It is the purpose of this work to evaluate the perfor-
nology like pressure swing adsorption,2,3 a very selective mance of a PSA unit for propylene purification. We have
adsorbent has to be used because propylene is the most studied a nearly equimolar C3 mixture with propylene/
adsorbed compound, being recovered in the blowdown propane ratios of 54-46 diluted to 50% with nitrogen
step simultaneously with partial regeneration of the (inert gas) found in propylene production from steam
adsorbent. cracking of gas oil. Additionally, the mixture with a
The propane/propylene separation by PSA is also in propylene/propane ratio of 85-15 also diluted to 50%
research stage, and some processes with specific adsor- with nitrogen was studied. Mixtures with 80-87%
bents have been patented.5-11 Many available com- propylene are obtained in the fluidized catalytic crack-
mercial adsorbents were previously evaluated for this ing (FCC) process. One of the novelties reported here,
separation.4,12-14 From all the commercial adsorbents when compared to previous works developed in our
tested, zeolite 4A presented the highest selectivity laboratory, is the study performed to eliminate nitrogen
toward propylene.12,15,16 In fac,t a PSA process using this from the PSA process.
zeolite as adsorbent was patented.17 Separation of The PSA cycle configuration employed has five steps
propane/propylene mixtures with different cycle schemes comprising the following: co-current pressurization,
was discussed in the literature.16,18,19 A brief description feed, rinse with pure propylene, depressurization to
of the PSA processes and their performances is shown intermediate pressure, and counter-current blowdown
in Table 1. It can be observed that very different values for bed regeneration and where propylene product (low-
of purity and recovery of propylene have been obtained pressure) is withdrawn. The effect of different step times
in these works. For equimolar mixtures, it was observed and operating conditions (temperature, inert content,
and feed pressure) on process performance was studied
* To whom correspondence should be addressed. Tel.: +351 to test the validity of the proposed mathematical model
22 508 1671. Fax: +351 22 508 1674. E-mail: arodrig@fe.up.pt. under very different conditions and to find operating
10.1021/ie050671b CCC: $30.25 © 2005 American Chemical Society
Published on Web 10/15/2005
8816 Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005

Table 1. Summary of State of the Art for Propane/Propylene Separation by PSA Using Zeolite 4A
T [K] cycle definitions purity recovery ref
373 four steps: pressurization, feed, rinse, blowdown; step times: 400 s (for all); 99.97 23.6
13
Phigh ) 1.0 bar; Plow ) 0.1 bar; feed: 70 C3H6/30 C3H8b 99.1 10.5
343
five steps: pressure equalization (9 s), counter-current 95.6 96.3
363 pressurization with propane (7 s), feed (34 s), 96.2 97.4
25
383 bed equalization (9 s), blowdown (41 s); Phigh ) 1.7 bar; 96.2 98.2
448 Plow ) 0.26-0.13 bar; feed: 88 C3H6/12 C3H8a 97.6 91.0

T [K] cycle definitions step time purity recovery ref


373 four steps: pressurization, feed, rinse, 100 99.94 7.95
blowdown; all step times have 400 99.01 12.16
14
equal duration; Phigh ) 1.0 bar; 600 99.98 27.29
Plow ) 0.1 bar; feed: 50 C3H6/50 C3H8b 800 99.97 23.59

T [K] cycle definitions P/F purity recovery ref


423 five steps: pressurization (60 s), feed (120 s), 0.78 91.2 20.0
393 rinse (120 s), depresurization to 0.45 97.4 9.4
423 intermediate pressure (60 s), blowdown 0.28 98.6 17.1 26
423 (120 s); Phigh ) 5.0 bar; Plow ) 0.1 bar; 0.23 94.5 27.3
423 feed: 25 C3H6/25 C3H8/50 N2; different total flow ratesa 0.13 87.9 46.5
a Experimental values. b Simulated values.

Table 2. Details of Equipment and Adsorbent Properties Used for Propane/Propylene Separation with Zeolite 4A
Extrudates (CECA)
column parameters adsorbent parameters (zeolite 4A)
column length, m 0.87 crystal radius, m 1.9 × 10-6
column radius, m 0.0105 pellet radius, m 8 × 10-4
column porosity 0.43 pellet density, kg/m3 1210
bulk density, kg/m3 758 pellet porosity 0.34
wall density, kg/m3 8238 pellet tortuosity 2.0
wall specific heat, J/kg‚K 500 solid specific heat, J/kg‚K 920
wall heat transfer coefficient, W/m2‚K 60
overall heat transfer coefficient, W/m2‚K 30
total flow rate, SLPM 1.10

conditions to produce polymer-grade propylene (purity being initially activated at 593 K under constant flow
higher than 99.5%). of helium for at least 24 h and kept under inert
environment until the finish of all experiments.
2. Experimental Section
3. Theoretical Section
The single-column PSA laboratory unit used in this
work was already installed in our laboratory for generic Zeolite adsorbents are bidisperse materials consisting
hydrocarbon gas separation.21,22 The operating ranges of an inert matrix (binder) that contains the zeolite
of the equipment are 313-673 K, 0.1-7 bar, 0.1-6 crystals. For this reason, macro- and mesopores of the
SLPM (standard liters per minute at 273 K and 1 bar). inert binder may control the mass transfer or this
The gas entering and exiting the column can be ana- process can be controlled by intracrystalline diffusion
lyzed via a multi-port valve system where 11 samples in the channels of the zeolite crystals or even by a
can be stored for subsequent analysis with FID (flame combination of both resistances. Also, a film mass
ionization detector) in a Chrompack 9001 gas chromato- transfer resistance may exist in the layer surrounding
graph. A full description of the unit (component speci- the pellet. The model used in this work takes into
fications, instruction for users, and control setup scheme) account these three resistances that will make the
was given elsewhere.22 In this experimental setup, we concentration fronts more disperse. The gas-phase
recorded pressure at the inlet and outlet of the column, dispersion was lumped into a single parameter, the axial
temperature at three different points of the column dispersion coefficient.
(0.18, 0.43, and 0.68m from feed inlet), and flow rates As we are working in bulk gas separation, non-
of each gas entering the column (independent mass flow isothermal behavior is expected due to the heat of
meters) and exiting the column (by GC analysis). adsorption/desorption; the heat balance has to be in-
The experiments reported in this work cover a tem- cluded in the model. Also due to bulk adsorption, the
perature range of 408-463 K. The total feed pressure velocity of the gas inside the column will not be
was also varied from 250 to 500 kPa according to the constant.
content of nitrogen used as inert gas. Equipment details The assumptions for the model that will be used below
and significant adsorbent properties are presented in are the following:
Table 2. (1) ideal gas;
Air Liquide provided all gases used in this report: (2) heat, mass, and momentum transport in the radial
propane N35, propylene N24 and nitrogen 50 (purity direction of the column are neglected and only axial
greater than 99.95, 99.4 and 99.999% respectively). coordinate is considered;
Zeolite 4A extrudates were kindly provided by CECA (3) momentum balance is simplified by using the
(France). Around 0.2 kg of extrudates was employed, Ergun equation;
Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005 8817

(4) meso- and macropore resistances are lumped in a equilibrium with the concentration of component i
single parameter, the macropore diffusivity that is averaged over the pellet, 〈ci〉.
obtained relating the Knudsen and molecular diffusion The energy balance will takes into account the three
via the Bosanquet equation; phases present: gas, solid, and column wall. The gas-
(5) macro- and micropore diffusion equations are phase energy balance is

( )
simplified by a bi-LDF (linear driving force) model
instead of the mass balances in the macropores and in ∂Tg ∂ ∂Tg ∂Tg ∂C
the zeolite crystals. This assumption has a large impact cCTC̃v ) λ - uCTC̃p + cRgTg -
∂t ∂z ∂z ∂z ∂t
in computational time; 2hw
(6) film mass transfer in the layer surrounding the (1 - c)ahf(Tg - Ts) - (T - Tw) (6)
pellets is considered; Rw g
(7) void fraction is uniform in the entire column.
With these assumptions, the fixed-bed model is where C̃v is the molar constant volumetric specific heat
described by the mass, energy, and momentum balance of the gas mixture, Tg is the temperature of the gas
equations. The component mass balance on the column phase, C̃p is the molar constant pressure specific heat
is22 of the gas mixture, Rg is the universal gas constant, hf
is the film heat transfer coefficient between the gas and

( )
∂Ci ∂yi ∂(uCi) a′kf,i the solid phase, Ts is the solid (extrudate) temperature,

c ) c DaxCT - - (1 - c) × hw is the film heat transfer coefficient between the gas
∂t ∂z ∂z ∂z Bii + 1 phase and the column wall, Rw is the column radius,
(Ci - 〈ci〉) (1) Tw is the wall temperature, and λ is the axial heat
dispersion calculated by23
where Ci ) yiCT is the gas-phase concentration of
λ
component i; ui is the superficial velocity; c is the ) 7 + 0.5PrRe (7)
column porosity; yi is the molar fraction; kf,i is the film kg
mass transfer resistance; Bii ) Rpkf,i/(5pDp,i) is the Biot
number; 〈ci〉 is the averaged concentration in the where kg is the thermal conductivity of the gas and Pr
macropores, all valid for component i; while CT is the is the Prandtl number.
total gas concentration; a′ is the pellet specific area; and The solid-phase energy balance is expressed by
Dax is the axial dispersion coefficient calculated by23 n n ∂Ts
cDax (1 - c)[p ∑ 〈ci〉C̃vi + Fp ∑ 〈qi〉C̃v,ads,i + FpC̃ps]
∂t
)
) 20 + 0.5SciRe (2) i)1 i)1
Dm,i
∂〈ci〉 n ∂〈qi〉
where Dm,i is the molecular diffusivity of component i; (1 - c)pRgTs
∂T
+ Fb ∑
i)1
(-∆Hi)
∂t
+
Sci ) µg/FgDm,i is the Schmidt number of component i;
and Re is the Reynolds number. (1 - c)a′hf(Tg - Ts) (8)
The momentum balance only considers the terms of
pressure drop and velocity changes and relates them where Fb is the bulk density of the column and (-∆Hi)
by the Ergun equation: is the isosteric heat of adsorption of component i not
considered a function of adsorbate loading.
2 Finally, the wall energy balance can be expressed by
∂P 150µg(1 - c) 1.75(1 - c)Fg
- ) 3 2
u+ |u|u (3) ∂Tw
∂z  d c p  3d c p FwC̃pw ) Rwhw(Tg - Tw) - RwlU(Tw - T∞) (9)
∂t
where P is the total pressure, µg is the gas viscosity, dp
is the pellet diameter, and Fg is the gas density. with
The LDF model was used to describe the mass Dw
transfer rate from the gas phase to the macropores: Rw ) (10)
e(Dw + e)
∂ci ∂〈qi〉 15Dp,i Bii
p + Fp ) p (Ci - ci) (4) 1

( )
∂t ∂t R 2 Bii + 1 Rwl ) (11)
p Dw + e
(Dw + e) ln
Dw
where Dp,i is the pore diffusivity, Rp is the pellet radius,
Fp is the particle density, p is the pellet porosity, and where Rw is the ratio of the internal surface area to the
〈qi〉 is the pellet averaged adsorbed phase concentra- volume of the column wall, Rwl is the ratio of the
tion. logarithmic mean surface area of the column shell to
The LDF equation for the crystals averaged over the the volume of the column wall, Dw is the internal
entire pellet is expressed by diameter of the column, e is the wall thickness, Ĉpw is
the specific heat of the column wall, U is the global
∂〈qi〉 15Dc,i / external heat transfer coefficient, and T∞ is the oven
) (〈qi 〉 - 〈qi〉) (5) constant set-point temperature.
∂t r2 c Adsorption equilibrium of pure components and bi-
nary mixtures of propane and propylene on zeolite 4A
where Dc,i is the crystal diffusivity, rc is the crystal were determined in a previous work20 and fitted with
radius, and 〈q/i 〉 is the adsorbed phase concentration in the multisite Langmuir model. The parameters for
8818 Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005

Table 3. Adsorption Equilibrium and Kinetic Qo is the inlet flow rate; and tfeed, trinse, and tblow are the
Parameters of Propylene and Propane in Zeolite 4A times of the feed, rinse. and counter-current blowdown
(CECA) steps, respectively.
qmax,i Ki0 ai -∆Hi D°c,i Ea,i The model described by eqs 1-15 was solved using
gas (mol/kg) (kPa-1) (-) (kJ/mol) (m2/s) (kJ/mol) gPROMS (PSA Enterprise, UK). The orthogonal col-
C3H6 2.600 8.44 × 10-6 2.612 28.265 4.66 × 10-14 15.610 location method on finite elements (OCFE) was used
C3H8 3.103 2.81 × 10-5 2.189 15.605 2.26 × 10-15 23.670 with 35 finite elements and two interior collocation
points in each element of the adsorption bed.
propane and propylene are given in Table 3. Nitrogen
is assumed to be a non-adsorbing gas at the tempera- 4. Results and Discussion
tures used here. The multisite Langmuir model is
expressed by24 4.1. Binary Fixed-Bed Experiments. The transport

( )
parameters calculated from correlations presented in
q/i q/i ai
the literature28-30 have to be checked. Before starting
qmax,i
) K iP 1 - ∑ qmax,i (12) with PSA experiments, binary fixed-bed runs are actu-
ally used as “mathematical model verification” experi-
ments, where values of the mass and energy parameters
where qmax,i is the maximum amount adsorbed, ai is the are inserted in the program for future use in PSA
number of sites occupied per molecule and with an simulations. Some fixed-bed experiments were per-
exponential temperature dependence for the adsorption formed with the binary mixture of propane and propyl-
constant Ki described as ene (diluted with nitrogen): one with a composition of

( )
-∆Hi 0.450 C3H6/0.035 C3H8/0.510 N2 (corresponding to a pro-
Ki ) Ki0 exp (13) pylene/propane ratio of 85/15) and another with a nearly
RTs equimolar C3 composition: 0.250 C3H6/0.240 C3H8/
0.510 N2. Both experiments were performed at a total
where Ki0 is the infinite adsorption constant and (-∆Hi) pressure of 250 kPa and 423 K with a total flow rate of
is the isosteric heat of adsorption, both for component 1.1 SLPM; results are reported in Figure 1. In Figure
i. 1, the solid lines correspond to the mathematical model
The crystal diffusivity of propane and propylene at described in the Theoretical Section. The parameters
low hydrocarbon concentration (determined in the linear used in the model are described in Table 2. It has to be
region of the isotherms) were also reported before25 as mentioned that the heat transfer coefficient at the wall
a function of temperature and described by (hw) was used as a fitting parameter to address the
∞ o
temperature changes in the column. It can be observed
Dc,i ) Dc,i exp(-Ea,i/RT) (14) that the mathematical model can describe well the
behavior of the hydrocarbon mixtures with two different
where D°c,i is the limiting diffusivity at high tempera- ratios of propylene to propane that correspond to typical
tures and Ea,i is the activation energy. The micropore industrial streams of propylene production. Tempera-
diffusivity as used in the LDF constant (eq 5) also ture increase due to propylene adsorption is also shown.
depends on concentration. In this work, we described In both curves a stream containing only propane can
this dependency by the Darken’s model:26 be taken out of the column without any propylene. Note
also that the temperature increase due to propane

d ln(Pi) adsorption is negligible while the one for propylene
Dc,i ) Dc,i (15) adsorption is around 12 K for higher propylene content,
d ln(qi)
which is why the process cannot be considered isother-
The diffusivity parameters for propane and propylene mal.
in zeolite 4A are also reported in Table 3. 4.2. Description of PSA Cycle and Definition of
The performance of the different experiments and Operating Conditions. The PSA cycle configuration
simulations was evaluated according to three basic employed for propane/propylene separation has five
parameters: purity and recovery of product and unit steps. These steps are as follows: co-current pressuriza-
productivity of the PSA. They are defined by27 tion with feed stream, feed, co-current rinse with pure
propylene, co-current depressurization to intermediate
∫0t blow pressure, and counter-current blowdown. The last step
CC3H6u|z)0 dt is performed using vacuum to withdrawn propylene
purity ) product and also to partially regenerate the adsorbent.
∫0t
(
blow
CC3H6u|z)0 dt + ∫0t blow
CC3H8u|z)0 dt) To illustrate the PSA cycle, a schematic diagram of the
(16) process is shown in Figure 2.
An open-ended design of the five-step cycle to be used
∫0t blow
CC3H6u|z)0 dt -∫0t rinse
CC3H6u|z)0 dt for C3 separation in the laboratory unit (with column
recovery ) t length and volume already specified) has the following
∫0 press
CC H u|z)0 dt + ∫0
3 6
t feed
CC3H6u|z)0 dt operating and process parameters: Tfeed, Trinse, Qpres,
(17) Qfeed, Qrinse, Phigh, Pinter, Plow, tpres, tfeed, trinse, tdepres, tblow,
and feed composition. The optimization of a process with
productivity ) so many parameters is very difficult, particularly when
( ∫0t blow
CC3H6u|z)0 dt - ∫0t rinse
CC3H6u|z)0 dt)Qo they are related by a system of partial differential
equations. In the group of parameters mentioned, we
(18)
ttotalwads can distinguish two general types: the operating pa-
rameters and the design parameters. To simplify the
where wads is the adsorbent mass loaded in the column; study of the process, it is desirable to reduce the number
Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005 8819

Figure 1. Propane/propylene breakthrough curves at 423 K and 250 kPa using 1.1 SLPM of total flow rate. (a) and (b) are molar flow
rate of gas and temperature profile inside the column (at 0.18, 0.43, and 0.68m from feed inlet) for a mixture 0.250 C3H6/0.240 C3H8/
0.510 N2 while (c) and (d) correspond to a mixture 0.450 C3H6/0.035 C3H8/0.510 N2. Solid lines are theoretical model predictions, and
solid points are experimental values.

parameters, it is convenient to give an example of an


experimental run obtained in a PSA experiment using
zeolite 4A (CECA, France). For this purpose an experi-
ment was performed with 60 s of pressurization, 70 s
for feed step, 130 s of rinse, 60 s of co-current depres-
surization, and 220 s for counter-current blowdown step.
Operating parameters were kept at the following: T )
433 K (for all inlet streams and surroundings of the
column); Phigh ) 500 kPa (pressurization and feed); Pinter
) 50 kPa (co-current depressurization); Plow ) 10 kPa
(counter-current blowdown); pressurization and feed
Figure 2. Schematic diagram of the PSA cycle used for propane/ flow rate: 3.16 SLPM; rinse flow rate: 2.70 SLPM;
propylene separation. Steps description: (1) pressurization with molarfractionofpressurizationandfeedstream: 0.453 C3H6/
feed; (2) feed; (3) rinse with pure propylene; (4) co-current 0.074 C3H8/0.473 N2 (ratio of 85/15 propylene/propane);
depressurization to intermediate pressure; (5) counter-current
blowdown at low pressure (vacuum) where product is withdrawn molar fraction of rinse stream: 0.077 C3H6/0.923 N2.
and adsorbent is partially regenerated. The relevant experimental information collected from
the PSA unit (pressure and temperature) and GC (molar
of operating conditions. The first assumption is to use flow rate of hydrocarbons exiting the column) can be
the same temperature for the feed (and pressurization) summarized in Figure 3. The pressure at the exit of the
and for the rinse streams, which was initially fixed at column and the temperatures measured by the three
433 K. Other important design parameters are the flow thermocouples located at 0.18, 0.43, and 0.68 m from
rates. In this work the flow rates of all streams (pres- the feed inlet are reported for the first 15 cycles. In this
surization, feed, and rinse) assumed a fixed value and figure we also show the molar flow rate analyzed by GC
will not be varied. Also, hydrocarbon composition in feed for the first step and for cycles 39 and 50 where no
was fixed at two different ratios of propylene to pro- variation of molar flow rate was experimentally de-
pane: 85/15 and 54/46. The change in feed composition tected.
studied in this work was the nitrogen removal from the The solid lines in the figures represent the prediction
process. Still the system has many design parameters of the model described in the Theoretical Section. The
to be defined: step pressures and step times. In this model is in good agreement with the experimental data
work, the effect of most of these parameters was studied. indicating that the cyclic column behavior is well
Initially, the step pressures Phigh ) 500 kPa; Pinter ) 50 predicted. Some differences exist in the experimental
kPa; Plow ) 10 kPa were chosen to perform most of the and simulated molar flow rates in the co-current
experimental data collection. After studying the effect depressurization step that may be due to dead volumes
of the step times in the cycle performance, the operating of the equipment.
conditions (inert content, temperature, and feed pres- The experimental purity of this example is 98.7%,
sure) will be addressed. even when simulated value is somewhat higher: 99.32%.
4.3. PSA Experiments with Zeolite 4A: Initial Differences between experimental and simulated values
Runs. Before studying the effects of the different may be due to dead volumes at the end of the PSA
8820 Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005

Figure 3. Experimental results obtained in the PSA unit for propane/propylene separation using zeolite 4A at 433 K with a mixture
0.450 C3H6/0.035 C3H8/0.510 N2: (a) pressure at the outlet of the column in the pressurization (1), feed (2), rinse (3), depressurization (4),
and blowdown (5); temperature histories in the bottom (b), middle (c), and top (d) thermocouples (0.18, 0.43, and 0.68 m from inlet) and
molar flow rate of propane and propylene in the second cycle (e) and in cycle 39-50 (f). Solid lines are predictions of the theoretical
model, and points are experimental values. Operating conditions are reported in Table 8.

column and/or because the propylene used for the specific flow rate (Qpres ) 2.785 SLPM), the pressuriza-
experiments has 0.5% of propane in its composition and tion step cannot take less than 54 s, and this value was
this may be critical, particularly in the rinse step. The used in almost all the experiments as fixed time for the
recovery of propylene in this experiment was 62.7% (see pressurization step.
Table 8). This value is higher than previously obtained This cycle has no counter-current purge with light
values using zeolite 4A Rhone-Poulenc.22 This difference product after the counter-current blowdown step. Light
may be due to different propane diffusion into the zeolite product purification is normally used when the light gas
structure. One possible explanation for the difference is the purified product.32 Having no counter-current
in the propane kinetics in different adsorbents can be purge allows a straight route to calculate the upper
due to the thermal treatment of the samples (activation limiting time of the feed step (before breakthrough of
protocol) that may dislocate the Na+ ions from the propylene). Assuming that the counter-current blow-
structure producing small differences in the channel down (last step of the cycle) is very long, the column
aperture as reported for smaller molecules.31 will reach adsorption equilibrium at 10 kPa with almost
4.4. Improving the Step Times (Design Param- pure propylene. Starting with a column filled with the
eters). Once all the operating parameters are specified, adsorbent saturated (in equilibrium) with propylene at
the other parameters to be studied are the step times 10 kPa and with a pressurization step of 54 s, the
(i.e., the design parameters, which determine the overall maximum feed time can be determined.
performance of the unit). Although the initial experi- The simulated behavior of the column (molar flow rate
ment was performed with propylene/propane ratio of 85/ exiting the column, temperature and propylene concen-
15, in this section, except when explicitly mentioned, tration and amount adsorbed at different times) is
the propylene/propane ratio will be 54/46. It was verified shown in Figure 4. Propylene is exiting the column since
experimentally that with the column used and for a time zero of the feed step, but a major breakthrough
Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005 8821

Figure 4. Behavior of the PSA column started with the bed saturated with propylene at 10 kPa and feed with a mixture 0.250 C3H6/
0.240 C3H8/0.510 N2: (a) molar flow rate of gases exiting the column; (b) temperature profiles at different times 54, 100, 150, 200, 225,
and 250 s.

Table 4. PSA Performance for Propane/Propylene Separation with Zeolite 4Aa


expt pressurization, feed, rinse, depressurization, blowdown, purity %, recovery %, productivity,
no. s s s s s simulated experimental mol/h‚kg
4 60 60 25 40 220 99.27 87.3 1.75
(98.7 ( 0.3)b
5 54 100 25 40 180 99.31 85.6 2.64
(98.6 ( 0.2)b
7 54 100 25 40 220 99.35 86.7 2.36
(98.7 ( 0.3)b
8 54 100 75 40 220 99.39 81.6 2.28
(98.8 ( 0.4)b
9 54 100 75 40 180 99.27 82.6 2.38
(98.7 ( 0.2)b
10 54 60 25 40 180 98.91 86.4 1.97
(98.4 ( 0.3)b
12 54 60 75 40 180 99.12 80.0 1.73
(98.6 ( 0.4)b
13 54 60 75 40 220 99.33 81.3 1.58
(99.0 ( 0.3)b
16 54 60 15 25 180 98.48 84.1 1.64
(98.2 ( 0.2)b
17 54 85 15 25 220 98.61 85.7 2.38
(98.3 ( 0.3)b
a Operating conditions were as follows: T ) 433 K; P
high ) 500 kPa; Pinter ) 50 kPa; Plow ) 10 kPa; pressurization and feed flow rates:
2.785 SLPM; yC3H6 ) 0.27, yC3H8 ) 0.23, yN2 ) 0.50. b Experimental values.

happens after 160 s of feed step (dotted line in Figure residence time of the gas into the column. Although the
4a). This time is the maximum limiting time because purpose of this step is to exclude propane from the
the blowdown step will never be large enough to allow column voidage and also from the larger macropores of
the column to reach equilibrium; therefore, more pro- the adsorbent and since some propylene will adsorb in
pylene will stay in the column, and the feed time has the zeolite, a reasonable limit of 25 s was assumed as
to be shortened. lower boundary.
Once the maximum feed step is known, some com- In Table 4, the result of different PSA experiments is
ments on the experiment shown in Figure 3 will be summarized. All the operating parameters were kept
made. In the molar flow rate plots, it can be seen that constant and only step times were changed. The math-
there is much propylene being lost in the feed step and ematical model predicts well all the collected data. Due
in the rinse step, even in the second cycle where the to reasons explained above (contamination of propane
column is only partially saturated of hydrocarbons and in the propylene bottle and dead volumes of the experi-
far away from cyclic steady state. The propylene losses mental setup), a difference of around 0.5 was detected
get worse for a large number of cycles. This is an in all the experiments (purity around 98.4-98.8%). For
indication that too much propylene is entering to the this reason the simulated and experimental values of
system. Also, the amount of propane leaving the column purity are presented in Table 4 while the recovery and
in the rinse step is only important in the first moments. productivity values (calculated from the integral of the
A way to reduce propylene losses to improve recovery propylene molar flow rate) correspond to the experi-
and also with positive effects on productivity is to reduce mental values.
the rinse step time. This decrease in the rinse time can For a constant value of all other step times, only the
be explained in terms of the very small value of the rinse time was changed from 25 to 75 s as can be seen
propane diffusivity: the amount of propane adsorbed in Table 4. In all the experiments when the rinse step
per cycle is small, but also this amount will not be easily is more than 25 s, the recovery drops to values around
desorbed from the zeolite in the rinse step. For this 80% instead of 85% and changes in purity are only of
reason, the rinse step has the only purpose of removing within 0.1%. Clearly the rinse time of 130 s is excessive
propane from the column and pellets (macropores) for this zeolite sample, and the decrease in the rinse
voidage. The lower boundary of the rinse step is the time leads directly to the possibility of a larger feed time,
8822 Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005

Figure 5. Experimental results obtained in the PSA unit for propane/propylene separation using zeolite 4A at 433 K with a mixture
0.250 C3H6/0.240 C3H8/0.510 N2: (a) pressure at the outlet of the column; (b) temperature at the bottom thermocouples (0.18 m from
inlet) and molar flow rate of propane and propylene in the first cycle (c) and in cycle 41 (d). Solid lines are predictions of the theoretical
model and points are experimental values. Operating conditions are reported in Table 4, run 4.

increasing the productivity of the unit. Note that with In this work we have used a single-column PSA
a decrease in the rinse time, the recovery of product in without reservoir tanks for product storage and recycle.
all the experiments jumped from 63% to more than 80%. For this reason, the rinse stream consists of purified
The co-current depressurization step can be reduced propylene instead of propylene resulting from the
only up to 30 s when purity begins to decrease. The product stream. The results obtained in this section may
intermediate cocurrent blowdown was a tradeoff situ- be different (lower product purity and recovery) if a
ation between desorption of propane from the extrudates more impure stream (recycle part of the product) is used
macropores (desired effect to increase propylene purity) in the rinse step.
and desorption of propylene from zeolite crystals (un- 4.5. Cyclic Steady State (CSS) and Multiplicity
desired effect resulting in decrease of product recovery). of Steady States. Before studying the effect of the
In this work this step time was kept constant at 40 s, a operating and design parameters, the cyclic steady state
little less than prior experiments, but still without and its multiplicity were investigated. A very small
negative effects on purity. diffusivity coefficient of propane can have detrimental
Blowdown step in this case is used to regenerate implications at large times. In Figure 3, the temperature
partially the adsorbent but also to extract the product. and pressure history were plotted for the first 15 cycles.
The molar flow rate of propane that contaminates the It can be seen that they reached the cyclic steady state.
product is mainly taken out of the column in the initial In the case of the molar flow rate, 50 cycles were
moments of the step. For this reason, shorter steps have performed, and no detectable difference was observed
lower purity, but a large step produces low productivity after cycle 20. Even though, if we perform simulations
of the unit. In Table 4 we show experiments with 180 for over 500 cycles and we see in detail the evolution of
and 220 s to show the increasing of purity with a larger all the variables, we can note that the product purity is
step. Periods higher than 220 s did not improve purity continuously decreasing up to a steady state value that
considerably but decreases the productivity. In almost is only reached after 250 cycles. This continuous purity
all experiments performed, increasing the blowdown decrease is due to a very small increase of the adsorbed
step also increases the recovery of the product (large phase concentration of propane, which result in a
amounts of propylene desorb from the zeolite and can slightly higher release of propane in the blowdown step,
be collected). There was a particular case (see expts 8 contaminating propylene. The evolution of product
and 9 from Table 4) where this situation was not valid, purity in run 1 (see Table 4) is shown in Figure 6. The
but this could be due to some experimental error of a experimental points collected in the first 50 cycles are
single point that has a large impact in recovery calcula- also plotted in this figure. The difference between the
tions. simulated values and the experimental ones may be due
As an example of the improvement of the PSA to dead volumes in the installation or even to the fact
performance, we show in Figure 5 a PSA cycle (molar that we are feeding propylene 99.4% purity with around
flow rate in the initial cycle and cycle 41 and bottom 0.5% impurity of propane in the rinse step.
temperature and pressure history). As the total time of The results shown in the dotted line in Figure 6 were
the cycle was diminished (see run 4 in Table 4), the obtained starting from an initially clean bed and then
productivity was also improved. passing an inert stream of nitrogen for 48 h. To confirm
Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005 8823

Figure 6. Purity evolution for the same experiment started with a clean bed passing a nitrogen flow before experiment started (squares
are experimental data, and dotted line is simulation) and a column initially presaturated with propane (triangles are experimental data,
and solid line is simulation). Operating conditions are detailed in Table 8, run 1.

Table 5. PSA Experiments Reducing the Inert Content in the Feed and Rinse Streams for Propane and Propylene
Separation at 433 K Using Zeolite 4Aa
expt flow, yC3H6, yC3H8, y N 2, Phigh, purity %, recovery %, productivity,
no. SLPM feed feed feed kPa simulated experimental mol/h‚kg
5 2.785 0.27 0.23 0.50 500 99.31 85.6 2.64
(98.9 ( 0.2)b
6 2.074 0.37 0.31 0.32 370 99.28 86.6 2.61
(98.7 ( 0.3)b
14 1.700 0.45 0.41 0.14 250 99.25 87.9 2.60
(98.9 ( 0.3)b
S1 1.700 0.55 0.45 0.00 250 99.09 89.5 3.41
a Step times: pressurization (54 s), feed (100 s), rinse (25 s), depressurization (40 s), and blowdown (180 s) at a pressure of 10 kPa.
b Experimental values.

the cyclic steady state and to check if multiplicity of (carrying consequent additional costs to the overall
steady states exists, the same experiment was repeated process). As we had 50% of nitrogen in the total flow
but starting from a column saturated with propane (125 rate, the strategy used to diminish the nitrogen was to
kPa partial pressure) for 3 h. Multiplicity of steady run two other experiments reducing the molar fraction
states in PSA applications was previously reported in of inert up to 14% in the feed and pressurization steps.
the separation of propane/propylene mixtures 33 and can Table 5shows the performance and conditions of the
also exist in this system that has non-isothermal different experiments where the partial pressures of
behavior and non-linear isotherms.34 propane and propylene are kept almost constant but
The experiment started with the column initially reducing the content of nitrogen continuously. In Figure
filled with propane; pressure and temperature histories 7, we show the molar flow rate of propane, propylene,
and molar flow rates of gases were also well described and nitrogen (nitrogen results corresponds only to
by the model. The evolution of the purity profile instead simulated values because we were not detecting nitro-
of starting from a very high value in the initial cycles gen in the PSA unit) of the three different experimental
and then decrease as shown before, in the case of the runs and the simulated one without nitrogen (S1). All
column previously saturated with propane, the purity the cycles shown were collected after reaching the
started from lower values and improves with time until thermal cyclic steady state.
a constant value around 98.6%. The purity evolution The most important aspect to mention is that only a
with time (simulated and experimental values) of this difference in (3 K in the temperature oscillation was
experiment is shown in solid line in Figure 6. The same verified. This increase is due to a lower flow rate of gas
cyclic steady state line was obtained (although in this to remove heat generated by propylene adsorption. As
case it starts from a lower value of purity passing it can be seen from Figure 6, the molar flow rate out of
through a maximum slightly higher than 99.5% and the column remains constant, indicating that nitrogen
decreasing to 99.32% where it stays constant) indicating was an inert that in this case is not required to improve
no multiplicity of steady states in runs starting with the system performance. Even though using the same
different saturation conditions of the column. step times, the recovery of product is higher when
4.6. Decrease in the Nitrogen Content. Another nitrogen content is decreased, the purity also decreases
item studied here was the decrease of inert in the so new conditions (increase the rinse step time) should
process. The fact of having an added inert in the process be established to improve purity without nitrogen.
makes it undesirable for industrial applications because When nitrogen content is reduced, the recovery is
additional units are required for separation of the olefin increased slightly due to small reduction in the axial
from the inert and for recycling-recompressing the inert dispersion (lower flow rate of gas). Even when the
that is not always available in a petrochemical plant nitrogen content was seriously decreased up to a molar
8824 Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005

Figure 7. Molar flow rate (when thermal cyclic steady state was achieved) at the end of the PSA column for propane/propylene ratio
54/46 with different nitrogen molar fractions: (a) yN2 ) 0.50; (b) yN2 ) 0.32; (c) yN2 ) 0.14; (d) yN2 ) 0.00 (simulated results). Solid lines
are predictions of the theoretical model, and points are experimental values. Experimental conditions and performance parameters are
reported in Table 5.

Table 6. Effect of Temperature in Propane/Propylene


Separation by PSA Using Zeolite 4A Extrudates (CECA)a
expt T, feed flow, purity %, recovery %, productivity,
no. K SLPM simulated experimental mol/h‚kg
20 408 1.700 99.43 84.3 2.57
(99.0 ( 0.2)b
14 433 1.700 99.25 87.9 2.60
(98.9 ( 0.3)b
S3 448 1.700 99.18 88.3 2.66
21 463 1.700 99.06 88.9 2.67
(98.7 ( 0.3)b
a Step times: pressurization (54 s), feed (100 s) at 250 kPa, rinse

(25 s), depressurization (40 s), and blowdown (180 s) at a pressure


Figure 8. Performance parameter of PSA runs for different molar of 10 kPa; yC3H6 ) 0.45; yC3H8 ) 0.41; yN2 ) 0.14. Rinse flow rate:
fraction of nitrogen in feed and pressurization steps with a 1.005 SLPM. b Experimental values
propylene/propane ratio of 54/46. Experimental conditions are
presented in Table 4. conditions and the model still works, there is a certain
confidence to say that the simulations will be valid in a
fraction of 0.14, the amount of inert in the blowdown wider region.
stream exiting the column together with the product The first operating condition to study is the temper-
remains near 5%, which is very similar with the product ature. All experiments presented above were performed
contamination when using 50% inert in the feed stream. at 433 K, chosen as the tradeoff condition between
The simulated performance parameters as a function kinetic selectivity and productivity based on calculations
of the nitrogen molar fraction in pressurization and feed of the kinetic selectivity factor with the explanation that
streams are shown in Figure 8. the productivity of the column decreases with temper-
As the nitrogen reduction did not show significant ature (less adsorption at higher temperatures). In this
detrimental changes in the PSA performance for the case we will explore two other temperatures: 408 and
study of other conditions (temperature and feed pres- 463 K. Simulations were also performed at 448 K, but
sure), the experiment with 14% of nitrogen will be used no experiment was done. As mentioned before, the
as the reference experiment at 433 K. pressurization and feed streams will have only 14% of
4.7. Effect of Temperature. In the experiments nitrogen. Experimental conditions at the different tem-
performed before, the set of operating values was peratures as well as the performance parameters (simu-
constant and the effect of different step times was lated purity and experimental recovery and productiv-
studied. It is also interesting to know the effect that the ity) are reported in Table 6.
operating conditions have in the process. As the model According to the performance parameters shown in
was able to fit experiments in a wide range of conditions Table 6, we can see that the recovery increases with
for a single set of operating parameters, if we use other temperature while purity of propylene decreases. The
Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005 8825

Figure 9. PSA results for propane/propylene separation at 408 K using zeolite 4A with a feed mixture of 0.250 C3H6/0.240 C3H8/0.510 N2:
(a) experimental pressure at the outlet of the column; (b) temperature in the bottom, middle, and top thermocouples (0.18, 0.43, and
0.68 m from inlet); (c) molar flow rate of propane and propylene in cycle 35 (for experimental conditions see Table 6, run 20); and (d)
simulated profiles of propane adsorption in different positions of the column. Solid lines are predictions of the theoretical model, and
points are experimental values.

purity of product recovered in the blowdown step is


lower because propane diffusivity increases with tem-
perature. On the other side, if we decrease the temper-
ature, the diffusivity of both gases is smaller and thus
propylene purity is higher (less adsorption/desorption
of propane), but also the cycling of propylene adsorption/
desorption is more difficult (smaller diffusivity coef-
ficient) leading to smaller recovery. Also, the produc-
tivity of the bed increases continuously with temperature.
In this case, the ∆qC3H6 between the feed and blowdown
steps together with the higher diffusivity of propylene
leads to the increase of productivity with temperature.
It has to be noticed that even when product recovery Figure 10. Temperature dependence of PSA performance pa-
and unit productivity increases with temperature, the rameters for propane and propylene separation using zeolite 4A
(CECA) for a feed mixture of 0.250 C3H6/0.240 C3H8/0.510 N2. The
requirement of a higher purity of product must prevail
empty point at 448 K represents simulated results for recovery.
in the final set of operating conditions of the process. Points for purity correspond to simulated values.
The product purity obtained experimentally at 408
K was 99.0 ( 0.2%, even when this value is lower that shows the performance parameters (recovery and pu-
the simulated value, it is higher than in the experiments rity) for the runs at 408, 433, 448, and 463 K. Open
at 433 K where purity of 89.4-89.8% was obtained. symbols correspond to simulated run at 448 K. The
Again the difference can be explained by dead volumes purity of product has a linear decrease with process
of the unit and the propane contamination in the temperature while recovery decreases faster at temper-
propylene stream used particularly in the rinse step. atures lower than 433 K. The higher purity at lower
The plot of the experimental values obtained for the temperatures can be explained by the faster decrease
experiment at 408 K (run 20) where propylene was of diffusion of propane (higher activation energy) when
obtained with higher purity (99.43% propylene simu- compared to propylene. Unfortunately, a decrease in
lated against 99.0% obtained experimentally) is shown propylene diffusion results in a smaller recovery of
in Figure 9. In this figure the time variation of the product and unit productivity.
amount adsorbed of propane in different positions of the 4.8. Effect of Step Pressures. In this section we
column is shown until cyclic steady state is reached. have chosen run 14 (see Table 6) as a reference. Note
Note that in these lines it is not possible to distinguish that the temperature in run 14 is 408 K where better
between adsorption and desorption of propane on a results were obtained. The results obtained in this
single cycle. experiment (with feed pressure of 250 kPa) were com-
As a brief summary of the results obtained when pared with simulated results using higher feed pres-
changing the temperature of the process, Figure 10 sures: 300 and 400 kPa. Unfortunately, if the feed
8826 Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005

Table 7. Simulated Results for Propane and Propylene


Separation Using PSA with Different Feed Pressures
and Step Timesa
expt pres, feed, rinse, Phigh, purity %, recovery %, productivity,
no. s s s kPa simulated simulated mol/h‚kg
20 54 100 25 250 99.43 84.3b 2.57b
(99.0 ( 0.2)b
S4 65 80 25 300 99.33 86.6 2.49
S5 80 60 20 400 99.12 89.3 2.16
S6 80 80 20 400 99.17 88.4 2.47
S7 80 100 20 400 99.21 87.3 2.73
S8 80 120 20 400 99.24 85.8 2.93
a Temperature ) 408 K; step times: depressurization (40 s) and

blowdown (180 s) at a pressure of 10 kPa; yC3H6 ) 0.45; yC3H8 ) Figure 12. Effect of feed step time in performance of a PSA unit
0.41; yN2 ) 0.14; feed flow rate: 1.700 SLPM; rinse flow rate: 1.005 using zeolite 4A for propane and propylene using feed stream of
SLPM. b Experimental value. 0.250 C3H6/0.240 C3H8/0.510 N2 at 400 kPa and 408 K (simulated
results). Operating conditions are specified in Table 7.

propylene is not occupying the last portion of the


column, more propane can be adsorbed, and desorbed
in the blowdown step, decreasing purity.
An alternative to improve purity at higher pressures
is to make a more effective use of the column. A possible
option can be the increase of the feed step time. Results
of simulations with the same conditions but increasing
the feed step time are presented for the case of feed
pressure at 400 kPa in Figure 12 and also in Table 7.
The number of moles of propane adsorbed in the last
portion of the column decreases when more propylene
Figure 11. Effect of feed pressure in performance of a PSA unit is adsorbed, and thus purity increases at the expense
for propane and propylene for similar number of moles treated of decreasing recovery (more propylene is lost in feed
using zeolite 4A at 408 K with a feed mixture of 0.250 C3H6/ and rinse steps).
0.240 C3H8/0.510 N2. Operating conditions are specified in Table 4.9 Mixtures with Ratio 85% Propylene/15%
7. Empty point corresponds to simulated values while solid point
Propane. Finally, a mixture having much more pro-
correspond to experimental value of run 20 (see Table 7).
pylene than propane was studied. The mixture with 85/
15 propylene/propane ratio may be obtained in the fluid
pressure is further increased over 250 kPa, the FID catalytic cracking (FCC) process optimized for propylene
detector of the gas chromatograph saturates in some of production. This characteristic composition is available
the steps of the PSA cycle. For this reason only, only when economic constraints are favorable to this
simulations were carried out for comparison. Low pres- operation.
sure (blowdown) and intermediate pressure (depres- The set of experiments performed is shown in Table
surization) were kept constant at 10 and 50 kPa, 8, together with the performance values obtained by
respectively. The feed pressures used for this parametric simulation of the process. These experiments were also
study were 250, 300, and 400 kPa. performed at 433 K and using nitrogen to dilute the
When the pressure of the pressurization and feed step mixture almost to 50%.
is changed, the times of these steps also have to be All the experiments reported here were well-predicted
changed. Experimental studies were performed at 300 by the model; the relation between experimental and
and 400 kPa, and the pressurization time corresponds simulated values of recovery and productivity are
to the real time that is necessary to pressurize the coincident. The experimental purity obtained ranged
column. For the feed step, the time was initially selected from 98.6 to 99.0%. These values were oscillating with
to introduce approximately the same number of moles (0.2% in the same experiment (all around 98.8%); as
as in the cases with feed at 250 kPa using the ideal law no effective trend was observed in the experiments, the
of gases. Also at 400 kPa the feed step was increased to simulated value is being reported. As productivity is
study this parameter. The complete set of operating expressed in moles of propylene treated per hour per
parameters for all the simulations is detailed in Table kilogram of zeolite, the values of productivity are higher
7. Simulated performance parameters (purity, recovery, than in the 54/46 mixtures because more moles of
and unit productivity) are detailed in this table. propylene per second are introduced to the column.
The first thing to notice is that the purity of propylene In these experiments, the general trend is the same
obtained as product decreases when feed pressure is as previously observed for the 54/46 (propylene/propane
increased. The opposite trend holds for recovery. To help ratio): if the rinse step is decreased to a minimum
in understanding these results, purity and recovery value, the recovery also increases while purity is only
versus feed pressure are presented in Figure 11. The slightly affected; when the blowdown time is reduced
explanation of this trend is the following: when pres- to 180 s instead of 220 s, the purity also decreases.
sure is increased, the capacity of the column also As an example of the experiments shown in Table 8
increases (favorable isotherm), so the number of moles we report in Figure 13 the temperature and pressure
of propylene initially distributed in the entire column profiles as well as the molar flow rates of propane and
now will be more concentrated near the entrance of the propylene leaving the column in cycles 1 and 72
column. For this reason less propylene is lost in the feed obtained in run 16. In the flow rate plot the nitrogen
and rinse steps, increasing the recovery. Also because flow is also reported. It can be seen that when compared
Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005 8827

Table 8. PSA Results for Propane/Propylene Separation by PSA Using Zeolite 4A (Mixture 85/15 Propylene/Propane
Ratio Diluted to 50% with Nitrogen)a
expt pressurization, feed, rinse, depressurization, blowdown, purity %, recovery %, productivity,
no. s s s s s simulated experimental mol/h‚kg
1 60 70 130 60 220 99.32 62.7 2.69
(99.0 ( 0.2)b
3 60 60 25 40 220 99.18 83.1 3.08
(98.9 ( 0.2)b
16 54 60 15 25 180 99.12 92.2 4.10
(98.6 ( 0.3)b
17 54 85 15 25 220 99.23 89.6 4.34
(98.8 ( 0.2)b
18 54 60 40 25 180 99.31 90.2 3.90
(98.5 ( 0.4)b
a Temperature ) 433 K; feed at 500 kPa; blowdown at 10 kPa; y
C3H6 ) 0.453; yC3H8 ) 0.074; yN2 ) 0.473; feed flow rate: 3.160 SLPM;
rinse flow rate: 2.700 SLPM. b Experimental values.

Figure 13. PSA results for propane/propylene separation for 85/15 propylene/propane ratio using zeolite 4A: (a) experimental pressure
at the outlet of the column; (b) molar flow rate of propane, propylene, and nitrogen (simulated) in cycle 72 (for experimental conditions
see Table 8, run 16); (c and d) temperature in the bottom and top thermocouples (0.18 and 0.68 m from inlet). Solid lines are predictions
of the theoretical model, and points are experimental values.

with experiments performed with 54/46 propylene/ The mathematical model proposed in this work could
propane ratio, the amount of nitrogen contaminating the predict the PSA behavior, which was confirmed experi-
propylene stream in the blowdown step is much less mentally in many different conditions.
than before, even though a process without nitrogen is Purity higher than 99% with recovery above 85% was
desired. obtained in many simulations performed in this work.
Single-column experiments produced a purity of propyl-
5. Conclusions ene between 98.4 and 99.1%. The difference can be due
An alternative process to cryogenic distillation for to 99.4% propylene purity used in the rinse step and
propane and propylene is presented in this work. also due to dead volumes of the unit.
Vacuum pressure swing adsorption process with five The cycle times were improved to have much higher
steps (pressurization, feed, rinse, depressurization to recovery of propylene than the 30% previously reported
intermediate pressure, and counter-current blowdown) in the literature. According to the experiments and the
was used. We focused on two mixtures with different simulations performed, it was noted that appropriate
propylene/propane ratio: 54/46 and 85/15 corresponding time for the rinse step results from a tradeoff situation
to steam cracking of gasoil and FCC sources of propyl- between displacement of propane from the column and
ene production. Initial dilution with 50% nitrogen was decrease of propylene recovery. Also, it is clear from
used, but further experiments showed that the use of experiments that a longer blowdown step produces
nitrogen does not offer any advantages, only has slight better product purity but with the cost of lower process
detrimental effects dispersing the hydrocarbon concen- productivity. The intermediate blowdown was also
tration profiles (higher axial dispersion due to higher reduced to improve the productivity and with almost
flow rates), and can be removed from the process. no effect in purity and recovery. This step has to be long
8828 Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005

enough to remove propane but short enough not to U ) global external heat transfer coefficient, W/m2‚K
desorb propylene. Different process temperatures and ui ) superficial velocity, m/s
feed pressures were evaluated. It was verified that xi ) adsorbed phase molar fraction of component i
better purities of propylene were obtained at lower yi ) molar fraction of component i in the gas phase
temperature (408 K) and lower feed pressure (250 kPa).
Greek Letters
Acknowledgment Rw ) ratio of internal surface area to volume of column
wall, m-1
The authors are thankful for financial support from Rwl ) ratio of logarithmic mean surface area of column shell
the Foundation for Science and Technology (FCT), to volume of column wall, m-1
Project POCTI/1999/EQU/32654. C.A.G acknowledges βeq ) equilibrium selectivity factor
FCT Grant SFRH/BD/11398/2002. This work is also part βsel ) kinetic selectivity factor calculated by eq 7.1
of the CYTED Project V.8 “Clean Technology for the Fg ) gas density, kg/m3
Separation of Light Olefins”. Fp ) adsorbent density, kg/m3
λ ) axial heat dispersion, W/m2‚K
Nomenclature (-∆Hi) ) heat of adsorption of component i, J/mol
c ) column void fraction
a′ ) area-to-volume ratio, m-1 p ) porosity of the pellet
ai ) number of neighboring sites occupied by component i τp ) pore tortuosity
Bii ) Biot number of component i µg ) gas viscosity, Pa‚s
Ci ) bulk molar concentration of component i in the gas
phase, mol/m3
〈ci〉 ) averaged concentration in the macropores for com- Literature Cited
ponent i, mol/m3
C̃p ) molar constant pressure specific heat of the gas (1) Eldridge, R. B. Olefin/paraffin separation technology: a
mixture, J/mol‚K review. Ind. Eng. Chem. Res. 1993, 32, 2208-2212.
C̃ps ) constant pressure specific heat of the adsorbent, J/kg‚ (2) Sircar, S. Pressure swing adsorption. Ind. Eng. Chem. Res.
K 2002, 41, 1389-1392.
Ĉpw ) specific heat of the column wall, J/kg‚K (3) Ruthven, D. M.; Farooq, S.; Knaebel, K. S. Pressure Swing
CT ) total gas concentration, mol/m3 Adsorption; VCH Publishers: New York, 1994.
C̃v ) molar constant volumetric specific heat of the gas (4) Yang, R. T. Adsorbents. Fundamentals and Applications;
John Wiley & Sons: New York, 2003.
mixture, J/mol‚K
(5) Cheng, L. S.; Padin, J.; Rege, S. U.; Wilson, S. T.; Yang,
C̃vi ) molar constant volumetric specific heat of component R. T. Process for purifying propylene. U.S. Patent 6,406,521,
i, J/mol‚K 2002.
Dax,i ) axial dispersion coefficient of component i, m2/s (6) Yang, R. T.; Padin, J.; Rege, S. U. Selective adsorption of
Dp,i ) pore diffusivity of component i, m2/s alkenes using supported metal compounds. U.S. Patent 6,423,881,
Dc,i ) crystal diffusivity of component i, m2/s 2001.

Dc,i ) infinite dilution crystal diffusivity of component i, (7) Cho, S. H.; Han, S. S.; Kim, J. N.; Choudary, N. V.; Kumar,
m2/s P.; Bhat, S. G. T. Adsorbents, method for the preparation and
∞ method for the separation of unsaturated hydrocarbons for gas
Dc,io ) infinite dilution crystal diffusivity of component i mixtures. U.S. Patent 6,315,816, 2001.
at infinite temperature, m2/s (8) Olson, D. H. Light hydrocarbon separation using 8-member
dp ) pellet diameter, m ring zeolites. U.S. Patent 6,488,741, 2002.
Keq,i ) adsorption constant of component i, 1/kPa (9) Reyes, S.; Krishnan, V. V.; De Martin, G. J.; Sinfelt, J. H.;
K°eq,i ) adsorption constant at limit T f ∞ for component Strohmaier, K. G.; Santiesteban, J. G. Separation of propylene
i, 1/kPa from hydrocarbon mixtures. International Patent WO 03/080548
hf ) film heat transfer coefficient between gas and solid A1, 2003.
phase, W/m2‚K (10) Kuznicki, S. M.; Bell, V. A. Olefin separation employing
hw ) film heat transfer coefficient between gas phase and ETS molecular sieves. U.S. Patent 6,517,611, 2003.
column wall, W/m2‚K (11) Choudary, N. V.; Kumar, P.; Puranik, V. R.; Bhat, S. G.
T. Adsorbents, method for the manufacture thereof and process
kf,i ) film mass transfer resistance, m/s for the separation of unsaturated hydrocarbons from gas mixture.
kg ) gas thermal conductivity, W/m‚K U.S. Patent Application US2003/0097933A1, 2003.
kg,ex ) thermal conductivity of gas surrounding the column, (12) Järvelin, H.; Fair, J. R. Adsorptive separation of propane-
W/m‚K propylene mixtures. Ind. Eng. Chem. Res. 1993, 32, 2201-
P ) total pressure, kPa 2207.
qi ) adsorbed phase concentration of component i, mol/kg (13) Da Silva, F. A.; Rodrigues, A. E. Propylene/propane
q/i ) equilibrium adsorbed phase concentration of compo- separation by VSA using commercial 13X zeolite pellets. AIChE
nent i, mol/kg J. 2001, 47, 341-357.
(14) Grande, C. A.; Silva, V. M. T. M.; Gigola, C.; Rodrigues,
〈qi〉 ) extrudate averaged adsorbed phase concentration, A. E. Adsorption of propane and propylene onto carbon molecular
mol/kg sieve. Carbon 2003, 41, 2533-2545.
qi ) crystal averaged adsorbed phase concentration, mol/ (15) Da Silva, F. A.; Rodrigues, A. E. Adsorption equilibria and
kg kinetics for propylene and propane over 13X and 4A zeolite pellets.
qmax,i ) saturation capacity of component i, mol/kg Ind. Eng. Chem. Res. 1999, 38, 2434-2438.
Rg ) ideal gas constant, 8.314 kJ/mol‚K (16) Padin, J.; Rege, S. U.; Yang, R. T.; Cheng, L. S. Molecular-
rc ) crystal radius, m sieve sorbents for kinetic separation of propane/propylene. Chem.
Eng. Sci. 2000, 55, 4525-4535.
tblow ) blowdown step time, s
(17) Ramachandran, R.; Dao, L. H.; Brooks, B. Method of
trinse ) rinse step time, s producing unsaturated hydrocarbons and separating the same
ttotal ) total cycle time, s from saturated hydrocarbons. U.S. Patent 5,365,011, 1994.
Tg ) temperature of the gas phase, K (18) Da Silva, F. A.; Rodrigues, A. E. Vacuum swing adsorption
Ts ) solid (extrudate) temperature, K for propylene/propane separation with 4A zeolite pellets. Ind. Eng.
Tw ) wall temperature, K Chem. Res. 2001, 40, 5758-5774.
Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005 8829

(19) Cheng, L. S.; Wilson, S. T. Vacuum swing adsorption (28) Ruthven, D. M. Principles of Adsorption and Adsorption
process for separating propylene from propane. U.S. Patent Processes; John Wiley & Sons: New York, 1984.
6,296,688, 2001. (29) Incropera, F. P.; Witt, D. P. D. Fundamentals of Heat and
(20) Grande, C. A.; Gigola, C. E.; Rodrigues, A. E. Propane- Mass Transfer, 4th ed.; John Wiley & Sons: New York, 1996.
propylene binary adsorption on zeolite 4A. Adsorption 2003, 9, (30) Bird, R. B.; Stewart, W. E.; Lightfoot, E. N. Transport
321-329. Phenomena, 2nd ed.; Wiley International: Singapore, 2002.
(21) Silva, J. A. C. Separation of n/iso-paraffins by adsorption (31) Ruthven, D. M. Short communication: diffusion of simple
process. Ph.D. Dissertation, University of Porto, Portugal, 1998. molecules in 4A zeolite. Adsorption 2001, 7, 301-304.
(22) Da Silva, F. A. Cyclic Adsorption processes: application (32) Cavenati, S.; Grande, C. A.; Rodrigues, A. E. Layered
to propane/propylene separation. Ph.D. Dissertation, University pressure swing adsorption for methane recovery from CH4/CO2/
of Porto, Portugal, 1999. N2 streams. Adsorption 2005, 11, 549-554.
(23) Wakao, N.; Funazkri, T. Effect of fluid dispersion coef- (33) Rege, S. U.; Yang, R. T. Propane/propylene separation by
ficients on particle-to-fluid mass transfer coefficients in packed pressure swing adsorption: sorbent comparison and multiplicity
beds. Chem. Eng. Sci. 1978, 33, 1375-1384. of cyclic steady states. Chem. Eng. Sci. 2002, 57, 1139-1149.
(24) Nitta, T.; Shigetomi, T.; Kuro-Oka, M.; Katayama, T. An (34) Sundaram, N.; Yang, R. T. On the pseudomultiplicity of
adsorption isotherm of multi-site occupancy model for homoge- pressure swing adsorption periodic states. Ind. Eng. Chem. Res.
neous surface. J. Chem. Eng. Jpn. 1984, 17, 39-45. 1998, 37, 154-158.
(25) Grande, C. A.; Rodrigues, A. E. Adsorption kinetics of
propane and propylene in zeolite 4A. Chem. Eng. Res. Des. 2005,
Received for review June 9, 2005
82, 1604-1612.
(26) Do, D. D. Adsorption Analysis: Equilibria and Kinetics;
Revised manuscript received August 30, 2005
Imperial College Press: London, 1998. Accepted September 15, 2005
(27) Rota, R.; Wankat, P. C. Intensification of pressure swing
adsorption processes. AIChE J. 1990, 36, 1299-1312. IE050671B