Microporous and Mesoporous Materials 132 (2010) 311–318

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Microporous and Mesoporous Materials

journal homepage: www.elsevier.com/locate/micromeso

SAPO-34 assisted C3 separation: Modeling and simulation

K. Agarwal a, M. John b, S. Pai b, B.L. Newalkar b, R. Bhargava a,*, N.V. Choudary b,**
a
Chemical Engineering Department, Indian Institute of Technology, Roorkee 247 667, India
b
Corporate R&D Centre, Bharat Petroleum Corporation Limited, Plot 2A, Udyog Kendra, Greater Noida 201 306, India

a r t i c l e i n f o a b s t r a c t

Article history: Chabazite (CHA) framework type SAPO-34 molecular sieve has been synthesized and its C3 (propane/pro-
Received 11 June 2009 pylene) uptake potential was evaluated in the temperature range of 303–323 K by measuring equilibrium
Received in revised form 21 January 2010 and kinetic adsorption data using volumetric/gravimetric adsorption measurement technique. The mea-
Accepted 28 February 2010
sured data were analyzed by Langmuir–Freundlich isotherm model and Crank’s equation respectively to
Available online 12 March 2010
estimate adsorption capacities, diffusivities and diffusion activation energies for C3 hydrocarbons. The
estimated diffusivity data suggested a high kinetic selectivity for propylene over propane on SAPO-34
Keywords:
framework. A Wicke-Kallenbach cell for propane/propylene separation over SAPO-34 membrane was
SAPO-34
C3 adsorption
modeled, validated and used to investigate the effect of feed pressure, and composition on the selectivity
Diffusion of propylene over propane at 303 K. This model was further extended to simulate the performance of
Modeling SAPO-34 tubular membrane for C3 separation for its practical utility. Based on the obtained results,
SAPO-34 is found to be a potential candidate for kinetic separation of C3 mixtures at near ambient
conditions.
Ó 2010 Elsevier Inc. All rights reserved.

1. Introduction development of selective adsorbent [4]. The designing of highly

Separation of low boiling mixtures, such as propane/propylene
having relative volatility close to unity is usually performed via
an energy intensive cryogenic distillation process using large num-
ber of contacting stages. Such process is commonly practiced in
petrochemical complexes world wide to produce chemical grade
(Purity > 95%+) and polymer grade (Purity > 99.5%) olefins [1].
The ongoing demand for propylene based polymers and petro-
chemicals is not only expected to lead to higher productions but
also expected to lead to commissioning of new distillation units
in future leading to huge capital investments and operating costs
to practice existing cryogenic distillation process for light olefin
separation [2,3]. Such scenario emphasizes the need for energy
efficient process for olefin/paraffin separation. In view of this,
development of alternate separation methods based on adsorption,
absorption, membrane separation, hybrid processes and reactive
distillation for light olefin/paraffin separation has gained prime
importance in recent years.
Among the potential alternate separation methods, light olefin
separation by means of selective adsorption has been judged to
be the least energy intensive operation. However, such method is
often limited by performance of adsorbents and hence demands
* Corresponding author. Tel.: +91 01332 285382; fax: +91 01332 276535.
** Corresponding author. Tel.: +91 0120 234118; fax: +91 0120 2354172.
E-mail addresses: ravibfch@iitr.ernet.in (R. Bhargava), choudarynv@bharatpe-
troleum.in (N.V. Choudary).
selective adsorbent system has been a focus of research for last
two decades.
Recent advances in molecular sieve synthesis have added impe-
tus to the development of adsorptive separation process for light
olefin separation. Thus, small pore molecular sieves namely
DD3R, Si–CHA, AlPO-14, ZSM-58, ITQ-3, ITQ-12 [5–8] have been
exploited to achieve propane/propylene separation based on the
differential diffusion behavior of propane and propylene, respec-
tively. Among these molecular sieves, DD3R, Si–CHA frameworks
are reported to have higher selectivity for propylene over propane
whereas ITQ-12 is reported to have infinite selectivity for propyl-
ene. In spite of excellent propylene selectivity, their practicality
is still a question as they are very expensive and extremely difficult
to synthesize. Thus, it is utmost important to investigate the
adsorptive potential of small pore molecular sieves which are easy
to synthesize and scale up. In this context, SAPO-34/AlPO-34, with
chabazite framework characteristics can be judged as ideal candi-
dates as their pore dimensions are closer to Si–CHA [9] which in
turn could offer higher diffusional constraint to propane leading
to better selectivity for propylene. However, synthesis of AlPO-34
framework demands use of F media which is corrosive in nature
[10]. This may limit its scale up. On the other hand, synthesis of
SAPO-34 framework is performed in the absence of F media but
demands high silica content in the gel for favouring the crystalliza-
tion of silico-aluminophosphate based CHA framework as synthe-
sis with low Si/Al ratio is difficult [11]. This in turn would result
into framework acidity which is expected to have detrimental

1387-1811/$ - see front matter Ó 2010 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2010.02.024
312 K. Agarwal et al. / Microporous and Mesoporous Materials 132 (2010) 311–318
Nomenclature
A membrane area (m2)
dT tube diameter (m)
F feed flow rate (mol/s)
Fij flow rate of ith component from jth grid (ml/min)
MR retentate flow rate (mol/s)
Pin feed side constant pressure (Pa)
fx mole fraction of C3 in feed
N1, N2 flux of C3 and C3 across the membrane (mol m2 s1),
respectively
P1r, P2r, Psr partial pressure of C3,C3 and inert gas on feed side
(Pa), respectively
X1r, X2r mole fraction of C3, C3 in retentate stream
S sweep gas flow rate (mol/s)
V cell volume (m3)
MP permeate Flow rate (mol/s)
Po sweep side constant pressure, (Pa)
P1p, P2p, Psp partial pressures (Pa) of C3, C3 and sweep in perme-
ate, respectively
X1p, X2p mole fraction of C3, C3 in permeate stream
[C] matrix of thermodynamic factors
effect in terms of coke formation at high temperature operations.
In view of this, it is imperative to evaluate SAPO-34 framework
for light olefin separation at near ambient conditions to counter
the problems related to framework acidity.
Thus, the present study aims at exploring the adsorptive poten-
tial of SAPO-34 (CHA) framework for separation of propane/propyl-
ene mixture. Here, chabazite (CHA) framework type, SAPO-34
molecular sieve was synthesized by templating silica, alumina
and phosphate precursors (silica sol, pseudoboehmite, ortho-phos-
phoric acid, respectively) using diethyl amine (DEA) as structure
directing agent at 473 K and its sorption potential is evaluated
for C3 hydrocarbons (propane/propylene) in the temperature range
303–323 K so as to avoid olefin polymerization at higher tempera-
tures due to framework acidity. The experimental data was ana-
lyzed using Langmuir–Freundlich isotherm model to estimate
adsorption parameters. Similarly, diffusivities of propane and pro-
pylene; activation energies for diffusion and selectivity for pro-
pane/propylene mixture adsorption are estimated using Crank’s
equation. Based on the estimated data, a transient model for
SAPO-34 membrane assisted C3 separation using Wicke-Kallen-
bach cell has been developed and validated. The system was sim-
ulated using estimated adsorption parameters to investigate the
effect of operating parameters such as feed pressure, and composi-
tion on the selectivity of propylene over propane over SAPO-34
framework at 303 K. Furthermore, the developed model was ex-
tended to a steady state tubular membrane which could be applied
for zeroing on scale up parameters.
2. Experimental
2.1. Synthesis
The reactive gel consisting of a molar composition 1.0Al2O3:0.8-
P2O5:0.6SiO2:2.0DEA:50H2O was prepared by mixing requisite
amounts of DEA, (99%, Merck), ortho-phosphoric acid (99%, Merck),
pseudoboehmite alumina (Catapal, 70.7% Sasol) and silica sol (Lu-
dox 30%, Sigma Aldrich) respectively. The gel thus obtained was
subjected to hydrothermal treatment for 16 h at 473 K [12]. Thus,
crystallized sample was washed, dried and finally calcined at
813 K in air.
mt mass adsorbed at time t (g)
m0 initial mass (g)
m1 mass at equilibrium loading at a particular sorbate con-
centration (g)
N is total molar flow rate (mol s-1 m2)
r crystal radius (m)
—
D surface diffusivity of i species (m2s1)
—
Dij binary diffusivity coefficient (m2s1)
D diffusivity (m2s1)
Do diffusivity pre-exponential factor (m2s1)
deq equivalent diameter (m)
hi is loading of ith component (mmol/g)
q zeolite density (kgm3)
q is the amount adsorbed at pressure given pressure
qsat
i is saturation loading of ith component
b interaction parameter (Langmuir and Freundlich con-
stant)
n heterogeneity parameter (Langmuir and Freundlich
constant)
(note: C3 refers to propane, C3 refers to propylene)
2.2. Characterization
X-ray diffraction pattern was recorded using a Philips X’pert
powder diffractometer system with CuKa radiation with a 0.02o
step size and 1s step time over the range 5o < 2h < 40o.
The morphology of the sample was investigated by means of
scanning electron microscope (SEM, Vega II-TSU, TESCAN, USA).
The textural properties of the samples were evaluated using
nitrogen adsorption/desorption measurements with an Autosorb-
1C (Quantachrome) unit. Nitrogen adsorption/desorption iso-
therms were measured at 77 K after degassing samples below
103 torr at 573 K for 4 h.
Temperature programmed desorption (TPD) of ammonia (NH3)
experiment was carried out with AMI 200 equipment (Alta Mira).
The sample was activated at 873 K (10 K/min) for 30 min under
20 ml/min of Helium and subsequently saturated with ammonia
at 383 K. The measurement of desorbed NH3 was performed from
383 to 1273 K (10 K/min) under Helium (40 ml/min).
The BET specific surface area (SBET) was estimated using adsorp-
tion data as per the ASTM method 4365 applicable for microporous
solids. The total pore volume, Vt, was estimated from the amount
adsorbed at a relative pressure of about 0.95 (with respect to P0 va-
lue of 1 atm).
2.3. Adsorption isotherm and diffusivity measurements
Adsorption isotherms for propane and propylene were mea-
sured up to 1 atm using volumetric adsorption measurement tech-
nique in the temperature range of 303–323 K. Data obtained were
analyzed using Langmuir–Freundlich isotherm model as described
elsewhere [13]. Likewise, the uptake profile of propane and propyl-
ene was measured by adopting gravimetric uptake measurement
technique using Cahn electromicrobalance system. The diffusivity
was estimated using transient diffusion equation (Eq. (1)), assum-
ing spherical geometry [14]. The equation was solved for D/r2, by
minimizing the residuals of D/r2 using nonlinear least square
method.
mt  m0 1
6 X 1
 2 2 
n p Dt
¼1 2 exp  ð1Þ
m1  m0 p n¼1 n2 r2
 K. Agarwal et al. / Microporous and Mesoporous Materials 132 (2010) 311–318 313

Based on the estimated diffusivity coefficient, binary diffusivity  Initial condition: t = 0

for propane/propylene mixture was calculated using Vignes rela- X 1r ¼ 0; X 2r ¼ 0; X 1p ¼ 0; X 2p ¼ 0 ðsystem initially filled with an
tionship (Eq. (2)). inert gasÞ
Pin ¼ 86—244 kPa;Po  86 kPa
hi   hj  Boundary Condition
Dij ¼ ½—
— Di hiþhj D—j hiþhj ð2Þ fx ¼ 0:1—0:9; F ¼ 20 ml=min; S ¼ 20 ml=min; 2Pin ¼ 86—244 kPa;
Po  86 kPa

2.4. Adsorption modeling and simulation for SAPO-34 membrane
A mathematical model was developed to evaluate the separa-
tion potential of SAPO-34 membrane. Firstly, a Wicke-Kallenbach
cell, which is conventionally used for experimental determination
of diffusive transport properties of components through mem-
branes, was simulated for estimating the membrane selectivity
and understanding the transient characteristics of the separation
process. Like wise, efficacy of a tubular membrane for C3 separa-
tion was studied by simulating its steady state profile.
2.4.1. Wicke-Kallenbach Cell Model
Adsorptive potential for SAPO-34 membrane to achieve pro-
pane/propylene separation was evaluated using Wicke-Kallenbach
cell model by solving Maxwell–Stefan’s (M–S) equations [15–19]
and adopting following assumptions:
Algorithm, as reported elsewhere [20], was used to solve the
equations listed in Table 1. Thus developed model was validated
with data elsewhere [19].
2.4.3. Tubular membrane model
Tubular membrane system was modeled for counter current
operation wherein feed was introduced to tube side and sweep
gas through outer shell. Assumptions and the flux equations for
mass transport in Wicke-Kallenbach cell were applied in solving
for the tubular membrane as well. To solve the system, the whole
membrane was divided into grids and the pressure at each grid is
calculated for the permeate and retentate side, respectively. Pres-
sure drop for a grid point was calculated by applying a mechanical
energy balance for a compressible gas [21] as per Eq. (3).
dp f ðMN2 RTPÞ
¼ 2   ð3Þ
dl dT A2 P2  MN2 RT
in

where, f is the friction factor given as

1. Intra-crystalline diffusion is the rate determining step and mass
transport occurs by configurational diffusion.
2. Maxwell–Stefan diffusivity is independent of loading.
3. Equilibrium adsorption occurs in the pores at both sides of the
membrane.
4. Langmuir–Freundlich parameters as obtained for the crystal are
same for the membrane.
5. Heat effects during adsorption are negligible.
6. Membrane is crack free and pressure drop across the support is
negligible.
7. Perfect mixing of components on both sides of the membrane.
8. Absence of back permeation of the inert gas.
Note. Mole fraction of propane/propylene in the permeate cell is
assumed to be variable and its contribution is taken in the flux cal-
culations across the membrane.
1
f ¼ 0:008ðdeq Þ3 ð4Þ
Thus, the system was divided into n number of grids with each grid
of length dl (dl = l/n, l is the membrane length) on both retentate
and permeate side, and solved for steady state, solving mass balance
equation (Table 2) across each grid iteratively. These set of equa-
tions were solved using an iterative procedure, as mentioned else-
where [20].
3. Results and discussion
The adsorptive potential of synthesized SAPO-34 molecular
sieve for C3 separation has been evaluated via modeling and sim-
ulation approach. The obtained results for SAPO-34 characteriza-
tion, C3 adsorption and membrane simulation for C3 separation
are discussed in the following sections.

2.4.2. Model equations 3.1. Characterization of SAPO-34

The mass balances and the M–S flux equations used for the
present system are reported in Table 1. The measured X-ray diffraction patterns for as-synthesized and
The initial and boundary conditions employed to solve the mod- calcined SAPO-34 samples are shown in Fig. 1 and are found to be
el equations are as follows: in good agreement with those reported in literature [22]. Upon

Table 1
Equations employed for solving transient Wicke-Kallenbach cell.

Component Retentate side Permeate Side

Propane dP1r
¼ RTðFfx  MR X 1r  N 1 AÞ=V dP 1p
¼ RTðN 1 A  M P X 1P Þ=V
dt dt
Propylene dP2r
¼ RTðFð1  fxÞ  MR X 2r  N 2A Þ=V dP 2p
¼ RTðN 2 A  M P X 2P Þ=V
dt dt
Inert gas dPsr
¼ RTM R ð1  X 1r  X 2r Þ=V dP sp
¼ RTðS  M P ð1  X 1p  X 2P ÞÞ=V
dt dt
Total pressure P in ¼ P 1r þ P 2r þ P sr Po ¼ P1p þ P2p þ Psp
Exit flows MR ¼ F  ðN 1 þ N 2 ÞA MP ¼ S þ ðN1 þ N2 ÞA
Flux of C3
hn o n o i
—
D —
D
qsat
1
—
D1 2
D ðC11 þC21 Þ rh1 þ C12 þh1 —
C11 þh1 — 2
D ðC12 þC22 Þ rh2
12 12
N 1 ¼ q —
D
1 2 —
D
D þh1 —
h2—
12D þ1 12


Flux of C3
hn o n o i
—1
D —
D
qsat
2
—
D2 C22 þh2 —
D12 ðC22 þC12 Þ rh2 þ C21 þh2 — 1
D ðC21 þC11 Þ rh1
12
N 2 ¼ q —
D1
h2 —
D2
—12 þh1
D
—
D12 þ1
314 K. Agarwal et al. / Microporous and Mesoporous Materials 132 (2010) 311–318

Table 2
Propane, propylene mass balance equations for retentate and permeate side of tubular membrane.

Grid Propane(retentate) Propylene(retentate) Propane(permeate) Propylene(permeate)

1 F11-F10 = -N112pr dl F21-F20 = -N212pr dl S11-S10 = -N112pr dl S21-S20 = -N212pr dl
2 F12-F11 = -N122pr dl F22-F21 = -N222pr dl S12-S11 = -N122pr dl S22-S21 = -N222pr dl
j F1j-F1(j-1) = -N1(j-1)2pr dl F2j-F2(j-1) = -N2(j-1)2pr dl S1j-S1(j-1) = -N1(j-1)2pr dl S2j-S2(j-1) = -N2(j-1)2pr dl
N F1n-F1(n-1) = -N1(n-1)2pr dl F2n-F2(n-1) = -N2(n-1)2pr dl S1n-S1(n-1) = -N1(n-1)2pr dl S2n-S2(n-1) = -N2(n-1)2pr dl

comparison with as-synthesized pattern, the calcined pattern dis- Estimated Langmuir–Freundlich parameters are compiled in
plays marked difference in peak intensities which in turn suggest Table 3.
relaxation of SAPO-34 framework to more symmetrical hexagonal A high value of ‘b’ for propylene over propane (Table 3) suggests
unit cell that is typical of CHA framework. Likewise, cubic-like strong interaction of propylene with SAPO-34 framework. This is
rhombohedral morphology (Fig. 2) of the prepared sample is found due to the fact that propylene, having a double bond, has greater
to be consistent with the reported one [12]. The measured textural dispersive interactions, and may even undergo electrostatic inter-
properties namely pore volume of 0.24 cm3/g and BET surface area
of 506 m2/g are also found to be in good agreement with the liter-
ature data [22]. Furthermore, NH3 TPD measurement of the pre-
pared sample displayed the presence of about 0.5 mmol/g acid
sites.

3.2. Propane/propylene adsorption isotherms

Fig. 3a and b display the measured adsorption isotherms for

propane and propylene, respectively in the temperature range of
303–323 K. It is interesting to note that equilibrium loading for
propane increases with an increase in temperature (Fig 3a)
whereas, a decrease in equilibrium loading is observed for propyl-
ene (Fig 3b). This signifies that equilibrium uptake capacity for pro-
pane over SAPO-34 is limited by diffusion whereas propylene
adsorption capacity is governed by equilibrium driven process un-
der experimental conditions. In order to reinforce the above argu-
ment, SAPO-34 sample is subjected to direct uptake measurements
using gravimetric adsorption measurement technique. A direct
correspondence is found in the isotherms measured by volumetric
and gravimetric measurement experiments.
The measured data is fitted to Langmuir–Freundlich (L–F) iso-
therm model as measured data is found to be well represented
by Langmuir–Freundlich isotherm model with correlation coeffi-
cient of >0.98 for both gases. L–F isotherm is represented by fol-
lowing equation.
n
bp
q ¼ qsat n where n < 1 ð5Þ
1 þ bp Fig. 2. SEM Morphology of SAPO-34.

Fig. 1. X-ray diffraction pattern for (a) as-synthesized and (b) calcined SAPO-34. Fig. 3a. Adsorption Isotherm for propane over SAPO-34 at 303, 323, and 343 K.
 K. Agarwal et al. / Microporous and Mesoporous Materials 132 (2010) 311–318
Fig. 3b. Adsorption Isotherm for propylene over SAPO-34 at 303, 313, and 323 K.
Table 3
Estimated Langmuir–Freundlich Parameters for propane and propylene at 303 K.
Property Propane
qsat (mmol/g) 3.12*
bi (Pa1) 9.34e6
n 0.905
*
As the propane adsorption is diffusion limited, the qsat for propane is estimated
based on its liquid packing density using the procedure described by Li et al. [9].
actions with SAPO-34 framework. Such trend is further reinforced
in terms of surface heterogeneity as it is evident from lower value
of ‘n’ for propylene over SAPO-34 framework (Table 3). The pres-
ence of surface heterogeneity over SAPO-34 framework is due to
silica incorporation in CHA cages resulting into polar framework
leading to strong interaction of propylene which has higher dipole
moment compared to propane.
3.3. Diffusivity estimation
Fig. 4 shows the differential diffusional behavior of propane and
propylene over SAPO-34 surface. The estimated D/r2 (reciprocal of
characteristic diffusion time scale) values are compiled in Table 4
and are compared with other potential materials reported for ki-
netic separation of propane/propylene mixture (Table 4). Based
on the comparison of diffusivity ratio, SAPO-34 having a diffusivity
ratio of around 18,000 can be judged as a potential candidate for C3
separation. Lower diffusivity values for C3 hydrocarbon can be
attributed to smaller channel size of SAPO-34 (3.8  4.3 Å) [23],
however, the same is found to increase with an increase in temper-
ature which in turn lowers the diffusivity ratio for propane and
Fig. 4. Uptake profile of propane/propylene on SAPO-34 at 50 torr and 303 K.
315
propylene. As the diffusivity is a function of activation energy, acti-
vation energies were estimated (Eact) for propane/propylene diffu-
sion by fitting Arrhenius type relationship and are reported in
Table 5.
Based on the obtained results, it is imperative that SAPO-34
molecular sieve can be exploited for propane/propylene separation
at lower temperatures by taking advantage of diffusional constraint
offered to propane molecules by the framework. However, strong
adsorption of propylene over propane could limit its ease of desorp-
tion from SAPO-34 framework under experimental conditions. In
order to address such problem, it is utmost important to derive
optimized conditions for effective propane/propylene separation.
In view of the above, attempts are made to model and simulate
binary component permeation through SAPO-34 membrane at
303 K, using experimentally determined adsorption and diffusion
parameters.
3.4. Simulation of Wicke-Kallenbach cell
The simulation experiments are performed as per following
Propylene
conditions.
2.25
5.588e2
0.338 Feed and sweep gas flow rate 20 ml/min
Feed/permeate cell pressure 86–244 kPa
Thickness of SAPO-34 1 lm
Density of SAPO-34 1800 kg/m3
Feed composition 25–90 mol% propane
(i.e. 75–10 mol% of propylene)
Membrane surface area 17.34  104 m2
Cell volume 5.2022e5 m3
The above system is simulated varying retentate side total pressure
and feed composition to study the effect of operating variables.
Thus obtained results are discussed in the following section. This
model has been verified using the analytical solution of permeation
as reported elsewhere [19].
3.4.1. Transient behavior
3.4.1.1. Effect of pressure gradient. The effect of pressure gradient,
maintained across the membrane is simulated for equimolar feed
composition by varying feed side pressure while keeping permeate
side pressure at 86 kPa. Figs. 5 and 6 display the effect of pressure
gradient on the transient state fluxes of propane and propylene,
respectively. It is found that with an increase in the feed pressure,
propane flux (Fig. 5) is found to increase whereas propylene flux
showed a reverse behavior (Fig. 6). The steady state is noticed in
all the cases within less than 50 s and the highest propylene flux
estimated for an equimolar feed is found to be 0.5625 g m2 h1
(3.72e6 mol m2 s1) as compared to corresponding propane flux
of 7.6e6 g m2 h1 (0.48e10 mol m2 s1). Interestingly, propyl-
ene showed transient flux maxima, this could be attributed to the
large difference in the propane and propylene diffusivities. Thus,
mole fraction of propane on feed side is expected to increase with
time leading to decrease of number of sites occupied by propylene
by displacing them. It is evident from the adsorption isotherm that
propylene saturation occurs at lower pressures; consequently any
increase in pressure does not contribute towards increase in load-
ing while propane loading tends to increase with pressure hence, it
brings down the flux of propylene to a lower, steady state value.
Thus, it is imperative that the maxima correspond to the point at
which propane displaces propylene molecules from the membrane
surface which is indeed observed (Fig. 6).
3.4.1.2. Effect of propane mole fraction. The effect of propane molar
composition of the feed stream is evaluated by varying propane
316 K. Agarwal et al. / Microporous and Mesoporous Materials 132 (2010) 311–318

Table 4
Comparison of D/r2values for propane and propylene on various 8-membered ring structures.

Zeolite Temperature (°C) Propylene D/r2 (s1) Propane D/r2 (s1) Diffusivity ratio of propylene to propane
ITQ-12 [7] 80 5.6e2 2.0e8 2,800,000
Si–CHA [6] 30 4.6e4 1e8 46,000
80 1.5e3 7.6e7 1970
SAPO-34 30 2.16e5 1.19e9 18,085
[Our work] 40 2.58e5 1.46e9 17,634
50 3.25e5 2.31e9 14,024
ITQ-3 [6] 30 1.5e3 2.2e6 690
45 3.8e3 7.4e6 510
ZSM-58 [6] 30 1.2E4 9.6E9 12,400
80 2.6E4 1.8E7 1410

Table 5 composition while maintaining feed/sweep gas pressure of 244/

Activation Energy and Do (pre-exponential factor) for Propane/Propylene over SAPO-
86 kPa, respectively, and its effect is observed on the steady state
34.
performance of the membrane. Thus, propane flux (Fig. 7) is
Property Propane Propylene found to increase with an increase in propane mole fraction in
Eact (kJ/mol) 11.71 7.22 feed whereas propylene flux (Fig. 8) is found to decrease with
Do (m2/s) 3.93e7 4.83e6 an increase in propane mole fraction. Furthermore, significant
Regression coefficient 0.944 0.991
maxima for transient flux value at lower propylene mole fraction
are noticed (Fig. 8). This may be due to higher interaction of pro-
pylene with SAPO-34 framework even at its lower partial pres-
sure. Such behavior can lead higher surface concentration of
propylene at initial period which gets reduced as the steady
state is reached. Thus, for higher propane concentration, there
is a momentary regime when propylene surface concentration
is much higher than that of propane corresponding to the flux
maxima. On the other hand at lower propane concentration, pro-
pylene surface coverage remains significantly higher and contin-
ues to increase until steady state is attained, hence flux maxima
peak, even if exists, is only marginally higher than the steady
state flux value.
The steady state behavior of SAPO-34 membrane is simulated
against feed pressure and its composition. Based on the simulation
results, variation of propylene selectivity as function of total pres-
sure and feed composition is simulated (Fig. 9). Propylene selectiv-
ity showed maxima of about 80,000 at about 0.3 mol fraction of
propane thus indicating higher separation efficiency of SAPO-34
membrane for C3 feed containing 30% propane under steady state
conditions at 303 K, 244/86 kPa pressure on feed and sweep gas
Fig. 5. Transient propane flux variation with pressure gradient maintained across
the membrane. side, respectively.

Fig. 6. Transient propylene flux variation with pressure gradient maintained across
the membrane. Fig. 7. Transient propane flux variation with propane mole fraction.
 K. Agarwal et al. / Microporous and Mesoporous Materials 132 (2010) 311–318 317

3.5. Simulation of tubular membrane

A steady state tubular membrane simulation is performed to

optimize operating conditions for C3 separation using SAPO-34
membrane. Thus, the system was simulated for the following phys-
ical dimensions of the membrane.

Length of the membrane: 0.25 m

Internal/external diameter of membrane: 0.007/0.01 m
Internal diameter of the membrane housing: 0.015 m
Feed/sweep gas flow rates: 1 ml/min

Fig. 8. Transient propylene flux variation with propane mole fraction.
Such trend of selectivity maxima, wherein selectivity is defined
as ratio of fluxes to ratio of mole fraction in feed, is due to two
counter effects namely an increase in propylene/propane flux ratio
and decrease in propane/propylene mole ratio with an increase in
propylene mole fraction.
Figs. 10 and 11 show the steady state fluxes, for the variation in the
feed pressure and composition of the system, respectively. An in-
crease in propane flux and a decrease in propylene flux are observed
in both the cases. As tubular membrane could be approximated as a
series of connected cells, the net flux across the membrane tends to
follow a similar pattern as seen in the case of Wicke-Kallenbach cell.
Fig. 12 shows the variation in the propylene selectivity with compo-
sition at different feed pressures. A maxima is observed in the selec-
tivity on varying feed composition whereas, selectivity decreases
monotonically with increase in pressure. The observed maximum
in the selectivity is seen to shift its position depending on feed
and sweep gas side pressure. In view of this, the feed side and
sweep gas side pressures could be adjusted using the model so as
to obtain maximum propylene selectivity. However, in this case it
is evident that it’s ideal to operate system at lower operating pres-
sure so as to have maximum selectivity.

Propane Mole Fraction

0 0.2 0.4 0.6 0.8 1
9.00E+04 3.10E+04

7.50E+04 3.05E+04
3.00E+04
Selectivity

Selectivity
6.00E+04
2.95E+04
4.50E+04
2.90E+04
3.00E+04
2.85E+04
1.50E+04 Pressure 2.80E+04
Mole Fraction
0.00E+00 2.75E+04
0 100 200 300 400 500 600
Pressure (KPa)

Fig. 9. Variation of selectivity with feed pressure and feed composition.

1.00E-06 6.00E-11
Propylene Flux(mol/m /s)

5.00E-11
Propane Flux(mol/m /s)

8.00E-07
2

4.00E-11
6.00E-07
3.00E-11
4.00E-07
2.00E-11

2.00E-07
Propylene Propane 1.00E-11

0.00E+00 0.00E+00
0 100 200 300 400 500 600
Pressure(KPa)

Fig. 10. Variation of steady state fluxes with variation in feed pressure.
318 K. Agarwal et al. / Microporous and Mesoporous Materials 132 (2010) 311–318

0 0.2 0.4 0.6 0.8 1

1.40E-06 8.00E-11

Propylene Flux (mol/m2/s)

1.20E-06 Propylene Propane 7.00E-11

Propane Flux (mol/m2/s)

6.00E-11
1.00E-06
5.00E-11
8.00E-07
4.00E-11
6.00E-07
3.00E-11
4.00E-07
2.00E-11
2.00E-07 1.00E-11
0.00E+00 0.00E+00
0 0.2 0.4 0.6 0.8 1
Propane Mole Fraction

Fig. 11. Variation of steady state fluxes with propane mole fraction.

tively. On the other hand, for a tubular membrane a shift in the

4.50E+04 Pin-244KPa,Po-86KPa Pin-220KPa,Po-86KPa
selectivity maxima position is seen on varying feed and sweep
Pin-200KPa,Po-86KPa gas side pressure.

4.00E+04 Acknowledgements
Selectivity

One of the authors (K.A.) thanks Bharat Petroleum Corporation

3.50E+04 Limited (BPCL) for financial assistance. The authors (M.J., S.P., B.L.N,
N.V.C.) express their sincere thanks to R&D management of BPCL
for permitting us to publish these results.
3.00E+04
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