Separation and Purication Technology 73 (2010) 377390

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Separation and Purication Technology

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

Ethane/ethylene and propane/propylene separation in hybrid membrane

distillation systems: Optimization and economic analysis
Marzouk Benali , Bora Aydin 1
Natural Resources Canada, CanmetENERGY, 1615 Lionel-Boulet Blvd., Varennes, Quebec J3X 1S6, Canada

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

Article history: The combination of membrane and distillation processes to form a hybrid separation system is proposed
Received 16 September 2009 as an alternative design to replace the current distillation technology. The main objective of this work is
Received in revised form 27 April 2010 to scrutinize the feasibility of numerous hybrid membrane distillation (HMD) schemes through simula-
Accepted 28 April 2010
tion. Silver nitrate is used for modeling/simulation as membrane carriers at a concentration of 6 mol L1 .
Different congurations are suggested to obtain highest product (ethylene or propylene) purity. These
Keywords:
technologies are compared in terms of capital, operating and utility costs with the conventional C2- and
Multicomponent distillation
C3-splitters. For the ethane/ethylene separation, the membrane cascade system resulted in the highest
Ethylene
Propylene
ethylene purity. However the series conguration is more economical than the membrane cascade sys-
Hybrid system tem. For propane/propylene separation, the top conguration outperformed the conventional C3-splitter
Membrane separation and other HMD congurations in terms of propylene purity.
Economic analysis Crown Copyright 2010 Published by Elsevier B.V. All rights reserved.

1. Introduction streams include caustic scrubber efuent, dilution steam conden-

Ethylene (C2 H4 ) is one of the most important and one of the
largest volume petrochemicals produced in the world today. The
importance of ethylene is derived from the double bond in its
molecular structure making it reactive and industrially convert-
ible to a variety of intermediate and end products. It serves as the
principal building block of the petrochemical industry. Worldwide
demand for ethylene has grown steadily in the past and is expected
to reach 140 million tons per year by 2010. The ethylene produc-
tion system is very capital intensive; the capital cost is strongly
dependent on the nature of the feedstock. In an ethylene plant, the
feedstock is subjected to thermal cracking to produce a mixture
of hydrocarbons ranging from hydrogen and methane to gasoline
and heavier components. In general, the production of ethylene
generates liquid, gaseous and solid wastes that have to be man-
aged in a safe manner. The amounts and types of waste streams
depend on the type of hydrocarbon feedstock. The major waste
Abbreviations: CEPCI, Chemical Engineering Plant Cost Index; FT, facilitated
transport; HIDiC, heat integrated distillation column; ICIS, International Chemical
Information Service; M1, membrane 1; M2, membrane 2; PR, PengRobinson; SCDS,
simultaneous correction distillation column; SRK, SoaveRedlichKwong; VR, vapor
recompression.
Corresponding author. Tel.: +1 450 652 5533; fax: +1 450 652 5198.
E-mail addresses: mbenali@nrcan.gc.ca (M. Benali), B.Aydin@tudelft.nl
(B. Aydin).
1
Present address: Delft University of Technology, Process and Energy Laboratory,
Leeghwaterstraat 44, 2628 CA Delft, The Netherlands.
sate, coke and tare at the condensate separators, and system vent
gases during start-ups and shutdowns. The waste gas streams are
generally burned either in a furnace or in a are. The are is one
of the most important and expensive parts of the ethylene plant
facility, which has to be optimized. The optimization opportuni-
ties include design changes, product purity enhancement, energy
reduction, production capacity increase, by-products minimizing,
revamp economics, and reduction of greenhouse gases. Thermal
cracking of propane and/or ethane as feedstocks in the presence
of steam remains one of the most important and widely employed
processes for ethylene production, which consists basically of four
distinct processes, namely: thermal cracking and quenching, com-
pression and acid gas removal (i.e. H2 S, CO2 ), subcooling and
product separation, and refrigeration. Fig. 1 illustrates a block ow
diagram for a typical ethylene plant. The feedstocks are fed to a bank
of parallel pyrolysis furnaces. In the convection zone of the fur-
nace, the feed is preheated to about 600 C and is then diluted with
steam that reduces coking and improves product selectivity. In the
radiation zone of the furnace, the feedstocksteam mixture passes
through vertical coils where pyrolysis takes place at temperatures
above 600 C. At the exit of the cracking furnace, the outputs are
immediately quenched to about 350 C in a transfer-line exchanger
to stop reactions and recover the waste heat for steam generation.
The cracked gases are cooled to about 40 C in a water quench tower
to condense the heavy products (e.g. fuel oil) and most of the dilu-
tion steam. The cooled gases are then compressed to about 3.5 MPa
in four compression stages. Between the 1st and 3rd compression
stages, the gases are scrubbed with caustic gas to remove H2 S and

1383-5866/$ see front matter. Crown Copyright 2010 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2010.04.027
378 M. Benali, B. Aydin / Separation and Purication Technology 73 (2010) 377390

CO2 . After the 4th compression stage, the gases are cooled to about
Nomenclature 15 C with propylene refrigerant and dehydrated with molecular
sieves. The dried gases are cooled to low temperatures in a series
Ci concentration of component i (mol m3 ) of heat exchangers before they enter the separation section. The
D diffusion coefcient (m2 s1 ) bottoms of the primary and secondary deethanizers are carried to a
F feed ow rate (mol s1 ) depropanizer where C3 components are separated from the heavier
J ux (mol m2 s1 ) components (C4+). The secondary deethanizer overhead is hydro-
Keq equilibrium constant (m3 mol1 ) genated in a catalytic reactor (diameter and volume are 1.818 m
kH Henrys constant (mol m3 Pa1 ) and 5.094 m3 , respectively) to convert acetylene into ethylene. As
 thickness of membrane (m) described above, in the purication/separation subsystem of the
Mcut membrane module cut rate plant, ethylene is separated from its by-products via a sequence of
n molar ow rate (mol s1 ) fractionation steps. Among these steps, several require a cascade
P permeate ow rate (mol s1 ) of propylene/ethylene refrigeration loops. Propylene refrigerant is
p pressure (Pa) used in the chillingdemethanizer subsystem. When the relative
Pc critical pressure (Pa) volatility between the key components is less than 1.2, the sepa-
RR retentate in Eq. (7) (mol s1 ) ration process becomes difcult. Subsequently, the distillation in
R gas constant in Eqs. (16)(18) this case requires high-energy consumption, increased refrigera-
S membrane surface area (m2 ) tion capacity as well as an increased number of stages, leading
T temperature (K) obviously to enhanced capital and operating costs. About 70% of the
Tc critical temperature (K) required energy is consumed in the purication/separation subsys-
Tr reduced temperature tem. Therefore, any reduction in the refrigeration load will result in
V volume (m3 ) a signicant decrease of the operating cost of the propylene refrig-
xFi mole fraction of component i in the feed eration closed-cycle system as well as the entire plant. As stated in
xPi mole fraction of component i in the permeate the literature [1], ethane/ethylene, and propane/propylene separa-
xRi mole fraction of component i in the retentate tions are potential steps for an energy saving of 33% through hybrid
z membrane axis technologies involving both membranes and distillation processes.
The selection of the best technologies for separation of ethylene
Greek letters from ethane, and propylene from propane is therefore conse-
i/j separation factor quential to minimize plant energy consumption and capital cost.
porosity Different technologies were investigated to intensify the traditional
 tortuosity distillation processes. Ghosh et al. [2] investigated the potential
acentric factor (log(P/Pc )Tr =0.7 ) 1 of a hybrid adsorptiondistillation system for propane/propylene
separation. According to their ndings, although there is a reduc-
Subscripts tion in energy consumption there is a need for an innovative
c critical value adsorptiondesorption process or for adsorbents having high selec-
eq equilibrium tivity. Schmal et al. [3] compared a heat integrated distillation
se silverethylidene column (HIDiC) with a vapor recompression (VR) distillation col-
tot total umn. They found HIDiC to be 14% more economical than VR
in operating cost. Finally, membranes combined with distillation
columns were demonstrated in the literature [48] as a technolog-

Fig. 1. Block ow diagram of a typical ethylene plant.

 M. Benali, B. Aydin / Separation and Purication Technology 73 (2010) 377390 379

poses and, subsequently, releases C2 H4 in the permeate and the

carrier Ag+ , which is then returned to the membrane feed side. The
chemical equilibrium can be written as follows:

Ag+ + C2 H4  (Ag C2 H4 )+
complex (aq) (1)

The equilibrium constant is

[Ag C2 H+
4
] Cse
Keq = = (2)
[Ag+ ][C2 H4 ] CAg+ CC2 H4

The equilibrium constant of the silverethylidene ion formation

Fig. 2. Schematic diagram of the facilitated transport membrane system.
ical option to optimize the performance of hydrocarbon separation
and purication. In this work, membrane separations, which are
generally less energy-intensive than distillation processes, have
been considered as promising alternatives to enhance the purity of
ethylene and propylene as well as to reduce the capital and operat-
ing costs of separation processes. In general, such an approach can
be also applied for separation of various close-boiling hydrocarbons
mixtures as styrene/ethylbenzene, and styrene/xylene isomers.
has been evaluated by several authors [1618]. Obviously, such
a constant varies with the concentration of AgNO3 solution. For
a given temperature and concentration of AgNO3 , the higher the
C2 H4 pressure, the greater the amount of C2 H4 absorbed in the form
of the silverethylidene complex. On the other hand, for a given
concentration of AgNO3 , the lower the temperature, the greater
the amount of C2 H4 absorbed in the form of the silverethylidene
complex.
The total carrier concentration within the membrane module is
obtained from the following balance:
Ctot = CAg+ + Cse (3)

2. Methods and design of hybrid separation ow diagrams Combining Eqs. (2) and (3), the concentration can be calculated as
follows:
Membrane separation technologies have several advantages Keq CC2 H4 Ctot
over existing mass transfer processes including high selectivity, Cse = (4)
1 + (Keq CC2 H4 )
low energy consumption and simple design [8]. The hybrid mem-
brane processes can be designed in two different congurations: a By assuming that the equilibrium occurs at the feed side and the
membrane process combined with a conventional separation pro- permeate side, the boundary concentrations of silverethylidene
cess and a membrane process combined with another membrane ion are determined as a function of known boundary concentrations
process. of ethylene:
The combination of membrane and distillation technologies to
Keq CC2 H4 (z=0) Ctot
form a hybrid separation system is proposed as an alternative
Cse(z=0) = 1 + (Keq CC H
design to replace the current distillation technology. Facilitated 2 4(z=0)
)
(5)
transport (FT) membrane technology is used to design several
Keq CC2 H4 (z=) Ctot
hybrid membrane distillation (HMD) congurations studied in Cse(z=) =
1 + (Keq CC2 H4 (z=) )
this work. The appropriateness of FT membranes for ethylene
and propylene recovery has been proven in [1], and [913]. FT where CC2 H4 (z=0) and CC2 H4 (z=) correspond to the solubility of C2 H4
membranes involve carrier-mediated transportation in addition at the feed side and the permeate side, respectively. These boundary
to permeate physical dissolution and diffusion. The presence of concentrations are determined using Henrys law, expressing the
a carrier that can react reversibly with permeate results in high pressure effects on the solubility of a gas in a saturated solution:
selectivity and high permeability. There are two types of FT mem- 
CC2 H4 (z=0) = (kH )C2 H4 pC2 H4 (z=0)
branes: one is a mobile carrier membrane (liquid membrane) where (6)
CC2 H4 (z=) = (kH )C2 H4 pC2 H4 (z=)
the carrier can diffuse into the membrane; the other is a xed car-
rier membrane where the carrier is immobilized in the membrane
[14]. The main objective of the present work is to scrutinize the 2.2. Membrane model
feasibility of numerous HMD schemes. The hybrid congurations
differ in the location of the membrane relative to the distillation The membrane model is based on the following assumptions:
column. Top, parallel, bottom, top-bottom and series congura-
tions, along with a membrane cascade system with recycling and - Cross-ow along the permeate side of the membrane
without a distillation step are investigated. Agrawal [15] already - Plug ow along the feed side of the membrane
discussed different possible membrane cascade congurations to - Steady state process
separate multicomponent gaseous mixtures. These congurations - Isothermal operation
were drawn based on the analogy with multicomponent distillation - Instantaneous ethylene/silver reaction.
schemes. - The local permeate-side composition is a function only of the local
feed-side composition.
2.1. Properties and equations of FT membrane separation process
The cross-ow pattern is used along all HMD congurations.
Fig. 2 shows the general principle of an ethane (C2 H6 )/ethylene The permeate composition changes along the membrane length
(C2 H4 ) FT membrane system consisting of an aqueous solution of and it is not affected by the composition of any other point along
silver nitrate (AgNO3 ) transported by capillarity in a microporous the membrane side. It is only affected by the local ux at that point.
membrane. At high pressure, C2 H4 reacts with silver ion (Ag+ ) to The overall mass balance for a membrane module is:
form a complex component named silverethylidene ion, which 
F = P + RR
diffuses freely across the membrane. Once this complex reaches the (7)
FxFi = PxPi + RR xRi
opposite low pressure side of the membrane, the complex decom- R
380 M. Benali, B. Aydin / Separation and Purication Technology 73 (2010) 377390

The overall mass balance across a differential area of a membrane into CHEMCAD is based on the following sequence: load CHEMCAD,
module is given by put data into CHEMCAD and run, load data. The Visual Basic server
interface allows starting CHEMCAD, loading a simulation case, and
dn  n
= J = Ji (8) transferring information back and forth from Excel in an automated
dS fashion.
i=1

The component mass balance is therefore given by 2.3. Ethane/ethylene hybrid separation
Fi )
d(nx
= Ji (9) The HMD system may be arranged in several congurations.
dS
Operating conditions may be varied for each conguration in order
Fi
ndx xFi dn to achieve optimum performance. However, the concentration of
+ = JxPi (10)
dS dS silver nitrate is maintained constant at 6 mol L1 . A series con-
The combination of Eqs. (8) and (10) gives: guration is investigated in which two membranes in series are
followed by a distillation column. In addition, a membrane cascade
dxFi J i system is explored as an alternative to a conventional C2-splitter to
= (x xPi ) (11)
dS n F recover ethylene from ethane. Fig. 3 illustrates a two-stage mem-
In contrary to distillation, in which separation is based on thermo- brane cascade based on two single-stage compressors for recycling
dynamics, the separations are inherently based on rate of transport, and a multistage compressor required to compress the ethylene
i.e. they depend on diffusion. The basic ux across the membrane product to the desired pressure, as in the case of a conventional
is equal to the ux across a thin lm as proposed by Whitman [19]. C2-splitter. The fresh stream (208, coming from the demethanizer),
For ethylene, the ux ji becomes JC2 H4 , which is proportional to the composed of 75.66% C2 H4 , 12.61% C2 H6 , 8.58% C3 H6 , 1.34% C3 H8 ,
concentration gradient and obeys to Ficks law: 1.80% CH4 , and 0.01% C3 H4 enters at a pressure of 2.61 MPa and a
temperature of 28 C, and then is mixed with the recycled stream
DC2 H4 
JC2 H4 = CC2 H4 (z=0) CC2 H4 (z=) (12) (207 and thereafter is fed to the rst membrane (M1) at a pressure
 of 2.61 MPa and temperature of 31 C. In M1, the recycled ethane
The quantity C2 H4 / obviously corresponds to a mass transfer coef- is separated as the retentate and directed to the cracking reactor.
cient. Due to the microscopic properties of the membrane (i.e. The recovered ethylene is concentrated as permeate at a pressure
porosity and tortuosity of the pores) and considering the lm model of 0.83 MPa and directed, after a compression step, to the second
[19], this coefcient can be dened as follows: membrane M2 as a feed at a pressure of 1.34 MPa and a temperature
DC2 H4 DC2 H4 of 33 C. The entire amount of C3 H8 , C3 H6 , CH4 , and C3 H4 is recov-
(13) ered in the retentate (stream 201). Thus, the stream 212 contains
  
only 99.99% C2 H4 and 0.01% C2 H6 . High pure C2 H4 is therefore pro-
In the case of a FT membrane, the ux should include the transport duced in M2 at a permeate pressure of 0.10 MPa and a temperature
diffusion related to the silverethylidene ion. Eq. (12) becomes: of 20 C. The retentate of M2 is compressed from 1.34 to 2.62 MPa
DC2 H4  before being mixed with the fresh feed. The surface area of M1
JC2 H4 = CC2 H4 (z=0) CC2 H4 (z=) is obviously greater than the surface area of M2 since the highest
 
Dse  recovery of C2 H4 occurs in the rst separation stage. The ratio of
+ Cse(z=0) Cse(z=) (14) surface area of M2 to surface area of M1 has been varied from 0.10
 
to 0.80, and the optimal value is 0.40 corresponding to surface areas
Considering that the membrane separation feature is strongly of 3243 and 8150 m2 , respectively.
inuenced by the partition of the solute (i.e. C2 H4 ) between the Fig. 4 illustrates the series conguration of the hybrid system. In
membrane and the adjacent solution (i.e. AgNO3 ), substitution of this case, the fresh feed (3.50 MPa; 4 C) is rst ashed at a pres-
Eqs. (5) and (6) in Eq. (14) gives:
DC2 H4
  
pC2 H4 (z=0) pC2 H4 (z=)
JC2 H4 = (kH )C2 H4 pC2 H4 (z=0) pC2 H4 (z=)
 
For ethane, which does not react with silver ion, the ux is given
by:
DC2 H6
 
JC2 H6 = (kH )C2 H6 pC2 H6 (z=0) pC2 H6 (z=)
 
For C3 H6 /C3 H8 separation, similar equations can be written to cal-
culate the local composition of each component in the permeate
side. The physicochemical properties of ethylene and propylene in
an aqueous silver solution are summarized in Table 1.
The membrane porosity, also termed the membrane void vol-
ume, is an important parameter affecting the membrane ux.
Membranes with higher porosity exhibit greater surface area. The
membrane porosity usually lies between 30 and 85%. The mem-
brane tortuosity is the average length of the pores compared to
membrane thickness. It is in the order of 24. The thickness of the
FT membrane is 170 m and the ratio of porosity to the tortuos-
ity used for both C2 H4 /C2 H6 and C3 H6 /C3 H8 separation is 0.258.
Eqs. (8) and (11) are solved numerically. The composition of per-
meate as well as the ux of permeate are calculated from transport
equations (14) and (15). The numerical data are incorporated into
CHEMCAD [22] by using Excel Integration feature. The integration

Dse
+ Keq Ctot (kH )se (15)
  1 + [Keq (kH )C2 H4 pC2 H4 (z=0) ] 1 + [Keq (kH )C2 H4 pC2 H4 (z=) ]
(16) sure of 2.61 MPa to reach a temperature of 16 C required to be
sent to two membranes in series. For optimal membrane cut rates
of 0.99 and 0.90, respectively for M1 and M2, the heat duties of
exchangers 102 and 103 are0.67 and 8.46 MW, respectively. In
case of series conguration, the permeate (stream 107) of mem-
brane M1 contains 78.08% C2 H4 , 7.86% C2 H6 , 10.29% C3 H6 , 1.60%
C3 H8 , 2.16% CH4 , and 0.01% C3 H4 while the permeate (stream 108)
of membrane M2 contains only 99.99% C2 H4 and 0.01% C2 H6 . The
resulting permeate is recovered as ethylene product and the reten-
tate leaves the second membrane at a pressure of 0.66 MPa and a
temperature of 50 C, and sent as the feed to the distillation column.
A high pressure difference is required to provide an enhanced driv-
ing force as well as a high feed concentration to produce high purity
ethylene product. The feed to the rst membrane stage comes from
the bottom of the demethanizer and ashes to a moderate pressure
before entering the membrane. The refrigeration load associated
with the feed stream is exchanged with other process streams to
minimize the overall quantity of propylene refrigerant used in the
 M. Benali, B. Aydin / Separation and Purication Technology 73 (2010) 377390 381

Table 1
Physicochemical properties of components involved in a membrane module.

Component Diffusivity (m2 s1 ) Chemical equilibrium constant (m3 mol1 ) Henrys constant (mol m3 Pa1 )
9
C2 H4 1.87 10 [20] 5.61 105 [present work]
C2 H6 2.39 105 [present work]
(AgC2 H4 )+ 1.13 109 [present work] 0.129 [present work]
Ag+ 1.66 109 [20]
C3 H6 1.63 109 [21] 6.17 105 [present work]
C3 H8 1.61 109 [21] 2.15 105 [present work]
(AgC3 H6 )+ 1.06 109 [21] 0.100 [present work]

Fig. 3. Two-stage membrane cascade system for ethane/ethylene separation.

plant. The feed temperature to the membrane system is set to main-
tain the membrane operation above the freezing point of the silver
nitrate solution. The feed from the rst stage is concentrated by
removing part of the recycled ethane as a retentate. The feed is then
directed to the second membrane where the separation yields a
high purity ethylene product. The retentate from the second mem-
brane is directed to a low pressure column while high pressure
distillation column is used in the conventional C2-splitter. The key
benets of such a conguration are downsizing the column, reduc-
ing the condenser duty, and minimizing the amount of refrigerant.

Fig. 4. Hybrid membrane distillation series conguration for ethane/ethylene separation.

382 M. Benali, B. Aydin / Separation and Purication Technology 73 (2010) 377390
Table 2
Design details of the conventional C3-splitter (two columns in parallel).
Column 1
Number of trays 115
Tray efciency 0.85
Column diameter (m) 5.30
Column pressure (MPa) 1.64
Column reux ratio 20.33
The diameter of the distillation column and the number of stages
are reduced by 67.0% and 78.7%, respectively, in comparison to a
conventional C2-splitter system.
2.4. Propane/propylene hybrid separation
Four different congurations were tested
propane/propylene separation: top, parallel, bottom and top-
bottom. The concentration of silver nitrate is 6 mol L1 . The
membrane can be located at the top of the distillation column
(Fig. 5). In this case, the membrane performs the nal purication.
The overhead of distillation column is fed to the membrane at
1.64 MPa and a temperature of 40 C. The retentate is recycled
and fed at the middle of the distillation column at a pressure of
1.66 MPa and a temperature of 48 C while the permeate pressure
is 0.10 MPa. The pressure drop along the feed side of the membrane
is assumed negligible. The membrane may also be combined with
the distillation column in a parallel conguration (Fig. 6). In
such a conguration, the membrane feed stream is withdrawn
from one of the intermediate stages of the distillation column,
more specically at the 40th stage. The permeate and retentate
streams leaving the membrane are compressed and fed back
to the distillation column at 20th and 60th stages, respectively.
These two streams enter the distillation column where the stream
composition is the same as the tray composition. In the bottom
conguration, the membrane performs the nal purication of the
propane sent from the distillation column (Fig. 7). Refrigerant is
required to cool the permeate to its dew point before entering the
distillation column. This conguration differs from the top one in
that a larger amount of refrigerant is required for the permeate
condenser. The feed to the membrane is a saturated liquid. Fig. 8
illustrates the top-bottom conguration in which one membrane
is located at the top of the distillation column while another one
is located at the bottom of the column. The optimal conditions
of top-bottom HMD conguration corresponds to the permeate
pressure set at 0.34 MPa for the top membrane and 1.66 MPa for
the bottom membrane. The separation within the top membrane is
in gas permeation as the membrane feed is a saturated vapor. The
bottom membrane is operated in a pervaporation mode since the
membrane feed is a saturated liquid. After a compression step, the
retentate of top membrane is fed at the 10th stage (1.67 MPa; 44 C)
of the distillation column while the permeate of bottom is fed at
the 2nd stage (1.09 MPa; 159 C). In all HMD systems associated
with C3 H6 /C3 H8 separation, the diameter of the distillation column
is kept the same (i.e. 5.30 m) as in the conventional C3-splitter for
retrot purpose whereas it is reduced by 25.7% for design purpose
of a new plant.
For all congurations, the fresh feed stream entering the hybrid
separation system is obviously the same as the one of the conven-
tional C3-splitter and is composed of 73.37% C3 H6 , 14.83% C3 H8 ,
0.03% C2 H6 , 0.20% C2 H2 , 1.80% CH4 , and 0.01% C3 H4 , 7.89% 1,3-
C4 H6 , 1.64% 1,-C4 H8 , 0.11% n-C4 H10 , and 1.92% i-C4 H10 . The design
details of the conventional C3-splitter are given in Table 2. Each
hybrid system has its distinctive minimum reux ratio. Two main
membrane features have a signicant effect on the selectivity and
the ux rate: silver nitrate concentration and permeate pressure.
For the top conguration, the surface area of membrane was varied
from 100 to 1000 m2 whereas the for bottom and parallel congu-
Column 2 rations it was ranged from 400 to 4000 m2 . The optimal values are
90 given in Table 5 for each HMD system.
0.85
5.30 2.5. Separation factor of membrane module
1.72
507.51
The parameter to describe the separation efciency for
ethane/ethylene, and propane/propylene mixtures fed to the mem-
brane is the separation factor, i/j , which is also called the selectivity
factor of the membrane. It can be formulated as below:
xiP /xjP
i/j = (17)
xiF /xjF
The membrane module cut rate is one of the major independent
variables for HMD systems. In practical terms, this variable repre-
for
sents the ratio of how much permeate is recovered per unit feed
to the membrane module. There is always a trade-off between the
purity and the ow rate of permeate and retentate streams. For a
given membrane module cut rate, the ow patterns have a signi-
cant effect on the degree of separation as well as on the membrane
area required to do so. When a perfect mixing is assumed on both
sides of the membrane module, the degree of separation decreases
with an increase of the membrane module cut rate. For the cross-
ow, as considered in the present work, the feed ows through the
upstream of membrane surface in plug ow with no longitudinal
mixing. There is no ow of permeate along the membrane surface.
Thus, the degree of separation increases very slightly (in the order
of magnitude of 210%) at low membrane module cut rate (typi-
cally 0 i/j 0.5). As i/j  0.5, the degree of separation increases
signicantly.
3. Results and discussion
The distillation column is simulated with CHEMCAD using
the simultaneous correction distillation (SCDS) column type
and SoaveRedlichKwong (SRK) state equation. SCDS is mainly
designed to simulate non-ideal K-value chemical systems. It cal-
culates the derivatives of each equation rigorously, including the
derivative of K-value with respect to composition (K/X) ( ) term,
which is signicant in chemical system simulation. The equations
related to SRK model are given as follows:
RT a
p= 2 (18)
V b V + bV
where
2
R2 Tc2 [1 + f (1 Tr0.5 )]
a = 0.42748 (19)
pc
RTc
b = 0.08664 (20)
pc
f = 0.48 + 1.574 0.1762 (21)
The simulation and optimization of the HMD system use two lim-
iting permeate pressures of 0.10 and 0.34 MPa. The lower value of
0.10 MPa provides high selectivity which minimizes the membrane
area required by the HMD system. However, the compression duty
was observed to increase when 0.10 MPa was selected as a per-
meate pressure. Contrarily, the compressor duty load decreased
with the upper permeate pressure limit (0.34 MPa). On the other
hand, lower selectivity (due to lower compressor load) leads to
increased membrane area. The economic performance of various
membrane hybrid congurations and membrane cascade system
has been assessed and compared to an ethylene production plant
with a yearly throughput of 500,000 metric-tons.
 M. Benali, B. Aydin / Separation and Purication Technology 73 (2010) 377390 383

Fig. 5. Top hybrid conguration for propane/propylene separation.

3.1. HMD system analysis Table 3

Comparison of the design specications of the conventional C2-splitter and series
conguration hybrid systems.
3.1.1. Ethane/ethylene separation
HMD systems are characterized by smaller equipment siz- Parameters Conventional Series conguration
C2-splitter hybrid system
ing and relatively low operating cost. As seen in Table 3, for
the series conguration hybrid system, the number of columns, Number of columns 2 1
number of trays and column diameter are lower than in conven- Number of trays per column 94 40
Tray efciency 0.85 0.85
tional C2-splitters. This results in a lower operating pressure and
Column diameter (m) 4.545 1.500
higher reux ratio. The optimal conguration could be dened Column pressure (MPa) 2.00 0.65
as producing the desired component at the highest purity and Column reux ratio 0.09 1.38
lowest operation cost. As explained in detail in the next section, Product purity 0.9965 0.9979

Fig. 6. Parallel hybrid conguration for propane/propylene separation.

384 M. Benali, B. Aydin / Separation and Purication Technology 73 (2010) 377390

Fig. 7. Bottom hybrid conguration for propane/propylene separation.

high product purity could be obtained with HMD systems at a
lower cost in comparison to the conventional C2-splitter cong-
uration.
Fig. 9 shows the effect of membrane module cut rate on the
ow rate of C2 H4 in the product and recovery lines (stream 113)
for the series conguration. In all HMD and membrane cascade sys-
tems, the membrane module cut rate is dened as the ratio of the
permeate to the membrane feed ow rate. The ow rate in the
product line increases with the increasing module cut rate of the
rst membrane at constant module cut rate of the second mem-
brane. At constant module cut rate of the rst membrane the effect
of the module cut rate of the second membrane on the ow rate
of C2 H4 in product line is minor. Higher module cut rate signi-
es higher amount of C2 H4 in the permeate (stream 107) of the
rst membrane. Thus, higher amount of C2 H4 is sent to the prod-
uct line via the permeate of the second membrane. In the recovery
line, the ow rate of C2 H4 decreases with the module cut rate of
the rst and second membrane. A minor effect of the module cut
rate on the recovery line is observed for the second membrane at
the cut rate values higher than 0.7. However the second membrane
should be operated at a membrane module cut rate of 0.9 to achieve
maximum throughput of C2 H4 in the product line. Fig. 10 shows
the effect of the membrane module cut rate on the separation fac-
tor for the series conguration. The membrane module cut rate is
expressed as the ratio of the permeate ow rate to the feed ow
rate. The mole fractions of C2 H4 and C2 H6 in the permeate and feed
were calculated for each membrane module cut rate to determine
the separation factor, which is directly proportional to the mole
fraction of C2 H4 in the permeate, i.e. enrichment of C2 H4 . The sepa-
ration factor increases linearly with the membrane module cut rate
for both membranes. High separation factor values for the second
membrane can be essentially explained with higher mole fraction

Fig. 8. Top-bottom hybrid conguration for propane/propylene separation.

 M. Benali, B. Aydin / Separation and Purication Technology 73 (2010) 377390 385

Fig. 9. Effect of rst membrane module cut rate (on the ow rate of C2 H4 in the
product and recovery lines for the series conguration.

Fig. 11. Inuence of membrane module cut rate of (a) rst membrane and (b) second
membrane on the ow rate of C2 H4 in the product and recovery lines for the cascade
system.

Fig. 10. Membrane module cut rate versus separation factor for the series.

of C2 H4 and lower mole fraction of C2 H6 in the permeate (stream

108) of the second membrane.
The effect of membrane module cut rate on the ow rate of
C2 H4 in the product and recovery lines (stream 212) for the cas-
cade system is shown in Fig. 11(a) and (b). The ow rate of C2 H4
in the permeate of the rst membrane increases with its module
cut rate. The permeate of the rst membrane (stream 202) is fed to
the second membrane and then it is sent to the product line via the
permeate of the second membrane (stream 210). At a given module
cut rate of the second membrane the ow rate of C2 H4 in the prod-
uct line increases with the module cut rate of the rst membrane
(Fig. 11a). Additionally the ow rate of C2 H4 in the product line Fig. 12. Membrane module cut rate versus separation factor for the cascade system.

increases with the module cut rate of the second membrane due to
higher ow rate of C2 H4 in the permeate. In the recovery line the
ow rate decreases abruptly with the membrane module cut rate
for both membranes. For the optimum module cut rate of the sec-
ond membrane (0.90), an increase in the module cut rate of the rst
membrane from 0.45 to 0.76 leads to a decrease of 99.7% of C2 H4
in the recovery line (Fig. 11b). Similarly for the second membrane;
an increase of the module cut rate from 0.50 to 0.90 results in a
decrease of 85.3% of C2 H4 in the recovery line which conrms the
separation efciency of both membranes. Fig. 12 shows the effect
of the membrane module cut rate on the separation factor for the
cascade system. The separation factor increases linearly with the
membrane module cut rate for both membranes. The mole fraction
of C2 H4 in the permeate increases while the mole fraction of C2 H6
in the permeate decreases with the increasing membrane module
cut rate. Higher separation factor values for the rst membrane are
due to lower mole fraction of C2 H4 and higher mole fraction of C2 H6
in the feed (stream 209) of the rst membrane.
The effect of membrane module cut rate on the total actual
compressor power and heat exchanger duty for the series cong-
uration is illustrated in Fig. 13. The heat exchanger duty increases
with increasingly membrane module cut rate for both membranes
where the actual compressor power decreases with the membrane
module cut rate. The effect of membrane module cut rate on the
actual compressor power is more pronounced for the second mem-
brane.
Fig. 14 shows the inuence of the membrane module cut rate on
the total actual compressor power and heat exchanger duty for the
cascade system. The actual compressor power and heat exchanger
duty increase when the membrane module cut rate increases for
both membranes where the effect of the membrane module cut
386 M. Benali, B. Aydin / Separation and Purication Technology 73 (2010) 377390

Fig. 13. Effect of rst membrane module cut rate (a) and second membrane module Fig. 15. Inuence of membrane module cut rate on the ow rate of C3 H6 in the
cut rate (b) on the actual compressor power and heat exchanger duty for the series product and recovery lines for top conguration.
conguration.

Fig. 14. Effect of rst membrane module cut rate on the actual compressor power
and heat exchanger duty for the cascade system. Fig. 16. The ow rate of C3 H6 in the product and recovery lines for different mem-
brane module cut rate values of bottom conguration.

rate is more pronounced for the rst membrane. The signicant

increase of the total actual compressor power and heat exchanger
duty is essentially due to the increase of 42.1% in the power of the
compressor 208 and the duty of the heat exchanger 209 located
on the product line (stream 212). Similar analysis for the second
membrane shows that the increase in the compressor power and
the heat exchanger duty is 24.3%. The corresponding increase of the
ow rate of C2 H4 in the permeate is 24.3%.

3.1.2. Propane/propylene separation

A systematic analysis as above was performed for the
propane/propylene separation. The composition of the product and
recovery lines as well as compressor and heat exchanger duties
were investigated for all HMD congurations at different mem-
brane module cut rate values.
Fig. 15 shows the inuence of membrane module cut rate on the
ow rate of C3 H6 in the product and recovery lines (streams 109 and
102, respectively) for the top conguration. The ow rate increases
with increasing membrane module cut rate. The overhead of the
distillation column is the feed of the membrane. The ow rate of
C3 H6 depends only on the membrane selectivity which could be
given as an explanation for the linear relation between the C3 H6
ow rate and membrane module cut rate.
As shown in Fig. 16, the ow rate of C3 H6 in the product line
(stream 206) increases whereas C3 H6 ow rate in the recovery line
(stream 203) decreases sharply with membrane module cut rate
for bottom HMD conguration. The bottoms of the distillation unit
is fed to the membrane of which separation efciency is measured
by the amount of C3 H6 recovered and recycled to the distillation
Fig. 17. The ow rate of C3 H6 in the product and recovery lines for different mem-
brane module cut rate values of parallel conguration.
column through the permeate of the membrane (stream 204). As
the membrane module cut rate increases, higher ow rate of C3 H6
in the permeate is obtained, which results in the decrease of C3 H6
ow rate in the recovery line by 98.5%. The permeate stream 204 is
obviously recycled to a stage in C3-splitter where the composition
is the same as that of permeate.
Fig. 17 exhibits the effect of membrane module cut rate on the
ow rate of C3 H6 in the product and recovery lines (streams 308
and 309 respectively) for the parallel conguration. It is clearly
indicated that the membrane module cut rate does not affect sig-
 M. Benali, B. Aydin / Separation and Purication Technology 73 (2010) 377390 387

Fig. 19. Membrane module cut rate versus separation factor for top, parallel and
top-bottom congurations.

Fig. 18. Effect of rst membrane module cut rate (a) and second membrane module
cut rate (b) on the ow rate of C3 H6 in the product and recovery lines for top-bottom
conguration.

nicantly the amount of C3 H6 in the product and recovery lines:

Fig. 20. Effect of membrane module cut rate on the compressor power and heat
the increase of the membrane module cut rate from 0.49 to 0.78
exchanger duty for top conguration.
results in only an increase of 0.34% and 0.87% for the product and
recovery lines respectively. The minimum number of stages occurs
when the membrane feed composition is close to the composition
of C3-splitter feed stage.
Fig. 18a and b depicts the effect of membrane module cut rate on
the ow rate of C3 H6 in the product and recovery lines (streams 410
and 403 respectively) for the top-bottom HMD conguration. The
ow rate in the product and recovery lines increases with increas-
ing membrane module cut rate for the rst membrane (Fig. 18a).
However the ow rate of C3 H6 in the recovery line is very low and
the increase is inconsequential. C3 H6 is sent to the product line
via the permeate stream of the rst membrane (stream 407). Thus,
C3 H6 ow rate in this permeate increases with the module cut rate
of the rst membrane. The ow rate of C3 H6 in the product line
increases and it decreases in the recovery line with increasingly
membrane module cut rate for the second membrane (Fig. 18b),
which favours the recycle of C3 H6 to the distillation column. The
permeate stream 404; whose composition is proportional to the
membrane module cut rate, is fed to the 2nd stage of the distilla- Fig. 21. Compressor power vs. membrane module cut rate for bottom conguration.
tion column. As most C3 H6 is sent to the column via permeate, the
ow rate of C3 H6 in the recovery line decreases as membrane mod- aration factor values for the top-bottom conguration are higher
ule cut rate increases to maximize the yield of the polymer grade than that for the top conguration. This conrms the separation
propylene. efciency of the membrane placed at the top of the column for the
The effect of the membrane module cut rate on the separation top-bottom conguration.
factor for top, parallel and top-bottom congurations is shown in The effect of membrane module cut rate on the actual com-
Fig. 19. The separation factor values for the top-bottom congu- pressor power and heat exchanger duty for different HMD
ration belongs to the membrane placed at the top of the column. congurations is illustrated in Figs. 2023. For the top cong-
It should be indicated that the similar separation factor values for uration, the actual compressor power and heat exchanger duty
top and parallel congurations does not result from similar mole augment with membrane module cut rate (Fig. 20). Higher mem-
fraction values of C2 H4 and C2 H6 in the permeate and feed. The sep- brane module cut rate results in a higher C3 H6 concentration in the
388 M. Benali, B. Aydin / Separation and Purication Technology 73 (2010) 377390
Fig. 22. Effect of membrane module cut rate on the total actual power and heat
exchanger duty for parallel conguration.
Fig. 23. Effect of rst membrane module cut rate on the actual compressor power
and heat exchanger duty for top-bottom conguration.
permeate. The increase in the total actual compressor power is due
to increase in the actual power of the compressor located in the
product line (equipment 105). For an increase of the membrane
module cut rate from 0.54 to 0.85 the compressor actual power
increases by 35.21% whereas the heat exchanger duty increases,
due to higher C3 H6 ow rate in the permeate (stream 106), by 15.6%.
As seen in Fig. 21, the actual compressor power increases with
the increase in membrane module cut rate for the bottom congu-
ration. Fig. 22 shows the effect of membrane module cut rate on the
total actual power of the compressor and heat exchanger duty for
the parallel conguration. The actual power decreases by 79.58%
increasing membrane module cut rate in contrast with the heat
exchanger duty which increases by 36.0%. The substantial decrease
in the total actual power is mainly explained by the tremendous
decrease of 88.7% in the actual power of the compressor 305 located
on the retentate line as the membrane module cut rate increases
from 0.49 to 0.78.
The effect of the membrane module cut rate on the total actual
compressor power and heat exchanger duty for the top-bottom
conguration is shown in Fig. 23. The actual compressor power
and heat exchanger duty increase with the membrane module cut
rate for the rst membrane. The ow rate of C3 H6 in the per-
meate increases with increasing rst membrane module cut rate.
Obviously, higher compression power (equipment 405) and heat
exchanger duty (equipment 406) is required for higher ow rate of
C3 H6 . The power and duty values are increasing function of mem-
brane module cut rate for the second membrane. The permeate of
the second membrane is composed of C3 H6 . As all C3 H6 coming
from the bottoms of the column should be recycled to the col-
umn via the permeate of the second membrane; higher membrane
module cut rate relatively higher ow rate of C3 H6 requires higher
compressor power and heat exchanger duty.
3.1.3. Economic analysis
For ethane/ethylene separation with the membrane cascade
system, ethylene purity of 0.9999 is obtained and the cost saving is
found to be 54.41%. For the series conguration a purity of 0.9979
and a cost saving of 61.45% are found (Table 4). The saving is for-
mulated as the ratio of total investment cost difference between a
hybrid conguration and a conventional column to the total invest-
ment cost of a conventional column. The expression for the total
investment cost is given below:
Total investment cost = Capital cost + Operating cost + Utility cost (22)
where
Capital cost = 1.82 Installed cost (23)
Operating cost = 0.20 Installed cost (24)
The installed cost was calculated with CHEMCAD by introducing
January 2009 Chemical Engineering Plant Cost Index (CEPCI). The
cost estimation calculation is based on the area of the equipment.
A rigorous costing routine was dened by the Parser programming
language for each equipment separately. Capital and operating
costs were calculated based on the denitions given by Douglas
[23]. The utility cost consists of electricity and steam prices for each
separation system. The cost of ethylene and propylene considered
in this work are 1.65 and 1.85 $ kg1 (2008-basis), respectively. The
prices of these two products were taken from the ICIS (Interna-
tional Chemical Information Service) database [24]. The membrane
module cost was taken as 215 $ m2 including all related elements.
The membrane replacement cost was assumed to be 95 $ m2 for a
lifetime of 3 years.
The comparison of the HMD systems with the conventional C2-
splitter is given in detail in Table 4. As mentioned above, the main
objective of the HMD system is to obtain the desired product at
high purity and low cost. For the series conguration, the purity of
ethylene is 0.9979 and the cost savings is 61.45%. The membrane
module cut rates are of 0.93 and 0.01 for M1 and M2, respectively.
For the membrane cascade, the purity of ethylene is enhanced to
0.9999 with membrane module cut rates of 0.75 and 0.90 for M1
and M2, respectively. Even though the total cost savings favours
the series conguration, the higher purity of ethylene is obtained
with the membrane cascade, showing a cost saving of 54.41%. Thus,
for a grass root design, the membrane cascade conguration can be
considered as the best alternative conguration to the conventional
C2-splitter. On the other hand, it cannot be recommended for a
retrot of an existing plant since its integration will be costly. One of
the disadvantages of series and membrane cascade congurations
is, however, that more compression duty is required for ethylene
product. In comparison to a conventional C2-splitter, the utility cost
is 2 times and 4 times higher for membrane cascade and the series
congurations respectively.
For propane/propylene separation, different HMD congura-
tions were compared with two columns in series. For a given HMD
conguration, the effect of the number of stages on the product
purity and the capital cost was analyzed. High propylene purity was
obtained for the simulation of a column with 90 and 100 stages. The
difference in the propylene purity between 90 and 100 is negligi-
ble, and 90 was selected as the optimum number of stages for all
HMD systems. The top conguration results in a propylene purity
of 0.9996 and a saving of 29.84% (Table 5). For the top-bottom con-
guration, propylene purity and saving were found to be 0.9985
and 36.57%, respectively. For bottom and parallel congurations,
the propylene purity is only 0.924. The top-bottom HMD system
Table 4
Ethane/ethylene separation: cost comparison.

Conguration Ethylene purity Membrane area (m2 ) Separation factor Capital cost (US$) 106 Operating cost (US$) 106 Utility cost (US$) 106 Total savings (%)

Series 0.9979 M1: 8150 M2: 890 M1: 1.92 M2: 99.92 7.88 0.87 1.86 61.45%
Membrane cascade 0.9999 M1: 8150 M2: 3243 M1: 998.98M2: 1.80 10.48 1.15 0.92 54.41%

M. Benali, B. Aydin / Separation and Purication Technology 73 (2010) 377390

Conventional C2-splitter 0.9950 24.4 2.7 0.5

Table 5
Propane/propylene separation: cost comparison for retrot purpose.

Conguration Distillation column Propylene purity Membrane area (m2 ) Separation Factor Capital cost (US$) 106 Operating cost (US$) 106 Utility cost (US$) 106 Total investment
cost savings (%)

Diameter (m) Number of trays

Top 5.30 90 0.9996 182 4.92 26.01 2.86 3.41 29.84

Bottom 5.30 90 0.9245 790 25.98 2.86 3.35 30.03
Top-bottom 5.30 90 0.9985 Top: 346Bottom: 527 19.70 23.11 2.54 3.53 36.57

Parallel 5.30 90 0.9239 2086 4.93 26.32 2.89 3.52 28.84

152 0.9948 3652 32.58 3.58 4.79 10.98

Conventional C3-splitter 5.30 205 0.9815 37.8 4.2 4.00

389
390 M. Benali, B. Aydin / Separation and Purication Technology 73 (2010) 377390
is the optimum hybrid system for propane/propylene separation
to obtain propylene at high purity with a remarkable cost saving
at optimal surface areas of 346 and 527 m2 for top and bottom
membranes, respectively. In case of designing a new plant inte-
grating top-bottom HMD system, the internal diameter of the 90
stages distillation column can be reduced from 5.30 to 3.94 com-
bined with two membranes having the same surface areas. Based on
these specications, the estimated savings are 53.64%, which makes
such HMD very competitive than two-stage distillation system for
C3 H6 /C3 H8 separation/purication.
As seen in Table 5 parallel conguration is the optimum design
in terms of the total investment cost saving for propane/propylene
separation. However, the product purity is low for this suggested
conguration. For higher propylene purity (0.99), a hybrid sys-
tem with a distillation column of more than 90 trays, should
be used. Similar conguration was presented by Kookos [25] in
which a distillation column having a diameter of 3.30 m and 250
trays including the condenser and reboiler combined with a mem-
brane of 2245 m2 was suggested to obtain a propylene purity
of 0.99. A 17.1% of total cost savings were obtained with the
hybrid system in comparison to a single column of 248 trays
including the condenser and reboiler and 3.86 m in diameter
[25]. The major savings were resulted from the cut in steam
cost.
In the present work a comparison was done between a hybrid
system with a distillation column of 90 trays and a FT membrane
of 2086 m2 , and a hybrid system with a column of 152 trays for
parallel conguration with a FT membrane of 3652 m2 (Table 5). A
propylene purity of 0.9948 was obtained by using a parallel hybrid
system with a column of 152 trays yielding total cost savings of
10.98% in comparison to conventional C3-splitter composed of two
columns having 115 and 90 stages. The product purity and total cost
saving for top-bottom conguration is close to the parallel cong-
uration involving a distillation column of 152 trays. However, the
utility cost is increased by 26.3% in comparison to the top-bottom
conguration.
4. Concluding remarks
For high product purity and incremented both energy and eco-
nomic savings, the HMD system is proposed as an alternative design
to replace current distillation technology. FT membrane technology
is clearly a favourable option for the intensication of C2 H4 /C2 H6
and C3 H6 /C3 H8 separation/purication. Different hybrid congu-
rations were compared with conventional C2- and C3-splitters for
ethane/ethylene and propane/propylene separation, respectively.
To obtain high product purity at relatively low cost, the membrane
cascade system is proposed as the optimum conguration for a
new ethane/ethylene separation plant. This is achieved at increased
membrane requirements corresponding to higher the utility cost
by 45.6% in comparison with conventional C2-splitter. However,
the separation of C2 H4 from a multicomponent mixture composed
of CH4 (1.80%), C2 H4 (75.66%), C2 H6 (12.61%), C3 H8 (1.34%), and
C3 H6 (8.58%), can be efciently achieved in the membrane cascade
scheme providing ultra-high purity (99.99%) as well as high yield
of C2 H4 . Such two-stage membrane cascade integrated with three
compressors can provide a competitive solution than the multi-
stage distillation of such a multicomponent mixture. HMD series
conguration is found to be suitable for the retrot of an ethylene
plant. The top-bottom HMD system is proposed as the preferred
design for propane/propylene separation from propylene purity
and yield point of view even though the total savings are slightly
favourable for parallel HMD system
Acknowledgements
The authors acknowledge the nancial support provided by the
Program of Energy Research and Development of Natural Resources
Canada. The authors note their gratitude to Chemstations for the
discussions with their technical support.
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