AIChE Paper 140E

Abstract # 293884
Stable Facilitated Transport Membrane for Olefin/Paraffin Separation

Ali A. Hamza
Process Engineering Manager
Imtex Membranes Corp.

I. Glenn Towe
President and CEO
Imtex Membranes Corp.

Majid Keyvani
Consulting Researcher
LyondellBasell Industries


Prepared for Presentation at the 25
th
Ethylene Producers Conference
San Antonio, Texas, April 29 May 2, 2013


AIChE and EPC shall not be responsible for statements or opinions contained in papers or
printed in its publications














Stable Facilitated Transport Membrane for Olefin/Paraffin Separation
Ali A. Hamza
Process Engineering Manager
Imtex Membranes Corp.
I. Glenn Towe
President and CEO
Imtex Membranes Corp.
Majid Keyvani
Consulting Researcher
LyondellBasell Industries


Abstract: Commercial scale separation of olefins (ethylene, propylene and butene(s)) from
paraffins (ethane, propane and butane(s)) in the petrochemical industry is accomplished
almost exclusively by distillation and is considered highly energy and capital intensive.
Consequently, there is an enormous economic incentive to explore alternative separation
technologies with lower energy consumption and an opportunity to achieve related reductions
in environmental impact from air pollutant and GHG emissions. There is also a major push at
many facilities to increase production output significantly without incurring the capital expense
of duplicating conventional process equipment. Several attempts have been made in the past
to develop alternative separation technologies, including significant work on facilitated
transport membranes. One of the main unresolved challenges was membrane instability over
time. Imtex Membranes Corp. has developed a membrane that has shown performance
stability over thousands of hours of operation on both coupons and larger area spiral wound
membrane elements. Imtex membranes are based on Chitosan, a natural polysaccharide
material, and silver nitrate as a facilitation agent. LyondellBasell Industries and Imtex
Membrane Corp. have undertaken a collaborative effort to evaluate the performance of Imtex
membranes in olefin/paraffin separation. The performance results were very encouraging for
C
2
, C
3
and C
4
splitter applications as greater than 99.5% purity was achieved in all cases. The
technology presents potential opportunities in upgrading refinery grade propylene to polymer
grade propylene as the membrane was evaluated under operating conditions comparable to
those of commercial plants. There is also a promising potential for butene/butane separations
where distillation separations require large numbers of trays and extremely high reflux ratios,
or are difficult to achieve at all. Applying Imtex membranes in C4 separation can have a very
positive impact on the economics of olefin metathesis, an increasingly important source of
propylene.
Introduction and Background

Olefin and Polyolefin production is a hundred billion dollar business globally. For many
decades, distillation has been the separation process for recovery of purified olefins from
mixtures with their respective paraffins. A recent DOE (Department of Energy) study [1]
indicated distillation operations account for 95% of the total separation energy used in the
refinery and chemical processing industries with 40,000 distillation columns operating in over
200 different processes. Another study stated that olefin production is the single most energy
consuming process in the chemical industry. The breakdown of the specific energy
consumption shows that 30% of the total yearly energy consumption is associated with
separation processes and 80% of that energy is utilized for olefin/paraffin separation [2]. This
large energy requirement provides an incentive to improve the energy efficiency in
olefin/paraffin separation. Furthermore, due to the difficulty of achieving these separations,
the distillation columns are often very tall, involving many trays, leading to high capital costs
for the equipment.
In light of the importance of olefin/paraffin separations, and because of the energy and
capital costs associated with distillation, alternative technologies continue to be the focus of
industry studies. Some recent literature [3,4] describe the current status of research. Reactive
absorption where silver or copper salts are used to extract the olefin from bulk gas in an
absorber/stripper type process is cited as a promising new technique. Union Carbide and
BP/Stone and Webster have taken this type of process to the pilot plant stage. Other
processes that have been evaluated include extractive distillation and molecular sieves [5].
However, despite the efforts, a viable alternative to conventional distillation has yet to be
developed.
One of the most thorough research studies in this subject area was carried by a DOE
sponsored program led by Membrane Technology and Research, Inc. (MTR), partnered with
SRI International and ABB Lummus Global [6]. The research focused on solid polymer
electrolyte membranes. Extensive testing was based on a polyether-polyamide block
copolymer (Pebax 2533) doped with Silver tetrafluoroborate (AgBF
4
) as a facilitation salt.
Other polymers that were examined included polyethylene oxide (PEO), polyvinyl pyrrolidone
(PVP) and poly(1-trimethylsilyl-1-propyne) (PTMSP). Pebax 2533 was selected as it gave the
highest steady state olefin permeances.
With respect to performance in ethane/ethylene separation, when feed pressure was
raised from 50 to 125 psig, the permeance dropped from 80 to 20 gpu and selectivity dropped
from 68 to 20. Permeance and selectivity were approximately 30 at a feed pressure of 100
psig. In these tests, the feed ethylene content was 65%. For 1-butene/isobutane separation,
selectivity was about 8.
Silver Nitrate was judged to be ineffective as an olefin carrier agent with the hypothesis
that the smaller anion NO
3
-
binds tightly to Ag
+
preventing the silver ion from complexing with
the olefin.
In an effort to identify additional effective or more stable carriers, various as well as
mixtures of carrier salts were tried. Chemical conditioners, such as a peroxide/acid mixture,
were also added to the membrane to stabilize the coating solution and preserve stored
membranes and to restore the properties of aged or poisoned membranes.
Performance stability was the most prominent challenge. There was clear deterioration
of performance with time, seen in periods as short as few hours. The study concluded that
silver salt-based facilitated transport membranes, regardless of the polymer matrix used, were
not stable even when exposure was limited to only ideal olefin/paraffin mixtures. They
attributed the issue to a previously unrecognized phenomenon labeled as olefin conditioning
implying that the very species targeted for separation by the carrier membranes (olefins) were
a source of membrane instability.
Imtex Membranes Corp. has successfully developed a synthetic membrane that
presents a viable alternative to distillation in separating olefins from their respective mixtures
with paraffin. The patented [7] Chitosan based Imtex membrane addresses the shortcomings
of the aforementioned alternative approaches, including the avoidance of the olefin
conditioning damaging phenomenon, even after much longer periods of operation than
experienced by MTR.
Due to the presence of hydroxyl (-OH) and the amino (-NH
2
) groups, Chitosan is a very
hydrophilic and chelating polymer with excellent film-forming characteristics and has an
excellent adsorption capacity for a number of metal ions such as the Silver cation. As
presented here, excellent olefin selectivities and permeabilities were obtained when using
Chitosan in olefin/paraffin separation tests. The facilitation mechanism of the Imtex membrane
is presumed to be through the olefin molecules hopping from one silver cation site to another
as well as through the expected mobility of the olefin-silver ion complex within the aqueous or
gel phase of the membrane. The membrane structure can be balanced by the degree of
deacetylation as well as by the silver loading level utilized. These aspects make Chitosan an
excellent base membrane for facilitated transport membranes.
LyondellBasell Industries and Imtex Membranes Corp. have undertaken a collaborative
effort to evaluate the performance of Imtex membranes in C2, C3 and C4 splitter applications.
In this paper, performance data for propylene/propane and ethylene/ethane separation is
presented. Membrane stability is reflected in the repeatability of performance over hundreds of
hours of testing. Some promising preliminary results for butenes/butanes are also shown.


Experimental

The Imtex membrane uses a flat sheet composite structure based on Chitosan material
and AgNO
3
as a facilitation agent. Chitosan is a linear polysaccharide produced commercially
by deacetylation of chitin, which is the structural element in the exoskeleton of crustaceans
(such as crabs and shrimp) and other arthropods. The membrane units used for these studies
included both small coupons as well as spiral wound elements. Each test coupon had a
surface area of approximately 12.6 cm
2
while the spiral wound elements used in this study had
each a nominal surface area of 500 cm
2
. The Chitosan layer thickness is estimated to be
between 4 to 7 micron. The tests were conducted with various ethylene/ethane,
propylene/propane and butane/butane feed compositions. The feed pressure ranged from 40
psig to 360 psig.
Below is a picture of the front panel (flow lines and valves) of the Imtex test Apparatus
used at LyondellBasell and also showing two housings of spiral wound elements.



Figure 1
Small Spiral Wound Modules and Test Apparatus used at LyondellBasell


Results and Discussion

Typical feed compositions to C2 and C3 splitters are 80/20 ethylene/ethane and
propylene/propane. Using synthetic gas mixtures and operating at 60 psig feed pressure,
selectivities greater than 100 were achieved when using a spiral wound module made from
first generation Imtex membrane LF1. This selectivity is higher than reported values in the
literature for polymeric membranes. Figure 2 shows the comparison.



Figure 2
Membrane Performance Curve for Ethane/Ethylene


Selectivity = (x
C2=
/ x
C2
)
perm
/ (x
C2=
/ x
C2
)
feed

Where x = mole fraction

The permeability was calculated based the classic Ficks diffusion law. The STP
(standard pressure and temperature) conditions defined as atmospheric and 68 F and
measured Permeate flow rate was used as the flux:








Where c= concentration, p = partial pressure, D= diffusion coefficient, and l= membrane
thickness

The excellent separation was seen over a wide range of feed composition. Figure 3
shows the performance of Imtex membrane LF1 as a function of ethylene content in the
ethylene/ethane feed mixture.
1
10
100
1000
1 10 100 1000
Permeability, Barrer
S
e
l
e
c
t
i
v
i
t
y
Facilitated Transport Circumvents Typical Selectivity-Permeability
Correlation
Typical Upper Limit Performance Curve from
Literature

Figure 3
Separating Ethylene/Ethane Mixtures at 66 psig and Room Temperature
Using a Spiral Wound Element with 0.05 m
2
Imtex LF1 Membrane

By increasing the feed pressure from 60 psig to 120 psig, the flux through the membrane was
almost doubled while product purity remained nearly the same. Figure 4 shows the concentration of
ethane in permeate stream, at the two pressures, over time.

50%
55%
60%
65%
70%
75%
80%
85%
90%
95%
100%
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
Feed Composition (% C2=)
P
e
r
m
e
a
t
e

p
u
r
i
t
y

(
%

C
2
=
)
0
20
40
60
80
100
120
140
160
180
200
P
e
r
m
e
a
t
e

F
l
o
w

R
a
t
e

(
c
c
/
m
i
n
)
Permeate Purity Permeate Flow Rate

Figure 4 - Separation of 80/20 Ethylene/Ethane at Different Pressures


A similar study was performed with 80/20 gas mixture of propylene/propane and a
comparable performance was achieved with this mixture. The following graphs, Figures 5 and
6, show the results:




Figure 5 - Separation of 80/20 Propylene/Propane at Different Pressures




Figure 6 Membrane Performance Curve for Propylene/Propane

All of the results under C2 and C3 splitter type conditions were encouraging, achieving
99.5% purity of ethylene and propylene with 90% olefin recovery. Imtex LF1 membrane was
also successfully tested over an operating pressure range applicable to typical C2 splitter
conditions. The membrane demonstrated higher permeation rates at higher pressures with a
small decrease in the selectivity. Figure 7 shows the membrane performance over an
operating feed pressure range between 60 and 360 psig.


Figure 7
Feed 85/15 Ethylene/Ethane Mixtures at room temperature and various pressures
Spiral Wound Element with 0.05 m
2
Imtex LF1 Membrane

While Imtex membrane LF1 steadily showed high permeate purities (in both C2= and
C3= cases) and higher permeabilities than those in the literature, however, for industrial
applications, further improvement in flux was still needed.
Further development work led to making changes in the chemical and physical structure
of the membrane. This resulted in the second generation of membranes referred to as HF3.
This second generation membrane still showed very high olefin product purities, in the same
range as Imtex LF1 membrane, but with an over three fold increase in the permeation rate.
Figure 8 shows the performance of Imtex HF3 membrane for both C2s and C3s. The
olefin mobility rate within the Chitosan (along with a bonded Ag+ cation or as a hopping
mechanism from one Ag+ site to another) seems to be similar for both ethylene and propylene.
The molar or volumetric rates observed were at nearly the same level or at times slightly lower
in the case of propylene. The difference in molecular weight between ethylene and propylene,
however, reveals the more established mass flow rate difference as shown in the figure.



0
50
100
150
200
250
300
350
0 50 100 150 200 250 300 350 400
Feed Pressure (psig)
P
e
r
m
e
a
t
e

F
l
o
w

R
a
t
e

(
c
c
/
m
i
n
)
97.0%
97.5%
98.0%
98.5%
99.0%
99.5%
100.0%
P
e
r
m
e
a
t
e

p
u
r
i
t
y

(
%
)
Permeate flowrate Permeate Purity


Figure 8
Separation of C2s and of C3s with Imtex HF3 Membrane
At 100 psig and room temperature

With HF3 being a promising candidate membrane for product scale-up and pilot
demonstration purposes, R&D at Imtex is shifting more to product development and testing of
spiral wound elements of various sizes. Figure 9 is a photo showing three sizes of rolled test
elements as well as elements housings.

0
200
400
600
800
1000
1200
1400
20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0
Average Feed Olefin Content (%)
P
e
r
m
e
a
t
e

F
l
o
w

R
a
t
e

(
g

m

h
r

)
90.0
91.0
92.0
93.0
94.0
95.0
96.0
97.0
98.0
99.0
100.0
P
e
r
m
e
a
t
e

P
u
r
i
t
i
e
s

(
o
l
e
f
i
n

%
)
Permeate purity (% olefin)
C3= PFR
C2= PFR



Figure 9 Various Spiral Wound Test Elements and Housings

In spite of all promising results for the C2 separation, it is believed that the application for
the C2 splitter faces many technical challenges, namely:
C2 splitter operation at cryogenic conditions
The permeate stream picks up moisture as it permeates through the membrane matrix. This
stream has to be dried prior to returning back to column
Presence of acetylenic compounds (e.g. acetylene, methyl acetylene (MA) and propadiene
(PD) also known as MAPD) in the feed. Ag
+
complex strength in the membrane can be
ranked strongest to weakest as follows:
PD > acetylene > methyl acetylene > ethylene > propylene
Thus, any MAPD in the feed could end up with the olefin product on the permeate side
or may form unsafe or undesirable compounds within the membrane.
On the other hand, the C3 splitter application does not involve many of the above
issues. In particular, the membrane will be best suited to upgrading the refinery grade
propylene to a polymer grade.
Using only one membrane module, we demonstrated excellent propylene recovery,
producing polymer grade propylene from a 80/20 propylene/propane gas mixture as shown in
Figure 10 below.






Figure 10 Effect of Stage Cut on Membrane Performance
Feed 80/20 (C3=/C3) at 66 psig and room temperature


Multiple Membrane Modules in Series

Currently the upgrading of the refinery grade to polymer grade is carried out in
distillation column; thus the distillation bottom will produce 90%+ propane as second
product. Using the membrane technology to replace distillation may be faced with a
challenge in producing a propane stream with such a high concentration. The implementation
of a hybrid system to achieve debottlenecking may be an attractive option. Hybrid systems will
be technically easier and more economical than replacing entire distillation systems with
membrane units. We presented various scenarios and performed extensive simulation work for
C2 splitters to quantify the energy savings through the retrofit of existing distillation columns
with membrane units [8].
Another alternative approach is to use multiple membrane modules to get the propane
to a reasonable concentration. We performed experiments with 2 modules in series.
The experimental results are presented below in Figures 11 and 12. As shown, while
polymer grade propylene was produced at the permeate side, the propane rich stream was
concentrated to 80% on the retentate side.

0
10
20
30
40
50
60
70
80
90
100
0 10 20 30 40 50 60 70 80
Stage Cut (%)
%

O
l
e
f
i
n

R
e
c
o
v
e
r
y
99.50
99.52
99.54
99.56
99.58
99.60
99.62
99.64
99.66
99.68
99.70
O
l
e
f
i
n

P
u
r
i
t
y

i
n

P
e
r
m
e
a
t
e
,

w
t
%
% Recovery
C3= in Permeate



Figure 11 Operation of Membrane Modules in Series


Figure 12 - Simulating RGP Feed to Membrane
Feed 30/70 Propane/Propylene at 120 psig

0
10
20
30
40
50
60
70
80
90
13:26 13:40 13:55 14:09 14:24 14:38 14:52 15:07 15:21 15:36
Operation Time
(
%
)

P
r
o
p
a
n
e

i
n

R
e
t
e
n
t
a
t
e

S
t
r
e
a
m
Module 2 Retentate % Propane
Module 1 Retentate % Propane


At a feed side pressure of 120 psig and with 20% olefin content, olefin feed side partial
pressure is less than 27 psia. As a result, there is only a small driving force against the nearly
14.7 psia on the permeate side. To obtain a retentate side paraffin content of 90%, feed side
pressure would need to be raised above 150 psig to be able to drive the needed olefin
transport across the membrane. Target retentate paraffin purity would be achievable with a
compromise between feed pressure level and membrane area.
Imtex HF3 membranes were also tested in separating C4s. Testing was conducted with
gas mixtures of 1-Butene/n-Butane at 40 psig and a temperature of 40
o
C. As shown in Figure
13, n-butane content in the permeate stream was between 0.1 to 0.3%. The molar
permeability of 1-butene was higher than either of ethylene and propylene. Accordingly, and
in addition to the molar mass difference, the mass permeate rate for C4= would be
significantly higher than for C2= or C3= if testing were to be performed at the same pressure.
However, more investigations at temperatures higher than 40
o
C need to be made before
higher pressures can be utilized for C4s separations.



Figure 13
1-Butene/n-Butane Separation at 40 psig and 40
o
C
Membrane area 12.6 cm
2



Imtex membranes were then subjected to testing for extended periods, covering
hundreds of hours to verify stability and show performance after extended use. Figure 14
0
2
4
6
8
10
12
14
60 65 70 75 80 85 90
Feed Mixture 1-Butene content (%)
P
e
r
m
e
a
t
e

F
l
o
w

R
a
t
e

(
c
c
/
m
i
n
)

99.0
99.1
99.2
99.3
99.4
99.5
99.6
99.7
99.8
99.9
P
e
r
m
e
a
t
e

1
-
B
u
t
e
n
e

(
%
)
shows repeatable excellent performance of a spiral wound module tested for over 1500 hours.
The Imtex membranes have consistently enabled achieving over 99.5% olefin purity under a
variety of feed conditions in long term tests. Combining this stable separation performance
with the equally stable membrane permeability that has been demonstrated in these tests has
built strong confidence in the potential commercial viability of the technology.




Figure 14 Stability over 1500 Hours of Testing
Feed 60/40 Ethylene/Ethane Mixtures at 66 psig and Room Temperature
Using a Spiral Wound Element with 0.05 m
2
Imtex HF3 Membrane


Potential Opportunities

Energy savings, when the membrane is used for olefin-paraffin separation, are
considered to be very attractive. In one particular example worked out with LyondellBasell
energy savings, when using a hybrid distillation / membrane arrangement, were estimated to
be on the order of $2 MM/yr for a commercial size C2 splitter. A retrofit of an existing splitter
may include compressors for both permeate and retentate streams and a dryer for the
permeate stream in addition to the membrane skid. The $2MM energy savings alone does not
justify the capital estimated for the retrofit. However, if the membrane were to achieve a 20%
debottleneck, the economics for C2 splitter would be very favorable.
Another promising application requiring olefin-paraffin separation is olefin metathesis
where polymer-grade propylene is produced by combining n-butene with ethylene.
Butene/butane separation is desired for the operation and it is not commercially attractive to
use distillation. When successful, a membrane process would increase reactant utilization of
99.1
99.2
99.3
99.4
99.5
99.6
99.7
99.8
99.9
100.0
0 155 310 465 620 775 930 1085 1240 1395 1550
Operating Time (hours)
P
e
r
m
e
a
t
e

P
u
r
i
t
y

(
C
3

=

%
)
0
50
100
150
200
250
300
350
0 155 310 465 620 775 930 1085 1240 1395 1550
Operating Time (hours)
P
e
r
m
e
a
t
e

F
l
o
w

R
a
t
e

(
c
c
/
m
i
n
)
metathesis plants and would thus result in attractive yield improvements as it enables the
production of more propylene from the same volume of feedstock.
The 1-butene membrane market opportunity, including fixed equipment and materials
costs, is estimated to be more that $400 million. This is in addition to expected energy
savings. Actual economic benefits will vary depending on the specifics of the application.


Conclusion

In addition to the excellent selectivity and permeability, Imtex membranes
demonstrated performance stability over time, which was one of the key shortcomings in prior
attempts to use facilitated transport membranes in olefin/paraffin separation.
Currently Imtex is actively seeking collaboration with an industrial partner for the
eventual commercial marketing and deployment of the technology. Work is underway at proof
of concept stage. Full size spiral wound membrane elements have been manufactured and a
test plan is being finalized to validate and refine the technology. Elements of this size will be
the modular building blocks for commercial installations.
The technology has great potential to offer significant benefits in various applications
related to olefin manufacturing operations, such as debottlenecking C2 splitters and upgrading
refinery grade propylene to chemical/polymer grade.
There is also a very promising potential for butene/butane separations where there are
technical challenges facing distillation. A successful application of Imtex membranes can have
a very positive impact on the economics of olefin metathesis which is used to produce
polymer-grade propylene by combining ethylene and n-butene. Also, better efficiencies can be
realized in the production of n-butene co-monomers for linear low density polyethylene
production.


Acknowledgement

Imtex Membranes Corp. gratefully acknowledges the financial support that has been
provided by the Industrial Research Assistance Program (IRAP) of the National Research
Council of Canada, Sustainable Technology Development Canada (SDTC) and the Innovation
Demonstration Fund (IDF) of the Ministry of Economic Development and Innovation of Ontario
to enable the development and advancement of Imtex membrane technology.


References

1- University of Texas at Austin, Oak Ridge National Laboratory and AIChE, (2005), Hybrid
Separation/Distillation Technology: Research Opportunities for Energy and Emission
Reduction. A study conducted under the Industrial Technologies Program of the U.S.
Department Of Energy, Energy Efficiency and Renewable Energy.
2- Tao Ren, Martin Patel, and Kornelis Blok, (2004), Energy Efficiency and Innovative
Emerging Technologies for Olefin Production, presented in European Conference on
Energy Efficiency, October, pp. 21-22.
3- R.B. Eldridge, (1993), "Olefin/Paraffin Separation Technology: A Review," Industrial &
Engineering Chemistry Research, 32, pp. 2208-12.
4- D.J. Safarik and R.B. Eldridge, (1998), "Olefin/Paraffin Separations by Reactive Absorption:
A Review," Industrial & Engineering Chemistry Research, 37, pp. 2571-81.
5- R. Schoellner and U. Mueller, (1986), Influence of Mono- and Bivalent Cations in 4A-
Zeolites on the Adsorption Separation of Ethylene and Propylene from Cracker Gases,
Adsorption Science and Technology, 3, 167.
6- Final report by Membrane Technology and Research, Inc. for DOE, (2007), Contract # DE-
FC36-04GO14151, Separation of Olefin/Paraffin Mixtures with Carrier Facilitated
Membranes.
7- P.S. Herrera, X. Feng, D. Payzant and J.H. Kim, (2008), Process for the Separation of
Olefins from Paraffins using Membranes, U.S. Patent 7,361,800.
8- Jose A. Caballero, Ignacio E. Grossmann, Majid Keyvani and Ellen S. Lenz, (2009), Design
of Hybrid Distillation-Vapor Membrane Separation Systems, Ind. Eng. Chem. Res., 48, pp.
91519162.