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JAIMIN PANDYA
ABSTRACT
Propylene/propane via cryogenic distillation is extremely energy-intensive, and membrane separation may provide an
attractive alternative. In this paper, Propylene/propane separation performance using polymeric membranes is
summarized,and an experimental Propylene/Propane polymeric upper bound based on literature data is presented. A
theoretical prediction of the Propylene/Propane upper bound is also presented, and shows good agreement with the
experimental upper bound. Further, two ways to overcome the Propylene /propane upper bound, based on increasing the
sorption or diffusion selectivity, is also discussed, and a review on advanced membrane types such as facilitated transport
membranes,zeolite and metal organic framework based membranes, and carbon molecular sieve membranes is
presented.Of these, carbon membranes have shown the potential to surpass the polymeric Propylene/propane upper
bound performance.Furthermore, a convenient, potentially scalable method for tailoring the performance of carbon
membranes for Propylene/propane separation based on tuning the pyrolysis conditions has also been demonstrated.
efficiency of a membrane) can be expressed as the ratio of the mole Plasticization of membranes
fractions of the two gas penetrant components A and B in the
Propylene and propane tend to plasticize glassy polymers even at a very
downstream and upstream yi and xi respectively,
low pressure (p = 2 bar) [18]. Plasticization occurs as a result of swelling
with a negligible downstream pressure compared to the upstream. to a significant swelling in the matrix This swelling causes an increase in
the fractional free volume (FFV) of the polymer. Due to this swelling, a
.For a particular gas pair penetration, respective permeabilities are
significant increase in segmental motion is observed. This is reflected by
the productivities of the particular gases and the selectivity is the
an upturn in the permeability-pressure plot for a particular gas pair and
efficiency of that gas pair.
both sorption and diffusion coefficients may deviate from the simple dual
SORPTION
mode expressions described earlier in such case. The upturn pressure is
The sorption in glassy polymers is represented by a dual mode model,
known as the plasticization pressure. Although the permeability increases
which accounts for penetrants in the normally densified and microvoid
for a plasticized membrane, the selectivity decreases significantly due to
regions of the polymer matrix. Specifically, the model accounts for the
the loss of diffusivity selectivity. In other words a plasticized membrane
differences in gas transport properties in both the idealized Henrys law
becomes less size selective. Figure-2.4 shows the response of a typical
and Langmuir domains of a glassy polymer The Langmuir concentration
CHA, for gas A, describes sorption in the microvoid or holes plasticized membrane. As shown in Figure-2.4, the permeability takes an
throughout the matrix, which are the packing defects in the non- upturn (propylene permeability is the red curve) and the selectivity
equilibrium glassy matrix. The sorption in glassy polymers is given by , decreases beyond the plasticization pressure. Propylene and propane,
diffusion jump.
Polymers provide a range of desirable properties that are important for gas
The rate of diffusion for a particular gas molecule depends on the separation processes including low cost, high permeability, good
frequency and the length of the random diffusion jump. In polymers, this mechanical stability, and ease of processing. However, polymeric
is governed by the thermal fluctuations, which vary according to the membranes based on rubbery polymers have very low selectivity for
polymeric chain structures. In case of glassy polymers, the thermal olefin/paraffin (especially propylene/propane) separations. Tanaka et al.
volume fluctuation is low giving much higher diffusion selectivity. reported a selectivity of 1.7 for a polybutadiene membrane at 50 0C
Burns and 6FDA- increase the molecular weight and the polydispersity index of the
33DMD 35 1.1 atm 0.15 13.2
Koros B polymer, synthesis conditions were modified.
6FDA-
The 6FDA-Durene polyimide, 6FDA-Durene/DABA (9/1) co-polyimide,
Tanaka et TrMPD
al. 50 2 atm 30 11 and 6FDA-Durene/DABA (7/3) co-polyimide were synthesized via a
(DAM)
Okamoto two-step chemical imidization in an NMP solution. For the preparation
[3 et 6FDA-
of polyamic acid, a designated molar ratio of Durene and DABA diamine
2] DDBT 50 2 atm 1.8 20
al. was dissolved in NMP under a nitrogen atmosphere and then an
[2 Tanaka 6FDA-
9] et al. DDBT 50 2 atm 0.76 27 equimolar of solid 6FDA was gradually added to the solution in a
shows a selected summary of pure polymer permeabilities and
moisture free flask with a magnetic stirring under a nitrogen atmosphere
selectivities for this particular gas pair [31].
A significant amount of research has been done on glassy polyimides at room temperature. The reason of adding solid 6FDA gradually is to
for propylene/propane separations [28-32]. Among all these, polyimides
based on 4,4-(hexafluorisopropylidene)dipthalic anhydride (6FDA) have suppress the reaction between water and 6FDA. Aromatic dianhydrides
exhibited the best performance. The upper bound is currently defined by
can react with water and other impurities in the amide solvents, but have
the 6FDA-based polymers prepared from the TrMPD (DAM) and DDBT.
The report showed an increase in selectivity with a decrease of a slower reaction rate relative to their reacting with diamines. Therefore,
temperature from 308K to 298K; however, as noted earlier strong gradually adding the solid 6FDA reduces its availability for competing
plasticization effects were seen at very low pressure for propylene at
reactions with water or other impurities, thus leads to a higher
lower temperature. In 50:50 propane/propylene mixed gas experiments,
conversion and molecular weight [1]. After reacted for 24 h, a high
the selectivity decreased with increasing feed pressure by as much as
molecular weight polyamic acid was formed. Then for the chemical
50% from ideal selectivity. Similarly most of the membranes for
4
imidization step, a mixture of acetic anhydride and triethylamine at 4:1 gas sorption experiments using a pressure decay method with un-
molar ratio was slowly added to the polyamic acid solution to perform annealed and annealed films have been discussed. These sorption
imidization for 24 h under nitrogen atmosphere. Finally, the co- experiments have been used to analyze the permeation data using the
polyimide was precipitated in methanol, filtered, washed and dried at dual-mode model. Mixed gas permeation results also have been explained
120 C in vacuum for 24 h. The schemes of co-polyimide synthesis and with dual mode and bulk flow transport models.
chemical structure of this co-polyimide are shown in figure using italics. Weights and measures should be expressed in SI units. All
non-standard abbreviations or symbols must be defined when first
mentioned, or a glossary provided.
Plasticization Suppression
effects in terms of plasticization suppression, permeability and selectivity modified imidization approach, it was expected that the results might
have been discussed in detail. According to our best knowledge, this is be little different than seen by others. This difference in the
for the first time plasticization suppression for propylene/propane has permeability and selectivity is perfectly within the acceptable range
been reported with any polyimide dense film membrane. Results of pure and were reproducible. To test the reproducibility, at least three
permeation tests were performed with each gas at a particular
study of the post treatment conditions was conducted. results, it was decided to follow annealing temperature of
temperature.
P C3H
C3
Pressur H6
6/C3
increase the annealing treatment temperature. Based on these results, effect. This result suggests that suppression of plasticization was indeed
it was decided to follow annealing temperature of 210 0C for 18-20 achieved by annealing the films and performing permeation experiments
hours for all experiments onwards to maintain consistency. From this at 700C. While this is for the first time we observed plasticization
point, any film dried at 1100C will be referred to as un-annealed, suppression of propylene with 6FDA-6FpDA up to 70 psi upstream
and films dried at 2100C as annealed. Table-5.5 summarizes the pressure, as mentioned earlier, mixed gas composition experiments are
propylene/propane annealing results with different permeation test the real tests for plasticization suppression. The next section describes the
temperatures. In the case of propylene/propane separations also we results from mixed gas experiments.
saw a decrease in permeability and increase in selectivity after
annealing.
least three films from different casted films were tested for each
pressure point. The results were within 5% error range. After each
MIXED MATRIX MEMBRANES WITH Thermal treatment temperature plays a significant role on fiber
6FDA-6FPDA AND ALPO-14 morphology. Fiber diameters shrunk after treatment. The 350
C treated fibers show higher permeances and lower
mixed matrix membranes were formed with 6FDA-6FpDA as the selectivities close to those of untreated fibers, while the 400 C
polymer matrix and AlPO-14 as the molecular sieve material. AlPO-14 treated fibers show higher selectivities but lower permeances
due to the skin densification and a higher degree of cross-
was chosen due to its success with PSA and VSA for propylene/propane
linking. As a result, the silicon rubber coating has a less effect
separations. AlPO-14 is a unique molecular sieve which is one on the 400 C treated fibers than the 350 C treated fibers.
dimensional for propylene and almost excludes propane from entering the
For CO2/CH4 separation, without silicon rubber coating,
interior cage. Permeation results with pure and mixed gases at 35 0C
sample D-400-BSRC show the best CO2/CH4 separation with a
showed very promising enhancements in both propylene permeability and CO2 permeance of 130 GPU and a selectivity of 15.5. After
silicon rubber coating, sample C-400-ASRC shows the best
propylene/propane selectivity. According to our best knowledge, this is selectivity of 20 and a CO2 permeance of 82 GPU. For
the first time enhanced selectivity and permeability were achieved in a C3H6/C3H8 separation, without silicon rubber coating, sample
D-400-BSRC show the best C3H6/C3H8 separation with a C3H6
mixed gas environment for this gas pair using the mixed matrix hybrid permeance of 73 GPU and a selectivity of 10.5. After silicon
material approach. The main observation we would like to highlight was rubber coating, sample B-400-ASRC shows the best selectivity
of 15.3 and a C3H6 permeance of 29 GPU.
the excellent polymer-sieve matching. A 6FDA-6FpDA-AlPO-14
1.1. Footnotes
2. Illustrations
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Acknowledgements
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