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Polymeric Membranes
By:JAIMIN PANDYA
TABLE OF CONTENTS
ABSTRACT
INTRODUCTION
SYNTHESIS OF MEMBRANE
Conclusion
References
ABSTRACT
Olefins are the most important building blocks of the petrochemical industry. Most olefins
are produced by steam cracking of ethane, propane, naphtha, or gas oil followed by repeated
compression and distillation to separate the complex vapour mixtures. The second step is
considered to be a highly energy-intensive process and have been extensively studied for
possible replacements. Production is highly energy intensive. Current distillation processes
for the separation of ethylene/ethane and propylene/propane mixtureswhich account for
most of the energy consumption and much of the capital cost of the steam crackerconsume
an estimated 120 trillion BTU energy in the US.
Firstly, the new flexible and high performance gas separation membranes were
fabricated by grafting various sizes of cyclodextrin to the cross-linkable co-polyimide
(6FDA-Durene/DABA (9/1)) matrix and then decomposing them at elevated
temperatures. The gas permeability of thermally treated pristine polyimide (referred as
the original PI) and CD grafted co-polyimide (referred as PI-g-CDs for 200 and 300
C and partially pyrolyzed membranes (PPM) - CDs for 350, 400, and 425 C) has
been determined. It was observed that permeability of all tested gases increased with
an increase in thermal treatment temperature from 200 to 425 C. However,
permeability increased more for those grafted with bigger size CD. The permeability
of the original PI thermally treated at 425 C was about 4-6 times higher than that
treated at 200 C. The permeability increase jumped to 8-10 times for PPM--CD and
15-17 times for PPM--CD due to CD decompose at high temperatures and bigger CD
creates bigger micro-pores. Interestingly, the permeability ratios of PPM--CD to
PPM--CD and PPM--CD to PPM--CD at 400 and 425 C were around 0.6 and 0.8,
respectively. These numbers were almost the same as the cavity diameter ratios of -
CD to -CD and -CD to -CD. Permselectivity decreased first with an increase in
thermal treatment temperature up to 350 C
and then increased. Permselectivity of thermally treated CD grafted co-polyimide
membranes were also slightly higher than that of the original PI due to higher
degrees of cross-linking in CD grafted co-polyimide membranes. In addition, for
co-polyimide membranes grafted by CDs, the higher thermal treatment
temperature resulted in membranes with the better plasticization resistance to CO2
and the better separation performance in 50:50 CO2/CH4 mixed gases.
INTRODUCTION
1. Gas separations have always been one of the key processes in the field of chemical engineering. With
industrys demand on lowering operating costs and increasing separation efficiency, more research is
being conducted on process improvements. Gas separation is usually achieved by physical or
physicochemical phenomena. Over the past two decades, gas separation using polymeric membranes
has drawn a great deal of interest from researchers due to many advantages such as low energy costs
and high selectivities. This is especially true for hydrocarbon separations performed by the
petrochemical industry. In particular, olefin/paraffin separations incur a heavy cost to petrochemical
companies. With a growing awareness of the importance of conserving natural resources, companies
are enthusiastic about finding ways to reduce energy consumption and to recycle purge or waste
streams. Traditionally, cryogenic distillation at elevated pressures in trayed fractionators is used to
separate olefins and paraffins. This distillation system is expensive to build and operate, and is currently
only economically attractive for streams containing high quality of olefins. Other available separation
technologies include extractive distillation, physical or chemical adsorption, physical or chemical
absorption, and more recently, membrane separation. A more thorough description of 1 CHAPTER 1.
INTRODUCTION 2 different separation technologies can be found in the review written by Eldridge
(1993)
The difficulty of the olefin/paraffin separation step stems from the low relative volatilities of the
components. As a result, very large distillation towers with 120-180 trays and high reflux ratios are
required. Even small improvements in these separations could result in significant energy and cost
savings to the petrochemical industry. The use of membranes has been the focal point of research as
a new means of olefin/paraffin separation due to its lower operating and capital costs. In this
article, a comprehensive review is presented for the application of polymeric membranes in light
olefin/paraffin separation. It covers all types of membrane materials starting from the
conventional polymers to more advanced ones such as polyimide and copolyimide membranes.
Permeation and separation characteristics of all polymeric membranes are summarized and
discussed in great details.
Membrane separation, compared to amine absorption, pressure swing adsorption, rectification and
cryogenic distillation, has advantages, including low energy consumption, easy operation and
maintenance, environmental benign and small footprint [19-21]. Many studies have been done on 3
membrane separation for the purpose of replacing traditional separation technologies [8]. Membranes,
especially polymeric membranes have been explored in various kinds of gas separation applications such
as natural gas sweetening [7-9,20-21], and olefin/paraffin separation [22-29]. In order to have a good
gas separation performance, membranes must have high permeability and permselectivity, excellent
chemical resistance (for resistance against corrosive materials such as H2S), great thermal stability (for
high temperature applications), good mechanical properties (for high pressure applications), and
superior plasticization resistance
Two of the most important petrochemicals are the olefins ethylene and propylene. In 2004, 146 and 82
billion pounds of ethylene and propylene, respectively, were produced worldwide [35]. Both are feed
stocks for many other important chemical products; the most important being polyethylene and
polypropylene. Worldwide, 72 billion pounds of polyethylene and 42 billion pounds of polypropylene
were produced in 2004. Propylene and propane are found in the low and middle fractions of the
distillation process, albeit in small amounts. Large amounts are formed when gasoline is made by
cracking or reforming. Other olefins and paraffins can be found throughout the refining process. The
separation of these two has been relatively more difficult than that of other gas pairs, mainly ascribed to
their close thermodynamic and physical properties. The simulated molecular dimension of propylene
and propane is presented in Figure 1.3 while the thermodynamic properties of both are tabulated in
Table 1.1. Table 1.1: Thermodynamic properties of propane and propylene [23] Molecular Formula
Molecular Weight (g/mol) Boiling Point (K) Critical Temp. (K) Propylene C3H6 42 226 365.2 Propane
C3H8 44 230.4 369.9 7 Figure 1.3: Simulated molecular dimension of propylene and propane [23] As can
be seen, both gases have similar molecular dimensions, boiling points and critical temperatures. The
only difference is that propane is saturated hydrocarbon and propylene is unsaturated hydrocarbon.
Compounds of carbon and hydrogen whose adjacent carbon atoms contain only one carbon-carbon
covalent bond are known as saturated hydrocarbons. They are called saturated compounds because all
the four bonds of carbon are fully utilized and no more hydrogen or other atoms can attach to it. These
saturated hydrocarbons are called alkanes and the general formula for an alkane is CnH2n+2. Due to the
presence of all single covalent bonds, these compounds are less reactive and the number of hydrogen
atoms is more when compared to its corresponding unsaturated hydrocarbon. Compounds contain
single carbon-Compounds of carbon and hydrogen that contain one double bond between carbon atoms
(carbon=carbon) or a triple bond between carbon atoms (carboncarbon) are called unsaturated
hydrocarbons. Unsaturated hydrocarbons can be divided into alkenes and alkynes depending on the
presence of double or triple bonds respectively. The general formulae are CnH2n for alkenes and CnH2n-
2 for alkynes. These compounds are more reactive and their high reactivity is due to the presence of pi-
bond in their structure. Then sorption and adsorption of these unsaturated hydrocarbon (alkene) in
polymer matrix or inorganic particles could be higher than saturated hydrocaron (alkan). Although
membranes can lead to extensive energy and cost savings, many researchers envision membrane
separation units fitted in line with current separation systems rather than completely replacing them.
Propylene/Propane Separations
steam cracking and FCC processes are still the main sources of propylene till date.
Unfortunately none of these processes produces pure enough propylene that can be used
are required. Currently, the separation of olefin and paraffin components is performed by
cryogenic distillation, which is expensive and energy intensive due to the low relative
volatilities of the components (b.p. of propylene is -470C and propane is -42.10C). The
necessary columns are normally 300 feet tall and contain over 200 trays
Due to the height of the column, two splitters are usually required instead of one.
Around 1.2 x 1014 BTU/year energy is used for olefin/paraffin separations. The bottom
product of C3 splitter tower is propane rich, while the overhead product is high purity
4
propylene. A typical propylene recovery unit from the co-products of FCC unit is
shown in Figure-1.3.
gaining popularity for propylene/propane separations. Baker predicts that the membrane
market will reach $30 million by 2010 and $125 by 2020 for vapor/vapor gas separations
completely replace a C3 splitter because of the purity limitations, but it can obviously be used to
reactor, propane enters as an impurity (99% propylene and 1% propane) and eventually
propylene monomer is lost incurring a $1 million loss per plant every year [6]. A
option. Figure-1and Figure-2 show these two possible membrane applications for
propylene/propane separations.
Studies have shown that several polymeric membranes offer promising potential, but separation
selectivity needs to be improved to be used as a cost effective separating membrane.
Considerable research has been done in glassy polyimides, and polyimide-co-polypyrrolones
with polyimides based on 6FDA (4,4-(hexafluorisopropylidene)dipthalic anhydride) exhibiting
the best performance . On the other hand, carbon molecular sieve and zeolite membranes
potentially offer superior selectivities; however, they are brittle and too costly (> $150/sq foot)
to be commercially useful for large scale applicat Figure-2: Use of membrane unit to recover
propylene in a polypropylene production plant
In this chapter, the materials that were studied, the membrane fabrication
techniques, characterization techniques, and the equipment used to
characterize these materials will be detailed. The specific materials selected
for this work are described in Section 3.1. Membrane formation techniques are
described in section 3.2 and material characterization techniques and
equipment are outlined in Section 3.3.
Materials
Polymers
The polymers selected for this work was a 6FDA-Durene polyimide and
6FDA-Durene/DABA cross-linkable co-polyimide. Figure 3.1 shows the
chemical structure of the monomers that was used in this study. 4,4'-
(hexafluoroisopropylidene) diphthalic anhydride (6FDA), supplied by
Clariant, and 3,5-diaminobenzoic acid (DABA) supplied by Aldrich
(Singapore) were purified by vacuum sublimation before usage. 2,3,5,6-
Tetramethyl-1,4-phenylenediamine (Durene diamine) supplied by Aldrich
(Singapore), was recrystallized two times from methanol. 1-methyl-2-
pyrrolidone (NMP) purchased from Merck Chemicals (Germany), was
distilled at 42 C under 1 mbar and was dried with molecular sieve before use.
Acetic anhydride was received from Aldrich (Singapore) and dried with
molecular sieve before usage. Other chemicals and solvents including
triethylamine, methanol, and p-toluenesulfonic acid were all reagent grades or
better from Aldrich (Singapore) and were used without further purification.
44
Figure 3.1: The synthetic scheme and chemical structure of co-polyimide
The nanoparticle used in this work to make mixed matrix membranes was zeolitic
imidazolate framework-8 (ZIF-8). The dispersed ZIF-8 nanoparticles were
synthesized at room temperature. In summary, a solution of Zn(NO3)26H2O
(7.332 g, 24.67 mmol) in 500 ml methanol was rapidly poured into a solution of
Hmim (16.222 g, 197.6 mmol) in 500 ml methanol under stirring with a magnetic
bar. The resultant solution slowly turned turbid and after 1 h the nano-crystals
were separated from the milky dispersion by centrifugation and washing with
fresh methanol. After washing and the 2nd centrifugation, the particles were re-
dispersed in fresh NMP before use. The yield of ZIF-8 was ~ 50% based on Zinc
[4].
3 Gases
All pure gases and gas mixtures used throughout this research (i.e., CO2, CH4,
C3H6, and C3H8) were research grade (99.999%) and supplied by SOXAL
(Singapore).
6FDA-6FpDA is another polyimide for this particular gas pair with very high
6FDA-6FpDA this polymer is 0.89 at 3.8 atm. The selectivity is 16 in this case. It should
be noted here that propylene pressure reported is 3.8 atm, instead of 2 atm like other
cases mentioned above. Due to dual mode pressure dependence, permeability at 2 atm
should be higher than 0.89 Barrer. Moreover, the permeation test for 6FDA-6FpDA was
done at 350C, instead of 500C like other cases. As mentioned in Chapter 2, high test
temperature also increases the permeability while the selectivity reduces. So effectively,
Following the difficulties with the DDBT monomer, 6FDA-6FpDA polymer was
selected for the current research work. Another advantage of 6FDA-6FpDA polyimide is the
excellent permeability matching with AlPO-14. As shown later in Chapter-6, polymer and
molecular sieve matching is very important for mixed matrix material success. A very highly
permeable molecular sieve can reduce the overall permeability of the mixed matrix
Thus using 6FDA-DAM as polymer matrix would have essentially reduced the
permeability of mixed matrix materials. This will be discussed in more details in Chapter-
were synthesized by the thermal imidization process described in Chapter-3. Both batches
had low Mw (highest molecular weight observed was ~50k with a PI >5.0) determined by
GPC. A detailed study identified three major areas of difficulty during synthesis process.
First, our 6FDA monomer was 99% pure, whereas 6FpDA was 98% pure creating a
stoichiometric discrepancy in the molar weight ratio. High Mw weight can be achieved
with desired end-group controlled by Carothers Equation [6] which depends strictly on
In the case of impure monomers, even if the monomers are added in a 1:1
stoichiometric ratio, impurities disturb the stoichiometric ratio, which is one of the most
important parameters for high Mw and low PI. When the ratio is not actually 1:1, two
possible reactions can take place during the polyamic acid formation step. First, the
excess monomer can form di-mers or tri-mers and stop growing in length. These
relatively small molecules then contribute to the formation of a much broader
polydispersity, thereby resulting in a much higher PI [7]. Second, if there are slow
reacting impurities in the solution, there will be a competitive reaction between the
impurities and monomers where impurities can end the chain growth in a
polycondensation reaction. In this case, low molecular weight oligomers [7] will form
instead of high Mw polymer. In all of these cases, a low molecular weight polyamic
temperature forming carboxylic acids. For the same reason, the number of available sites
for diamine addition for a given amount of anhydride decreases the probability of
creating the desirable repeat unit. This again results in a low molecular weight polymer.
Lastly, one important parameter during synthesis is the local hot zone formation during
6FDA addition. 6FDA is added in a diamine solution (in NMP). As soon as the
and increases the temperature locally. Consecutively, the reaction stops in that particular
region. It is desirable to have an ice bath during polyamic formation step of synthesis thus
The following changes in the polyamic formation process were made to ensure
Before monomer sublimation, both monomers were dried in a vacuum oven for
overnight, around 200C below its sublimation point. (To increase the
sublimation yield)
Each monomer was sublimed twice to achieve required purity. (Yield increased
Before the synthesis experiment, sublimed monomers were again dried in the
vacuum oven overnight to eliminate residual water. (To remove any ambient
moisture)
molecular sieves.
An exact amount of diamine was added, while stirring the reaction flask
continuously.
The reaction was carried out first at low temperature and then at RT, with constant
temperature monitoring.
Conclusion
In this work three 6FDA-based cross-linkable co-polyimide with high gas separation
performance for C3H6/C3H8 (propane-propylene) were fabricated. Synthesis Of High
Molecular Weight 6FDA-6FpDA is discussed which is the best way for the membrane preparation
As a conventional way is very energy intensive for olefin /paraffin separation we can choose the
middle way and make an hybrid process of utilizing advantages of both system distillation and
membrane system. In these paper we have discussed the material which is best suitable for propane
/propylene separation and its synthesis.
References
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