Preparation of Carbon Molecular Sieve Membranes and Their Gas

Chapter 21

Preparation of Carbon Molecular Sieve Membranes and Their Gas Separation Properties

Downloaded by UNIV OF CALIFORNIA SAN DIEGO on June 4, 2015 | http://pubs.acs.org Publication Date: December 29, 1999 | doi: 10.1021/bk-2000-0744.ch021

Ken-ichi Okamoto, Makoto Yoshino, Kenji Noborio, Hiroshi Maeda, Kazuhiro Tanaka, and Hidetoshi Kita Department of Advanced Materials Science and Engineering, Faculty of Engineering, Yamaguchi University, Ube, Yamaguchi 755, Japan

Carbon molecular sieve (CMS) membranes were prepared by pyrolyzing flat membranes of 3,3',4,4'-diphenylhexafluoro isopropylidene tetracarboxylic dianhydride (6FDA)-based polyimide and polypyrrolone and composite membranes of phenolic resin coated on alumina tubes at 500-800°C in N . The gas permeability and selectivity depended significantly on the precursor polymers and pyrolysis conditions. With increasing pyrolysis temperature, the permeability decreased and the selectivity increased, because the membranes became denser and the effective pore size for molecular sieving became smaller, whereas gas adsorption increased. C M S membranes from the polyimide and polypyrrolone displayed high performance for gas separation applications such as CO /CH , /N , and propylene/propane. C M S membranes made from a phenolic resin displayed high performance for CO /N separation. 2

2

O2

4

2

2

2

In adsorption applications, carbon molecular sieve membranes produced by the pyrolysis of polymeric materials have been studied extensively (7). There is growing interest in using molecular sieve membranes to separate gas mixtures with very similar molecular dimensions or organic vapor mixtures. However, it is very difficult to prepare carbonized membranes free of pinholes and with a molecular sieving effect (2). Some recent work reported on lab-scale carbon molecular sieve (CMS) membranes with excellent performance for gas separation applications (317). However, it is not clear from previous work how much the precursor polymers and pyrolysis conditions affected the gas separation performance of C M S membranes. Here, we report on the preparation of CMS membranes from three different precursor polymers, that is, polyimide, polypyrrolone, and a phenolic resin, and their characterization, gas adsorption and gas separation properties.

314

© 2000 American Chemical Society

In Membrane Formation and Modification; Pinnau, I., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1999.

315 CMS Membranes from Polyimide and Polypyrrolone Preparation and Characterization. Figure 1 shows the chemical structures of the precursor polymers used in this work. Polyimide was prepared from 3,3 ,4,4diphenylhexafluoroisopropylidene tetracarboxylic dianhydride (6FDA) and mphenylenediamine (mPD) by a chemical imidization method. Polypyrrolone was prepared from 6FDA and 3,3'-diaminobenzidine (DABZ) by a two-step synthesis. Poly(amic acid) films were thermally imidized at 150°C for 12 h in vacuum, followed by thermal cyclodehydration to the polypyrrolone at 300°C for 2h. The glass transition temperatures of 6FDA-mPD polyimide and that of 6FDA-DABZ polypyrrolone were 298°C and >470°C, respectively. The membranes were heated up to the pyrolysis temperature (500-800°C) at a heating rate of 5°C/min under nitrogen atmosphere and held for 0-5 h to yield carbon membranes (40-50 μιη in thickness and 3 cm in diameter). The weight loss amounted to 20 and 40% for the polyimide carbonized for 1 h at 500 and 700°C, respectively, and 15 and 31% for the polypyrrolone, respectively. TG-MS analysis indicated that carbonization began to occur at 500°C (Figure 2) with the evolution of carbon monoxide, carbon dioxide, hydrogen fluoride, and carbon tetrafluoride. The Ο and F atomic contents decreased significantly and the C content increased at 500-600°C, whereas the Ν and Η contents changed rather slightly (Figure 3). From these results, it can be assumed that the initial pyrolysis process for the polypyrrolone occurred as shown in Figure 4. The cleavage of hexafluoroisopropylidene groups leads to evolution of HF and C F . The cleavage of cyclic imide leads to evolution of CO and formation of cyclic imidazole. The cleavage of cyclic imidazole leads to evolution of CO and formation of nitrile groups. The presence of nitrile groups in the membranes pyrolyzed at 500-600°C was confirmed from the IR spectra. A similar cleavage of hexafluoro-isopropylidene groups and cyclic imide can be assumed for the polyimide.


,

4

The d-spacing values of the carbonized membranes were determined from the diffraction peak angles and are listed in Table I together with the density values determined from the weight and apparent volume. Both the density and d-spacing hardly changed with heating up to 500°C. On the other hand, with heating above 700°C, the density increased and the d-spacing decreased, indicating that the membranes became much denser with increasing pyrolysis temperature above 700°C. Gas Adsorption and Permeation Properties. Adsorption and desorption isotherms of N for the membranes belonging to Type 1 sorption isotherms, without hysteresis in the desorption isotherms, indicated no capillary condensation. Figure 5 shows adsorption isotherms of N , C H , and C 0 for the polypyrrolone and its carbonized membranes. The adsorption amounts were larger for the membranes pyrolyzed at a higher temperature. The carbonized polyimide 2

2

4

2


316


6FDA-mPD polyimide

6FDA-DABZ polypyrrolone OH

OH

OH

HOCH -^rCH jQ 2

irt^"

2

CH -CH

2

^ H

2

2

CH OH

2

2

^OOÎZÇ-CHZQ^H °

H

^

™

H

2

phenolic resin

Figure 1. Chemical structures of 6FDA-mPD polyimide and 6FDA-DABZ polypyrrolone and a phenolic resin.

200

400

600

800

τ ra Figure 2. Thermograms of 6FDA-DABZ mPDpolyimide.

polypyrrolone

and 6FDA-


317


100

100 200 300 400 500 600 700 800 Heat treatment temperature

Figure 3. Variation in atomic content of 6FDA-DABZ polypyrrolone and 6FDA-mPD polyimide with heat treatment.

6FDA-DABZ Polypyrrolone cleavage of -C(CF3) --group

cleavage of cyclic imide

cleavage of cyclic imidazole

2

9 •F,

C-NI

CF

o

3

CN

^hydrogen transfer)

HF , CF t 4

cot,

(cleavage of cyclic imidazole ^ Figure 4.

Initial pyrolysis process of 6FDA-DABZ polypyrrolone.



318


319 membranes showed a similar adsorption behavior, although their levels of adsorption were smaller compared with those of the carbonized polypyrrolone. Table I. Physical properties of carbonized membranes. Precursor polymer


6FDA-mPD

6FDA-DABZ

Pyrolysis conditions 200°C, 20h 500°C, l h 600°C, l h 70Q°e, l h 300°C,2h 400°C, lOh 500°C, l h 550°C, l h 700°C, l h 800°C, l h

d-spacing (nm)

Density (g/cm ) 1.475 1.411 1.472 1.525 1.401 1.412 1.398 3

0.59 0.59 0.58 0.49 0.44

1.581 1.643

The micropore volumes were determined from C 0 adsorption using the Dubinin-Radushkevich equation and are listed in Table II together with the data of the carbonized membranes of other polyimides (10,18). The micropore volume increased slightly with increasing pyrolysis temperature. This result may be due to the shift of the pore size distribution towards smaller pores. The carbonized membranes had similar values of micropore volumes, indicating that the micropore volume depends rather weakly on the chemical structure of the precursor polymers. 2

Table II. Micropore volumes (W ) evaluated from D-R equation of C 0 adsorption. 0

Precursor polymer 6FDA-mPD 6FDA-DABZ BPDA-ODA

Kapton

Pyrolysis conditions 500°C, l h 700°C, l h 500°C, l h 700°C, l h 600°C 700°C 800°C 600°C, l h 700°C, l h 800°C, l h

2

W (cm /g) 0.21 0.22 0.22 0.24 0.22 0.25 0.36 0.24 0.27 0.25 0

Ref.

3

this this this this

work work work work 10 10 10 18 18 18


320 Gas permeation experiments were carried out by a vacuum time-lag method. The permeability coefficient, Ρ, (1 Barrer = l x l O ' cm (STP>cm/(cm -s*cmHg))and the permeance, P/l, (1 G P U = lxlO" cm (STP)/(cm «s-cmHg) used here are common units for gas permeation properties. 10


6

3

3

2

2

Figure 6 shows the relationship between the permeability coefficients and kinetic diameters of penetrant gases for the polypyrrolone and its carbonized membranes. Pyrolysis at 500°C for 1 h enhanced the gas permeability about 100fold. With increasing the pyrolysis temperature to 700°C, the gas permeability decreased, but its dependence on the kinetic diameter became more pronounced. Pyrolysis at 800°C decreased the gas permeability significantly, and the membranes became permeable essentially only to H . A similar behavior was observed for carbonized polyimide membranes. The gas permeation properties, the density, and d-spacing data mentioned above indicate that the effective pore size of molecular sieve membranes became smaller with increasing pyrolysis temperature from 500°C to 800°C. It should be noted that the effect of the pyrolysis temperature on the gas permeability was quite different from that of gas adsorption, that is, the gas permeability decreased significantly with increasing temperature from 500°C to 700°C, whereas both gas adsorption and the micropore volume increased. Although any open pore can take part in gas adsorption, only penetrating micropores can take part in gas permeation. Moreover, bottle-neck type micropores can control the gas permeation and separation properties of the CMS membranes. Figure 7 shows plots of the permeability ratio of C 0 / C H versus C 0 permeability for pure-gas measurements for the 6FDA-mPD polyimide and 6FDAD A B Z polypyrrolone and their carbonized membranes together with the reference data of the carbonized membranes of polyimide from 3,3'4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and 4,4 -oxydianiline (ODA). Figure 7 also shows the upper bound line reported by Robeson (19). This line denotes the upper limit of the C 0 / C H separating ability of polymers known up to 1991. The data for 6FDA-mPD polyimide and 6FDA-DABZ polypyrrolone are below and above the upper bound line, respectively. On the other hand, the data for the carbonized membranes are much above the upper bound line, indicating that the carbonized membranes have much better performance than the precursor polymers. The membrane performance depended significantly on the pyrolysis conditions such as temperature and time. With increasing the pyrolysis temperature from 500°C to 700°C, the C 0 permeability decreased, but the selectivity increased, indicating that the membranes acted more like a "molecular sieve" for the C 0 / C H gas pair. Increasing the heating time from 1 h to 2 or 5 h resulted in a significant decrease in the selectivity. The 6FDA-DABZ polypyrrolone membranes carbonized at 500 or 700°C for 1 h had better gas separation properties than those of the carbonized polyimide membranes. 2

2

4

2

f

2

4

2

2


4


321

0.3

0.35

0.4

Kinetic diameter [nm]

Figure 6. Relationship between permeability and kinetic diameter of gases for polypyrrolone (open symbols) and its carbonized membranes.

200

[-"τη

• • ' ' ""1

· • '••

35^,1 atm

Ο , · : 6FDA-mPD Δ , Λ : 6FDA-DABZ

T00-1

m

4

•

:BPDA-0DA ^

150 -

500-1

•

^100 "

-

600-0 700-5

j500-2

A

700-0

\

Δ

Ο

A

7 0 0

"

0

700-1

\

600-1 •

• • I 0 •• 10 1

1 . • • 1 III 10

1.

2

i 10

P

C02

t

500-1

3

10

Barrer

4

l

Figure 7. Plots of P C 0 / P C H versus P C 0 for precursor polymers (open symbols) and carbonized membranes. The solid line is the upper bound line (19). The numerals refer to pyrolysis temperature and time. 2

4

2



322 Tables III and IV show comparisons of membrane performance toward several gas pairs among C M S membranes studied here and reported in the literature. Jones and Koros reported on the performance of membranes prepared by pyrolyzing hollow-fibers of 6FDA/BPDA-TrMPD (2,4,6-trimethyl-l,3-phenylene diamine) polyimide at 500-550°C. The carbonized membranes of 6FDA-mPD polyimide and 6 F D A - D A B Z polypyrrolone had very high permeability and, therefore, the flat membranes of around 50^m-thick displayed high permeance values, comparable to those of the carbonized hollow fiber or tubular membranes having an active layer as thin as a few μιη or less. This is probably due to their less efficient polymer chain packing and the more pronounced effect of pyrolysis because of the hexafluoroisopropylidene group. It is noteworthy that the gas permeability and selectivity depended significantly on the precursor polymers. Propylene/Propane Separation. Membrane separation of olefins and paraffins is another important research objective. Solid polymeric membranes have rather poor performance for propylene/propane separation. For example, 6FDA-TrMPD polyimide has a fairly high C H permeability of 30 Barrers but has a relatively low selectivity of 10 (20). 6FDA-DABZ polypyrrolone has a fairly high selectivity of 45, but its C H permeability is only about 1 Barrer. Furthermore, the selectivity decreased significantly to 15 in gas mixture experiments. Therefore, in this study we also investigated the propylene/propane separation properties of carbonized membranes. Table V lists the performance of carbonized membranes for propylene/propane separation. Carbonized 6FDA-DABZ polypyrrolone membranes displayed a high C H permeability of 170 Barrers and a pure-gas selectivity of 78. In mixed-gas permeation experiments, the permeability decreased to 94 Barrers and the propylene/propane selectivity, a, decreased to 44. However, the performance of the carbonized membrane was much better than that of the precursor polypyrrolone membrane. A similar behavior was observed for carbonized 6FDA-mPD polyimide membranes. The performance of these membranes was much better than that of the carbonized B P D A - O D A polyimide membranes and of the carbonized Kapton polyimide membrane mildly modified with water steam. This is because their less dense structure was more suitable to sieving by gases with larger molecular size differences. The 6FDA-mPD polyimide membranes carbonized at 700°C displayed a significant reduction in gas permeability after exposure to propane, probably because of micropore clogging due to irreversible adsorption. Only a slight recovery of the permeability was observed by the desorption treatment at 150°C in vacuum. After exposure to propane, the membrane reached a newly organized state and, thereafter, gave a reproducible performance for propylene/propane separation (Figure 8), which is listed in Table V . The irreversible reduction in gas permeability became much smaller with lower pyrolysis temperature. The 6FDA-mPD 3

3

6

6

3


6


b

0

b

Pyrolysis conditions this study 500°C, l h 700 °C, l h this study 600°C, l h 700°C, l h 4 800°C,1 h 7,8 800°C, 2h 950°C, l h 10 600°C,Oh

Ref.

25

20 35

35

Τ (°C) 35

1

2

Permeability (Barrers) H CO, 0, 6,600 3,000 670 1,700 250 68 19,000 16,000 3.100 11,000 4,600 950 13 1.2 670 130 35 53 3.5 0.92 330

e

2

10,12

Pyrolysis conditions 500°C, l h 700 °C, l h 950°C 700°C, 4 min. 500°C, 2h 550°C, 2h 600°C, Oh 700°C, Oh 25

RT 50 RT

Τ (°C) 35

-

(170)

-

2

130 (100) (73) 160 79

-

2

760

co o 2

22

f

14 1.4 190 43 (20-50) (15-40)

Permeance (GPU) 59 5.0

2

H 130 34

-

_

(450)

-

-

200

270 1,200

H2/CH4

2

30 55

(55)

20

-

d

-

(190) 80 57

33

_

Selectivity C0 /N CO2/CH4 40 120 39 180 2

Selectivity COy/N? CO?/CH4 40 120 39 180 26 32 39 60 50 42 83 30 80

b

2

2

f

0 /N : 20 mol% 0 ; Permeance is given in GPU (1 GPU=lxlO"W(STP)/cm *s-cmHg); dense andflat-sheet,50 μπι thickness; precursor polymer unspecified, hollow fiber (effective thickness of 6±1 urn), activated: d hollow fiber "tubular; at 65°C.

d

3 13 5

unspecified BPDA-ΡΓ BPDA/6FDATrMPD BPDA-ODA

0

this study

6FDA-DABZ

1

-

_

_

Hz/CH, 270 1,200 39 140

Table IV. Permeance (P/l) and selectivity of carbon molecular sieve membranes.*

Ref.

c

Membrane

b

' Single-gas permeation; Ρ is given in Barrer (1 Barrer^ixlO" W(STP)*cm/cm^s»cmHg); dense and flat-sheet; tubular (effective thickness of 2 μιη).

BPDA-ODA

Kapton Kapton

6FDA-mPD

6FDA-DABZ

" " 1

Membrane

Table ΠΙ. Permeability (Ρ) and selectivity of carbon molecular sieve membranes.

5


7.5

2

f

2

2

0 /N 9.1 11 8.0 6.7 (8.5-12) (11-14)

2

0 /N 9.1 11 5.2 8.0 4.6 12 22

324 polyimide and 6FDA-DABZ polypyrrolone membranes carbonized at 500°C displayed reproducible performance for propylene/propane separation even at room temperature. Table V . Performance of carbon molecular sieve membranes for propylene/propane separation at 35°C. a

Membrane

Reference

Pyrolysis C H Permeability Selectivity conditions (Barrers) C^H(J C H pure-gas mixed-gas pure-gas mixed-gas this study 500°C,lh 13 1,600 1,100 25 600°C, l h 1,200 660 33 16 700°C, l h 26 530 130 53 this study 500°C,lh 94 44 170 78 3

6


3

6FDA-mPD

6FDADABZ Modified Kapton BPDA-ODA

b

8

b

9

1,000°C

10

11

700°C, Oh

14

e

-

20

14

54

-

e

0

d

46

a

mixed-gas permeation performed with a propylene/propane mixture (50:50 mol%); dense and flat-sheet (50 μπι thick); dense and flat-sheet (113 μπι thick); tubular; at 100°C.

b

c

d

e

Figure 8 shows the temperature dependence of the permeability and selectivity for a propylene/propane mixture. With increasing temperature, the permeability increased, whereas the selectivity decreased. The CMS membranes should be used at higher temperature to eliminate the complicated effects of adsorption of coexisting components and contaminants. Figure 9 shows the time dependence of adsorption of propylene and propane in the carbonized polyimide membranes. For membranes carbonized at 500°C, the equilibrium sorption amount is only a little larger for propylene than for propane, whereas the adsorption rate was much faster for propylene. For membranes carbonized at 700°C, equilibrium adsorption was attained for propylene in about 5 hours. On the other hand, equilibrium adsorption for propane required at least 100 hours. Separation of propylene/propane mixtures through the carbonized membranes is clearly due to a molecular sieving effect rather than a difference in adsorption properties. The mixed-gas, steady-state permeation properties were obtained within a much shorter time compared with the pure-component sorption and pure-gas permeation of propane. This result indicates that the presence of propylene enhanced the diffusion and permeability of propane.


325 ,

. .

,

"»-I—|-T"1--f-

,

700t

100

soot


. 1. , . .

2.5

3

3.5

4

ιοοο/Γ [κ: ] 1

Figure 8. Temperature dependence of Ρ and α of C H6/C Hg for 6FDA-mPD polyimide membranes carbonized at 500 and 700°C. 3

3

Figure 9. Time-dependence of C H and C H adsorption (0.5 arm, 75°C) for 6FDA-mPD polyimide membranes carbonized at 500 and 700°C. 3

6

3

8


326 C M S Membranes from Phenolic Resin


A phenolic resin was also selected as a precursor polymer on the basis of its high carbon yield and thermosetting properties without deforming the deposition layer on a substrate during heating and pyrolysis. Preparation and Characterization. A phenolic resin (Bellpearl S-895) used as the starting material was supplied by Kanebo Ltd. Porous α-alumina tubes, supplied by Mitsui Grinding Wheel Co., had a mean pore diameter of 1 μπι with a porosity of about 50%, and their dimensions were 1 cm in outer diameter, 0.2 cm in thickness, and 5 cm in effective length. Colloidal silica (EG-ST, supplied by Nissan Chemical Ind.) was dip-coated onto the α-alumina tubes in order to reduce the pore size of the substrate. The silica-coated alumina tubes thus prepared were used as substrate. In addition, another type of porous α-alumina tubes supplied by N O K Co. was used. These support membranes had a mean pore diameter of 0.15 μιη with a porosity of 44% and their dimensions were 0.23 cm in outer diameter, 0.03 cm in thickness, and were 3.3 cm in effective length. The membranes from phenolic resin were formed by a dip process in which the porous substrate capped with silicone rubber was dipped into a 40 wt% (or 20 wt% as noted below) phenolic resin solution in methanol for 20 min at room temperature. The coated substrate was then pulled out at a rate of 1 or 20 cm/min. After air-drying at 50°C for one day and vacuum-drying at 50°C for one day, the membranes were heated up to 500700°C at a heating rate of 5°C/min under nitrogen atmosphere and held at the temperature for 1 h. The coating-pyrolysis cycle was repeated two or three times. After the second cycle, the coating was carried out using a 20 wt% solution in methanol. Thermogravimetry showed that a significant weight loss occurred around 200, 380, and 555°C, respectively, followed by gas evolution. The evolved gases were carbon monoxide, carbon dioxide, water, and larger molecules. The weight loss was about 45% at 800°C. S E M analysis indicated a nonporous carbon layer on the substrate with a thickness of several micrometers. To reduce the thickness of the carbon layer, the 20 wt% phenolic resin solution was used even for the first coating. In this case, the surface carbon layer was so thin that the porous structure of the substrate could be observed from the surface view of the SEM. The cross-section view of the S E M indicated that the carbon layer was formed on the substrate in a depth of about 3 μηι from the surface (Membrane ND2-3 in Table VI). The micropore volume determined from nitrogen adsorption for the phenolic resin membrane carbonized at 600°C for 2h was 0.23 cm /g, which was smaller than that of the 6FDA-DABZ polypyrrolone membrane (0.30 cm /g). 3

3


327 Gas Separation Properties. Gas permeation experiments were carried out by the vacuum time-lag method. Single-component or mixed-gas was fed to the outer side of the membrane in a permeation cell. The membrane was sealed in the cell module with a fluoro-rubber o-ring and the effective membrane area was 15.2 or 2.4 cm . For the silica-coated substrate (Type S), the permeance decreased sharply with the second coating and started to level off after the third coating. Thus, three coatings gave highly selective membranes. For the alumina substrate having pores of 1 μηι, more than 4 coatings were necessary to give a pinhole-free membrane. On the other hand, for the alumina substrate having pores of 0.14 μηι (Type N), only two coatings gave highly selective membranes. Table V I shows a comparison of membrane performance toward several gas pairs of C M S membranes from a phenolic resin. The gas permeation properties depended significantly on the type of substrate.


2

Table VI. Permeance (P/L) and selectivity of carbon molecular sieve membranes from phenolic resin at 35°C. a

Membrane Pyrolysis conditions SD3-1 700°C, l h ND2-1 ND2-2 ND2-3 ND2-4

Permeance (GPU) C0 H o2 210 150 35 (150) 500°C, l h 380 83 19 (84) 600°C, l h 410 73 15 (63) 600°C,lh 330 40 210 (210) 700°C, l h 110 20 4.2 (17) 2

2

Selectivity H2/CH4 C 0 / N C 0 / C H 24 63 110 (30) 34 82 370 (51) 34 70 390 (51) 38 32 63 (36) 44 690 140 (55) 2

2

2

4

0 /N 5.2 2

2

7.9 7.3 6.2 8.9

a

data in parenthesis are for mixed-gas permeation; 20 mol% C 0 . Membrane code refers to substrate (S = silica-coated alumina tube, Ν = smaller size alumina tube; coating process of phenolic resin (D = dip), coating times and sample identification. ND2-3: 20 wt% phenolic resin solution was used even for the first coating. 2

Membrane ND2-4 had a larger penetrant-size dependence of the permeance and a higher selectivity than the membrane SD3-1. With increasing the pyrolysis temperature from 500 to 700°C, the permeance decreased, but the selectivity increased. This is similar to the behavior of the C M S membranes made from the polyimide and polypyrrolone. The permeance of N and C H increased with increasing temperature. The permeances of H , He, and 0 were essentially independent of temperature. On the other hand, the C 0 permeance decreased with increasing temperature. This behavior suggests contribution of surface diffusion for C 0 permeation. As compared with the single-component system, the C 0 2

2

4

2

2

2

2


328 permeance in the mixed-component system was essentially constant, but the N permeance decreased. As a result, the selectivity increased by about 30-50%. The decrease in the N permeance may be due to preferential adsorption of C 0 in the micropores of the membrane and, therefore, hindrance by adsorbed C 0 molecules to N transport through the pores of the membrane. The C M S membranes from the phenolic resin displayed fairly high performance for C 0 / N separation, that is, the C 0 permeance was 84 G P U and the C 0 / N selectivity was 51 at 35°C. Table VII shows the performance for propylene/propane separation of the carbonized membranes. The carbonized phenolic resin membranes displayed fairly high performance for single-gas permeation, but in mixed-gas permeation experiments, the propylene permeance decreased significantly and the propylene/propane selectivity decreased. As a result, the performance of this membrane type was inferior to that of the carbonized B P D A - O D A polyimide membranes {11). Both membranes had a similar composite structure composed of the carbonized polymer layer on a porous α-alumina tube (NOK). However the membranes showed a very different behavior for gas mixtures, indicating that the adsorption behavior of the hydrocarbon vapor was dependent on the precursor polymer and the pyrolysis conditions. Further investigations are necessary for a more detailed evaluation for propylene/propane separation of the C M S membranes made from phenolic resin. 2

2

2

2

2

2


2

2

2

2

Table VII. Performance of carbon molecular sieve membranes for propylene/propane separation at 35°C. a

Membrane

Pyrolysis conditions 500°C; 1 h 500°C;1 h

b

6FDA-mPD 6FDADABZ BPDA-ODA

(P/L) propylene (GPU) mixed-gas pure-gas (19) 28 (1.7) 3.1

C H6/C3H selectivity pure-gas mixed-gas (13) 25 78 (44) 3

8

b

c

Phenolic resin ND2-3 ND2-5

700°C;0h

(2.4) (8.7 )

2.6 9.3

(46) (33 )

54 29

d

d

54 (II ) 30 (0.19) (2.0 ) data in parenthesis are for mixed-gas permeation (50%C H6/50% C H ); flat-sheet, 50 μηι thick. tubular (réf. 11); at 100°C; at 90°C. 600°C; 1 h 500°C; 1 h

19 7.7

e

e

a

3

0

d

3

8

e

(II ) (27) (18 ) dense and e

e

Conclusions With increasing pyrolysis temperature, the permeability decreased and the selectivity of heat-treated polymeric membranes increased, because the membranes


329 became denser and the effective pore size for molecular sieving became smaller, whereas gas adsorption increased slightly. C M S polyimide and polypyrrolone membranes displayed high performance for certain gas separation applications, such as C 0 / C H , 0 / N , and propylene/propane. C M S membranes made from a phenolic resin displayed high performance for C O 2 / N 2 separation. 2

4

2

2


Acknowledgments This work was supported partly by Grand-in-aid for Developmental Scientific Research (No. 08455367) from the Ministry of Education, Science, and Culture of Japan, and also by the Petroleum Energy Center and Japan High Polymer Center at the R & D project for membrane for petroleum component separation. Literature Cited 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20.

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Preparation of Carbon Molecular Sieve Membranes and Their Gas

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