JP6030060B2 - 炭素膜を製造するための方法 - Google Patents
炭素膜を製造するための方法 Download PDFInfo
- Publication number
- JP6030060B2 JP6030060B2 JP2013530741A JP2013530741A JP6030060B2 JP 6030060 B2 JP6030060 B2 JP 6030060B2 JP 2013530741 A JP2013530741 A JP 2013530741A JP 2013530741 A JP2013530741 A JP 2013530741A JP 6030060 B2 JP6030060 B2 JP 6030060B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylenically unsaturated
- carbon
- porous
- temperature
- oxide layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 75
- 229910052799 carbon Inorganic materials 0.000 title claims description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000012528 membrane Substances 0.000 claims description 57
- 238000000197 pyrolysis Methods 0.000 claims description 34
- 239000000758 substrate Substances 0.000 claims description 32
- 239000000919 ceramic Substances 0.000 claims description 31
- 239000011148 porous material Substances 0.000 claims description 31
- 238000000926 separation method Methods 0.000 claims description 30
- 229920006305 unsaturated polyester Polymers 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 17
- 229920000728 polyester Polymers 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 14
- 229920000620 organic polymer Polymers 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 10
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical group CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 239000005373 porous glass Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 230000035699 permeability Effects 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 229910052786 argon Inorganic materials 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- -1 alkalis Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000005011 phenolic resin Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000003618 dip coating Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000007849 furan resin Substances 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229920000368 omega-hydroxypoly(furan-2,5-diylmethylene) polymer Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 239000012465 retentate Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HIBWGGKDGCBPTA-UHFFFAOYSA-N C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 HIBWGGKDGCBPTA-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 206010013395 disorientation Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- VOXVCYMHFQQEMC-UHFFFAOYSA-O triethylazanium;nitrate Chemical compound [O-][N+]([O-])=O.CC[NH+](CC)CC VOXVCYMHFQQEMC-UHFFFAOYSA-O 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0067—Inorganic membrane manufacture by carbonisation or pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/08—Specific temperatures applied
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Carbon And Carbon Compounds (AREA)
Description
a)多孔性の基材を、熱分解によって炭素膜に変換することができる少なくとも1種の有機ポリマーの溶液で被覆する工程、
b)多孔性の基材上のポリマー被覆物を、溶媒を除去することによって乾燥させる工程、
c)ガスの分離に適切な炭素膜を形成するために、多孔性の基材上のポリマー被覆物を熱分解させる工程、
を含み、工程a)から工程c)までの各工程、又は工程a)から工程c)までのシーケンスは、複数回行うことができ、及び工程c)での熱分解が、多孔性の基材の焼き付け温度よりも高い温度で行われることを特徴とする、ガスの分離に適切な炭素膜を製造するための方法によって解決される。
芳香族ジカルボン酸は、適切な任意の芳香族ジカルボン酸から選ぶことができる。これは例えば、フタル酸、イソフタル酸、又はテレフタル酸であっても良い。好ましくは、芳香族ジカルボン酸は、フタル酸である(これは不飽和ポリエステルを製造するために、無水フタル酸のとして使用される)。
(例えば、脱水素化における)C1から高い側の炭化水素からの水素の分離。
実施例1
ジオールと少なくとも1種の不飽和カルボン酸を反応させて、不飽和ポリエステルを形成し、次にオレフィンを加えることによって、前駆体溶液を製造した。特定の場合では、250mlの2クビフラスコ中に、19.98gの1,2−プロパンジオール(0.25モル+5%過剰;VWR)、12.26gの無水マレイン酸(0.125モル;VWR)、及び18.52gの無水フタル酸(0.125モル;VWR)を計量導入した。次に(予定よりも早い重合−又は架橋の進行を回避するために)0.01gのヒドロキノン(VWR)を重合抑制剤として加えた。窒素下に、計量導入した材料を、オイル槽を使用して反応温度200℃に加熱した。鎖構造の形成をチェックするために、規則的な間隔で、KOH−溶液を使用した滴定で、酸価を測定した。約50の酸価で、140℃に迅速に冷却することによって反応を中断させた。次に滴下漏斗を使用して、強く攪拌させながら1分以内に50gのスチレン(スチロール)を架橋剤として加えた。加えたスチレンは、事前に50℃に加熱した。ポリエステル−スチレン−混合物の早期の重合を回避するために、不飽和ポリエステル樹脂溶液を水槽中で、室温に冷却した。この後、ポリエステル−スチレン−混合物中に、1%のジベンゾイルペルオキシド(VWR)を遊離基形成剤として加え、そして次に5分間、室温で攪拌した。
1.窒素中で、室温から380℃へと、0.5K/分で昇温
2.窒素中、380℃で、1時間の保持時間、
3.窒素中、380℃から500℃へと、0.6K/分で昇温
4.窒素中、500℃で10分間、保持
5.窒素からアルゴンへと雰囲気を変換
6.アルゴン中、500℃から最終的な熱分解温度へと1K/分で昇温
7.アルゴン中、最終的な熱分解温度での1時間の保持時間
8.アルゴン中、最終的な熱分解温度から500℃へと5K/分で冷却
9.アルゴンから窒素へと雰囲気を変換
10.窒素中、500℃から室温へと5K/分で冷却
ベーマイト−ゾルを、浸漬被覆法を使用して、小さくなる孔径を有する複数の層の複合体から構成される、チューブ状の非対称のセラミック担体の内側に施した。担体は、7mmの内径、10mmの外径、及び105mmの長さを有していた。被覆の後、試料を空気中で室温で乾燥させ、そして300℃、500℃、及び800℃でか焼させた。乾燥およびか焼させたベーマイト層を、浸漬被覆法を使用して前駆体で被覆した。このために、フェノール樹種溶液で膜チューブ内を満たし、そして1分間の滞留時間の後、再度排出した。溶液の製造のために、2種のフェノール樹脂粉を使用した:
1.窒素中で、0.5K/分で、室温から380℃へと昇温
2.窒素中、380℃で、1時間の保持時間
3.窒素中で、0.6K/分で、380℃から500℃へと昇温
4.窒素中、500℃で10分間の保持時間
5.窒素からアルゴンへと雰囲気を変換
6.アルゴン中で、500℃から最終的な熱分解温度へと1K/分で昇温
7.アルゴン中、最終的な熱分解温度での1時間の保持時間
8.アルゴン中、最終的な熱分解温度から500℃へと5K/分で冷却
9.アルゴンから窒素へと雰囲気を変換
10.窒素中、500℃から室温へと5K/分で冷却
Pa=無水フタル酸 *Nm3=stpでのm2
前駆体溶液の製造(ポリエステル:25モル% 無水マレイン酸、25モル%無水フタル酸、及び50モル%1,2−プロパンジオール;溶液:50質量%PES及び50質量%スチレン)、被覆のために使用される担体(最上の中間層:500℃でか焼したベーマイトゾル)、前駆体溶液を使用した被覆、乾燥(空気中、室温で24時間)、架橋(空気中、80℃で12時間)、最終的な熱分解(Ar中、650℃で1時間)を、実施例1に詳細に記載したように行った。
I:300℃における、供給−/保持圧力の、2.6〜10.2バール絶対圧の範囲での変化
II:7.1バール絶対圧の供給−/保持圧力での、200〜350℃の範囲における温度の変化
Claims (8)
- a)基材担体層の上に、表面のメソ多孔性セラミック酸化物層を有する多孔性の基材を、熱分解によって炭素膜に変換することができる少なくとも1種の有機ポリマーの溶液で被覆する工程、
b)多孔性の基材上のポリマー被覆物を、溶媒を除去することによって乾燥させる工程、
c)ガスの分離に適切な炭素膜を形成するために、多孔性の基材上のポリマー被覆物を熱分解させる工程、
を含み、
工程a)で使用される表面のメソ多孔性セラミック酸化物層は、孔径が2〜9nmの範囲であり、及び
工程a)から工程c)までの各工程、又は工程a)から工程c)までのシーケンスは、複数回行うことができ、及び工程c)での熱分解が、多孔性の基材の焼き付け温度よりも高い温度で行われ、
焼かれていない状態の、表面のメソ多孔性セラミック酸化物層が、少なくとも1種の有機ポリマーの溶液で被覆され、及び工程c)での熱分解が、500〜900℃の範囲の温度で行われ、
前記少なくとも1種の有機ポリマーが、脂肪族ジオール、芳香族ジカルボン酸、及びエチレン性不飽和ジカルボン酸の繰り返し単位を有するエチレン性不飽和のポリエステルであることを特徴とする、ガスの分離に適切な炭素膜を製造するための方法。 - 基材担体層が、多孔性金属、多孔性セラミック、多孔性ガラス、及びこれらの多孔性複合体から選ばれることを特徴とする請求項1に記載の方法。
- 表面のメソ多孔性セラミック酸化物層が、ゾル−ゲル−技術で製造されることを特徴とする請求項1又は2の何れかに記載の方法。
- 表面のメソ多孔性セラミック酸化物層が、TiO2、ZrO2、Al2O3、SiO2、又はこれらの混合物から形成されることを特徴とする請求項1〜3の何れか1項に記載の方法。
- 表面のメソ多孔性セラミック酸化物層が、γ−Al2O3で形成されることを特徴とする請求項4に記載の方法。
- 前記脂肪族ジオールが、C2−12−アルカンジオールであり、及び前記エチレン性不飽和ジカルボン酸が、マレイン酸であることを特徴とする請求項1に記載の方法。
- エチレン性不飽和のポリエステルの溶液が、追加的に、架橋されるエチレン性不飽和モノマー、及び架橋開始剤としての遊離基形成剤を含むことを特徴とする請求項1〜6の何れか1項に記載の方法。
- 架橋されるエチレン性不飽和のモノマーが、スチレン又はα−メチルスチレンであることを特徴とする請求項7に記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10186168 | 2010-10-01 | ||
EP10186168.0 | 2010-10-01 | ||
PCT/EP2011/067073 WO2012041999A1 (de) | 2010-10-01 | 2011-09-30 | Verfahren zur herstellung von kohlenstoffmembranen |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2013541413A JP2013541413A (ja) | 2013-11-14 |
JP6030060B2 true JP6030060B2 (ja) | 2016-11-24 |
Family
ID=44735918
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2013530741A Expired - Fee Related JP6030060B2 (ja) | 2010-10-01 | 2011-09-30 | 炭素膜を製造するための方法 |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP2621610B1 (ja) |
JP (1) | JP6030060B2 (ja) |
CN (1) | CN103237588B (ja) |
WO (1) | WO2012041999A1 (ja) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102014118892A1 (de) | 2014-12-17 | 2016-06-23 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Kohlenstoffmembran, Verfahren zur Herstellung von Kohlenstoffmembranen und deren Verwendung |
JP6956608B2 (ja) * | 2017-11-29 | 2021-11-02 | 京セラ株式会社 | 炭素膜付き多孔質体 |
KR20210005011A (ko) | 2018-05-02 | 2021-01-13 | 다우 글로벌 테크놀로지스 엘엘씨 | 탄소 분자체 막의 향상된 제조 방법 |
CN111111465A (zh) * | 2018-11-01 | 2020-05-08 | 中国科学院宁波材料技术与工程研究所 | 一种co2/n2气体分离膜、其制备方法及应用 |
CN113877444B (zh) * | 2020-07-02 | 2023-01-24 | 中国石油化工股份有限公司 | 一种多孔支撑体复合碳膜及其制备和应用 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IL108883A (en) | 1994-03-07 | 1998-03-10 | Rotem Ind Ltd | Process for the production of hollow carbon fiber membranes |
JP3647985B2 (ja) * | 1996-08-09 | 2005-05-18 | カネボウ株式会社 | 分子ふるい炭素膜およびその製造法 |
WO2000053299A1 (en) * | 1999-03-12 | 2000-09-14 | E.I. Du Pont De Nemours And Company | Supported nanoporous carbogenic gas separation membrane and process for preparation thereof |
ES2155381B1 (es) * | 1999-04-15 | 2001-12-01 | Consejo Superior Investigacion | Procedimiento para la preparacion de membranas de carbono para la separacion de gases. |
JP2004509735A (ja) * | 2000-06-22 | 2004-04-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 混合マトリックスナノポーラスカーボンメンブレン |
JP2002066280A (ja) * | 2000-08-30 | 2002-03-05 | Kyocera Corp | ガス分離フィルタおよびその製造方法 |
CN101351263B (zh) * | 2006-07-20 | 2012-09-05 | 日本碍子株式会社 | 陶瓷过滤器 |
-
2011
- 2011-09-30 CN CN201180057905.7A patent/CN103237588B/zh not_active Expired - Fee Related
- 2011-09-30 WO PCT/EP2011/067073 patent/WO2012041999A1/de active Application Filing
- 2011-09-30 JP JP2013530741A patent/JP6030060B2/ja not_active Expired - Fee Related
- 2011-09-30 EP EP11764168.8A patent/EP2621610B1/de not_active Not-in-force
Also Published As
Publication number | Publication date |
---|---|
EP2621610B1 (de) | 2018-08-22 |
CN103237588A (zh) | 2013-08-07 |
WO2012041999A1 (de) | 2012-04-05 |
CN103237588B (zh) | 2015-09-16 |
JP2013541413A (ja) | 2013-11-14 |
EP2621610A1 (de) | 2013-08-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8608828B2 (en) | Process for producing carbon membranes | |
JP6219165B2 (ja) | 炭素膜の製造方法 | |
Tanco et al. | Composite-alumina-carbon molecular sieve membranes prepared from novolac resin and boehmite. Part I: Preparation, characterization and gas permeation studies | |
Bhuwania et al. | Engineering substructure morphology of asymmetric carbon molecular sieve hollow fiber membranes | |
Suda et al. | Gas permeation through micropores of carbon molecular sieve membranes derived from Kapton polyimide | |
JP3647985B2 (ja) | 分子ふるい炭素膜およびその製造法 | |
JP6030060B2 (ja) | 炭素膜を製造するための方法 | |
Fuertes et al. | Preparation of supported carbon molecular sieve membranes | |
Hou et al. | Carbon nanotube networks as nanoscaffolds for fabricating ultrathin carbon molecular sieve membranes | |
Li et al. | Synthesis of tubular ZIF-8 membranes for propylene/propane separation under high-pressure | |
Abd Jalil et al. | Vacuum-assisted tailoring of pore structures of phenolic resin derived carbon membranes | |
Zhou et al. | Preparation and gas permeation properties of carbon molecular sieve membranes based on sulfonated phenolic resin | |
Wang et al. | Intermediate gel coating on macroporous Al2O3 substrate for fabrication of thin carbon membranes | |
Weng et al. | Effect of SBA-15 texture on the gas separation characteristics of SBA-15/polymer multilayer mixed matrix membrane | |
JP5523560B2 (ja) | 炭素膜複合体およびその製造方法ならびに分離膜モジュール | |
JP5897458B2 (ja) | 浸透気化分離方法 | |
KR102144807B1 (ko) | 폴리이미드 전구체의 전처리를 통한 탄소분자체막의 제조방법 및 이에 의해 제조된 탄소분자체막 | |
US8608837B2 (en) | Process for producing carbon membranes | |
Zhang et al. | Preparation and characterization of supported ordered nanoporous carbon membranes for gas separation | |
JP2004123533A (ja) | 含浸−ローリング法による熱的安定性に優れたシリカ複合膜の製造方法 | |
CN109351202A (zh) | 一种基于陶瓷管为支撑体复合炭膜的制备方法 | |
US11786870B2 (en) | CMS membrane, method for the production thereof and use thereof | |
Setnickova et al. | Realizing the impact of the intermediate layer structure on the CO2/CH4 separation performance of carbon molecular sieving membranes: insights from experimental synthesis and molecular simulation | |
TW201908003A (zh) | 流體分離用碳膜及其製造方法 | |
US20190070568A1 (en) | Permeation membrane and method for producing a permeation membrane |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140922 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20150624 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150630 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20150917 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20151021 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160308 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20160530 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20160729 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160829 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160920 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20161019 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6030060 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |