JP4965927B2 - CO2 facilitated transport membrane and method for producing the same - Google Patents
CO2 facilitated transport membrane and method for producing the same Download PDFInfo
- Publication number
- JP4965927B2 JP4965927B2 JP2006209816A JP2006209816A JP4965927B2 JP 4965927 B2 JP4965927 B2 JP 4965927B2 JP 2006209816 A JP2006209816 A JP 2006209816A JP 2006209816 A JP2006209816 A JP 2006209816A JP 4965927 B2 JP4965927 B2 JP 4965927B2
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- group
- facilitated transport
- porous membrane
- carbon dioxide
- 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.)
- Active
Links
- 239000012528 membrane Substances 0.000 title claims description 286
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 193
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 96
- 239000001569 carbon dioxide Substances 0.000 claims description 90
- 229920002125 Sokalan® Polymers 0.000 claims description 63
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 49
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 49
- 239000000654 additive Substances 0.000 claims description 48
- 230000002209 hydrophobic effect Effects 0.000 claims description 45
- 230000000996 additive effect Effects 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 34
- PECYZEOJVXMISF-UHFFFAOYSA-N 3-aminoalanine Chemical compound [NH3+]CC(N)C([O-])=O PECYZEOJVXMISF-UHFFFAOYSA-N 0.000 claims description 26
- -1 tetrafluoroborate ions Chemical class 0.000 claims description 25
- 108010025899 gelatin film Proteins 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 20
- 239000012530 fluid Substances 0.000 claims description 19
- 239000004584 polyacrylic acid Substances 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- 230000035699 permeability Effects 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 10
- 125000001033 ether group Chemical group 0.000 claims description 10
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 7
- 230000001737 promoting effect Effects 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229920000083 poly(allylamine) Polymers 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229940006460 bromide ion Drugs 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 193
- 229910002091 carbon monoxide Inorganic materials 0.000 description 193
- 239000007789 gas Substances 0.000 description 88
- 230000032258 transport Effects 0.000 description 67
- 229910052739 hydrogen Inorganic materials 0.000 description 51
- 239000001257 hydrogen Substances 0.000 description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 41
- 239000011148 porous material Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- 239000002994 raw material Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- 238000002156 mixing Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 13
- 238000002407 reforming Methods 0.000 description 13
- 230000007547 defect Effects 0.000 description 12
- 239000012466 permeate Substances 0.000 description 11
- 239000000446 fuel Substances 0.000 description 10
- 230000007423 decrease Effects 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000036961 partial effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000000629 steam reforming Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- PJRDBXPGKMQTIW-UHFFFAOYSA-M 2-(3-methylimidazol-3-ium-1-yl)ethanol;bromide Chemical compound [Br-].CN1C=C[N+](CCO)=C1 PJRDBXPGKMQTIW-UHFFFAOYSA-M 0.000 description 3
- OXFBEEDAZHXDHB-UHFFFAOYSA-M 3-methyl-1-octylimidazolium chloride Chemical compound [Cl-].CCCCCCCCN1C=C[N+](C)=C1 OXFBEEDAZHXDHB-UHFFFAOYSA-M 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- VBWHCNAJCDFROZ-UHFFFAOYSA-M 1-(2-methoxyethyl)-3-methylimidazol-3-ium;bromide Chemical compound [Br-].COCC[N+]=1C=CN(C)C=1 VBWHCNAJCDFROZ-UHFFFAOYSA-M 0.000 description 1
- GWQYPLXGJIXMMV-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCN1C=C[N+](C)=C1 GWQYPLXGJIXMMV-UHFFFAOYSA-M 0.000 description 1
- RRJMJVTWXXRBPT-UHFFFAOYSA-N 2-ethyl-3-methyl-1H-imidazol-3-ium trifluoromethanesulfonate trifluoromethanesulfonic acid Chemical compound CCC1=[N+](C)C=CN1.[O-]S(C(F)(F)F)(=O)=O.OS(C(F)(F)F)(=O)=O RRJMJVTWXXRBPT-UHFFFAOYSA-N 0.000 description 1
- UINDRJHZBAGQFD-UHFFFAOYSA-O 2-ethyl-3-methyl-1h-imidazol-3-ium Chemical compound CCC1=[NH+]C=CN1C UINDRJHZBAGQFD-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- MKHFCTXNDRMIDR-UHFFFAOYSA-N cyanoiminomethylideneazanide;1-ethyl-3-methylimidazol-3-ium Chemical compound [N-]=C=NC#N.CCN1C=C[N+](C)=C1 MKHFCTXNDRMIDR-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- KHHDKFZTSKLKFF-UHFFFAOYSA-N fluorane Chemical compound F.F.F.F.F.F.F.F KHHDKFZTSKLKFF-UHFFFAOYSA-N 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- GTDKXDWWMOMSFL-UHFFFAOYSA-M tetramethylazanium;fluoride Chemical compound [F-].C[N+](C)(C)C GTDKXDWWMOMSFL-UHFFFAOYSA-M 0.000 description 1
- JCQGIZYNVAZYOH-UHFFFAOYSA-M trihexyl(tetradecyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC JCQGIZYNVAZYOH-UHFFFAOYSA-M 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Description
本発明は、二酸化炭素の分離に用いられるＣＯ２促進輸送膜に関し、特に、水素を主成分とする燃料電池用等の改質ガスに含まれる二酸化炭素を水素に対する高い選択比率で分離可能なＣＯ２促進輸送膜に関する。 The present invention relates to a CO 2 facilitated transport membrane used for separation of carbon dioxide, and in particular, CO that can separate carbon dioxide contained in reformed gas for a fuel cell or the like containing hydrogen as a main component at a high selectivity to hydrogen. 2 relates to facilitated transport membrane.
現在開発中の水素ステーション用改質システムでは、水蒸気改質により炭化水素を水素、一酸化炭素（ＣＯ）に改質し、更に、ＣＯ変成反応を用いて一酸化炭素を水蒸気と反応させることにより水素を製造している。 In the reforming system for the hydrogen station currently under development, the hydrocarbon is reformed to hydrogen and carbon monoxide (CO) by steam reforming, and further, the carbon monoxide is reacted with steam using a CO shift reaction. Produces hydrogen.
しかし、これらの技術はケミカルプラント用の大規模な水素製造プロセスとして開発されたものであり、日産数１０万ｍ３以上の大規模なものが普通で、しかも工場内に設置され、高圧・連続運転が前提となっている。これに対し、将来の水素エネルギ社会を支える重要なインフラとして天然ガスや石油からオンサイトで水素を製造し燃料電池自動車等に水素を供給する水素ステーションでは、水素を製造する規模や設置環境、運転パターンにおいて、従来の大規模水素プラントと大きく異なっており、それに起因する問題が多く残されている。 However, these techniques has been developed as a large-scale hydrogen production processes for chemical plants, Nissan number 100,000 m 3 or more ones are usually large, yet installed in the factory, high-continuous Driving is assumed. On the other hand, in the hydrogen station that produces hydrogen on-site from natural gas and oil as an important infrastructure that will support the future hydrogen energy society and supplies hydrogen to fuel cell vehicles, etc., the scale, installation environment, and operation of hydrogen production The pattern is greatly different from the conventional large-scale hydrogen plant, and many problems resulting from it remain.
性能面の課題としては、水素ステーションの場合、水素需要（具体的には、水素供給対象の燃料電池自動車の数量等）に対応して、頻繁な起動停止や負荷変化に対応する必要がある。特に、改質システム中でもサイズが最も大きく熱容量の大きなＣＯ変成器に対して、起動時間や負荷応答性等の面で改善が必要となっている。 As a performance problem, in the case of a hydrogen station, it is necessary to respond to frequent start / stop and load changes in response to hydrogen demand (specifically, the number of fuel cell vehicles to be supplied with hydrogen, etc.). In particular, the CO transformer having the largest size and the largest heat capacity among reforming systems needs to be improved in terms of start-up time and load response.
また、燃料電池用改質システムの普及促進に必須とされる家庭用システムでのＤＳＳ（毎日の起動停止）運転に対しても、起動時間や負荷応答性等において、改質システム中でもＣＯ変成器に課題が多く残されており、特に、ＣＯ変成器の小型化、低温度化が最大の課題である。 In addition, even for DSS (daily start / stop) operation in home systems, which is essential for promoting the reforming of fuel cell reforming systems, the CO transformer is also used in reforming systems in terms of start-up time and load responsiveness. Many problems remain, and in particular, downsizing and lowering the temperature of the CO transformer are the biggest problems.
更に、自動車用への適用についても、水蒸気改質方式はサイズや起動時間の点で目標との大きなギャップがあり、自動車業界ではオンボード改質に関しては効率の高い水蒸気改質よりは、寧ろ昇温反応性に優れた部分酸化方式での実用化を目指す傾向がある。しかし、部分酸化方式では、改質器については大幅な小型化が期待できるものの、ＣＯ変成器を伴うため、実用化に向けてはＣＯ変成器の小型化が大きな課題となっている。このようにＣＯ変成器の小型化は水素ステーションだけではなく、自動車用を含む燃料電池改質システムに共通の課題と言える。 In addition, the steam reforming method has a large gap with respect to the target in terms of size and start-up time for automotive applications, and the on-board reforming in the automotive industry is rather more efficient than steam reforming, which is highly efficient. There is a tendency to aim at practical use with a partial oxidation method with excellent temperature reactivity. However, in the partial oxidation method, although the reformer can be expected to be greatly reduced in size, since it is accompanied by a CO converter, downsizing of the CO converter is a major issue for practical use. Thus, it can be said that downsizing of the CO converter is a common problem not only for the hydrogen station but also for the fuel cell reforming system including for automobiles.
また、効率面から見ても、水蒸気改質を行う際、Ｓ／Ｃ（スチームと炭素（原料炭化水素）のモル比）の低下が熱効率上望ましいが、ＣＯ変成反応の化学平衡上の制約から効率の高い低Ｓ／Ｃ条件が採用されていなかった。 Also, from the viewpoint of efficiency, when steam reforming is performed, a decrease in S / C (molar ratio of steam to carbon (raw hydrocarbon)) is desirable in terms of thermal efficiency, but due to restrictions on the chemical equilibrium of the CO shift reaction. Highly efficient low S / C conditions were not employed.
コスト面での課題としては、水素ステーション全体のコストで最大の割合を占めるのがＰＳＡ（プレッシャー・スイング・アドソープション）であることから、そのコストダウンに直接繋がる水素濃度を上げる改質方式が望まれていた。改質器の出口ガス組成は水素以外に、１０％程度の一酸化炭素及び二酸化炭素が含まれており、ＣＯ変成器では一酸化炭素は減少するものの二酸化炭素は増加するため、現状のプロセス（水蒸気改質＋ＣＯ変成）では、１％程度のメタンとともに、２０％程度の二酸化炭素と１％以下の一酸化炭素の残留は避けられず、その精製のために大型・高コストのＰＳＡ装置を設置せざるを得なかった。 As a cost issue, PSA (Pressure Swing Adsorption) accounts for the largest percentage of the total cost of the hydrogen station, so there is a reforming method that increases the hydrogen concentration that directly leads to cost reduction. It was desired. The reformer outlet gas composition contains about 10% carbon monoxide and carbon dioxide in addition to hydrogen. In the CO converter, carbon monoxide decreases, but carbon dioxide increases. In steam reforming + CO conversion), about 20% of carbon dioxide and less than 1% of carbon monoxide remain together with about 1% of methane, and a large and high-cost PSA system is installed for purification. I had to do it.
従来のＣＯ変成器において、小型化や起動時間の短縮を阻害する原因として、以下の（化１）に示すＣＯ変成反応の化学平衡上の制約から、多量のＣＯ変成触媒が必要となっていることが挙げられる。一例として、５０ｋＷのＰＡＦＣ（リン酸型燃料電池）用改質システムでは、改質触媒が２０Ｌ必要であるのに対して、ＣＯ変成触媒は７７Ｌと約４倍の触媒が必要となる。このことが、ＣＯ変成器の小型化や起動時間の短縮を阻害する大きな要因となっている。 In conventional CO converters, a large amount of CO conversion catalyst is required as a cause of hindering miniaturization and shortening of the start-up time due to restrictions on the chemical equilibrium of the CO conversion reaction shown in the following (Chemical Formula 1). Can be mentioned. As an example, a reforming system for a 50 kW PAFC (phosphoric acid fuel cell) requires 20 L of reforming catalyst, whereas a CO conversion catalyst requires 77 L, which is about four times as much as the catalyst. This is a major factor that hinders downsizing the CO transformer and shortening the startup time.
（化１）
ＣＯ ＋ Ｈ２Ｏ → Ｈ２ ＋ＣＯ２
(Chemical formula 1)
CO + H 2 O → H 2 + CO 2
そこで、ＣＯ変成器に二酸化炭素を選択的に透過させるＣＯ２促進輸送膜を備え、上記（化１）のＣＯ変成反応で生成された右側の二酸化炭素を効率的にＣＯ変成器外部に除去することで、化学平衡を水素生成側（右側）にシフトさせることができ、同一反応温度において高い転化率が得られる結果、一酸化炭素及び二酸化炭素を平衡の制約による限界を超えて除去することが可能となる。図１０及び図１１に、この様子を模式的に示す。図１１（Ａ）と（Ｂ）は、夫々、ＣＯ２促進輸送膜を備えている場合と備えていない場合における、ＣＯ変成器の触媒層長に対する一酸化炭素及び二酸化炭素の各濃度変化を示している。 Therefore, the CO converter is provided with a CO 2 facilitated transport membrane that selectively allows carbon dioxide to permeate, and the right-side carbon dioxide generated by the CO conversion reaction of (Chemical Formula 1) is efficiently removed outside the CO converter. As a result, the chemical equilibrium can be shifted to the hydrogen production side (right side), and a high conversion rate can be obtained at the same reaction temperature. As a result, carbon monoxide and carbon dioxide can be removed beyond the limit due to equilibrium constraints. It becomes possible. 10 and 11 schematically show this state. FIGS. 11A and 11B show changes in the concentrations of carbon monoxide and carbon dioxide with respect to the catalyst layer length of the CO converter with and without the CO 2 facilitated transport membrane, respectively. ing.
上記のＣＯ２促進輸送膜を備えたＣＯ変成器（ＣＯ２透過型メンブレンリアクター）により、一酸化炭素及び二酸化炭素を平衡の制約による限界を超えて除去することが可能となるため、水素ステーションのＰＳＡの負荷低減及び低Ｓ／Ｃ化が図れ、水素ステーション全体のコスト低減及び高効率化が図れる。また、ＣＯ２促進輸送膜を備えることで、ＣＯ変成反応の高速化（高ＳＶ化）が図れるため、改質システムの小型化及び起動時間の短縮が図れる。 The CO converter (CO 2 permeable membrane reactor) equipped with the above CO 2 facilitated transport membrane makes it possible to remove carbon monoxide and carbon dioxide beyond the limits due to equilibrium constraints. The PSA load and S / C can be reduced, and the cost and efficiency of the entire hydrogen station can be reduced. Further, by providing the CO 2 facilitated transport film, the CO conversion reaction can be speeded up (higher SV), so that the reforming system can be downsized and the startup time can be shortened.
かかるＣＯ２透過型メンブレンリアクターの先行例としては、下記の特許文献１（或いは、同じ発明者による同一内容の特許文献２）に開示されているものがある。 As a prior example of such a CO 2 permeable membrane reactor, there is one disclosed in the following Patent Document 1 (or Patent Document 2 having the same contents by the same inventor).
該特許文献１、２において提案されている改質システムは、炭化水素、メタノール等の燃料を燃料電池自動車用の水素に車上で改質する際に発生する改質ガスの精製及び水性ガスシフト反応（ＣＯ変成反応）に有用なＣＯ２促進輸送膜プロセスを提供するもので、代表的な４種類のプロセスが、同文献の図１〜図４に示されている。炭化水素（メタンを含む）を原料とする場合、水性ガスシフターにＣＯ２促進輸送膜を備えたメンブレンリアクターを用いて二酸化炭素を選択的に除去することにより、一酸化炭素の反応率を高め一酸化炭素濃度を低下させるとともに生成水素の純度を向上させている。また、生成水素中に残留する％オーダーの一酸化炭素及び二酸化炭素はメタネーターで水素と反応させてメタンに変換して濃度を低下させ、燃料電池の被毒等による効率低下を防いでいる。 The reforming systems proposed in Patent Documents 1 and 2 are directed to purifying reformed gas and water gas shift reaction generated when reforming a fuel such as hydrocarbon or methanol into hydrogen for a fuel cell vehicle on the vehicle. The present invention provides a CO 2 facilitated transport membrane process useful for (CO shift reaction), and representative four types of processes are shown in FIGS. When hydrocarbons (including methane) are used as raw materials, carbon monoxide is selectively removed using a membrane reactor equipped with a CO 2 facilitated transport membrane in the water gas shifter to increase the carbon monoxide reaction rate. While reducing the carbon oxide concentration, the purity of the produced hydrogen is improved. In addition, carbon monoxide and carbon dioxide remaining in the generated hydrogen are reacted with hydrogen by a methanator and converted to methane to reduce the concentration, thereby preventing a decrease in efficiency due to poisoning of the fuel cell.
該特許文献１、２では、ＣＯ２促進輸送膜として、主としてハロゲン化四級アンモニウム塩（（Ｒ）４Ｎ＋Ｘ−）を二酸化炭素キャリアとして含むＰＶＡ（ポリビニルアルコール）等の親水性ポリマー膜が使用されている。また、該特許文献１、２の実施例６には、二酸化炭素キャリアとしてテトラメチルアンモニウムフルオリド塩５０重量％を含む膜厚４９μｍ５０重量％のＰＶＡ膜とそれを支持する多孔質ＰＴＦＥ（四フッ化エチレン重合体）膜よりなる複合膜で形成されたＣＯ２促進輸送膜の作製方法が開示され、同実施例７には、混合ガス（２５％ＣＯ２、７５％Ｈ２）を全圧３気圧、２３℃で処理したときの当該ＣＯ２促進輸送膜の膜性能が開示されている。当該膜性能として、ＣＯ２パーミアンスＲＣＯ２が７．２ＧＰＵ（＝２．４×１０−６ｍｏｌ／（ｍ２・ｓ・ｋＰａ））、ＣＯ２／Ｈ２選択率が１９となっており、後述するように、ＣＯ２透過型メンブレンリアクターのＣＯ２促進輸送膜に適用するには十分な性能とは言えない。 In Patent Documents 1 and 2, a hydrophilic polymer film such as PVA (polyvinyl alcohol) mainly containing a halogenated quaternary ammonium salt ((R) 4 N + X − ) as a carbon dioxide carrier is used as the CO 2 facilitated transport film. in use. In Example 6 of Patent Documents 1 and 2, a PVA membrane having a film thickness of 49 μm and 50 wt% containing 50 wt% of tetramethylammonium fluoride salt as a carbon dioxide carrier and porous PTFE (tetrafluoride tetrafluoride) supporting the PVA membrane. A method for producing a CO 2 facilitated transport film formed of a composite film made of an ethylene polymer) film is disclosed. In Example 7, a mixed gas (25% CO 2 , 75% H 2 ) is mixed with a total pressure of 3 atm. The membrane performance of the CO 2 facilitated transport membrane when treated at 23 ° C. is disclosed. As the membrane performance, CO 2 permeance R CO2 is 7.2 GPU (= 2.4 × 10 −6 mol / (m 2 · s · kPa)), and CO 2 / H 2 selectivity is 19, which will be described later. Thus, it cannot be said that the performance is sufficient for application to the CO 2 facilitated transport membrane of the CO 2 permeable membrane reactor.
ＣＯ２促進輸送膜は、基本機能として二酸化炭素を選択的に分離することから、地球温暖化の原因となっている二酸化炭素の吸収或いは除去等を目的とした開発も行われている。しかしながら、ＣＯ２促進輸送膜は、ＣＯ２透過型メンブレンリアクターへの応用を考えた場合、使用温度、ＣＯ２パーミアンス、ＣＯ２／Ｈ２選択率等に対して、一定以上の性能が要求される。つまり、ＣＯ変成反応に供するＣＯ変成触媒の性能が温度とともに低下する傾向にあるため、使用温度は最低でも１００℃が必要と考えられる。また、ＣＯ２パーミアンス（二酸化炭素透過性の性能指標の一つ）は、ＣＯ変成反応の化学平衡を水素生成側（右側）にシフトさせ、一酸化炭素濃度と二酸化炭素濃度を平衡の制約による限界を超えて例えば０．１％程度以下に低減し、且つ、ＣＯ変成反応の高速化（高ＳＶ化）を図るためには、一定レベル以上（例えば、２×１０−５ｍｏｌ／（ｍ２・ｓ・ｋＰａ）＝６０ＧＰＵ程度以上）が必要と考えられる。更に、ＣＯ変成反応で生成された水素が二酸化炭素とともにＣＯ２促進輸送膜を通して外部に廃棄されたのでは、当該廃棄ガスから水素を分離回収するというプロセスが必要となる。水素は当然に二酸化炭素より分子サイズが小さいので、二酸化炭素を透過可能な膜は水素も透過できることになるが、膜中の二酸化炭素キャリアによって二酸化炭素のみを選択的に膜の供給側から透過側に向けて輸送可能な促進輸送膜が必要となり、その場合のＣＯ２／Ｈ２選択率として９０〜１００程度以上が必要と考えられる。 Since the CO 2 facilitated transport membrane selectively separates carbon dioxide as a basic function, development for the purpose of absorbing or removing carbon dioxide causing global warming has also been performed. However, when considering application to a CO 2 permeable membrane reactor, the CO 2 facilitated transport membrane is required to have a certain performance or more with respect to the operating temperature, CO 2 permeance, CO 2 / H 2 selectivity, etc. . In other words, since the performance of the CO shift catalyst for use in the CO shift reaction tends to decrease with temperature, the use temperature is considered to be at least 100 ° C. CO 2 permeance (one of the performance indicators of carbon dioxide permeability) shifts the chemical equilibrium of the CO shift reaction to the hydrogen production side (right side) and limits the carbon monoxide concentration and carbon dioxide concentration due to equilibrium constraints. Over a certain level, for example, about 0.1% or less, and in order to speed up the CO shift reaction (high SV), for example, 2 × 10 −5 mol / (m 2 · s · kPa) = 60 GPU or more) is considered necessary. Furthermore, when the hydrogen produced by the CO shift reaction is discarded outside together with carbon dioxide through the CO 2 facilitated transport membrane, a process of separating and recovering hydrogen from the waste gas is required. Since hydrogen is naturally smaller in molecular size than carbon dioxide, a membrane that can permeate carbon dioxide can also permeate hydrogen, but only carbon dioxide is selectively passed from the membrane supply side to the permeate side by the carbon dioxide carrier in the membrane. It is considered that a facilitated transport membrane that can be transported toward the surface is required, and the CO 2 / H 2 selectivity in that case is required to be about 90 to 100 or more.
本発明は、上述の問題点に鑑みてなされたものであり、その目的は、ＣＯ２透過型メンブレンリアクターに適用可能なＣＯ２促進輸送膜を安定して提供することにある。 The present invention has been made in view of the above problems, its object is to provide stably applicable CO 2 -facilitated transport membrane to CO 2 permeable membrane reactor.
上記目的を達成するための本発明に係るＣＯ２促進輸送膜は、ポリビニルアルコール‐ポリアクリル酸共重合体ゲル膜に２，３‐ジアミノプロピオン酸を添加したゲル層を、親水性の多孔膜に担持させてなることを第１の特徴とする。 In order to achieve the above object, the CO 2 facilitated transport membrane according to the present invention comprises a gel layer obtained by adding 2,3-diaminopropionic acid to a polyvinyl alcohol-polyacrylic acid copolymer gel membrane, and a hydrophilic porous membrane. The first feature is that it is supported.
更に、本発明に係るＣＯ２促進輸送膜は、上記第１の特徴に加え、前記親水性の多孔膜に担持された前記ゲル層が疎水性の多孔膜によって被覆支持されていることを第２の特徴とする。 Further, the CO 2 facilitated transport membrane according to the present invention is characterized in that, in addition to the first feature, the gel layer supported on the hydrophilic porous membrane is supported by a hydrophobic porous membrane. It is characterized by.
更に、本発明に係るＣＯ２促進輸送膜は、上記第１または第２の特徴に加え、前記多孔膜が１００℃以上の耐熱性を備えていることを第３の特徴とする。 Furthermore, the CO 2 facilitated transport membrane according to the present invention has a third feature that, in addition to the first or second feature, the porous membrane has heat resistance of 100 ° C. or higher.
更に、本発明に係るＣＯ２促進輸送膜は、上記何れかの特徴に加え、前記ポリビニルアルコール‐ポリアクリル酸共重合体ゲル膜内に、２，３‐ジアミノプロピオン酸の他に、二酸化炭素透過性を促進するための添加剤として、イオン性流体（イオン液体とも呼称される）、または、グリセリン、ポリグリセリン、ポリエチレングリコール、ポリプロピレングリコール、ポリエチレンオキサイド、ポリエチレンイミン、ポリアリルアミン、ポリアクリル酸の中から選択される化学物質を含有することを第４の特徴とする。 Furthermore, the CO 2 facilitated transport membrane according to the present invention has a carbon dioxide permeation in addition to 2,3-diaminopropionic acid in the polyvinyl alcohol-polyacrylic acid copolymer gel membrane in addition to any of the above features. As an additive for promoting sexuality, ionic fluid (also called ionic liquid) or glycerin, polyglycerin, polyethylene glycol, polypropylene glycol, polyethylene oxide, polyethyleneimine, polyallylamine, polyacrylic acid The fourth feature is to contain a selected chemical substance.
更に、本発明に係るＣＯ２促進輸送膜は、上記第４の特徴に加え、前記イオン性流体が、下記のカチオン、アニオンの組合せよりなる化合物から選択される化学物質であり、前記カチオンが、１，３位に以下の置換基を有するイミダゾリウムで、置換基としてアルキル基、ヒドロキシアルキル基、エーテル基、アリル基、アミノアルキル基を有するもの、または、第４級アンモニウムカチオンで、置換基としてアルキル基、ヒドロキシアルキル基、エーテル基、アリル基、アミノアルキル基を有するものであり、前記アニオンが、塩化物イオン、臭化物イオン、四フッ化ホウ素イオン、硝酸イオン、ビス（トリフルオロメタンスルホニル）イミドイオン、ヘキサフルオロリン酸イオン、または、トリフルオロメタンスルホン酸イオンであることを第５の特徴とする。 Furthermore, in the CO 2 facilitated transport membrane according to the present invention, in addition to the fourth feature, the ionic fluid is a chemical substance selected from a compound comprising a combination of the following cation and anion, and the cation is: Imidazolium having the following substituents at the 1,3-positions, having an alkyl group, hydroxyalkyl group, ether group, allyl group, aminoalkyl group as a substituent group, or a quaternary ammonium cation, as a substituent group It has an alkyl group, a hydroxyalkyl group, an ether group, an allyl group, an aminoalkyl group, and the anion is chloride ion, bromide ion, boron tetrafluoride ion, nitrate ion, bis (trifluoromethanesulfonyl) imide ion, Hexafluorophosphate ion or trifluoromethanesulfonate ion Is a fifth feature.
また、上記目的を達成するための本発明に係る上記第１の特徴のＣＯ２促進輸送膜の製造方法は、ポリビニルアルコール‐ポリアクリル酸共重合体と２，３‐ジアミノプロピオン酸を含む水溶液からなるキャスト溶液を作製する工程と、前記キャスト溶液を前記親水性の多孔膜にキャストした後にゲル化してゲル層を作製する工程と、を有することを第１の特徴とする。 In addition, the method for producing a CO 2 facilitated transport membrane according to the first aspect of the present invention for achieving the above object is an aqueous solution containing a polyvinyl alcohol-polyacrylic acid copolymer and 2,3-diaminopropionic acid. The first feature is to have a step of producing a cast solution, and a step of producing a gel layer by casting the cast solution into the hydrophilic porous membrane and then gelling.
更に、本発明に係るＣＯ２促進輸送膜の製造方法は、上記第１の特徴に加え、前記キャスト溶液を作製する工程において、前記水溶液中に、イオン性流体、または、グリセリン、ポリグリセリン、ポリエチレングリコール、ポリプロピレングリコール、ポリエチレンオキサイド、ポリエチレンイミン、ポリアリルアミン、ポリアクリル酸の中から選択される化学物質が更に含まれていることを第２の特徴とする。 Furthermore, in addition to the first feature, the method for producing a CO 2 facilitated transport membrane according to the present invention includes an ionic fluid, glycerin, polyglycerin, polyethylene in the aqueous solution in the step of producing the cast solution. The second feature is that a chemical substance selected from glycol, polypropylene glycol, polyethylene oxide, polyethyleneimine, polyallylamine, and polyacrylic acid is further contained.
上記第１の特徴のＣＯ２促進輸送膜によれば、ポリビニルアルコール‐ポリアクリル酸（ＰＶＡ／ＰＡＡ）共重合体ゲル膜中に、２，３‐ジアミノプロピオン酸（ＤＡＰＡ）が含まれることから、当該ＤＡＰＡが透過物質であるＰＶＡ／ＰＡＡゲル層の二酸化炭素の高濃度側界面から低濃度側界面へと二酸化炭素を捕獲して輸送する二酸化炭素キャリアとして機能し、１００℃以上の高温において９０〜１００程度以上の対水素選択率（ＣＯ２／Ｈ２）、及び、２×１０−５ｍｏｌ／（ｍ２・ｓ・ｋＰａ）（＝６０ＧＰＵ）程度以上のＣＯ２パーミアンスを達成可能となる。 According to the CO 2 facilitated transport membrane of the first feature, 2,3-diaminopropionic acid (DAPA) is contained in the polyvinyl alcohol-polyacrylic acid (PVA / PAA) copolymer gel membrane, The DAPA functions as a carbon dioxide carrier that captures and transports carbon dioxide from the high concentration side interface of carbon dioxide to the low concentration side interface of the PVA / PAA gel layer, which is a permeating substance. It becomes possible to achieve a selectivity for hydrogen (CO 2 / H 2 ) of about 100 or more and a CO 2 permeance of about 2 × 10 −5 mol / (m 2 · s · kPa) (= 60 GPU) or more.
また、ＰＶＡ／ＰＡＡゲル層を担持する多孔膜が親水性であるので、欠陥の少ないゲル層を安定して作製することができ、高い対水素選択率を維持できる。一般に、多孔膜が疎水性であると、１００℃以下においてＰＶＡ／ＰＡＡゲル膜内の水分が多孔膜内の細孔に侵入して膜性能を低下させるのを防止でき、また、１００℃以上においてＰＶＡ／ＰＡＡゲル膜内の水分が少なくなる状況でも同様の効果が期待できると考えられるため、疎水性の多孔膜の使用が推奨されるところ、本発明のＣＯ２促進輸送膜では、以下の理由から親水性多孔膜を使用することで、欠陥が少なく高い対水素選択率を維持できるＣＯ２促進輸送膜を安定して作製できるようになった。 Moreover, since the porous membrane which carries a PVA / PAA gel layer is hydrophilic, a gel layer with few defects can be produced stably and a high selectivity for hydrogen can be maintained. In general, when the porous membrane is hydrophobic, it is possible to prevent moisture in the PVA / PAA gel membrane from entering the pores in the porous membrane at 100 ° C. or lower and lowering the membrane performance. since the moisture in the PVA / PAA gel membrane is considered the same effect can be expected even less becomes situations, where the use of a hydrophobic porous membrane is recommended, in a CO 2 -facilitated transport membrane of the present invention, the following reasons Thus, by using the hydrophilic porous membrane, it has become possible to stably produce a CO 2 facilitated transport membrane that can maintain a high selectivity for hydrogen with few defects.
親水性の多孔膜上に、ＰＶＡ／ＰＡＡ共重合体とＤＡＰＡの水溶液からなるキャスト溶液をキャストすると多孔膜の細孔内が液で満たされ、更に、多孔膜の表面にキャスト溶液が塗布される。このキャスト溶液をゲル化すると、多孔膜の表面のみならず細孔内にもゲル層が充填されるので欠陥が生じ難くなり、ゲル層の製膜成功率が高くなる。細孔部分の割合（多孔度）、及び、細孔が膜表面に垂直に真っ直ぐではなく曲がりくねっていること（屈曲率）を考慮すると、細孔内のゲル層はガス透過の大きな抵抗となるので、多孔膜表面のゲル層と比較して透過性は低くなり、ガスパーミアンスは低下する。他方、疎水性の多孔膜上にキャスト溶液をキャストすると多孔膜の細孔内は液で満たされずに多孔膜の表面のみにキャスト溶液が塗布され細孔はガスで満たされるので、疎水性多孔膜上のゲル層におけるガスパーミアンスは、親水性多孔膜と比較して水素及び二酸化炭素の両方において高くなる。しかし、細孔内のゲル層と比較して膜表面のゲル層は欠陥が生じ易く、ゲル層の製膜成功率は低下する。水素は二酸化炭素より分子サイズが小さいので、微小な欠陥個所或いは局所的にガスパーミアンスが高い個所では二酸化炭素より水素の方が、ガスパーミアンスが高くなる可能性があるが、促進輸送機構で透過する二酸化炭素の透過速度は物理的な溶解拡散機構で透過する水素のパーミアンスよりも格段に大きいので，二酸化炭素パーミアンスは膜の局所的な欠陥の影響を殆ど受けないのに対して、水素のパーミアンスは欠陥により著しく増加する。結果として、疎水性多孔膜を使用した場合の対水素選択率（ＣＯ２／Ｈ２）は、親水性多孔膜を使用した場合と比較して低下することになる。従って、実用化の観点からは、ＣＯ２促進輸送膜の安定性、耐久性が非常に重要となり、対水素選択率（ＣＯ２／Ｈ２）の高い親水性多孔膜を使用する方が有利となる。また、親水性多孔膜の使用は、ＰＶＡ／ＰＡＡゲル層に二酸化炭素キャリアとしてＤＡＰＡを添加することで高いＣＯ２パーミアンスを達成可能であることを前提に実現できるものである。尚、疎水性多孔膜と親水性多孔膜の違いによるガスパーミアンスの差は、キャスト溶液中に予め二酸化炭素キャリアであるＤＡＰＡを添加せずにゲル化後に含侵させても、細孔内のゲル層がガス透過の大きな抵抗となる点は同じであり、同様に発現するものと推定される。 When a cast solution made of an aqueous solution of PVA / PAA copolymer and DAPA is cast on a hydrophilic porous membrane, the pores of the porous membrane are filled with the liquid, and the cast solution is applied to the surface of the porous membrane. . When the cast solution is gelled, not only the surface of the porous membrane but also the pores are filled with the gel layer, so that defects are less likely to occur, and the success rate of forming the gel layer is increased. Considering the ratio of the pores (porosity) and the fact that the pores are not perpendicular to the membrane surface but bends (flexibility), the gel layer in the pores has a large resistance to gas permeation. As compared with the gel layer on the surface of the porous membrane, the permeability is lowered and the gas permeance is lowered. On the other hand, when the cast solution is cast on the hydrophobic porous membrane, the inside of the pores of the porous membrane is not filled with liquid, but the cast solution is applied only to the surface of the porous membrane and the pores are filled with gas. The gas permeance in the upper gel layer is higher in both hydrogen and carbon dioxide compared to the hydrophilic porous membrane. However, the gel layer on the membrane surface is more likely to have defects than the gel layer in the pores, and the success rate of film formation of the gel layer is reduced. Hydrogen has a smaller molecular size than carbon dioxide, so hydrogen may have higher gas permeance than carbon dioxide at small defects or where the gas permeance is locally high. Since the permeation rate of carbon dioxide is much larger than the hydrogen permeance that permeates through the physical dissolution and diffusion mechanism, the carbon dioxide permeance is hardly affected by local defects in the membrane, whereas the hydrogen permeance is Significant increase due to defects. As a result, the selectivity for hydrogen (CO 2 / H 2 ) when using a hydrophobic porous membrane will be lower than when using a hydrophilic porous membrane. Therefore, from the viewpoint of practical use, the stability and durability of the CO 2 facilitated transport membrane are very important, and it is advantageous to use a hydrophilic porous membrane having a high selectivity to hydrogen (CO 2 / H 2 ). Become. The use of the hydrophilic porous membrane can be realized on the assumption that high CO 2 permeance can be achieved by adding DAPA as a carbon dioxide carrier to the PVA / PAA gel layer. Note that the difference in gas permeance due to the difference between the hydrophobic porous membrane and the hydrophilic porous membrane is the same as the gel in the pores even if the cast solution is impregnated after gelation without adding the carbon dioxide carrier DAPA in advance. The point that the layer has a large resistance to gas permeation is the same, and it is presumed that the layer develops similarly.
以上より、上記第１の特徴のＣＯ２促進輸送膜によれば、１００℃以上の使用温度、２×１０−５ｍｏｌ／（ｍ２・ｓ・ｋＰａ）（＝６０ＧＰＵ）程度以上のＣＯ２パーミアンス、及び、９０〜１００程度以上のＣＯ２／Ｈ２選択率が実現でき、ＣＯ２透過型メンブレンリアクターへ応用可能なＣＯ２促進輸送膜が提供可能となり、ＣＯ変成器の小型化、起動時間の短縮、及び、高速化（高ＳＶ化）が図れる。 From the above, according to the CO 2 facilitated transport membrane of the first feature, the operating temperature is 100 ° C. or higher, and the CO 2 permeance is about 2 × 10 −5 mol / (m 2 · s · kPa) (= 60 GPU) or higher. In addition, a CO 2 / H 2 selectivity of about 90 to 100 or more can be realized, and a CO 2 facilitated transport membrane applicable to a CO 2 permeable membrane reactor can be provided. Shortening and high speed (high SV) can be achieved.
更に、上記第２の特徴のＣＯ２促進輸送膜によれば、親水性の多孔膜で担持されたゲル層が疎水性の多孔膜によって保護され、使用時におけるＣＯ２促進輸送膜の強度が増す。この結果、ＣＯ２促進輸送膜をＣＯ２透過型メンブレンリアクターへ応用した場合に、ＣＯ２促進輸送膜の両側（反応器内外）での圧力差が大きく（例えば、２気圧以上）なっても十分な膜強度を確保できる。更に、ゲル層が疎水性の多孔膜によって被覆されるため、水蒸気が疎水性の多孔膜の膜表面に凝縮しても当該多孔膜が疎水性のために水がはじかれてゲル層内にしみ込むのを防止している。よって、疎水性の多孔膜によって、ゲル層中の二酸化炭素キャリアが水で薄められ、また、薄められた二酸化炭素キャリアがゲル層から流出することを防止できる。 Further, according to the CO 2 facilitated transport membrane of the second feature, the gel layer supported by the hydrophilic porous membrane is protected by the hydrophobic porous membrane, and the strength of the CO 2 facilitated transport membrane during use is increased. . As a result, when the CO 2 facilitated transport membrane is applied to a CO 2 permeable membrane reactor, it is sufficient even if the pressure difference between both sides (inside and outside the reactor) of the CO 2 facilitated transport membrane is large (for example, 2 atmospheres or more). A sufficient film strength. Furthermore, since the gel layer is covered with a hydrophobic porous membrane, even if water vapor is condensed on the membrane surface of the hydrophobic porous membrane, the porous membrane is hydrophobic and water is repelled and penetrates into the gel layer. Is preventing. Therefore, the hydrophobic porous membrane can dilute the carbon dioxide carrier in the gel layer with water, and can prevent the thinned carbon dioxide carrier from flowing out of the gel layer.
更に、上記第３の特徴のＣＯ２促進輸送膜によれば、常温から１００℃以上に亘る広範な温度範囲での使用が可能となる。具体的には、多孔膜が１００℃以上の耐熱性を備えることで１００℃以上の温度領域での使用が可能となる。 Furthermore, according to the CO 2 facilitated transport film of the third feature, it can be used in a wide temperature range from room temperature to 100 ° C. or more. Specifically, since the porous film has heat resistance of 100 ° C. or higher, it can be used in a temperature region of 100 ° C. or higher.
更に、上記第４または第５の特徴のＣＯ２促進輸送膜によれば、親水性と二酸化炭素キャリアとの相容性と二酸化炭素との親和性を兼ね備えたイオン性流体またはグリセリン等の添加剤を含有するため、二酸化炭素透過性が促進され、１００℃以上のＰＶＡ／ＰＡＡゲル膜内の水分が少なくなる高温下においても、高いＣＯ２パーミアンスが実現できる。ＣＯ２促進輸送膜を１００℃以上の高温環境で使用すると、ＰＶＡ／ＰＡＡゲル膜の架橋が更に進行し、二酸化炭素キャリアによる二酸化炭素の促進輸送が阻害され二酸化炭素透過性が低下する虞があるところ、当該添加剤が含まれることで、架橋の進行が抑制される結果、高温下での使用による二酸化炭素透過性の低下が抑制されることが、高ＣＯ２パーミアンスの理由として考えられる。尚、当該添加剤の効果は、温度に依存するものの、特定の温度では、特にＣＯ２促進輸送膜の両側（反応器内外）での圧力差が３気圧以下において顕著に現れ、２気圧以下でより顕著に現れることが実験結果より認められる。 Furthermore, according to the CO 2 facilitated transport membrane of the fourth or fifth feature, an additive such as ionic fluid or glycerin having both hydrophilicity, compatibility with carbon dioxide carrier and affinity for carbon dioxide Therefore, high CO 2 permeance can be realized even at high temperatures where carbon dioxide permeability is promoted and moisture in the PVA / PAA gel membrane at 100 ° C. or higher is reduced. When the CO 2 facilitated transport membrane is used in a high temperature environment of 100 ° C. or higher, the cross-linking of the PVA / PAA gel membrane further proceeds, and the facilitated transport of carbon dioxide by the carbon dioxide carrier may be inhibited, resulting in a decrease in carbon dioxide permeability. However, it is considered as a reason for the high CO 2 permeance that the addition of the additive suppresses the progress of the crosslinking, thereby suppressing the decrease in carbon dioxide permeability due to use at high temperatures. The effect of the additive depends on the temperature, but at a specific temperature, the pressure difference between both sides of the CO 2 facilitated transport membrane (inside and outside the reactor) appears remarkably at 3 atm or less, and at 2 atm or less. It is recognized from the experimental results that it appears more prominently.
ところで、膜内に水分が無い場合でも二酸化炭素は促進輸送されるが、その透過速度は一般に非常に小さいため、高い透過速度を得るには膜内の水分が不可欠となる。従って、親水性の添加剤を使用することにより、可能な限り膜内に水分を保持することが可能となり、二酸化炭素透過性が促進される。また、二酸化炭素キャリアとの相容性と二酸化炭素との親和性を兼ね備えた添加剤を使用することで、二酸化炭素キャリアであるＤＡＰＡの二酸化炭素の促進輸送を阻害することなく、添加剤がＤＡＰＡとともに膜内に均質に分布でき、二酸化炭素透過性が促進される。 By the way, although carbon dioxide is facilitated and transported even when there is no moisture in the membrane, its permeation rate is generally very small, so that moisture in the membrane is indispensable for obtaining a high permeation rate. Therefore, by using a hydrophilic additive, moisture can be retained in the membrane as much as possible, and carbon dioxide permeability is promoted. In addition, by using an additive having compatibility with carbon dioxide carrier and affinity for carbon dioxide, the additive is DAPA without inhibiting the facilitated transport of carbon dioxide of DAPA as a carbon dioxide carrier. At the same time, it can be uniformly distributed in the membrane, and carbon dioxide permeability is promoted.
更に、上記第１の特徴のＣＯ２促進輸送膜の製造方法によれば、膜材料（ＰＶＡ／ＰＡＡ）に対する二酸化炭素キャリアの配分を適正に調整したキャスト溶液が予め準備されるため、最終的なＰＶＡ／ＰＡＡゲル膜内の二酸化炭素キャリアの配合比率の適正化が簡易に実現でき、膜性能の高性能化が実現できる。 Furthermore, according to the method for producing the CO 2 facilitated transport membrane of the first feature, since a cast solution in which the distribution of carbon dioxide carriers to the membrane material (PVA / PAA) is appropriately adjusted is prepared in advance, Optimization of the mixing ratio of the carbon dioxide carrier in the PVA / PAA gel membrane can be easily realized, and high performance of the membrane performance can be realized.
更に、上記第２の特徴のＣＯ２促進輸送膜の製造方法によれば、膜材料（ＰＶＡ／ＰＡＡ）に対する二酸化炭素キャリアと添加剤の配分を適正に調整したキャスト溶液が予め準備されるため、最終的なＰＶＡ／ＰＡＡゲル膜内の二酸化炭素キャリアと添加剤の配合比率の適正化が簡易に実現でき、膜性能の高性能化が実現できる。 Furthermore, according to the method for producing the CO 2 facilitated transport membrane of the second feature, a cast solution in which the distribution of carbon dioxide carrier and additive to the membrane material (PVA / PAA) is appropriately adjusted is prepared in advance. Optimization of the mixing ratio of the carbon dioxide carrier and the additive in the final PVA / PAA gel membrane can be easily realized, and high performance of the membrane performance can be realized.
本発明に係るＣＯ２促進輸送膜及びその製造方法（以下、適宜「本発明膜」及び「本発明方法」という。）の実施の形態につき、図面に基づいて説明する。 Embodiments of a CO 2 facilitated transport membrane and a method for producing the same according to the present invention (hereinafter referred to as “the membrane of the present invention” and “the method of the present invention” as appropriate) will be described with reference to the drawings.
〈第１実施形態〉
本発明膜は、水分を含むゲル膜内に二酸化炭素キャリアを含有したＣＯ２促進輸送膜であって、１００℃以上の使用温度、高い二酸化炭素透過性とＣＯ２／Ｈ２選択率を有するＣＯ２透過型メンブレンリアクターへ応用可能なＣＯ２促進輸送膜である。更に、本発明膜は、高いＣＯ２／Ｈ２選択率を安定して実現するために、二酸化炭素キャリアを含有したゲル膜を担持する支持膜として、親水性の多孔膜を採用している。
<First Embodiment>
The membrane of the present invention is a CO 2 facilitated transport membrane containing a carbon dioxide carrier in a gel membrane containing moisture, and has a use temperature of 100 ° C. or higher, high carbon dioxide permeability and CO 2 / H 2 selectivity. This is a CO 2 facilitated transport membrane applicable to a two- permeable membrane reactor. Furthermore, the membrane of the present invention employs a hydrophilic porous membrane as a support membrane for supporting a gel membrane containing a carbon dioxide carrier in order to stably realize a high CO 2 / H 2 selectivity.
具体的には、本発明膜は、膜材料として、ポリビニルアルコール‐ポリアクリル酸（ＰＶＡ／ＰＡＡ）共重合体を使用し、二酸化炭素キャリアとして、２，３‐ジアミノプロピオン酸（ＤＡＰＡ）を使用する。また、本発明膜は、図１に模式的に示すように、二酸化炭素キャリアを含有するＰＶＡ／ＰＡＡゲル膜１を担持した親水性多孔膜２が、２枚の疎水性多孔膜３，４に挟持される３層構造で構成される。以下、二酸化炭素キャリアを含有するＰＶＡ／ＰＡＡゲル膜を、二酸化炭素キャリアを含有しないＰＶＡ／ＰＡＡゲル膜、及び、２枚の疎水性多孔膜を備えた構造の本発明膜と区別するために、適宜「含有ゲル膜」と略称する。また、この含有ゲル膜中のＰＶＡ／ＰＡＡとＤＡＰＡの全重量を基準として、含有ゲル膜中において、ＰＶＡ／ＰＡＡは約２０〜８０重量％の範囲で存在し、ＤＡＰＡは約２０〜８０重量％の範囲で存在する。 Specifically, the membrane of the present invention uses a polyvinyl alcohol-polyacrylic acid (PVA / PAA) copolymer as a membrane material and 2,3-diaminopropionic acid (DAPA) as a carbon dioxide carrier. . In addition, as schematically shown in FIG. 1, the membrane of the present invention comprises a hydrophilic porous membrane 2 carrying a PVA / PAA gel membrane 1 containing a carbon dioxide carrier in two hydrophobic porous membranes 3 and 4. It is composed of a three-layer structure that is sandwiched. Hereinafter, in order to distinguish a PVA / PAA gel membrane containing a carbon dioxide carrier from a PVA / PAA gel membrane not containing a carbon dioxide carrier, and a membrane of the present invention having a structure comprising two hydrophobic porous membranes, It is abbreviated as “containing gel film” as appropriate. Further, based on the total weight of PVA / PAA and DAPA in the contained gel film, in the contained gel film, PVA / PAA is present in a range of about 20 to 80% by weight, and DAPA is about 20 to 80% by weight. It exists in the range.
二酸化炭素キャリアであるＤＡＰＡは、水酸化セシウム（ＣｓＯＨ）等のアルカリと中和させて、後述のキャスト溶液中に溶解して解離したＮＨ３ ＋をＮＨ２に変換する必要がある。これは、ＮＨ３ ＋が二酸化炭素と反応しないためである。ここで、アルカリとして水酸化セシウム（ＣｓＯＨ）を用いても、炭酸セシウム（Ｃｓ２ＣＯ３）を用いても最終のｐＨ値が同じであれば、同等物となる。但し、炭酸セシウム（Ｃｓ２ＣＯ３）を用いた場合には、含有ゲル膜中に、炭酸イオン、炭酸水素イオンが存在することになるが、当該イオンによる二酸化炭素の促進輸送への寄与は小さいと考えられる。 DAPA, which is a carbon dioxide carrier, must be neutralized with an alkali such as cesium hydroxide (CsOH) to convert NH 3 + dissolved and dissociated in a cast solution described later to NH 2 . This is because NH 3 + does not react with carbon dioxide. Here, even if cesium hydroxide (CsOH) is used as an alkali or cesium carbonate (Cs 2 CO 3 ) is used, it is equivalent if the final pH value is the same. However, when cesium carbonate (Cs 2 CO 3 ) is used, carbonate ions and hydrogen carbonate ions are present in the contained gel film, but the contribution of the ions to the facilitated transport of carbon dioxide is small. it is conceivable that.
親水性多孔膜は、親水性に加えて、１００℃以上の耐熱性、機械的強度、含有ゲル膜との密着性を有するのが好ましく、更に、多孔度（空隙率）が５５％以上で、細孔径は０．１〜1μｍの範囲にあるのが好ましい。本実施形態では、これらの条件を備えた親水性多孔膜として、親水性化した四フッ化エチレン重合体（ＰＴＦＥ）多孔膜を使用する。 The hydrophilic porous membrane preferably has, in addition to hydrophilicity, heat resistance of 100 ° C. or higher, mechanical strength, and adhesion with the contained gel membrane, and further has a porosity (porosity) of 55% or more, The pore diameter is preferably in the range of 0.1 to 1 μm. In the present embodiment, a hydrophilic tetrafluoroethylene polymer (PTFE) porous membrane is used as the hydrophilic porous membrane having these conditions.
疎水性多孔膜は、疎水性に加えて、１００℃以上の耐熱性、機械的強度、含有ゲル膜との密着性を有するのが好ましく、更に、多孔度（空隙率）が５５％以上で、細孔径は０．１〜1μｍの範囲にあるのが好ましい。本実施形態では、これらの条件を備えた疎水性多孔膜として、親水性化していない四フッ化エチレン重合体（ＰＴＦＥ）多孔膜を使用する。 In addition to hydrophobicity, the hydrophobic porous membrane preferably has heat resistance of 100 ° C. or higher, mechanical strength, and adhesiveness with the contained gel membrane, and further has a porosity (porosity) of 55% or more, The pore diameter is preferably in the range of 0.1 to 1 μm. In the present embodiment, a non-hydrophilic tetrafluoroethylene polymer (PTFE) porous membrane is used as the hydrophobic porous membrane having these conditions.
次に、本発明膜の作製方法（本発明方法）の一実施形態について、図２を参照して説明する。 Next, an embodiment of a method for producing a film of the present invention (method of the present invention) will be described with reference to FIG.
先ず、ＰＶＡ／ＰＡＡ共重合体とＤＡＰＡを含む水溶液からなるキャスト溶液を作製する（工程１）。より詳細には、ＰＶＡ／ＰＡＡ共重合体（例えば、住友精化製の仮称ＳＳゲル）を１ｇ、ＤＡＰＡ一塩酸塩を０．２５ｇ、水酸化セシウム（ＣｓＯＨ）を０．５４ｇ（ＤＡＰＡ一塩酸塩に対して２当量）、サンプル瓶に秤取し、これに水２０ｇを加えて室温で一昼夜攪拌して溶解させてキャスト溶液を得る。 First, a cast solution composed of an aqueous solution containing a PVA / PAA copolymer and DAPA is prepared (step 1). More specifically, 1 g of a PVA / PAA copolymer (for example, a temporary name SS gel manufactured by Sumitomo Seika), 0.25 g of DAPA monohydrochloride, 0.54 g of cesium hydroxide (CsOH) (DAPA monohydrochloride) 2 equivalents), weighed in a sample bottle, added 20 g of water, and stirred and dissolved at room temperature overnight to obtain a cast solution.
ここで、ＤＡＰＡ（ＮＨ２‐ＣＨ２‐ＣＨ（ＮＨ２）‐ＣＯＯＨ）はその一塩酸塩(ｍｏｎｏｈｙｄｒｏｃｈｌｏｒｉｄｅ)として市販されており、水に溶解すると［ＮＨ３ ＋‐ＣＨ２‐ＣＨ（ＮＨ３ ＋Ｃｌ−）‐ＣＯＯ−］のように解離する。二酸化炭素はプロトン化したＮＨ３ ＋とは反応せず、フリーのＮＨ２と反応する。従って、二酸化炭素キャリアとしてＤＡＰＡを用いるには、市販のＤＡＰＡ一塩酸塩に対して２当量の水酸化セシウムを添加してアミノ基をプロトン化していないフリーのアミノ基に変換する必要がある。 Here, DAPA (NH 2 —CH 2 —CH (NH 2 ) —COOH) is commercially available as its monohydrochloride, and when dissolved in water, [NH 3 + —CH 2 —CH (NH 3 + Cl -) -COO -] dissociates as. Carbon dioxide does not react with protonated NH 3 + but reacts with free NH 2 . Therefore, in order to use DAPA as a carbon dioxide carrier, it is necessary to add 2 equivalents of cesium hydroxide to commercially available DAPA monohydrochloride to convert the amino group into a free amino group that is not protonated.
次に、工程１で得たキャスト溶液中の気泡を除去するために、遠心分離（回転数５０００ｒｐｍで３０分間）を行う（工程２）。 Next, in order to remove bubbles in the cast solution obtained in Step 1, centrifugation (rotation speed: 5000 rpm for 30 minutes) is performed (Step 2).
次に、工程２で得たキャスト溶液を、親水性ＰＴＦＥ多孔膜（例えば、アドバンテック製、Ｈ０１０Ａ１４２Ｃ、膜厚３５μｍ、細孔径０．１μｍ、空隙率７０％）と疎水性ＰＴＦＥ多孔膜（例えば、住友電工製、フロロポアＦＰ０１０、膜厚６０μｍ、細孔径０．１μｍ、空隙率５５％）を２枚重ね合わせた層状多孔膜の親水性ＰＴＦＥ多孔膜側の面上に、アプリケータでキャストする（工程３）。尚、後述する実施例のサンプルでのキャスト厚は５００μｍである。ここで、キャスト溶液は、親水性ＰＴＦＥ多孔膜中の細孔内に浸透するが、疎水性のＰＴＦＥ多孔膜の境界面で浸透が停止し、層状多孔膜の反対面までキャスト溶液がしみ込まず、層状多孔膜の疎水性ＰＴＦＥ多孔膜側面にはキャスト溶液が存在せず取り扱いが容易となる。 Next, the cast solution obtained in step 2 is mixed with a hydrophilic PTFE porous membrane (for example, manufactured by Advantech, H010A142C, film thickness 35 μm, pore diameter 0.1 μm, porosity 70%) and hydrophobic PTFE porous membrane (for example, Sumitomo Cast with an applicator on the surface of the porous PTFE porous membrane side of a layered porous membrane in which two sheets made by Denko, Fluoropore FP010, film thickness 60 μm, pore diameter 0.1 μm, porosity 55%) are laminated (Step 3) ). In addition, the cast thickness in the sample of the Example mentioned later is 500 micrometers. Here, the cast solution penetrates into the pores in the hydrophilic PTFE porous membrane, but the penetration stops at the boundary surface of the hydrophobic PTFE porous membrane, and the cast solution does not penetrate to the opposite surface of the layered porous membrane, There is no casting solution on the side surface of the porous porous membrane of the layered porous membrane, and the handling becomes easy.
次に、キャスト後の親水性ＰＴＦＥ多孔膜を室温で約半日自然乾燥させ、キャスト溶液をゲル化させゲル層を生成する（工程４）。本発明方法では、工程３において、キャスト溶液を層状多孔膜の親水性ＰＴＦＥ多孔膜側の表面にキャストするため、工程４において、ゲル層は、親水性ＰＴＦＥ多孔膜の表面（キャスト面）に形成されるのみならず細孔内にも充填して形成されるので、欠陥（ピンホール等の微小欠陥）が生じ難くなり、ゲル層の製膜成功率が高くなる。尚、工程４において、自然乾燥させたＰＴＦＥ多孔膜を、更に、１２０℃程度の温度で、２時間程度熱架橋するのが望ましい。尚、後述する実施例及び比較例のサンプルでは、何れも熱架橋を行っている。 Next, the hydrophilic PTFE porous membrane after casting is naturally dried at room temperature for about half a day, and the cast solution is gelled to form a gel layer (step 4). In the method of the present invention, in Step 3, the cast solution is cast on the surface of the layered porous membrane on the hydrophilic PTFE porous membrane side, so in Step 4, the gel layer is formed on the surface (cast surface) of the hydrophilic PTFE porous membrane. In addition to being formed, the pores are filled and formed, so that defects (micro-defects such as pinholes) are less likely to occur, and the success rate of gel layer deposition is increased. In step 4, it is desirable that the naturally dried PTFE porous membrane is further thermally crosslinked at a temperature of about 120 ° C. for about 2 hours. In the samples of Examples and Comparative Examples described later, thermal crosslinking is performed.
次に、工程４で得た親水性ＰＴＦＥ多孔膜表面のゲル層側に、工程３で用いた層状多孔膜の疎水性ＰＴＦＥ多孔膜と同じ疎水性ＰＴＦＥ多孔膜を重ね、図１に模式的に示すように、疎水性ＰＴＦＥ多孔膜／ゲル層（親水性ＰＴＦＥ多孔膜に担持された含有ゲル膜）／疎水性ＰＴＦＥ多孔膜よりなる３層構造の本発明膜を得る（工程５）。尚、図１において、含有ゲル膜１が親水性ＰＴＦＥ多孔膜２の細孔内に充填している様子を模式的に直線状に表示している。 Next, the same hydrophobic PTFE porous membrane as that of the layered porous membrane used in Step 3 is superimposed on the gel layer side of the hydrophilic PTFE porous membrane surface obtained in Step 4, and is schematically shown in FIG. As shown, a membrane of the present invention having a three-layer structure comprising a hydrophobic PTFE porous membrane / gel layer (containing gel membrane supported on a hydrophilic PTFE porous membrane) / hydrophobic PTFE porous membrane is obtained (step 5). In addition, in FIG. 1, a mode that the containing gel film | membrane 1 is filling in the pore of the hydrophilic PTFE porous film 2 is displayed typically linearly.
以上、工程１〜工程５を経て作製された本発明膜は、ＣＯ２透過型メンブレンリアクターへ応用可能な膜性能、即ち、使用温度１００℃、２×１０−５ｍｏｌ／（ｍ２・ｓ・ｋＰａ）（＝６０ＧＰＵ）程度以上のＣＯ２パーミアンス、及び、１００程度以上のＣＯ２／Ｈ２選択率が実現できる。 As described above, the membrane of the present invention produced through the steps 1 to 5 has a membrane performance applicable to a CO 2 permeable membrane reactor, that is, a use temperature of 100 ° C., 2 × 10 −5 mol / (m 2 · s · CO 2 permeance of about kPa) (= 60 GPU) or more and CO 2 / H 2 selectivity of about 100 or more can be realized.
また、ゲル層を疎水性ＰＴＦＥ多孔膜で挟持した３層構造とすることにより、一方の疎水性ＰＴＦＥ多孔膜は、工程３及び工程４で用いられ、含有ゲル膜を担持する親水性ＰＴＦＥ多孔膜の支持とキャスト溶液の浸透防止に供せられ、他方の疎水性ＰＴＦＥ多孔膜は、含有ゲル膜を他方面側から保護するのに用いられる。 Further, by forming a three-layer structure in which the gel layer is sandwiched between the hydrophobic PTFE porous membranes, one of the hydrophobic PTFE porous membranes is used in Step 3 and Step 4, and is a hydrophilic PTFE porous membrane supporting the contained gel membrane. The other hydrophobic PTFE porous membrane is used to protect the contained gel membrane from the other surface side.
更に、水蒸気が疎水性ＰＴＦＥ多孔膜の膜表面に凝縮しても当該ＰＴＦＥ多孔膜が疎水性のために水がはじかれて含有ゲル膜にしみ込むのを防止している。よって、他方のＰＴＦＥ多孔膜によって、含有ゲル膜中の二酸化炭素キャリアが水で薄められ、また、薄められた二酸化炭素キャリアが含有ゲル膜から流出することを防止できる。 Furthermore, even if water vapor is condensed on the surface of the hydrophobic PTFE porous membrane, the PTFE porous membrane is hydrophobic and prevents water from being repelled and penetrating into the contained gel membrane. Therefore, it is possible to prevent the carbon dioxide carrier in the contained gel film from being diluted with water by the other PTFE porous membrane, and to prevent the diluted carbon dioxide carrier from flowing out of the containing gel film.
以下、具体的な実施例の膜性能について説明する。 Hereinafter, the film performance of specific examples will be described.
先ず、含有ゲル膜を担持する多孔膜として、親水性ＰＴＦＥ多孔膜を使用した実施例と、疎水性ＰＴＦＥ多孔膜を使用した比較例の各サンプルの膜組成について説明する。実施例のサンプルは、上述の作製方法により作製した。（ＰＶＡ／ＰＡＡ：ＤＡＰＡ）の配合比率は、記載の順に、（８０重量％：２０重量％）となっている。比較例のサンプルは、上述の作製方法において、親水性ＰＴＦＥ多孔膜と疎水性ＰＴＦＥ多孔膜の層状多孔膜に代えて１層の疎水性ＰＴＦＥ多孔膜を使用して作製された。従って、比較例のサンプルは、図３に模式的に示すように、二酸化炭素キャリアを含有するＰＶＡ／ＰＡＡゲル膜１が、２枚の疎水性多孔膜３，４の間に挟持される３層構造で構成される。（ＰＶＡ／ＰＡＡ：ＤＡＰＡ）の配合比率は、実施例と同じである。尚、何れのサンプルも上述の３層構造を更にシリコンをコーティングしたポリプロピレン多孔膜で補強した４層構造としたものを使用した。 First, the film composition of each sample of an example using a hydrophilic PTFE porous film and a comparative example using a hydrophobic PTFE porous film as a porous film carrying the gel gel will be described. The sample of the example was manufactured by the above-described manufacturing method. The blending ratio of (PVA / PAA: DAPA) is (80% by weight: 20% by weight) in the order of description. The sample of the comparative example was prepared by using one layer of a hydrophobic PTFE porous membrane in place of the layered porous membrane of the hydrophilic PTFE porous membrane and the hydrophobic PTFE porous membrane in the above-described production method. Therefore, in the sample of the comparative example, as schematically shown in FIG. 3, the PVA / PAA gel film 1 containing the carbon dioxide carrier is sandwiched between the two hydrophobic porous films 3 and 4. Composed of structure. The blending ratio of (PVA / PAA: DAPA) is the same as in the examples. Each sample used was a four-layer structure in which the above three-layer structure was further reinforced with a polypropylene porous film coated with silicon.
次に、実施例、及び、比較例の各サンプルの膜性能を評価するための実験装置の構成及び実験方法について、図４を参照して説明する。 Next, the configuration of the experimental apparatus and the experimental method for evaluating the film performance of each sample of the example and the comparative example will be described with reference to FIG.
図４に示すように、各サンプル１０は、ステンレス製の流通式ガス透過セル１１（膜面積：２．８８ｃｍ２）の原料側室１２と透過側室１３の間に、２枚のフッ素ゴム製ガスケットをシール材として用いて固定されている。原料ガス（ＣＯ２、Ｈ２、Ｈ２Ｏからなる混合ガス）ＦＧを、２．２４×１０−２ｍｏｌ／ｍｉｎの流量で原料側室１２に供給し、スイープガス（Ａｒガス）ＳＧを、８．１８×１０−４ｍｏｌ／ｍｉｎの流量で透過側室１３に供給する。原料側室１２の圧力は、排気ガスの排出路の途中の冷却トラップ１４の下流側に設けられた背圧調整器１５で調整される。透過側室１３の圧力は大気圧である。透過側室１３から排出するスイープガスＳＧ’中の水蒸気を冷却トラップ１６で除去した後のガス組成をガスクロマトグラフ１７で定量し、これとスイープガスＳＧ中のＡｒの流量よりＣＯ２及びＨ２のパーミアンス［ｍｏｌ／（ｍ２・ｓ・ｋＰａ）］を計算し、その比より、ＣＯ２／Ｈ２選択率を算出する。 As shown in FIG. 4, each sample 10 has two fluororubber gaskets between the raw material side chamber 12 and the permeation side chamber 13 of a stainless steel flow type gas permeation cell 11 (membrane area: 2.88 cm 2 ). It is fixed by using it as a sealing material. A source gas (mixed gas composed of CO 2 , H 2 , H 2 O) FG is supplied to the source side chamber 12 at a flow rate of 2.24 × 10 −2 mol / min, and a sweep gas (Ar gas) SG is supplied at 8 Supplied to the permeation side chamber 13 at a flow rate of 18 × 10 −4 mol / min. The pressure in the raw material side chamber 12 is adjusted by a back pressure regulator 15 provided on the downstream side of the cooling trap 14 in the middle of the exhaust gas discharge path. The pressure in the transmission side chamber 13 is atmospheric pressure. The gas composition after the water vapor in the sweep gas SG ′ discharged from the permeation side chamber 13 is removed by the cooling trap 16 is quantified by the gas chromatograph 17 and the permeance of CO 2 and H 2 from this and the flow rate of Ar in the sweep gas SG. [Mol / (m 2 · s · kPa)] is calculated, and the CO 2 / H 2 selectivity is calculated from the ratio.
原料ガスＦＧは、ＣＯ変成器内における原料ガスを模擬するために、ＣＯ２、Ｈ２、Ｈ２Ｏからなる混合ガスを、ＣＯ２：３．６５％、Ｈ２：３２．８５％、Ｈ２Ｏ：６３．５％の混合比率（モル％）に調整した。具体的には、１０％ＣＯ２と９０％Ｈ２（モル％）よりなる混合ガス流（２５℃での流量：２００ｃｍ３／ｍｉｎ、８．１８×１０−３ｍｏｌ／ｍｉｎ）に水を定量送液ポンプ１８で送入し（流量：０．２５６ｃｍ３／ｍｉｎ、１．４２×１０−２ｍｏｌ／ｍｉｎ）、１００℃以上に加熱して水分を蒸発させて、上記混合比率の混合ガスを調製し、これを原料側室１２に供給した。 In order to simulate the raw material gas in the CO converter, the raw material gas FG is a mixed gas composed of CO 2 , H 2 , and H 2 O, CO 2 : 3.65%, H 2 : 32.85%, H 2 O: Adjusted to a mixing ratio (mol%) of 63.5%. Specifically, water is quantified in a mixed gas flow (flow rate at 25 ° C .: 200 cm 3 / min, 8.18 × 10 −3 mol / min) composed of 10% CO 2 and 90% H 2 (mol%). It was fed by the liquid feed pump 18 (flow rate: 0.256 cm 3 / min, 1.42 × 10 −2 mol / min), heated to 100 ° C. or more to evaporate the water, and the mixed gas having the above mixing ratio was This was prepared and supplied to the raw material side chamber 12.
スイープガスＳＧは、サンプル膜を透過する被測定ガス（ＣＯ２、Ｈ２）の透過側室側の分圧を低くして、透過推進力を維持するために供給され、被測定ガスと異なるガス種（Ａｒガス）を用いる。具体的には、Ａｒガス（２５℃での流量：２０ｃｍ３／ｍｉｎ、８．１３×１０−４ｍｏｌ／ｍｉｎ）を透過側室１３に供給した。 The sweep gas SG is supplied in order to reduce the partial pressure on the permeate side chamber side of the gas to be measured (CO 2 , H 2 ) that permeates the sample membrane and maintain the permeation driving force, and is a gas type different from the gas to be measured. (Ar gas) is used. Specifically, Ar gas (flow rate at 25 ° C .: 20 cm 3 / min, 8.13 × 10 −4 mol / min) was supplied to the permeation side chamber 13.
尚、図示していないが、サンプル膜の使用温度、及び、原料ガスＦＧとスイープガスＳＧの温度を一定温度に維持するために、サンプル膜を固定した流通式ガス透過セル１１と上記ガスを加熱する予熱コイルを、所定温度に設定したオイル恒温槽内に浸している。 Although not shown, in order to maintain the use temperature of the sample film and the temperatures of the source gas FG and the sweep gas SG at a constant temperature, the flow type gas permeable cell 11 with the sample film fixed and the gas are heated. The preheating coil is immersed in an oil thermostat set at a predetermined temperature.
次に、図５に、実施例と比較例の各サンプルのＣＯ２パーミアンスＲＣＯ２とＣＯ２／Ｈ２選択率を、原料側室１２内の原料ガスＦＧの圧力を１５０ｋＰａ〜３５０ｋＰａの範囲の加圧状態で測定した結果を示す。尚、測定温度は１２５℃である。 Next, FIG. 5 shows the CO 2 permeance R CO2 and CO 2 / H 2 selectivity of each sample of the example and the comparative example, and the pressure of the raw material gas FG in the raw material side chamber 12 is in the range of 150 kPa to 350 kPa. The result measured in the state is shown. The measurement temperature is 125 ° C.
図５より、ＣＯ２パーミアンスは、疎水性ＰＴＦＥ多孔膜を使用した比較例のサンプルの方が、親水性ＰＴＦＥ多孔膜を使用した実施例のサンプルより、全圧力範囲で僅かに高くなっているが、ＣＯ２／Ｈ２選択率では、実施例のサンプルの方が、比較例のサンプルより大幅に改善されていることが分かる。これは、親水性ＰＴＦＥ多孔膜を使用した場合に、ＰＴＦＥ多孔膜の表面のみならず細孔内にもゲル層が充填されるので欠陥（ピンホール等の微小欠陥）が生じ難くなり、当該微小欠陥を介してガスパーミアンス、特に、水素パーミアンスが上昇するのが抑制されるためと考えられる。 From FIG. 5, the CO 2 permeance is slightly higher in the entire pressure range in the sample of the comparative example using the hydrophobic PTFE porous membrane than in the sample of the example using the hydrophilic PTFE porous membrane. In the CO 2 / H 2 selectivity, it can be seen that the sample of the example is significantly improved over the sample of the comparative example. This is because when a hydrophilic PTFE porous membrane is used, the gel layer is filled not only on the surface of the PTFE porous membrane but also in the pores, so that defects (minute defects such as pinholes) are less likely to occur. It is considered that gas permeance, particularly hydrogen permeance, is prevented from rising through the defect.
また、上記特許文献１，２に開示されたＣＯ２促進輸送膜では、１００℃以上の使用温度、２×１０−５ｍｏｌ／（ｍ２・ｓ・ｋＰａ）程度以上のＣＯ２パーミアンス、及び、９０〜１００程度以上のＣＯ２／Ｈ２選択率の何れも満足していないのに対して、図５に示す実施例及び比較例の各サンプルは、全ての要件を概ね満足しており、特に、実施例のサンプルにおいて、良好な結果が得られていることが分かる。比較例のサンプルでは、３００ｋＰａ以上でＣＯ２／Ｈ２選択率が１００を下回り、温度を更に上昇させるとＣＯ２／Ｈ２選択率の低下がより顕著に現れる。 In addition, in the CO 2 facilitated transport membrane disclosed in Patent Documents 1 and 2, a use temperature of 100 ° C. or more, a CO 2 permeance of about 2 × 10 −5 mol / (m 2 · s · kPa), and While none of the CO 2 / H 2 selectivity of about 90 to 100 or more is satisfied, each sample of the example and comparative example shown in FIG. 5 generally satisfies all the requirements. It can be seen that good results are obtained in the samples of the examples. In the sample of the comparative example, the CO 2 / H 2 selectivity falls below 100 at 300 kPa or more, and the CO 2 / H 2 selectivity decreases more significantly when the temperature is further increased.
次に、図６に、実施例と比較例の各サンプルのＣＯ２パーミアンスＲＣＯ２とＣＯ２／Ｈ２選択率を、原料側室１２内の原料ガスＦＧの圧力を１５０ｋＰａ〜５５０ｋＰａの範囲の加圧状態で測定した結果を示す。尚、測定温度は１４０℃である。 Next, FIG. 6 shows the CO 2 permeance R CO2 and CO 2 / H 2 selectivity of each sample of the example and the comparative example, and the pressure of the raw material gas FG in the raw material side chamber 12 is in the range of 150 kPa to 550 kPa. The result measured in the state is shown. The measurement temperature is 140 ° C.
図６より、温度が１２５℃から１４０℃に上昇したことにより、ＣＯ２パーミアンスＲＣＯ２とＣＯ２／Ｈ２選択率の何れもが低下しているが、温度上昇によってＰＶＡ／ＰＡＡゲル膜内の二酸化炭素の促進輸送に寄与する水分が減少したことに起因するものである。しかし、実施例のサンプルでは、温度が１４０℃に上昇しても、比較例のサンプルより高いＣＯ２／Ｈ２選択率が得られるため、原料ガスＦＧの圧力が３５０ｋＰａ以上において、２×１０−５ｍｏｌ／（ｍ２・ｓ・ｋＰａ）程度以上のＣＯ２パーミアンス、及び、９０〜１００程度以上のＣＯ２／Ｈ２選択率の何れも概ね満足できるのに対し、比較例のサンプルでは、ＣＯ２／Ｈ２選択率で期待値を大幅に下回る結果となっている。 From FIG. 6, both the CO 2 permeance R CO2 and the CO 2 / H 2 selectivity are decreased by increasing the temperature from 125 ° C. to 140 ° C., but the increase in temperature causes an increase in the PVA / PAA gel membrane. This is due to a decrease in moisture that contributes to facilitated transport of carbon dioxide. However, in the sample of the example, even when the temperature rises to 140 ° C., a higher CO 2 / H 2 selectivity than that of the sample of the comparative example can be obtained. Therefore, when the pressure of the source gas FG is 350 kPa or more, 2 × 10 − Both the CO 2 permeance of about 5 mol / (m 2 · s · kPa) and the CO 2 / H 2 selectivity of about 90 to 100 or more are generally satisfactory, whereas the sample of the comparative example has CO 2 It has resulted in significantly less than the expected value at 2 / H 2 selectivity.
〈第２実施形態〉
第２実施形態の本発明膜は、水分を含むゲル膜内に二酸化炭素キャリアを含有したＣＯ２促進輸送膜であって、１００℃以上の使用温度、高い二酸化炭素透過性とＣＯ２／Ｈ２選択率を有するＣＯ２透過型メンブレンリアクターへ応用可能なＣＯ２促進輸送膜であり、高い二酸化炭素透過性を実現するために、二酸化炭素キャリアに加えて、二酸化炭素透過性を促進するための添加剤をゲル膜内に含有する。従って、ゲル膜内に添加剤が追加されている点で、第１実施形態の本発明膜と相違する。
Second Embodiment
The membrane of the present invention of the second embodiment is a CO 2 facilitated transport membrane containing a carbon dioxide carrier in a gel membrane containing moisture, and has a use temperature of 100 ° C. or higher, high carbon dioxide permeability and CO 2 / H 2. CO 2 -facilitated transport membrane applicable to CO 2 permeable membrane reactors with selectivity, added to promote carbon dioxide permeability in addition to carbon dioxide carrier to realize high carbon dioxide permeability The agent is contained in the gel film. Therefore, it differs from the membrane of the present invention of the first embodiment in that an additive is added in the gel membrane.
具体的には、本発明膜は、膜材料として、ポリビニルアルコール‐ポリアクリル酸（ＰＶＡ／ＰＡＡ）共重合体を使用し、二酸化炭素キャリアとして、２，３‐ジアミノプロピオン酸（ＤＡＰＡ）を使用し、添加剤として、グリセリン、または、イオン性流体を使用する。また、本発明膜は、二酸化炭素キャリアと添加剤を含有するＰＶＡ／ＰＡＡゲル膜を担持した親水性多孔膜２が、２枚の疎水性多孔膜３，４に挟持される３層構造（図１に示す第１実施形態の３層構造と同じ）で構成される。以下、二酸化炭素キャリアと添加剤を含有するＰＶＡ／ＰＡＡゲル膜を、二酸化炭素キャリアと添加剤を含有しないＰＶＡ／ＰＡＡゲル膜、及び、２枚の疎水性多孔膜を備えた構造の本発明膜と区別するために、適宜「含有ゲル膜」と略称する。また、この含有ゲル膜中のＰＶＡ／ＰＡＡとＤＡＰＡと添加剤の全重量を基準として、含有ゲル膜中において、ＰＶＡ／ＰＡＡは約２０〜８０重量％の範囲で存在し、ＤＡＰＡは約２０〜８０重量％の範囲で存在し、添加剤は約０〜３０重量％の範囲で存在する。 Specifically, the membrane of the present invention uses a polyvinyl alcohol-polyacrylic acid (PVA / PAA) copolymer as a membrane material, and uses 2,3-diaminopropionic acid (DAPA) as a carbon dioxide carrier. , Glycerin or ionic fluid is used as an additive. The membrane of the present invention has a three-layer structure in which a hydrophilic porous membrane 2 carrying a PVA / PAA gel membrane containing a carbon dioxide carrier and an additive is sandwiched between two hydrophobic porous membranes 3 and 4 (see FIG. 1 is the same as the three-layer structure of the first embodiment shown in FIG. Hereinafter, a PVA / PAA gel film containing a carbon dioxide carrier and an additive, a PVA / PAA gel film containing no carbon dioxide carrier and an additive, and a membrane of the present invention having a structure comprising two hydrophobic porous films In order to distinguish them from each other, they are appropriately abbreviated as “containing gel film”. Further, based on the total weight of PVA / PAA, DAPA and additives in the containing gel film, PVA / PAA is present in the range of about 20 to 80% by weight in the containing gel film, and DAPA is about 20 to It is present in the range of 80% by weight, and the additive is present in the range of about 0-30% by weight.
添加剤は、イオン性流体やオリゴマー等の低蒸気圧の液体であって、親水性、熱安定性、二酸化炭素に対する親和性、及び、二酸化炭素キャリアであるＤＡＰＡとの相溶性が必要である。かかる条件を備えたイオン性流体として、下記のカチオン、アニオンの組合せよりなる化合物から選択される化学物質が利用できる。
カチオン：１，３位に以下の置換基を有するイミダゾリウムで、置換基としてアルキル基、ヒドロキシアルキル基、エーテル基、アリル基、アミノアルキル基を有するもの、または、第４級アンモニウムカチオンで、置換基としてアルキル基、ヒドロキシアルキル基、エーテル基、アリル基、アミノアルキル基を有するもの。
アニオン：塩化物イオン、臭化物イオン、四フッ化ホウ素イオン、硝酸イオン、ビス（トリフルオロメタンスルホニル）イミドイオン、ヘキサフルオロリン酸イオン、または、トリフルオロメタンスルホン酸イオン。
The additive is a low vapor pressure liquid such as an ionic fluid or an oligomer, and requires hydrophilicity, thermal stability, affinity for carbon dioxide, and compatibility with DAPA which is a carbon dioxide carrier. As an ionic fluid having such conditions, a chemical substance selected from a compound comprising a combination of the following cation and anion can be used.
Cation: Imidazolium having the following substituents at positions 1 and 3, substituted with an alkyl group, hydroxyalkyl group, ether group, allyl group, aminoalkyl group as a substituent group, or substituted with a quaternary ammonium cation A group having an alkyl group, a hydroxyalkyl group, an ether group, an allyl group or an aminoalkyl group as a group.
Anion: Chloride ion, bromide ion, boron tetrafluoride ion, nitrate ion, bis (trifluoromethanesulfonyl) imide ion, hexafluorophosphate ion, or trifluoromethanesulfonate ion.
また、当該イオン性流体の具体例として、１‐アリル‐３‐エチルイミダゾリウムブロミド、１‐エチル‐３-メチルイミダゾリウムブロミド、１‐（２‐ヒドロキシエチル）‐３‐メチルイミダゾリウムブロミド、１‐（２‐メトキシエチル）‐３‐メチルイミダゾリウムブロミド、１‐オクチル‐３‐メチルイミダゾリウムクロリド、Ｎ，Ｎ‐ジエチル‐Ｎ‐メチル‐Ｎ‐（２‐メトキシエチル）アンモニウムテトラフルオロボラート、エチルメチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド、エチルメチルイミダゾリウムビストリフルオロメタンスルホン酸、エチルメチルイミダゾリウムジシアナミド、及び、塩化トリヘキシルテトラデシルホスホニウム等が利用できる。また、添加剤として、イオン性流体以外に、グリセリン、ポリグリセリン、ポリエチレングリコール、ポリプロピレングリコール、ポリエチレンオキサイド、ポリエチレンイミン、ポリアリルアミン、ポリアクリル酸の中から選択される化学物質が利用できる。 Specific examples of the ionic fluid include 1-allyl-3-ethylimidazolium bromide, 1-ethyl-3-methylimidazolium bromide, 1- (2-hydroxyethyl) -3-methylimidazolium bromide, 1 -(2-methoxyethyl) -3-methylimidazolium bromide, 1-octyl-3-methylimidazolium chloride, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate, Ethylmethylimidazolium bis (trifluoromethanesulfonyl) imide, ethylmethylimidazolium bistrifluoromethanesulfonic acid, ethylmethylimidazolium dicyanamide, trihexyl tetradecylphosphonium chloride, and the like can be used. In addition to the ionic fluid, a chemical substance selected from glycerin, polyglycerin, polyethylene glycol, polypropylene glycol, polyethylene oxide, polyethyleneimine, polyallylamine, and polyacrylic acid can be used as an additive.
二酸化炭素キャリアであるＤＡＰＡ、親水性多孔膜、及び、疎水性多孔膜は、第１実施形態で使用したものと同じであるので、重複する説明は省略する。 Since DAPA, which is a carbon dioxide carrier, a hydrophilic porous membrane, and a hydrophobic porous membrane are the same as those used in the first embodiment, overlapping description will be omitted.
次に、本発明膜の作製方法の一実施形態（本発明方法の第２実施形態）について、図７を参照して説明する。 Next, an embodiment of a method for producing a film of the present invention (second embodiment of the method of the present invention) will be described with reference to FIG.
先ず、ＰＶＡ／ＰＡＡ共重合体とＤＡＰＡと添加剤を含む水溶液からなるキャスト溶液を作製する（工程１）。より詳細には、ＰＶＡ／ＰＡＡ共重合体（例えば、住友精化製の仮称ＳＳゲル）を１ｇ、ＤＡＰＡ一塩酸塩を０．２５ｇ、水酸化セシウム（ＣｓＯＨ）を０．５４ｇ（ＤＡＰＡ一塩酸塩に対して２当量）、添加剤（イオン性流体ＡＥＢ等）を０．２ｇ、サンプル瓶に秤取し、これに水２０ｇを加えて室温で一昼夜攪拌して溶解させてキャスト溶液を得る。キャスト溶液中に添加剤を加えた点以外は、第１実施形態の作製方法と同じあり、ＤＡＰＡの処理方法についても重複する説明は割愛する。 First, a cast solution composed of an aqueous solution containing a PVA / PAA copolymer, DAPA and an additive is prepared (step 1). More specifically, 1 g of a PVA / PAA copolymer (for example, a temporary name SS gel manufactured by Sumitomo Seika), 0.25 g of DAPA monohydrochloride, 0.54 g of cesium hydroxide (CsOH) (DAPA monohydrochloride) 2 g), 0.2 g of additive (ionic fluid AEB, etc.), weighed in a sample bottle, added with 20 g of water, and stirred at room temperature for 24 hours to dissolve to obtain a cast solution. Except for the point that an additive is added to the cast solution, it is the same as the manufacturing method of the first embodiment, and the description of the DAPA processing method is omitted.
次に、工程１で得たキャスト溶液中の気泡を除去するために、遠心分離（回転数５０００ｒｐｍで３０分間）を行う（工程２）。 Next, in order to remove bubbles in the cast solution obtained in Step 1, centrifugation (rotation speed: 5000 rpm for 30 minutes) is performed (Step 2).
次に、工程２で得たキャスト溶液を、親水性ＰＴＦＥ多孔膜（例えば、アドバンテック製、Ｈ０１０Ａ１４２Ｃ、膜厚３５μｍ、細孔径０．１μｍ、空隙率７０％）と疎水性ＰＴＦＥ多孔膜（例えば、住友電工製、フロロポアＦＰ０１０、膜厚６０μｍ、細孔径０．１μｍ、空隙率５５％）を２枚重ね合わせた層状多孔膜の親水性ＰＴＦＥ多孔膜側の面上に、アプリケータでキャストする（工程３）。尚、後述する実施例及び比較例のサンプルでのキャスト厚は２５４μｍである。 Next, the cast solution obtained in step 2 is mixed with a hydrophilic PTFE porous membrane (for example, manufactured by Advantech, H010A142C, film thickness 35 μm, pore diameter 0.1 μm, porosity 70%) and hydrophobic PTFE porous membrane (for example, Sumitomo Cast with an applicator on the surface of the porous PTFE porous membrane side of a layered porous membrane in which two sheets made by Denko, Fluoropore FP010, film thickness 60 μm, pore diameter 0.1 μm, porosity 55%) are laminated (Step 3) ). In addition, the cast thickness in the sample of the Example and comparative example which are mentioned later is 254 micrometers.
次に、キャスト後の親水性ＰＴＦＥ多孔膜を室温で約半日自然乾燥させ、キャスト溶液をゲル化させゲル層を生成する（工程４）。本発明方法では、工程３において、キャスト溶液を層状多孔膜の親水性ＰＴＦＥ多孔膜側の表面にキャストするため、工程４において、ゲル層は、親水性ＰＴＦＥ多孔膜の表面（キャスト面）に形成されるのみならず細孔内にも充填して形成されるので、欠陥（ピンホール等の微小欠陥）が生じ難くなり、ゲル層の製膜成功率が高くなる。尚、工程４において、自然乾燥させたＰＴＦＥ多孔膜を、更に、１２０℃程度の温度で、２時間程度熱架橋するのが望ましい。尚、後述する実施例及び比較例のサンプルでは、何れも熱架橋を行っている。 Next, the hydrophilic PTFE porous membrane after casting is naturally dried at room temperature for about half a day, and the cast solution is gelled to form a gel layer (step 4). In the method of the present invention, in Step 3, the cast solution is cast on the surface of the layered porous membrane on the hydrophilic PTFE porous membrane side, so in Step 4, the gel layer is formed on the surface (cast surface) of the hydrophilic PTFE porous membrane. In addition to being formed, the pores are filled and formed, so that defects (micro-defects such as pinholes) are less likely to occur, and the success rate of gel layer deposition is increased. In step 4, it is desirable that the naturally dried PTFE porous membrane is further thermally crosslinked at a temperature of about 120 ° C. for about 2 hours. In the samples of Examples and Comparative Examples described later, thermal crosslinking is performed.
次に、工程４で得た親水性ＰＴＦＥ多孔膜表面のゲル層側に、工程３で用いた層状多孔膜の疎水性ＰＴＦＥ多孔膜と同じ疎水性ＰＴＦＥ多孔膜を重ね、疎水性ＰＴＦＥ多孔膜／ゲル層（親水性ＰＴＦＥ多孔膜に担持された含有ゲル膜）／疎水性ＰＴＦＥ多孔膜よりなる３層構造の本発明膜を得る（工程５）。工程２〜工程５の各処理は、第１実施形態の作製方法と全く同じある。 Next, the same hydrophobic PTFE porous membrane as that of the layered porous membrane used in Step 3 is stacked on the gel layer side of the hydrophilic PTFE porous membrane surface obtained in Step 4, and the hydrophobic PTFE porous membrane / A membrane of the present invention comprising a gel layer (containing gel membrane supported on a hydrophilic PTFE porous membrane) / hydrophobic PTFE porous membrane is obtained (step 5). Each process of step 2 to step 5 is exactly the same as the manufacturing method of the first embodiment.
以上、工程１〜工程５を経て作製された本発明膜は、ＣＯ２透過型メンブレンリアクターへ応用可能な膜性能、即ち、使用温度１００℃、２×１０−５ｍｏｌ／（ｍ２・ｓ・ｋＰａ）（＝６０ＧＰＵ）程度以上のＣＯ２パーミアンス、及び、１００程度以上のＣＯ２／Ｈ２選択率が実現できる。 As described above, the membrane of the present invention produced through the steps 1 to 5 has a membrane performance applicable to a CO 2 permeable membrane reactor, that is, a use temperature of 100 ° C., 2 × 10 −5 mol / (m 2 · s · CO 2 permeance of about kPa) (= 60 GPU) or more and CO 2 / H 2 selectivity of about 100 or more can be realized.
また、ゲル層を疎水性ＰＴＦＥ多孔膜で挟持した３層構造とすることにより、一方の疎水性ＰＴＦＥ多孔膜は、工程３及び工程４で用いられ、含有ゲル膜を担持する親水性ＰＴＦＥ多孔膜の支持とキャスト溶液の浸透防止に供せられ、他方の疎水性ＰＴＦＥ多孔膜は、含有ゲル膜を他方面側から保護するのに用いられる。 Further, by forming a three-layer structure in which the gel layer is sandwiched between the hydrophobic PTFE porous membranes, one of the hydrophobic PTFE porous membranes is used in Step 3 and Step 4, and is a hydrophilic PTFE porous membrane supporting the contained gel membrane. The other hydrophobic PTFE porous membrane is used to protect the contained gel membrane from the other surface side.
以下、添加剤として下記の４種類のイオン性流体を個々に使用した４つの実施例１〜４の各サンプルを参考にして、夫々の膜性能について説明する。４種類のイオン性流体は、実施例１：１‐アリル‐３‐エチルイミダゾリウムブロミド、実施例２：１‐（２‐ヒドロキシエチル）‐３‐メチルイミダゾリウムブロミド、実施例３：１‐オクチル‐３‐メチルイミダゾリウムクロリド、実施例４：Ｎ，Ｎ‐ジエチル‐Ｎ‐メチル‐Ｎ‐（２‐メトキシエチル）アンモニウムテトラフルオロボラートである。 Hereinafter, each membrane performance is demonstrated with reference to each sample of four Examples 1-4 which used the following four types of ionic fluid as an additive individually. The four ionic fluids are: Example 1: 1-allyl-3-ethylimidazolium bromide, Example 2: 1- (2-hydroxyethyl) -3-methylimidazolium bromide, Example 3: 1-octyl -3-Methylimidazolium chloride, Example 4: N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate.
先ず、実施例１〜４の各サンプルの膜組成について説明する。実施例１のサンプルは、添加剤として１‐アリル‐３‐エチルイミダゾリウムブロミドを使用して、上述の作製方法により作製した。（ＰＶＡ／ＰＡＡ：ＤＡＰＡ：添加剤）の配合比率は、記載の順に、（６６．３重量％：２０重量％：１３．７重量％）となっている。実施例２のサンプルは、添加剤として１‐（２‐ヒドロキシエチル）‐３‐メチルイミダゾリウムブロミドを使用して、上述の作製方法により作製した。（ＰＶＡ／ＰＡＡ：ＤＡＰＡ：添加剤）の配合比率は、記載の順に、（６６．３重量％：２０重量％：１３．７重量％）となっている。実施例３のサンプルは、添加剤として１‐オクチル‐３‐メチルイミダゾリウムクロリドを使用して、上述の作製方法により作製した。（ＰＶＡ／ＰＡＡ：ＤＡＰＡ：添加剤）の配合比率は、記載の順に、（６６．３重量％：２０重量％：１３．７重量％）となっている。実施例４のサンプルは、添加剤としてＮ，Ｎ‐ジエチル‐Ｎ‐メチル‐Ｎ‐（２‐メトキシエチル）アンモニウムテトラフルオロボラートを使用して、上述の作製方法により作製した。（ＰＶＡ／ＰＡＡ：ＤＡＰＡ：添加剤）の配合比率は、記載の順に、（６６．３重量％：２０重量％：１３．７重量％）となっている。 First, the film composition of each sample of Examples 1 to 4 will be described. The sample of Example 1 was prepared by the above-described preparation method using 1-allyl-3-ethylimidazolium bromide as an additive. The blending ratio of (PVA / PAA: DAPA: additive) is (66.3 wt%: 20 wt%: 13.7 wt%) in the order of description. The sample of Example 2 was made by the above-described preparation method using 1- (2-hydroxyethyl) -3-methylimidazolium bromide as an additive. The blending ratio of (PVA / PAA: DAPA: additive) is (66.3 wt%: 20 wt%: 13.7 wt%) in the order of description. The sample of Example 3 was prepared by the above-described preparation method using 1-octyl-3-methylimidazolium chloride as an additive. The blending ratio of (PVA / PAA: DAPA: additive) is (66.3 wt%: 20 wt%: 13.7 wt%) in the order of description. The sample of Example 4 was prepared by the above-described preparation method using N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate as an additive. The blending ratio of (PVA / PAA: DAPA: additive) is (66.3 wt%: 20 wt%: 13.7 wt%) in the order of description.
次に、実施例１〜４の各サンプルで使用した添加剤の効果、即ち、二酸化炭素透過性の促進効果を評価するために作製したＰＶＡ／ＰＡＡゲル膜内に添加剤を加えない比較用サンプルは、第１実施形態の実施例のサンプルと同条件で作製されたものを使用する。 Next, a comparative sample in which no additive is added to the PVA / PAA gel membrane prepared in order to evaluate the effect of the additive used in each sample of Examples 1 to 4, that is, the carbon dioxide permeability promoting effect. Uses those manufactured under the same conditions as the samples of the example of the first embodiment.
実施例１〜４、及び、比較用の各サンプルの膜性能を評価するための実験装置の構成は、第１実施形態と同じであるので、重複する説明は省略する。但し、実験方法は、原料ガス及びスイープガスの組成と流量以外は、第１実施形態と同じである。原料ガス（ＣＯ２、Ｎ２、Ｈ２Ｏからなる混合ガス）ＦＧを、２．２４×１０−２ｍｏｌ／ｍｉｎの流量で原料側室１２に供給し、スイープガス（Ｈｅガス）ＳＧを、８．１８×１０−４ｍｏｌ／ｍｉｎの流量で透過側室１３に供給する。 Since the configurations of Examples 1 to 4 and the experimental apparatus for evaluating the film performance of each sample for comparison are the same as those in the first embodiment, redundant description is omitted. However, the experimental method is the same as that of the first embodiment except for the composition and flow rate of the source gas and the sweep gas. A source gas (mixed gas composed of CO 2 , N 2 , H 2 O) FG is supplied to the source side chamber 12 at a flow rate of 2.24 × 10 −2 mol / min, and a sweep gas (He gas) SG is supplied to 8 Supplied to the permeation side chamber 13 at a flow rate of 18 × 10 −4 mol / min.
原料ガスＦＧは、ＣＯ２、Ｎ２、Ｈ２Ｏからなる混合ガスを、ＣＯ２：３．６５％、Ｎ２：３２．８５％、Ｈ２Ｏ：６３．５％の混合比率（モル％）に調整した。具体的には、１０％ＣＯ２と９０％Ｎ２（モル％）よりなる混合ガス流（２５℃での流量：２００ｃｍ３／ｍｉｎ、８．１８×１０−３ｍｏｌ／ｍｉｎ）に水を定量送液ポンプ１８で送入し（流量：０．２５６ｃｍ３／ｍｉｎ、１．４２×１０−２ｍｏｌ／ｍｉｎ）、１００℃以上に加熱して水分を蒸発させて、上記混合比率の混合ガスを調製し、これを原料側室１２に供給した。 The raw material gas FG is a mixed gas composed of CO 2 , N 2 , and H 2 O with a mixing ratio (mol%) of CO 2 : 3.65%, N 2 : 32.85%, H 2 O: 63.5%. ). Specifically, water is quantified in a mixed gas flow (flow rate at 25 ° C .: 200 cm 3 / min, 8.18 × 10 −3 mol / min) composed of 10% CO 2 and 90% N 2 (mol%). It was fed by the liquid feed pump 18 (flow rate: 0.256 cm 3 / min, 1.42 × 10 −2 mol / min), heated to 100 ° C. or more to evaporate the water, and the mixed gas having the above mixing ratio was This was prepared and supplied to the raw material side chamber 12.
スイープガスＳＧは、サンプル膜を透過する被測定ガス（ＣＯ２、Ｎ２）の透過側室側の分圧を低くして、透過推進力を維持するために供給され、被測定ガスと異なるガス種（Ｈｅガス）を用いる。具体的には、Ｈｅガス（２５℃での流量：２０ｃｍ３／ｍｉｎ、８．１３×１０−４ｍｏｌ／ｍｉｎ）を調製し、これを透過側室１３に供給した。 The sweep gas SG is supplied in order to lower the partial pressure on the permeate side chamber side of the gas to be measured (CO 2 , N 2 ) that permeates the sample membrane and maintain the permeation driving force, and is a gas type different from the gas to be measured. (He gas) is used. Specifically, He gas (flow rate at 25 ° C .: 20 cm 3 / min, 8.13 × 10 −4 mol / min) was prepared and supplied to the permeation side chamber 13.
次に、図８に、実施例１〜４、及び、比較用の各サンプルのＣＯ２パーミアンスＲＣＯ２とＣＯ２／Ｎ２選択率、原料側室１２内の原料ガスＦＧの圧力を１５０ｋＰａ〜４５０ｋＰａの範囲の加圧状態で測定した結果を示す。尚、測定温度は１４０℃である。 Next, in FIGS. 8A and 8B, the CO 2 permeance R CO2 and CO 2 / N 2 selectivity of each sample for comparison and the pressure of the raw material gas FG in the raw material side chamber 12 are 150 kPa to 450 kPa. The result measured in the pressurization state of the range is shown. The measurement temperature is 140 ° C.
図８より、本発明膜は、１４０℃の高温条件であっても、添加剤を用いることで、原料ガスＦＧの圧力が３５０ｋＰａ以下でも、添加剤を用いない比較用サンプルに比べて、ＣＯ２パーミアンスが改善されることが分かる。また、ＣＯ２／Ｎ２選択率に関しては、３００ｋＰａ以下の圧力範囲で、一部の実施例１、２及び４で比較用サンプルに比べて改善されることが分かる。 From FIG. 8, the membrane of the present invention uses CO 2 at a high temperature condition of 140 ° C., so that even when the pressure of the raw material gas FG is 350 kPa or less, compared with a comparative sample using no additive, It can be seen that the permeance is improved. It can also be seen that the CO 2 / N 2 selectivity is improved in comparison with the comparative samples in some Examples 1, 2, and 4 in the pressure range of 300 kPa or less.
次に、図９に、添加剤の使用によるＣＯ２パーミアンス改善効果をＣＯ２／Ｈ２系の原料ガスで確認した測定結果を示す。図９は、添加剤として上記実施例１と同じイオン性流体の１‐アリル‐３‐エチルイミダゾリウムブロミドを添加した実施例５、及び、比較用の各サンプルのＣＯ２パーミアンスＲＣＯ２とＣＯ２／Ｈ２選択率、原料側室１２内の原料ガスＦＧの圧力を１５０ｋＰａ〜４５０ｋＰａの範囲の加圧状態で測定した結果を示す。尚、測定温度は１４０℃である。 Next, FIG. 9 shows a measurement result of confirming the CO 2 permeance improvement by the use of additives in the feed gas of CO 2 / H 2 system. FIG. 9 shows Example 5 in which 1-allyl-3-ethylimidazolium bromide of the same ionic fluid as Example 1 was added as an additive, and CO 2 permeance R CO2 and CO 2 of each sample for comparison. / H 2 selectivity, shows the result of measuring the pressure of the feed gas FG in the raw material side chamber 12 under pressure in the range of 150KPa～450kPa. The measurement temperature is 140 ° C.
実施例５のサンプルは、添加剤として１‐アリル‐３‐エチルイミダゾリウムブロミドを使用して、上述の作製方法により作製した。（ＰＶＡ／ＰＡＡ：ＤＡＰＡ：添加剤）の配合比率は、記載の順に、（６６．３重量％：２０重量％：１３．７重量％）となっている。ＰＶＡ／ＰＡＡゲル膜内に添加剤を加えない比較用のサンプルは、第１実施形態の実施例のサンプルと同条件で作製されたものを使用する。 The sample of Example 5 was prepared by the above-described preparation method using 1-allyl-3-ethylimidazolium bromide as an additive. The blending ratio of (PVA / PAA: DAPA: additive) is (66.3 wt%: 20 wt%: 13.7 wt%) in the order of description. As a comparative sample in which no additive is added to the PVA / PAA gel film, a sample prepared under the same conditions as the sample of the example of the first embodiment is used.
実施例５及び比較用の各サンプルの膜性能を評価するための実験装置の構成は、第１実施形態と同じであるので、重複する説明は省略する。但し、実施例５及び比較用の各サンプルの膜面積は、第１実施形態及び実施例１〜４のサンプルと異なり、３．６５ｃｍ２である。また、実験方法は、原料ガス及びスイープガスの組成と流量以外は、第１実施形態と同じである。原料ガス（ＣＯ２、Ｈ２、Ｈ２Ｏからなる混合ガス）ＦＧを、１．６４×１０−２ｍｏｌ／ｍｉｎの流量で原料側室１２に供給し、スイープガス（Ａｒガス）ＳＧを、８．１８×１０−４ｍｏｌ／ｍｉｎの流量で透過側室１３に供給する。 Since the configuration of the experimental apparatus for evaluating the film performance of Example 5 and each sample for comparison is the same as that of the first embodiment, a duplicate description is omitted. However, the film area of Example 5 and each sample for comparison is 3.65 cm 2 unlike the samples of the first embodiment and Examples 1-4. The experimental method is the same as that of the first embodiment except for the composition and flow rate of the source gas and the sweep gas. A source gas (mixed gas composed of CO 2 , H 2 , H 2 O) FG is supplied to the source side chamber 12 at a flow rate of 1.64 × 10 −2 mol / min, and a sweep gas (Ar gas) SG is supplied to 8 Supplied to the permeation side chamber 13 at a flow rate of 18 × 10 −4 mol / min.
原料ガスＦＧは、ＣＯ２、Ｈ２、Ｈ２Ｏからなる混合ガスを、ＣＯ２：５％、Ｈ２：４５％、Ｈ２Ｏ：５０％の混合比率（モル％）に調整した。具体的には、１０％ＣＯ２と９０％Ｈ２（モル％）よりなる混合ガス流（２５℃での流量：２００ｃｍ３／ｍｉｎ、８．１３×１０−３ｍｏｌ／ｍｉｎ）に水を定量送液ポンプ１８で送入し（流量：０．１４７ｃｍ３／ｍｉｎ、８．０６×１０−３ｍｏｌ／ｍｉｎ）、１００℃以上に加熱して水分を蒸発させて、上記混合比率の混合ガスを調製し、これを原料側室１２に供給した。 As the source gas FG, a mixed gas composed of CO 2 , H 2 , and H 2 O was adjusted to a mixing ratio (mol%) of CO 2 : 5%, H 2 : 45%, and H 2 O: 50%. Specifically, water is quantified in a mixed gas flow (flow rate at 25 ° C .: 200 cm 3 / min, 8.13 × 10 −3 mol / min) composed of 10% CO 2 and 90% H 2 (mol%). was fed at a liquid feed pump 18 (flow rate: 0.147cm 3 /min,8.06×10 -3 mol / min ), the water is evaporated by heating to above 100 ° C., a mixed gas of the mixed ratio This was prepared and supplied to the raw material side chamber 12.
スイープガスＳＧは、サンプル膜を透過する被測定ガス（ＣＯ２、Ｈ２）の透過側室側の分圧を低くして、透過推進力を維持するために供給され、被測定ガスと異なるガス種（Ａｒガス）を用いる。具体的には、Ａｒガス（２５℃での流量：２０ｃｍ３／ｍｉｎ、８．１３×１０−４ｍｏｌ／ｍｉｎ）を透過側室１３に供給した。 The sweep gas SG is supplied in order to reduce the partial pressure on the permeate side chamber side of the gas to be measured (CO 2 , H 2 ) that permeates the sample membrane and maintain the permeation driving force, and is a gas type different from the gas to be measured. (Ar gas) is used. Specifically, Ar gas (flow rate at 25 ° C .: 20 cm 3 / min, 8.13 × 10 −4 mol / min) was supplied to the permeation side chamber 13.
図９より、本発明膜は、１４０℃の高温条件であっても、添加剤を用いることで、原料ガスＦＧの圧力が１５０〜４５０ｋＰａの全圧力範囲で、添加剤を用いない比較用サンプルに比べて、ＣＯ２パーミアンス及びＣＯ２／Ｈ２選択率が改善されることが分かる。 From FIG. 9, the membrane of the present invention can be used as a comparative sample using no additive in the whole pressure range of 150 to 450 kPa of the pressure of the raw material gas FG by using an additive even under a high temperature condition of 140 ° C. In comparison, it can be seen that the CO 2 permeance and the CO 2 / H 2 selectivity are improved.
尚、添加剤の使用によるＣＯ２パーミアンス改善効果が低圧側で発現する理由は、低圧下では水蒸気分圧が低くＰＶＡ／ＰＡＡゲル膜内の水分量が減少するので、添加剤が一種の可塑化剤の役割を果しているためと考えられる。 The reason why the CO 2 permeance improvement effect due to the use of the additive appears on the low pressure side is that the water vapor partial pressure is low and the water content in the PVA / PAA gel membrane is reduced at low pressure, so the additive is a kind of plasticization. This is thought to be due to the role of the agent.
以下に、本発明に係るＣＯ２促進輸送膜の別実施形態につき説明する。 Hereinafter, another embodiment of the CO 2 facilitated transport membrane according to the present invention will be described.
〈１〉上記実施形態では、本発明膜は、ＰＶＡ／ＰＡＡ共重合体と二酸化炭素キャリアのＤＡＰＡ（またはＤＡＰＡと添加剤）を含む水溶液からなるキャスト溶液を、ゲル膜担持用の親水性ＰＴＦＥ多孔膜にキャストした後にゲル化して作製したが、本発明膜は、当該作製方法以外の作製方法で作製しても構わない。例えば、ＰＶＡ／ＰＡＡ共重合体ゲル膜に、ＤＡＰＡと添加剤の少なくとも何れか一方を後から含浸させて作製しても構わない。 <1> In the above embodiment, the membrane of the present invention comprises a cast solution composed of an aqueous solution containing a PVA / PAA copolymer and a carbon dioxide carrier DAPA (or DAPA and an additive) as a hydrophilic PTFE porous material for supporting a gel membrane. Although it was produced by gelling after casting to a film, the film of the present invention may be produced by a production method other than the production method. For example, the PVA / PAA copolymer gel film may be produced by impregnating at least one of DAPA and an additive later.
〈２〉上記実施形態では、本発明膜は、疎水性ＰＴＦＥ多孔膜／ゲル層（親水性ＰＴＦＥ多孔膜に担持された含有ゲル膜）／疎水性ＰＴＦＥ多孔膜よりなる３層構造としたが、本発明膜の支持構造は、必ずしも当該３層構造に限定されない。例えば、疎水性ＰＴＦＥ多孔膜／ゲル層（親水性ＰＴＦＥ多孔膜に担持された含有ゲル膜）よりなる２層構造でも構わない。 <2> In the above embodiment, the membrane of the present invention has a three-layer structure composed of a hydrophobic PTFE porous membrane / gel layer (containing gel membrane supported on a hydrophilic PTFE porous membrane) / hydrophobic PTFE porous membrane. The support structure for the membrane of the present invention is not necessarily limited to the three-layer structure. For example, a two-layer structure composed of a hydrophobic PTFE porous film / gel layer (containing gel film supported on a hydrophilic PTFE porous film) may be used.
〈３〉上記実施形態では、本発明膜がＣＯ２透過型メンブレンリアクターへ応用される場合を想定したが、本発明膜は、ＣＯ２透過型メンブレンリアクター以外にも、二酸化炭素を選択的に分離する目的で使用可能である。従って、本発明膜に供給される原料ガスは、上記実施形態に例示した混合ガスに限定されるものではない。 <3> In the above embodiment, it is assumed that the membrane of the present invention is applied to a CO 2 permeable membrane reactor, but the membrane of the present invention selectively separates carbon dioxide in addition to the CO 2 permeable membrane reactor. Can be used for the purpose. Therefore, the source gas supplied to the membrane of the present invention is not limited to the mixed gas exemplified in the above embodiment.
〈４〉上記実施形態において例示した、本発明膜の組成における各成分の混合比率、膜の各部の寸法等は、本発明の理解の容易のための例示であり、本発明はそれらの数値のＣＯ２促進輸送膜に限定されるものではない。 <4> The mixing ratio of each component in the composition of the film of the present invention exemplified in the above embodiment, the dimensions of each part of the film, etc. are examples for easy understanding of the present invention. It is not limited to a CO 2 facilitated transport membrane.
本発明に係るＣＯ２促進輸送膜は、二酸化炭素の分離に利用可能であり、特に、水素を主成分とする燃料電池用等の改質ガスに含まれる二酸化炭素を水素に対する高い選択比率で分離可能なＣＯ２促進輸送膜に利用可能であり、更には、ＣＯ２透過型メンブレンリアクターに有用である。 CO 2 facilitated transport membrane according to the present invention is applicable to separation of carbon dioxide, in particular, the separation of carbon dioxide contained in the reformed gas such as a fuel cell mainly composed of hydrogen at a high selectivity ratio to hydrogen It can be used for possible CO 2 facilitated transport membranes, and is further useful for CO 2 permeable membrane reactors.
１： 二酸化炭素キャリアを含有するＰＶＡ／ＰＡＡゲル膜（ゲル層）
２： 親水性多孔膜
３、４： 疎水性多孔膜
１０： ＣＯ２促進輸送膜（サンプル）
１１： 流通式ガス透過セル
１２： 原料側室
１３： 透過側室
１４、１６： 冷却トラップ
１５： 背圧調整器
１７： ガスクロマトグラフ
１８： 定量送液ポンプ
ＦＧ： 原料ガス
ＳＧ、ＳＧ’： スイープガス
1: PVA / PAA gel film (gel layer) containing carbon dioxide carrier
2: Hydrophilic porous membrane 3, 4: Hydrophobic porous membrane 10: CO 2 facilitated transport membrane (sample)
11: Flow-through gas permeation cell 12: Raw material side chamber 13: Permeation side chamber 14, 16: Cooling trap 15: Back pressure regulator 17: Gas chromatograph 18: Metering pump FG: Raw material gas SG, SG ': Sweep gas
Claims (7)
１００℃以上の温度条件下でＣＯ ２ ／Ｈ ２ 選択性能を有し、
前記多孔膜が１００℃以上の耐熱性を備えていることを特徴とするＣＯ２促進輸送膜。 Polyvinyl alcohol - the gel layer containing the 2,3-diaminopropionic acid in polyacrylic acid copolymer gel membrane, Ri Na be supported on the hydrophilic porous membrane,
CO 2 / H 2 selection performance under temperature conditions of 100 ° C. or higher ,
The porous membrane is characterized that you have provided a 100 ° C. or more refractory CO 2 -facilitated transport membrane.
前記イオン性流体が、下記のカチオン、アニオンの組合せよりなる化合物から選択される化学物質であり、
前記カチオンが、１，３位に以下の置換基を有するイミダゾリウムで、置換基としてアルキル基、ヒドロキシアルキル基、エーテル基、アリル基、アミノアルキル基を有するもの、または、第４級アンモニウムカチオンで、置換基としてアルキル基、ヒドロキシアルキル基、エーテル基、アリル基、アミノアルキル基を有するものであり、
前記アニオンが、塩化物イオン、臭化物イオン、四フッ化ホウ素イオン、硝酸イオン、ビス（トリフルオロメタンスルホニル）イミドイオン、ヘキサフルオロリン酸イオン、または、トリフルオロメタンスルホン酸イオンであることを特徴とする請求項１に記載のＣＯ２促進輸送膜。 In the polyvinyl alcohol-polyacrylic acid copolymer gel film, in addition to 2,3-diaminopropionic acid, as an additive for promoting carbon dioxide permeability, an ionic fluid, or glycerin, polyglycerin, Contains a chemical selected from polyethylene glycol, polypropylene glycol, polyethylene oxide, polyethyleneimine, polyallylamine, polyacrylic acid ,
The ionic fluid is a chemical substance selected from a compound consisting of a combination of the following cation and anion,
The cation is an imidazolium having the following substituents at the 1,3-positions, having an alkyl group, a hydroxyalkyl group, an ether group, an allyl group, an aminoalkyl group as a substituent, or a quaternary ammonium cation. , Having an alkyl group, a hydroxyalkyl group, an ether group, an allyl group, an aminoalkyl group as a substituent,
Wherein the anion is chloride, bromide, tetrafluoroborate ions, which nitrate ions, bis (trifluoromethanesulfonyl) imide ion, hexafluorophosphate ion, or wherein the ion der Rukoto trifluoromethanesulfonic acid Item 2. The CO 2 facilitated transport membrane according to Item 1 .
前記ポリビニルアルコール‐ポリアクリル酸共重合体ゲル膜内に、２，３‐ジアミノプロピオン酸の他に、二酸化炭素透過性を促進するための添加剤として、イオン性流体、または、グリセリン、ポリグリセリン、ポリエチレングリコール、ポリプロピレングリコール、ポリエチレンオキサイド、ポリエチレンイミン、ポリアリルアミン、ポリアクリル酸の中から選択される化学物質を含有し、
前記イオン性流体が、下記のカチオン、アニオンの組合せよりなる化合物から選択される化学物質であり、
前記カチオンが、１，３位に以下の置換基を有するイミダゾリウムで、置換基としてアルキル基、ヒドロキシアルキル基、エーテル基、アリル基、アミノアルキル基を有するもの、または、第４級アンモニウムカチオンで、置換基としてアルキル基、ヒドロキシアルキル基、エーテル基、アリル基、アミノアルキル基を有するものであり、
前記アニオンが、塩化物イオン、臭化物イオン、四フッ化ホウ素イオン、硝酸イオン、ビス（トリフルオロメタンスルホニル）イミドイオン、ヘキサフルオロリン酸イオン、または、トリフルオロメタンスルホン酸イオンであることを特徴とするＣＯ２促進輸送膜。 A gel layer containing 2,3-diaminopropionic acid is supported on a hydrophilic porous membrane on a polyvinyl alcohol-polyacrylic acid copolymer gel membrane,
In the polyvinyl alcohol-polyacrylic acid copolymer gel film, in addition to 2,3-diaminopropionic acid, as an additive for promoting carbon dioxide permeability, an ionic fluid, or glycerin, polyglycerin, Contains a chemical selected from polyethylene glycol, polypropylene glycol, polyethylene oxide, polyethyleneimine, polyallylamine, polyacrylic acid ,
The ionic fluid is a chemical substance selected from a compound consisting of a combination of the following cation and anion,
The cation is an imidazolium having the following substituents at the 1,3-positions, having an alkyl group, a hydroxyalkyl group, an ether group, an allyl group, an aminoalkyl group as a substituent, or a quaternary ammonium cation. , Having an alkyl group, a hydroxyalkyl group, an ether group, an allyl group, an aminoalkyl group as a substituent,
CO wherein the anion is chloride, bromide, tetrafluoroborate ions, which nitrate ions, bis (trifluoromethanesulfonyl) imide ion, hexafluorophosphate ion, or wherein the ion der Rukoto trifluoromethanesulfonic acid 2 facilitated transport membrane.
ポリビニルアルコール‐ポリアクリル酸共重合体と２，３‐ジアミノプロピオン酸を含む水溶液からなるキャスト溶液を作製する工程と、
前記キャスト溶液を前記親水性の多孔膜にキャストした後にゲル化して前記ゲル層を作製する工程と、
を有することを特徴とするＣＯ２促進輸送膜の製造方法。 A method of manufacturing a CO 2 -facilitated transport membrane according to claim 1,
Producing a cast solution comprising an aqueous solution containing a polyvinyl alcohol-polyacrylic acid copolymer and 2,3-diaminopropionic acid;
A step of casting the cast solution into the hydrophilic porous membrane and then gelling to produce the gel layer;
Method for producing a CO 2 -facilitated transport membrane which is characterized by having a.
ポリビニルアルコール‐ポリアクリル酸共重合体と２，３‐ジアミノプロピオン酸を含む水溶液からなるキャスト溶液を作製する工程と、
前記キャスト溶液を前記親水性の多孔膜にキャストした後にゲル化して前記ゲル層を作製する工程と、を有し、
前記キャスト溶液を作製する工程において、前記水溶液中に、イオン性流体、または、グリセリン、ポリグリセリン、ポリエチレングリコール、ポリプロピレングリコール、ポリエチレンオキサイド、ポリエチレンイミン、ポリアリルアミン、ポリアクリル酸の中から選択される化学物質が更に含まれ、
前記イオン性流体が、下記のカチオン、アニオンの組合せよりなる化合物から選択される化学物質であり、
前記カチオンが、１，３位に以下の置換基を有するイミダゾリウムで、置換基としてアルキル基、ヒドロキシアルキル基、エーテル基、アリル基、アミノアルキル基を有するもの、または、第４級アンモニウムカチオンで、置換基としてアルキル基、ヒドロキシアルキル基、エーテル基、アリル基、アミノアルキル基を有するものであり、
前記アニオンが、塩化物イオン、臭化物イオン、四フッ化ホウ素イオン、硝酸イオン、ビス（トリフルオロメタンスルホニル）イミドイオン、ヘキサフルオロリン酸イオン、または、トリフルオロメタンスルホン酸イオンであることを特徴とするＣＯ ２ 促進輸送膜の製造方法。
A method for producing a CO 2 facilitated transport membrane comprising a gel layer containing 2,3-diaminopropionic acid on a polyvinyl alcohol-polyacrylic acid copolymer gel membrane supported on a hydrophilic porous membrane ,
Producing a cast solution comprising an aqueous solution containing a polyvinyl alcohol-polyacrylic acid copolymer and 2,3-diaminopropionic acid;
A step of casting the cast solution into the hydrophilic porous membrane and then gelling to produce the gel layer,
In the step of preparing the cast solution, the ionic fluid in the aqueous solution or a chemistry selected from glycerin, polyglycerin, polyethylene glycol, polypropylene glycol, polyethylene oxide, polyethyleneimine, polyallylamine, and polyacrylic acid. Contains further substances ,
The ionic fluid is a chemical substance selected from a compound consisting of a combination of the following cation and anion,
The cation is an imidazolium having the following substituents at the 1,3-positions, having an alkyl group, a hydroxyalkyl group, an ether group, an allyl group, an aminoalkyl group as a substituent, or a quaternary ammonium cation. , Having an alkyl group, a hydroxyalkyl group, an ether group, an allyl group, an aminoalkyl group as a substituent,
CO 2 , wherein the anion is chloride ion, bromide ion, boron tetrafluoride ion, nitrate ion, bis (trifluoromethanesulfonyl) imide ion, hexafluorophosphate ion, or trifluoromethanesulfonate ion. Method for producing facilitated transport membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006209816A JP4965927B2 (en) | 2006-08-01 | 2006-08-01 | CO2 facilitated transport membrane and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006209816A JP4965927B2 (en) | 2006-08-01 | 2006-08-01 | CO2 facilitated transport membrane and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008036463A JP2008036463A (en) | 2008-02-21 |
| JP4965927B2 true JP4965927B2 (en) | 2012-07-04 |
Family
ID=39172091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006209816A Active JP4965927B2 (en) | 2006-08-01 | 2006-08-01 | CO2 facilitated transport membrane and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4965927B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015160159A (en) * | 2014-02-26 | 2015-09-07 | 旭化成株式会社 | gas separation membrane and manufacturing method |
| EP3456403A1 (en) | 2017-09-15 | 2019-03-20 | Sumitomo Chemical Company, Limited | Gas separation method |
| EP3456402A1 (en) | 2017-09-15 | 2019-03-20 | Sumitomo Chemical Company, Limited | Gas separation method |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8197576B2 (en) | 2008-01-24 | 2012-06-12 | Renaissance Energy Research Corporation | CO2-facilitated transport membrane and method for producing the same |
| US7938892B2 (en) * | 2008-06-10 | 2011-05-10 | Palo Alto Research Center Incorporated | Producing articles that include ionic liquids |
| US7938890B2 (en) * | 2008-07-08 | 2011-05-10 | Palo Alto Research Center Incorporated | Separating gas using immobilized buffers |
| JP5078798B2 (en) * | 2008-08-06 | 2012-11-21 | Ｊｘ日鉱日石エネルギー株式会社 | Carbon dioxide concentration membrane and carbon dioxide concentration method |
| JP5378841B2 (en) * | 2009-03-18 | 2013-12-25 | 一般財団法人石油エネルギー技術センター | Carbon dioxide gas separation membrane |
| US8673067B2 (en) | 2009-05-21 | 2014-03-18 | Battelle Memorial Institute | Immobilized fluid membranes for gas separation |
| US8715392B2 (en) * | 2009-05-21 | 2014-05-06 | Battelle Memorial Institute | Catalyzed CO2-transport membrane on high surface area inorganic support |
| US8481187B2 (en) | 2009-09-10 | 2013-07-09 | Battelle Memorial Institute | High-energy metal air batteries |
| CA2780796C (en) | 2009-11-12 | 2018-07-10 | National Research Council Of Canada | Polymers of intrinsic microporosity containing tetrazole groups |
| JP5526055B2 (en) | 2010-02-10 | 2014-06-18 | 富士フイルム株式会社 | Gas separation membrane, gas separation membrane manufacturing method, gas mixture separation method, gas separation membrane module, and gas separation device |
| US8992668B2 (en) | 2010-03-29 | 2015-03-31 | Fujifilm Corporation | Gas separation membrane and method for producing the same, and method for separating gas mixture, gas separation membrane module and gas separation apparatus using the same |
| CA2804302A1 (en) * | 2010-07-26 | 2012-02-02 | Osamu Okada | Steam permselective membrane, and method using same for separating steam from mixed gas |
| JP5765850B2 (en) * | 2010-08-12 | 2015-08-19 | 国立研究開発法人日本原子力研究開発機構 | Lithium recovery method and lithium recovery device |
| CA2897623C (en) * | 2010-12-24 | 2016-08-16 | Renaissance Energy Research Corporation | Gas separation apparatus, membrane reactor, and hydrogen production apparatus |
| JP5904479B2 (en) * | 2011-03-31 | 2016-04-13 | Ｊｘエネルギー株式会社 | Gas separation membrane |
| JP5835937B2 (en) * | 2011-05-09 | 2015-12-24 | 日立造船株式会社 | CO2 zeolite membrane separation and recovery system |
| JP5877961B2 (en) * | 2011-05-31 | 2016-03-08 | Ｊｘ日鉱日石エネルギー株式会社 | Gas separation gel membrane |
| JP2013027806A (en) * | 2011-07-27 | 2013-02-07 | Fujifilm Corp | Carbon dioxide separation membrane, support for carbon dioxide separation membrane, and method of manufacturing them |
| CN104168988A (en) * | 2011-08-01 | 2014-11-26 | 株式会社新生能源研究 | Co2-facilitated transport membrane, and method for manufacturing same |
| AU2012354917C1 (en) | 2011-12-22 | 2015-04-30 | Renaissance Energy Research Corporation | CO shift conversion device and shift conversion method |
| CN104379241B (en) * | 2012-05-30 | 2017-09-01 | 东丽株式会社 | Carbon dioxide separation film |
| JP5945478B2 (en) * | 2012-09-04 | 2016-07-05 | 日東電工株式会社 | Separation membrane, composite separation membrane and method for producing separation membrane |
| EP2910581A4 (en) | 2012-10-22 | 2016-07-13 | Sumitomo Chemical Co | Copolymer and carbon dioxide gas separation membrane |
| JP6392412B2 (en) * | 2013-03-29 | 2018-09-19 | 富士フイルム株式会社 | Acid gas separation composite membrane manufacturing method and acid gas separation module |
| JP6071004B2 (en) | 2013-03-29 | 2017-02-01 | 富士フイルム株式会社 | Method for producing acid gas separation composite membrane and acid gas separation membrane module |
| JP6161124B2 (en) * | 2013-03-29 | 2017-07-12 | 富士フイルム株式会社 | Method for producing acid gas separation composite membrane and acid gas separation membrane module |
| KR20150134315A (en) | 2013-03-29 | 2015-12-01 | 가부시키가이샤 르네상스 에너지 리서치 | Facilitated co2 transport membrane, method for manufacturing same, resin composition to be used in method for manufacturing same, co2 separation module, co2 separation method and co2 separation device |
| KR102313274B1 (en) | 2014-08-11 | 2021-10-18 | 스미또모 가가꾸 가부시키가이샤 | Composition for co2 gas separation membrane, co2 gas separation membrane and method for producing same, and co2 gas separation membrane module |
| JP6645983B2 (en) | 2014-11-18 | 2020-02-14 | 住友化学株式会社 | Carbon dioxide gas separation membrane, method for producing the same, and carbon dioxide gas separation membrane module |
| CN108883378B (en) * | 2016-04-04 | 2021-08-24 | 住友化学株式会社 | Acid gas separation membrane, acid gas separation method using same, acid gas separation module, and acid gas separation device |
| CN111094725B (en) | 2017-09-07 | 2022-08-26 | 株式会社新生能源研究 | Power generation system |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07102310B2 (en) * | 1993-10-19 | 1995-11-08 | 工業技術院長 | Carbon dioxide separation gel membrane and method for producing the same |
| US6315968B1 (en) * | 1995-01-18 | 2001-11-13 | Air Products And Chemicals, Inc. | Process for separating acid gases from gaseous mixtures utilizing composite membranes formed from salt-polymer blends |
| JP3506793B2 (en) * | 1995-01-18 | 2004-03-15 | 呉羽化学工業株式会社 | Resin composition and film formed therefrom |
| JP4150428B2 (en) * | 1997-03-14 | 2008-09-17 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | Membranes comprising amino acid salts in polyamine polymers and blends |
| JP3096696B2 (en) * | 1999-02-09 | 2000-10-10 | 工業技術院長 | Carbon dioxide absorbent |
| JP3999423B2 (en) * | 1999-10-27 | 2007-10-31 | 独立行政法人科学技術振興機構 | Carbon dioxide separation and dehumidification method and apparatus using liquid membrane |
| KR20050072921A (en) * | 2004-01-08 | 2005-07-13 | 한국과학기술연구원 | Facilitated transport membranes for an alkene hydrocarbon separation |
-
2006
- 2006-08-01 JP JP2006209816A patent/JP4965927B2/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015160159A (en) * | 2014-02-26 | 2015-09-07 | 旭化成株式会社 | gas separation membrane and manufacturing method |
| EP3456403A1 (en) | 2017-09-15 | 2019-03-20 | Sumitomo Chemical Company, Limited | Gas separation method |
| EP3456402A1 (en) | 2017-09-15 | 2019-03-20 | Sumitomo Chemical Company, Limited | Gas separation method |
| US10315156B2 (en) | 2017-09-15 | 2019-06-11 | Sumitomo Chemical Company, Limited | Gas separation method |
| US10441917B2 (en) | 2017-09-15 | 2019-10-15 | Sumitomo Chemical Company, Limited | Gas separation method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008036463A (en) | 2008-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4965927B2 (en) | CO2 facilitated transport membrane and method for producing the same | |
| JP4965928B2 (en) | Carbon dioxide separator and method | |
| JP5553421B2 (en) | CO2-facilitated transport membrane and method for producing the same | |
| JP5474172B2 (en) | Carbon dioxide separator | |
| CA2790195C (en) | Method for using a co2-facilitated transport membrane to remove carbon dioxide from a gas | |
| KR101330336B1 (en) | Gas separation device, membrane reactor, hydrogen production device, gas separation method, hydrogen production method | |
| US10858248B2 (en) | Method for separating CO2 using facilitated CO2 transport membrane | |
| Okada et al. | CO2-facilitated transport membrane and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090731 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100715 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110415 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110419 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110616 |
|
| 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: 20120306 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120330 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4965927 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150406 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150406 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150406 Year of fee payment: 3 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313114 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150406 Year of fee payment: 3 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150406 Year of fee payment: 3 |
|
| R370 | Written measure of declining of transfer procedure |
Free format text: JAPANESE INTERMEDIATE CODE: R370 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150406 Year of fee payment: 3 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313114 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150406 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150406 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150406 Year of fee payment: 3 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S201 | Request for registration of exclusive licence |
Free format text: JAPANESE INTERMEDIATE CODE: R314201 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S211 | Written request for registration of transfer of exclusive licence |
Free format text: JAPANESE INTERMEDIATE CODE: R314211 |
|
| S804 | Written request for registration of cancellation of exclusive licence |
Free format text: JAPANESE INTERMEDIATE CODE: R314803 |
|
| R371 | Transfer withdrawn |
Free format text: JAPANESE INTERMEDIATE CODE: R371 |
|
| S211 | Written request for registration of transfer of exclusive licence |
Free format text: JAPANESE INTERMEDIATE CODE: R314211 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S804 | Written request for registration of cancellation of exclusive licence |
Free format text: JAPANESE INTERMEDIATE CODE: R314803 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |