CN109963641A - 制造改良聚酰亚胺分离膜的方法 - Google Patents
制造改良聚酰亚胺分离膜的方法 Download PDFInfo
- Publication number
- CN109963641A CN109963641A CN201780065957.6A CN201780065957A CN109963641A CN 109963641 A CN109963641 A CN 109963641A CN 201780065957 A CN201780065957 A CN 201780065957A CN 109963641 A CN109963641 A CN 109963641A
- Authority
- CN
- China
- Prior art keywords
- polyimide film
- gas
- halogen
- polyimides
- film containing
- 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.)
- Granted
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 113
- 239000004642 Polyimide Substances 0.000 title claims abstract description 51
- 238000000926 separation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000012528 membrane Substances 0.000 title abstract description 14
- 230000006872 improvement Effects 0.000 title description 3
- 239000007789 gas Substances 0.000 claims abstract description 97
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 52
- 150000002367 halogens Chemical class 0.000 claims abstract description 52
- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 28
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 27
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 26
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000005977 Ethylene Substances 0.000 claims abstract description 26
- 150000002366 halogen compounds Chemical class 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- -1 halogenated aromatic epoxides Chemical class 0.000 claims abstract description 17
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 239000001294 propane Substances 0.000 claims abstract description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 8
- 238000007493 shaping process Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 230000035699 permeability Effects 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 230000003252 repetitive effect Effects 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 239000010408 film Substances 0.000 description 35
- 239000000835 fiber Substances 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 235000012489 doughnuts Nutrition 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZVDSMYGTJDFNHN-UHFFFAOYSA-N 2,4,6-trimethylbenzene-1,3-diamine Chemical compound CC1=CC(C)=C(N)C(C)=C1N ZVDSMYGTJDFNHN-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- ABSXMLODUTXQDJ-UHFFFAOYSA-N 4-(4-sulfophenyl)benzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1C1=CC=C(S(O)(=O)=O)C=C1 ABSXMLODUTXQDJ-UHFFFAOYSA-N 0.000 description 1
- MBJAPGAZEWPEFB-UHFFFAOYSA-N 5-amino-2-(4-amino-2-sulfophenyl)benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1C1=CC=C(N)C=C1S(O)(=O)=O MBJAPGAZEWPEFB-UHFFFAOYSA-N 0.000 description 1
- CLRPIHPGUFHCGI-UHFFFAOYSA-N N'-methyl-N-phenyl-N'-(2,3,4-trimethylphenyl)methanediamine Chemical compound CC1=C(C(=C(N(CNC2=CC=CC=C2)C)C=C1)C)C CLRPIHPGUFHCGI-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 1
- 229940026110 carbon dioxide / nitrogen Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
- B01D67/00111—Polymer pretreatment in the casting solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
- B01D69/087—Details relating to the spinning process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/46—Epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
- B01D71/522—Aromatic polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D2053/221—Devices
- B01D2053/223—Devices with hollow tubes
- B01D2053/224—Devices with hollow tubes with hollow fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/16—Hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/02—Specific process operations before starting the membrane separation process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/218—Additive materials
- B01D2323/2182—Organic additives
- B01D2323/21839—Polymeric additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/219—Specific solvent system
- B01D2323/22—Specific non-solvents or non-solvent system
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/28—Pore treatments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/34—Molecular weight or degree of polymerisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
一种聚酰亚胺分离膜,其由聚酰亚胺、可溶于所述聚酰亚胺的卤素化合物(例如卤化芳香族环氧化物)和具有2到5个碳的烃(例如乙烷、乙烯、丙烷或丙烯)构成。与不含有所述卤素化合物或烃的聚酰亚胺膜相比,气体分离膜对于如氢气的小气体分子具有改善的选择性。所述聚酰亚胺分离膜可以通过以下来制造:使由聚酰亚胺、可溶于所述聚酰亚胺的含卤素化合物构成的铸模溶液成形,去除溶剂并且然后将未处理的聚酰亚胺膜暴露于包含具有2到5个碳的烃的处理气氛达足够的时间以形成所述聚酰亚胺膜。
Description
技术领域
本发明涉及用以分离气体的聚酰亚胺膜(PM)。明确地说,本发明涉及用于产生具有改善选择性的PM的方法。
背景技术
膜广泛地用于分离气体与液体,包括例如分离酸性气体,如从天然气中分离CO2和H2S,并且特别地从空气中移除O2。通过所述膜的气体传输通常由吸附-扩散机制建模。众所周知聚合物膜聚酰亚胺膜是用于分离气体的,如美国专利Re.30,351和美国专利第4,705,540号和第4,717,394号中所描述的那些气体。
聚酰亚胺以及其它聚合物膜已经掺入增溶小分子以改善作为膜或中空纤维的气体分离膜的选择性,但是这总是导致渗透率或生产率也随之降低(参见例如《抗增塑对气体 分离膜的选择性和生产率的作用(Effect of Antiplasticization on Selectivity and Productivity of Gas Separation Membranes)》,Y.Maeda和D.R.Paul,《膜科学杂志(J.Mem.Sci.)》,30(1987)1-9和美国专利第4,983,191号)。
期望提供制造避免上述问题的聚酰亚胺膜的方法。同样地,期望提供能够可行地分离其它气体并且特别地较小气体分子(例如来自甲烷、乙烷、乙烯、丙烯或丙烷的氢气)的聚酰亚胺膜。
发明内容
本发明的第一方面为制造含卤素聚酰亚胺膜的方法,其包含:
(i)提供由聚酰亚胺、可溶于聚酰亚胺中的含卤素化合物和溶剂构成的铸模溶液;
(ii)使铸模溶液成形以形成初始成形膜;
(iii)从初始成形膜中去除溶剂以形成未处理的聚酰亚胺膜;和
(iv)将未处理的聚酰亚胺膜暴露于包含具有2到5个碳的烃的处理气氛一段时间以形成含卤素聚酰亚胺膜。
本发明的方法可以实现具有改善的选择性和渗透率组合的聚酰亚胺气体分离膜。示例性地,所述方法允许聚酰亚胺膜对于类似尺寸的气体分子(例如氢气/乙烯)具有良好的选择性,同时仍具有目标渗透气体分子(例如氢气)高渗透率。也就是说,与未暴露于处理气氛的聚酰亚胺膜相比,选择性大体上得到改善并且氢气渗透率几乎没有任何损失。
第二方面为从气体进料中分离气体分子的方法,所述气体进料由所述气体分子和至少一种其它气体分子构成,所述方法包含
(i)提供第一方面的含卤素聚酰亚胺膜;和
(ii)使气体进料流过所述含卤素聚酰亚胺膜以产生具有增加浓度的所述气体分子的第一物料流和具有增加浓度的其它气体分子的第二物料流。
第三方面为气体分离模块,其包含由以下构成的可密封外壳:多个聚酰亚胺膜,其包含含于可密封外壳内的至少一个第一方面的含卤素聚酰亚胺膜;用于引入由至少两种不同气体分子构成的气体进料的入口;用于准许渗透气流流出的第一出口;和用于流出滞留气流的第二出口。
第四方面为含卤素聚酰亚胺膜,其由于聚酰亚胺卤素膜中的聚酰亚胺、溶于聚酰亚胺的卤素化合物和具有2到5个碳的烃构成。
气体分离方法特别适用于分离具有极类似分子尺寸的气体进料中的气体分子,如氢气/乙烯、乙烷/乙烯和丙烷/丙烯。其还可以用于从大气中分离气体(如氧气)或分离天然气进料中的气体(例如甲烷)。
具体实施方式
用于分离气体的含卤素聚酰亚胺膜可以呈任何有用的形式,如薄膜或不对称膜,并且特别地具有于纤维外表面上的薄致密层并且具有于纤维内表面上的更宽更大微孔/中孔/大孔层的中空纤维。期望地,中空纤维大体上无缺陷。“无缺陷”意指通过中空纤维膜的气体对(通常为氧气(O2)和氮气(N2))的选择性为通过由与用于制造聚合物前体中空纤维膜的组合物相同的组合物制备的致密膜的相同气体对的选择性的至少90%。作为示例,6FDA/BPDA(1:1)-DAM聚合物的固有O2/N2选择性(也称为“致密膜选择性”)为4.1。
当制造膜时,可以使用所属领域中已知的常规工序(参见例如美国专利第5,820,659号;第4,113,628号;第4,378,324号;第4,460,526号;第4,474,662号;第4,485,056号;第4,512,893号和第4,717,394号)。示例性方法包括共挤压工序,包括如干喷湿纺工艺(dry-jet wet spinning process)(其中在纺丝头的尖端与凝固或骤冷浴之间存在气隙)或湿纺工艺(具有零气隙距离),其可以用于制造中空纤维。
为了制造聚酰亚胺膜,使用由聚酰亚胺、卤素化合物和溶剂构成的铸模溶液。通常,当制造薄膜隔膜时,例如当浇铸到平板上并去除溶剂时,使用由溶解聚酰亚胺的溶剂构成的铸模溶液。当制造中空纤维时,通常使用作为增溶聚酰亚胺的溶剂和不增溶(或在有限程度上增溶)聚酰亚胺但与增溶聚酰亚胺的溶剂可溶的第二溶剂的混合物的铸模溶液。可用于增溶聚酰亚胺的示例性溶剂包括N-甲基-2-吡咯烷酮(NMP)、四氢呋喃(THF)、二甲基乙酰胺(DMAc)和二甲基甲酰胺(DMF)。不增溶聚酰亚胺但与增溶聚酰亚胺的溶剂可溶的示例性溶剂包括甲醇、乙醇、水和1-丙醇。
聚酰亚胺可以为任何聚酰亚胺,如美国专利第4,983,191号第2列第65行到第5列第28行所描述的芳香族聚酰亚胺。美国专利第4,717,394号、第4,705,540号和第re30351号描述可以使用的其它芳香族聚酰亚胺。期望的聚酰亚胺通常含有选自以下的至少两种不同的部分:2,4,6-三甲基-1,3-苯二胺(DAM)、氧联二苯胺(ODA)、二甲基-3,7-二氨基二苯基-噻吩-5,5'-二氧化物(DDBT)、3,5-二氨基苯甲酸(DABA)、2.3,5,6-四甲基-1,4-苯二胺(均四甲苯)、间苯二胺(m-PDA)、2,4-二氨基甲苯(2,4-DAT)、四甲基亚甲基二苯胺(TMMDA)、4,4'-二氨基2,2'-联苯二磺酸(BDSA);5,5'-[2,2,2-三氟-1-(三氟甲基)亚乙基]-1,3-异苯并呋喃二酮(6FDA)、3,3',4,4'-联苯四甲酸二酐(BPDA)、苯均四酸二酐(PMDA)、1,4,5,8-萘四甲酸二酐(NTDA)以及二苯酮四甲酸二酐(BTDA),其中优选6FDA、BPDA和DAM中的两个或更多个为优选的。
标记为6FDA/BPDA-DAM的特别有用的聚酰亚胺可以通过热方法或化学方法由以下三种单体的组合来合成:DAM;6FDA和BPDA,各自可例如从西格玛奥德里奇公司(Sigma-Aldrich Corporation)商购获得。下式1显示具有调整X与Y之间的比率以调节聚合物性质的潜能的6FDA/BPDA-DAM的代表性结构。如下文实例中所使用,组分X与组分Y的1:1比率也可以缩写为6FDA/BPDA(1:1)-DAM。
式1.6FDA/BPDA-DAM的化学结构
标记为6FDA-DAM的第二种特别有用的聚酰亚胺不含BPDA以使得上式1中的Y等于零。下式2显示此聚酰亚胺的代表性结构。
式2.6FDA-DAM的化学结构
第三种有用的聚酰亚胺为MATRIMIDTM 5218(亨斯迈先进材料公司(HuntsmanAdvanced Materials)),即作为3,3',4,4'-苯并-苯基酮四甲酸二酐和5(6)-氨基-1-(4'-氨基苯基)-1,3,3-三甲基茚满(BTDA-DAPI)的共聚物的可商购聚酰亚胺。
应当注意,聚酰亚胺可以以铸模溶液中的前体单体形式来提供,并且如果需要的话,在通过施加热量而成形之后进行聚合,这也描述于上文所引用的现有技术中,但这不为优选的。
卤素化合物可以为含有卤素并且可溶于所用聚酰亚胺中的任何卤素化合物。一般来说,这意味着至少约0.5%的卤素化合物可溶于聚酰亚胺中。同样地,应当理解,可溶意指所形成的膜具有均匀地处于所形成的含卤素聚酰亚胺膜内的卤素。期望地,卤素化合物为芳香族环氧化物。优选地,卤素化合物具有至少一个溴,并且甚至更优选地,卤素化合物中的所有卤素均为溴。一般来说,芳香族环氧化物的分子量为50到50,000,但期望地,分子量为500到5000。
在特定实施例中,芳香族环氧化物为具有至少一个由以下表示的卤素取代基的低聚或聚合残余物:
其中Ar表示以下形式的二价芳香族基团:
其中R1为直接键或以下二价基团中的任一个:
期望地,Ar被至少一个卤素并且优选超过一个卤素取代,并且最期望地,卤素为溴。在特定实施例中,芳香族环氧化物的每个芳香环被上述的与缩水甘油醚端基邻位的卤素取代。特定芳香族环氧化物为具有由以下表示的重复单元的低聚物或聚合物:
n的值可以为任何值,但一般为实现上文所描述的芳香族环氧化物的上述分子量的值。
在形成铸模溶液之后,使溶液成形为如上文所描述的膜。在成形之后,通过任何方便的方法如施加热量、真空、流动气体或其组合并包括所属领域中已知的那些方法来去除溶剂。
在去除溶剂之后,使所形成的或未处理的膜暴露于包含具有2到5个碳的烃的处理气氛于处理气氛达足以制造含卤素聚酰亚胺膜的时间。时间可以取决于所用的特定烃、聚酰亚胺或卤素化合物和所用卤素化合物的量而变化。不需要在暴露时将含卤素聚酰亚胺膜制成分离模块(能够使气体流过聚酰亚胺膜的装置),但是可以例如仅暴露于容器中的处理气氛。
在暴露期间,在暴露期间,处理气氛可以为静态的、流动的或其组合。期望地,处理气氛在暴露期间的至少一部分时间内流动,并且优选地在整个暴露时间内流动。尽管可以使聚酰亚胺膜间歇地暴露于处理气氛(例如用另一种气体或真空间歇地取代处理气氛),但期望地,使含卤素聚酰亚胺膜连续地暴露于处理气氛。在实施例中,使调节气氛内的至少一部分气体流过聚酰亚胺膜壁。
调节气氛的压力可以为任何有用的压力,并且可以在低于大气压的压力到每平方英寸几百磅(psi)范围内。期望地,压力为约10到300psi。在暴露期间压力也可以变化。当暴露膜时,其中使调节气氛中的至少一部分气体流过中空纤维膜壁,跨壁压差可以为任何有用的压差,如几psi到几百psi。期望地,压差为约1、5或10到25、50或100psi。
暴露时间可以为足以实现如下文进一步所描述的所期望的改善聚酰亚胺膜特征的任何时间,并且可以取决于特定膜(例如聚酰亚胺和卤素化合物的类型)而变化。一般来说,时间的量为几小时到几天或甚至一周或10天。通常,时间为约4小时到4、3或2天。
处理气氛由具有2到5个碳的烃构成。通常,烃为烷烃或烯烃,所述烷烃或烯烃一般为直链的。优选地,烃为烯烃。示例性烃包括乙烷、乙烯、丙烷、丙烯、丁烷、丁烯或其混合物。示例性地,调节气氛期望地由至少大部分烃构成。优选地,调节气氛由至少75%、90%、99%或甚至基本上100%烃构成。当使用具有少于99%渗透分子的调节气氛时,期望地,调节气氛中的其它气体分子小于烃,如氢气。
膜的气体渗透性质可以通过气体渗透实验来确定。两个固有性质用于评估膜材料的分离性能:其“渗透率”(膜固有生产率的量度);和其“选择性”(膜分离效率的量度)。通常以巴(1巴=10-10[cm3(STP)cm]/[cm2s cmHg]为单位测定“渗透率”,其计算为将通量(ni)除以膜上游与下游之间的分压差(Δpi),并且乘以膜厚度(l)。
另一个术语“渗透率”在本文中定义为不对称中空纤维膜的生产率,并且通常以气体渗透单位(GPU)(1GPU=10-6[cm3(STP)]/[cm2s cmHg])为单位进行测量,其通过将渗透率除以有效膜分离层厚度来测定。
最后,“选择性”在本文中定义为一种气体渗透通过膜的能力或相对于另一种气体的相同性质的渗透率。其以无单位比形式来测量。
在特定实施例中,所述方法产生由聚酰亚胺、可溶于聚酰亚胺中的卤素化合物和具有2到5个碳的烃构成的含卤素聚酰亚胺膜。一般来说,卤素化合物均匀地分布于整个膜中的聚酰亚胺内。可以吸附烃或将其溶入聚酰亚胺中或其组合。出乎意料地,含卤素聚酰亚胺膜可以在氢气渗透率无任何大幅降低的情况下大体上改善例如氢气/乙烯气体混合物中的氢气的选择性,然而在不存在卤素化合物的情况下的相同聚酰亚胺不如此。在特定实施例中,含卤素聚酰亚胺膜的来自氢气/乙烯气体混合物的氢气选择性为至少40并且在35℃下的氢气渗透率为至少250GPU。优选地,含卤素聚酰亚胺膜的来自氢气/乙烯气体混合物的氢气选择性为至少50并且在35℃下的氢气渗透率为至少300GPU。
含卤素聚酰亚胺膜特别适合于分离尺寸类似(如上文所描述)的气体,并涉及使含有所期望气体分子和至少一种其它气体分子的气体进料流过膜。流动产生具有增加浓度的所期望气体分子的第一物料流和具有增加浓度的其它气体分子的第二物料流。所述方法可以用于分离任何数量的气体对,并且特别地适合于从乙烯、乙烷、丙烯、丙烯或其混合物中分离氢气或从任何低分子量烃、氮气、氧气、CO2或空气中分离氢气。当实践所述方法时,期望地将膜制成包含可密封外壳的模块,所述可密封外壳由多个聚酰亚胺膜构成,所述聚酰亚胺膜由含于可密封外壳内的至少一个通过本发明方法生产的聚酰亚胺膜构成。可密封外壳具有用于引入由至少两种不同的气体分子构成的气体进料的入口;准许流出渗透气流的第一出口;和用于流出滞留气流的第二出口。
实例
在无卤素情况下的聚酰亚胺膜制备(PM):
使用6FDA:BPDA-DAM聚合物制造膜。6FDA:BPDA-DAM是从俄亥俄州阿克伦(Akron,OH)的Akron Polymer Systems获得的。将聚合物在110℃下在真空下干燥24小时,并且然后形成涂料。通过以下来制造涂料:将6FDA:BPDA-DAM聚合物与表1中的溶剂和化合物混合,并且在用聚四氟乙烯(TEFLONTM)盖密封的QorpakTM玻璃瓶中和5转/分钟(rpm)辊速进行辊混合约3周时间段,形成均匀涂料。
表1:比较实例1涂料配方
NMP=N-甲基-2-吡咯烷酮;THF=四氢呋喃;EtOH=乙醇
将均匀涂料装入500毫升(mL)注射泵中,并通过使用加热带将泵加热到50℃设定点温度来使涂料脱气过夜。
将孔流体(bore fluid)(以总孔流体重量计80wt%NMP和20wt%水)装入单独100mL注射泵中,并且然后将涂料和孔流体共挤压通过以对于涂料100毫升/小时(mL/hr)、100mL/hr孔流体的流速操作的纺丝头,使用40μm和2μm金属过滤器过滤输送泵与纺丝头之间的管线中的孔流体和涂料。使用放置于纺丝头、涂料过滤器和涂料泵上的热电偶和加热带将温度控制在70℃设定点温度下。
在通过两厘米(cm)气隙之后,将由纺丝头形成的初生纤维在水浴(50℃)中骤冷并使纤维相分离。使用越过TEFLON引导装置并以5米/分钟(M/min)吸取速率操作的0.32米(M)直径的聚乙烯鼓形圆桶来收集纤维。
将纤维从鼓形圆桶上切下并在48小时跨度内在单独水浴中冲洗至少四次。将经冲洗纤维放置于容器中,并且用甲醇进行三次溶剂交换达20分钟,并且然后用己烷进行溶剂交换达20分钟,之后回收纤维并将其在100℃设定点温度下在UHP氩气吹扫下干燥两小时以形成聚酰亚胺膜。
含卤素聚酰亚胺膜(PMCH)制备:
遵循上文相同工序,不同之处在于铸模溶液组合物如表2中所示并且纺丝条件如下所列。
F-2016(目录编号)为可从ICL Industrial Products(以色列贝尔谢巴(BeerSheva,Israel))获得的分子量为1600的溴化环氧低聚物。F-2016的结构如下所示,其中n为约2.7。
将纺丝温度、骤冷浴温度和气隙分别设定为50℃、35℃和15厘米。
表2:实例1涂料配方
膜的测试和气体暴露:
将一种或多种中空纤维罐装到1/4英寸(0.64cm)(外径,OD)不锈钢管中。将每个管末端与1/4英寸(0.64cm)不锈钢T形件连接;并且将每个T形件与1/4英寸(0.64cm)凹和凸NPT管适配器连接,用环氧树脂将所述适配器密封到NPT连接件。氩气扫掠气体用作渗透物侧中的扫掠气体。通过Bios Drycal流量计测量组合的扫掠气体和渗透气体的流速,同时通过气相色谱法测量组成。然后使用流速和组成以计算气体渗透率。以个别气体渗透率的比率形式计算每个气体对的选择性。在维持在35℃下的恒定压力渗透***中测试气体渗透,并且如果不特别指出,则将进料和渗透/扫掠压力分别保持在52和2psig下。将CO2/N2(10mol%/90mol%)进料气体预混合并由Airgas供应。使用质量流量控制器混合H2/C2H4混合物进料气体。设定滞留物流量以保持分级截除率(stage cut)(渗透物与进料流速比)低于1%。
实例1
如上文所描述,使PMCH纤维暴露于含有50%乙烯和50%氢气的气体,并且当膜暴露于乙烯时随时间推移的氢气渗透率示于图1中并且氢气选择性示于图2中。
比较实例1
重复实例1,不同之处在于使用PM纤维。图3和4显示当膜暴露于乙烯时随时间推移的氢气渗透率和H2/C2H4选择性。
从图表(图1-4)中显而易见,PMCH纤维的氢气(渗透物)渗透率基本上为稳定并且平的,而膜的选择性随着暴露于乙烯的时间而大大提高。这与PM纤维形成对比,在PM纤维情况下氢气渗透率为稳定的,但选择性保持相对相同,并且氢气渗透率和选择性均大体上低于PMCH的氢气渗透率和选择性。
实例2:
在此实例中,在暴露PMCH纤维之前,首先执行基线氢气渗透率和氢气/氮气气体混合物的选择性。在上文所描述的相同暴露测试标准情况下,气体混合物全部为50摩尔%/50摩尔%混合物。在基线建立之后,进行~2.2小时暴露/测试,然后将纤维暴露于氢气/乙烷气体混合物2小时,随后将纤维暴露于氢气/乙烯混合物66.2小时。然后,再次测定氮气和乙烷中的氢气渗透率。
从表3中所示的结果中显而易见,在暴露于乙烷和乙烯之后的PMCH没有降低氢气渗透率,并且氢气/氮气和氢气/乙烷气体混合物中的选择性均得到改善。
表3:
实例3
在此实例中,在将PMCH纤维暴露于具有2到5个碳的烃之前,首先执行基线二氧化碳渗透率和二氧化碳/氮气气体混合物的选择性,随后执行二氧化碳/甲烷气体混合物的基线。在上文所描述的相同暴露测试标准情况下,气体混合物全部为50摩尔%/50摩尔%混合物。在基线建立后,然后将纤维暴露于氢气/乙烯气体混合物68.4小时。然后,再次测定甲烷和氮气中的二氧化碳渗透率。
从表4中所示的结果中显而易见,在暴露于乙烯之后的PMCH在一定程度上降低了二氧化碳渗透率,但改善了其在二氧化碳/氮气和二氧化碳/甲烷气体混合物中的选择性。
表4:
Claims (33)
1.一种制造含卤素聚酰亚胺膜的方法,其包含:
(i)提供由聚酰亚胺、可溶于所述聚酰亚胺中的含卤素化合物和溶剂构成的铸模溶液;
(ii)使所述铸模溶液成形以形成初始成形膜;
(iii)从所述初始成形膜中去除溶剂以形成未处理的聚酰亚胺膜;和
(iv)将所述未处理的聚酰亚胺膜暴露于包含具有2到5个碳的烃中的至少一种的处理气氛一段时间以形成所述含卤素聚酰亚胺膜。
2.根据权利要求1所述的方法,其中处理气体进一步包含氢气。
3.根据前述权利要求中任一项所述的方法,其中所述烃为烷烃、烯烃或其混合物。
4.根据前述权利要求中任一项所述的方法,其中所述烃为烯烃。
5.根据权利要求1至3中任一项所述的方法,其中所述烃为乙烷、乙烯、丙烷、丙烯、丁烷、丁烯或其混合物。
6.根据前述权利要求中任一项所述的方法,其中所述处理气氛由至少99%的所述烃构成。
7.根据前述权利要求中任一项所述的方法,其中所述处理气氛为静态的。
8.根据权利要求1至6中任一项所述的方法,其中所述处理气氛为流动的。
9.根据前述权利要求中任一项所述的方法,其中所述处理气氛处于高于大气压的压力下。
10.根据前述权利要求中任一项所述的方法,其中所述卤素为溴。
11.根据权利要求1至6或8至10中任一项所述的方法,其中在所述含卤素聚酰亚胺膜上存在压差以使得使气体进料中的至少一部分抽吸通过所述含卤素聚酰亚胺膜。
12.根据权利要求11所述的方法,其中所述压差为1到100磅/平方英寸。
13.根据前述权利要求中任一项所述的方法,其中所述暴露持续至少2小时到10天的时间。
14.根据权利要求13所述的方法,其中所述时间为至少4小时到4天。
15.根据前述权利要求中任一项所述的方法,其中所述烃为乙烯、丙烯或丁烯。
16.根据权利要求15所述的方法,其中所述烃为乙烯或丙烯。
17.根据前述权利要求中任一项所述的方法,其中所述含卤素聚酰亚胺膜具有至少40的来自乙烯的氢气选择性和在35℃下至少250 GPU的氢气渗透率。
18.根据前述权利要求中任一项所述的方法,其中所述含卤素聚酰亚胺膜具有至少50的来自乙烯的氢气选择性和在35℃下至少300 GPU的氢气渗透率。
19.一种用于从气体进料中分离气体分子的方法,所述气体进料由所述气体分子和至少一种其它气体分子构成,所述方法包含
(i)提供根据前述权利要求中任一项所述的含卤素聚酰亚胺膜;和
(ii)使所述气体进料流过所述含卤素聚酰亚胺膜以产生具有增加浓度的所述气体分子的第一物料流和具有增加浓度的所述其它气体分子的第二物料流。
20.根据权利要求19所述的方法,其中所述气体分子和其它气体分子为:氢气和乙烯;乙烯和乙烷;丙烯和丙烷;氧气和氮气;二氧化碳和甲烷;或二氧化碳和氮气。
21.根据权利要求20所述的方法,其中所述气体分子和其它气体分子为氢气和乙烯。
22.一种包含可密封外壳的气体分离模块,所述可密封外壳由以下构成:多个聚酰亚胺膜,其包含含于所述可密封外壳内的至少一个根据权利要求1至18中任一项所述的含卤素聚酰亚胺膜;用于引入由至少两种不同的气体分子构成的气体进料的入口;用于准许流出渗透气流的第一出口;和用于流出滞留气流的第二出口。
23.一种含卤素聚酰亚胺膜,其由聚酰亚胺、可溶于所述聚酰亚胺中的卤素化合物和具有2到5个碳的烃构成。
24.根据权利要求23所述的含卤素聚酰亚胺膜,其中所述烃为乙烯、乙烷、丙烯、丙烷、丁烯、丁烷或其混合物。
25.根据权利要求24所述的含卤素聚酰亚胺膜,其中所述烃为乙烯、乙烷、丙烯、丙烷或其混合物。
26.根据权利要求23至25中任一项所述的含卤素聚酰亚胺,其中所述卤素化合物为芳香族环氧化物。
27.根据权利要求26所述的含卤素聚酰亚胺膜,其中所述芳香族环氧化物为具有至少一个下式的卤素取代基的低聚或聚合残余物:
其中Ar表示以下形式的二价芳香族基团:
其中R1为直接键或以下二价基团中的任一个:
28.根据权利要求27所述的含卤素聚酰亚胺膜,其中所述芳香族环氧化物,其中Ar被至少一个卤素取代。
29.根据权利要求28所述的含卤素聚酰亚胺膜,其中所述卤素为Br。
30.根据权利要求28或29中任一项所述的含卤素聚酰亚胺膜,其中Ar的每个芳香环被与缩水甘油醚基邻位的卤素取代。
31.根据权利要求23至30中任一项所述的含卤素聚酰亚胺膜,其中所述芳香族环氧化合物为具有由以下表示的重复单元的低聚物或聚合物:
其中n为使得所述低聚物或聚合物的分子量为700到40,000的值。
32.根据权利要求23至31中任一项所述的含卤素聚酰亚胺膜,其中所述卤素化合物的分子量为1000到5000。
33.根据权利要求23至31中任一项所述的含卤素聚酰亚胺膜,其中所述聚酰亚胺为3,3',4,4'-苯并-苯基酮四甲酸二酐和5(6)-氨基-1-(4'-氨基苯基)-1,3,3-三甲基茚满的共聚物;或由以下表示的以下聚酰亚胺中的一种:
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201662417557P | 2016-11-04 | 2016-11-04 | |
US62/417557 | 2016-11-04 | ||
PCT/US2017/053151 WO2018084958A1 (en) | 2016-11-04 | 2017-09-25 | Method of making improved polyimide separation membranes |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109963641A true CN109963641A (zh) | 2019-07-02 |
CN109963641B CN109963641B (zh) | 2022-06-28 |
Family
ID=60084074
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201780065957.6A Active CN109963641B (zh) | 2016-11-04 | 2017-09-25 | 制造改良聚酰亚胺分离膜的方法 |
Country Status (8)
Country | Link |
---|---|
US (1) | US20190247806A1 (zh) |
EP (2) | EP4085992A1 (zh) |
JP (1) | JP7160804B2 (zh) |
KR (1) | KR102446807B1 (zh) |
CN (1) | CN109963641B (zh) |
CA (1) | CA3042217A1 (zh) |
ES (1) | ES2939628T3 (zh) |
WO (1) | WO2018084958A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113578076A (zh) * | 2020-12-31 | 2021-11-02 | 太原科技大学 | 一种化学交联带羧基的聚酰亚胺氢气分离膜及其制备方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109012238B (zh) * | 2018-08-13 | 2021-05-11 | 南京林业大学 | 一种高强度高通量的油水分离膜的制备方法及油水分离膜 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4983191A (en) * | 1989-10-10 | 1991-01-08 | E. I. Du Pont De Nemours And Company | Production of aromatic polyimide membranes |
EP0649675A1 (en) * | 1993-10-20 | 1995-04-26 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Treatment of gas separation membranes with inert solvent |
CN1784260A (zh) * | 2003-04-18 | 2006-06-07 | 液体空气乔治洛德方法利用和研究的具有监督和管理委员会的有限公司 | 包含丙烷和丙烯的气体混合物的处理方法 |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2193634A1 (en) | 1972-07-20 | 1974-02-22 | Du Pont | Polyimide semi-permeable membranes |
US4113628A (en) | 1974-06-05 | 1978-09-12 | E. I. Du Pont De Nemours And Company | Asymmetric polyimide membranes |
EP0023406B1 (en) | 1979-07-26 | 1983-04-13 | Ube Industries, Ltd. | Process for preparing aromatic polyimide semipermeable membranes |
JPS57167414A (en) | 1981-04-03 | 1982-10-15 | Ube Ind Ltd | Production of polyimide hollow fiber |
JPS57170936A (en) | 1981-04-14 | 1982-10-21 | Ube Ind Ltd | Preparation of porous polyimide film |
GB2101137B (en) | 1981-04-14 | 1984-09-26 | Ube Industries | Producing porous aromatic imide polymer membranes |
JPS57209607A (en) | 1981-06-22 | 1982-12-23 | Ube Ind Ltd | Preparation of polyimide separation film |
US4705540A (en) | 1986-04-17 | 1987-11-10 | E. I. Du Pont De Nemours And Company | Polyimide gas separation membranes |
US4717394A (en) | 1986-10-27 | 1988-01-05 | E. I. Du Pont De Nemours And Company | Polyimide gas separation membranes |
US4880442A (en) * | 1987-12-22 | 1989-11-14 | E. I. Du Pont De Nemours And Company | Polyimide gas separation membranes |
US5015270A (en) * | 1989-10-10 | 1991-05-14 | E. I. Du Pont De Nemours And Company | Phenylindane-containing polyimide gas separation membranes |
JP2631253B2 (ja) * | 1991-08-23 | 1997-07-16 | 宇部興産株式会社 | 高選択性ガス分離膜及びその製法 |
US5266100A (en) * | 1992-09-02 | 1993-11-30 | E. I. Du Pont De Nemours And Company | Alkyl substituted polyimide, polyamide and polyamide-imide gas separation membranes |
JPH07236822A (ja) * | 1994-02-28 | 1995-09-12 | Dainippon Ink & Chem Inc | 表面改質ポリイミド系樹脂気体分離膜及びその製造方法 |
US5468430A (en) * | 1994-05-19 | 1995-11-21 | L'air Liquide S.A. | Process of making multicomponent or asymmetric gas separation membranes |
JP3992345B2 (ja) * | 1998-01-05 | 2007-10-17 | 日東電工株式会社 | 分離膜およびこれを用いたオレフィンの分離方法 |
JP3361755B2 (ja) * | 1998-08-17 | 2003-01-07 | 財団法人石油産業活性化センター | 炭化水素の選択的分離方法 |
JP3644630B2 (ja) * | 2000-11-22 | 2005-05-11 | 日東電工株式会社 | 炭化水素の膜分離方法 |
JP3644629B2 (ja) * | 2000-11-22 | 2005-05-11 | 日東電工株式会社 | 分離膜による炭化水素の分離方法 |
US7628841B2 (en) * | 2005-01-21 | 2009-12-08 | Ube Industries, Ltd. | Method for manufacturing polyimide asymmetric membrane, and polyimide asymmetric membrane |
-
2017
- 2017-09-25 ES ES17784458T patent/ES2939628T3/es active Active
- 2017-09-25 US US16/334,920 patent/US20190247806A1/en active Pending
- 2017-09-25 CA CA3042217A patent/CA3042217A1/en active Pending
- 2017-09-25 JP JP2019520790A patent/JP7160804B2/ja active Active
- 2017-09-25 EP EP22181809.9A patent/EP4085992A1/en active Pending
- 2017-09-25 EP EP17784458.6A patent/EP3535048B1/en active Active
- 2017-09-25 KR KR1020197014079A patent/KR102446807B1/ko active IP Right Grant
- 2017-09-25 CN CN201780065957.6A patent/CN109963641B/zh active Active
- 2017-09-25 WO PCT/US2017/053151 patent/WO2018084958A1/en active Search and Examination
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4983191A (en) * | 1989-10-10 | 1991-01-08 | E. I. Du Pont De Nemours And Company | Production of aromatic polyimide membranes |
EP0649675A1 (en) * | 1993-10-20 | 1995-04-26 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Treatment of gas separation membranes with inert solvent |
US5868992A (en) * | 1993-10-20 | 1999-02-09 | L'air Liquide, S.A. | Treatment of gas separation membranes with inert solvent |
CN1784260A (zh) * | 2003-04-18 | 2006-06-07 | 液体空气乔治洛德方法利用和研究的具有监督和管理委员会的有限公司 | 包含丙烷和丙烯的气体混合物的处理方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113578076A (zh) * | 2020-12-31 | 2021-11-02 | 太原科技大学 | 一种化学交联带羧基的聚酰亚胺氢气分离膜及其制备方法 |
CN113578076B (zh) * | 2020-12-31 | 2024-03-29 | 太原科技大学 | 一种化学交联带羧基的聚酰亚胺氢气分离膜及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
KR102446807B1 (ko) | 2022-09-26 |
CA3042217A1 (en) | 2018-05-11 |
KR20190095917A (ko) | 2019-08-16 |
CN109963641B (zh) | 2022-06-28 |
JP7160804B2 (ja) | 2022-10-25 |
WO2018084958A1 (en) | 2018-05-11 |
EP4085992A1 (en) | 2022-11-09 |
ES2939628T3 (es) | 2023-04-25 |
EP3535048B1 (en) | 2023-02-15 |
JP2019534141A (ja) | 2019-11-28 |
BR112019007877A2 (pt) | 2019-07-09 |
US20190247806A1 (en) | 2019-08-15 |
EP3535048A1 (en) | 2019-09-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104254384B (zh) | 中空纤维碳分子筛膜及其制备和用途 | |
CN104684967B (zh) | 聚合物、聚合物膜及其制备方法 | |
KR102648494B1 (ko) | 탄소 분자체 막을 제조하는 방법 | |
US11084000B2 (en) | Method of making carbon molecular sieve membranes | |
CN111225736B (zh) | 含第13族金属的碳分子筛膜和其制造方法 | |
KR102447406B1 (ko) | 탄소 분자체 중공 섬유 멤브레인을 제조하기 위한 개선 방법 | |
CN111971113A (zh) | 制造碳分子筛膜的改进方法 | |
US20220080361A1 (en) | Carbon Molecular Sieve Membrane Produced From A Carbon Forming Polymer-Polyvinylidene Chloride Copolymer Blend | |
CN109963641A (zh) | 制造改良聚酰亚胺分离膜的方法 | |
KR20210048509A (ko) | 가교 폴리이미드 멤브레인 및 이로부터 제조된 탄소 분자체 중공 섬유 멤브레인 | |
KR20240037283A (ko) | 중공 섬유 탄소 멤브레인의 제조 방법 | |
CN111954569B (zh) | 制造碳分子筛膜的改进方法 | |
BR112019007877B1 (pt) | Método de fabricação de uma membrana de poli-imida, processo para separar uma molécula de gás de uma alimentação de gás, e, membrana de poliimida que contém halogênio |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |