EP3852909A1 - Cms membrane, method for the production thereof and use thereof - Google Patents
Cms membrane, method for the production thereof and use thereofInfo
- Publication number
- EP3852909A1 EP3852909A1 EP19769458.1A EP19769458A EP3852909A1 EP 3852909 A1 EP3852909 A1 EP 3852909A1 EP 19769458 A EP19769458 A EP 19769458A EP 3852909 A1 EP3852909 A1 EP 3852909A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- membrane
- polyimide
- cms
- pyrolysis
- cms membrane
- 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.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 254
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 19
- 229920001721 polyimide Polymers 0.000 claims abstract description 66
- 239000004642 Polyimide Substances 0.000 claims abstract description 61
- 238000000926 separation method Methods 0.000 claims abstract description 54
- 238000000197 pyrolysis Methods 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 6
- CGSKOGYKWHUSLC-UHFFFAOYSA-N 1-(4-aminophenyl)-1,3,3-trimethyl-2h-inden-5-amine Chemical compound C12=CC=C(N)C=C2C(C)(C)CC1(C)C1=CC=C(N)C=C1 CGSKOGYKWHUSLC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 230000018044 dehydration Effects 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 238000007654 immersion Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000003618 dip coating Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- CVIUJSXIENVAGJ-UHFFFAOYSA-N 1-methyl-2H-pyrrol-2-ide Chemical compound CN1C=CC=[C-]1 CVIUJSXIENVAGJ-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 61
- 239000010410 layer Substances 0.000 description 46
- 239000011148 porous material Substances 0.000 description 37
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 28
- 230000007547 defect Effects 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 238000005373 pervaporation Methods 0.000 description 17
- 239000002808 molecular sieve Substances 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 16
- 229910021389 graphene Inorganic materials 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 230000035699 permeability Effects 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 229910001593 boehmite Inorganic materials 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 9
- 239000012466 permeate Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 7
- 229920005597 polymer membrane Polymers 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000004626 scanning electron microscopy Methods 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000012510 hollow fiber Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 125000005462 imide group Chemical group 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004697 Polyetherimide Substances 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 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 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000003889 chemical engineering Methods 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000002296 dynamic light scattering Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 239000012229 microporous material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920001601 polyetherimide Polymers 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241000270295 Serpentes Species 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- -1 ethanol and methanol Chemical class 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007783 nanoporous material Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229920000368 omega-hydroxypoly(furan-2,5-diylmethylene) polymer Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- 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
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-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
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- 229940044174 4-phenylenediamine Drugs 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
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 1
- 238000003109 Karl Fischer titration Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920001646 UPILEX Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 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 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
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- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 1
- 238000004870 electrical engineering Methods 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000012704 polymeric precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007723 transport mechanism Effects 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0067—Inorganic membrane manufacture by carbonisation or pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
- B01D67/00411—Inorganic membrane manufacture by agglomeration of particles in the dry state by sintering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0048—Inorganic membrane manufacture by sol-gel transition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/108—Inorganic support material
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- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
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- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1216—Three or more layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/025—Aluminium oxide
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/448—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by pervaporation
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- 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
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- 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
- B01D2256/245—Methane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2257/80—Water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/08—Specific temperatures applied
- B01D2323/081—Heating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/10—Specific pressure applied
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
- B01D2325/02832—1-10 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
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- 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
- B01D69/04—Tubular membranes
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- 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
Definitions
- the present invention relates to an ultra-thin defect-free carbon membrane which is suitable for the separation of gases and for the separation of liquids, a process for the production of this membrane and its use for the separation of gases or liquids
- Membrane technology is seen as an energy-efficient alternative to the separation of numerous gases and solvent mixtures compared to mature technologies such as pressure swing adsorption and cryogenic distillation. Specific examples include the separation of hydrogen from gasification and separation of hydrocarbons, the upgrading of biogas and landfill gas, exhaust gas treatment, methane cleaning and the dehydration of organic solvents.
- membrane candidates intensively examined due to their thermal and chemical stability.
- the membrane candidates are, for example, silica, zeolites, carbon molecular sieves and graphene / graphene oxide membranes.
- the membrane separation is shown schematically in FIG. 20.
- the molecular sieve mechanism is based on size exclusion for the separation of gas mixtures. Pores within the membrane have a strictly controlled size relative to the kinetic diameter of the gas molecules. This enables the diffusion of the smaller gas molecules at a much higher rate than that of the larger gas molecules.
- CMS membranes Carbon molecular sieve membranes (hereinafter referred to as CMS membranes) as one of the most promising inorganic microporous membranes have recently increased
- Carbon molecular sieve membranes are typically made by pyrolysis (carbonization) of various types of polymer precursors in vacuo or in an inert atmosphere. After the thermally unstable polymer components have decomposed, a thermally stable carbon structure is formed, which is composed of micropores (0.7-2 nm) which are connected by ultra-micropores (less than 0.7 nm).
- CMS membranes are essentially amorphous and their ultrapore size is not uniform within the membrane. CMS membranes are chemically very inert. They have sp 2 and sp 3 bonds and therefore show properties between those of graphite and diamond.
- the microstructure and permeation properties of the carbon membrane resulting from pyrolysis are significantly affected by the pyrolysis conditions (temperature, atmosphere, rate of heating and exposure time) and the nature (i.e. chemical structure and morphology) of the polymer precursor.
- various carbon molecular sieve membranes have been successfully used for the separation of various important gas and
- Solvent mixtures developed like H2 / propane, CO2 / N2, C0 2 / methane,
- CMS membranes lie either as self-supporting membranes in the form of thin films, as hollow fibers or as supported membranes on a suitable one
- Known carrier materials are, for example, porous
- inorganic oxides such as aluminum oxide or metals such as iron or steel.
- H. Richter et al., Angew. Chem. Int. Ed. 2017, 56, 7760-7763 discloses a CMS membrane obtained by pyrolysis of unsaturated linear polyester, which is applied to a carrier made of a-AbOa. A thin layer of y-AbOa is provided as the intermediate layer between the support and the CMS membrane.
- CMS membranes produced from unsaturated linear polyesters as precursors, are known from US 2012/0079943. They are present on a porous substrate, in particular on a-AbOs with an overlying layer of y-A Os, on which the CMS membrane is then applied by immersion in a polyimide solution, drying and pyrolysis.
- Membranes each on a carrier made of a-AbOs with an intermediate layer made of T ⁇ O2.
- Self-supporting CMS membranes made of polyimide precursors are described in WO 2017/165098. According to this document, conventional or fluorinated polyimides can be used to produce CMS membranes. Such
- Polyimides usually contain at least two different units selected from 2,4,6-trimethyl-1,3-phenylenediamine (DAM), oxydianalin (ODA),
- Matrimid® 5218 manufactured by Huntsman Advanced Materials
- BTDA-D API 5 (6) -amino-1 - (4'-aminophenyl ) -1,3,3-trimethylindane
- polyimide 6FDA / BPDA-DAM of the following formula:
- Self-supporting CMS membranes also made from Matrimid® 5218 are disclosed in WO 2016/196595.
- CMS membranes in the form of hollow fibers are known from US 2015/0290596.
- Matrimid® 5218 is disclosed as a suitable precursor, in addition to the following polyimides, which can also be used in a mixture:
- US 2011/0100211 discloses hollow fiber and self-supporting film CMS membranes which are made from Matrim id® 5218 or 6FDA / BPDA-DAM, polyimides are obtained by polycondensation between tetracarboxylic acid dianhydrides with diamines or by reaction of dianhydrides with diisocyanates. They are often not meltable and chemically very resistant (also to many solvents and acids). Because of their heat resistance, low outgassing, radiation resistance, flame resistance and insulation properties in electronics / electrical engineering, they are used in the form of semi-transparent foils or as thin lacquer insulation. An important application is also that in X-ray windows in the form of thin foils.
- Known commercially available polyimides include Matrimid® 5218, e.g. Kapton® (DuPont), Vespel® (DuPont), Apical® (Kaneka Americas Holding Inc.), Kinel® (Vyncolit NV), Meldin® (Saint Gobain), P84 (Evonik Industries ) and Upilex® (Ube Industries).
- Matrimid® 5218 e.g. Kapton® (DuPont), Vespel® (DuPont), Apical® (Kaneka Americas Holding Inc.), Kinel® (Vyncolit NV), Meldin® (Saint Gobain), P84 (Evonik Industries ) and Upilex® (Ube Industries).
- the IUPAC names of the monomers are: 1- (4-aminophenyl) -1, 3,3-trimethyl-2H-inden-5-amine and 5- (1, 3-dioxo-2-benzofuran-5-carbonyI-2 -benzofuran-1, 3-dione.
- Thermo Fisher (Kandel) GmbH GmbH, Düsseldorf and is available in the form of powder or as foils of various thicknesses.
- the flash point is> 93 ° C and the melting point is> 300 ° C.
- the density at 20 ° C is 1.2.
- Tg is 305 ° C.
- the inherent viscosity is 0.60 to 0.70 dl / g at 25 ° C.
- CMS membranes made from this polyimide Alfa Aesar are not yet known. Polyimides are generally characterized by high glass transition temperatures and a high carbon content.
- Supported CMS membranes in the form of hollow tubes are particularly suitable for large-scale applications and have already been used in catalytic applications
- Used membrane reactors in which the supported CMS membrane for selective Separation of the products resulting from the catalytic reaction can be used.
- the object of the invention is to provide an ultra-thin defect-free CMS membrane which is suitable for the efficient separation of gases with little difference in the kinetic diameter and of similar liquids, in particular for the separation of H2 / CO2 and for the dehydration of alcohols such as ethanol and methanol, and a process for their preparation.
- the invention further provides a supported CMS membrane according to claim 2. Further
- Embodiments of the invention are the manufacturing process for the supported CMS membrane according to claim 4 and the use of the membranes according to
- FIG. 1 shows photographic images of an a-AhOs / y-AbOs-supported polyimide or CMS membrane according to the invention before (A) and after (B, C) the pyrolysis at 700X.
- FIG. 2 shows ATR-FTI R-S pe ktre n of an a-AkOa / y-AkOs-supported polyimide or CMS membrane according to the invention before (lower spectrum) and after (upper spectrum) the pyrolysis at 700 ° C.
- FIG 3 shows SEM images of the surface (a, b) and the section (c, d) of a planar CMS membrane supported by a-AkC y-AkOs according to the invention.
- FIG. 4 shows C1s XPS spectra of an a-AkOa / y-AkOs-supported polyimide or CMS membrane according to the invention before (upper graph) and after the heat treatment at 700 ° C. (lower graph).
- FIG. 5 shows a Raman spectrum of an a-AkOa / y-AkOa-supported CMS membrane according to the invention.
- FIG. 6 shows the single gas permeation through an a-AkCk / y-AkOs-supported CMS membrane according to the invention with an inflow pressure of 2 bar at 200 ° C.
- the insert shows the ideal separation factors.
- FIG. 7 shows the temperature dependence of the individual gas permeance (A) and the perm selectivity (B) for an a-AkCk / y-AkOs-supported CMS membrane according to the invention at an inflow pressure of 2 bar.
- solid line represents the upper Robeson limit of the polymer.
- 9 shows representative shapes and water contact angles of water drops on an a-AkOa / y-AkOs-supported polyimide or CMS membrane according to the invention before (left figure) or after (right figure) the heat treatment.
- Fig. 10 shows Nz Permporosimetrie measurements with a N 2 / fko mixture at 20 0 C on an inventive tubular a-AKOA-carrier, which is coated with a y-AkCk- layer.
- FIG. 11 shows N1s XPS spectra of an a-AkOa / y-AkOs-supported polyimide or CMS membrane according to the invention before (upper illustration) or after (lower illustration) the heat treatment at 700 ° C.
- FIG. 13 shows the single gas permeation through an a-AkOs / y-AkOa-supported CMS membranes according to the invention within a batch, tested at 200 ° C. at an inflow pressure of 2 bar. The gas permeances were measured in three samples with one
- (A) is a photograph of a 2% by weight solution of the Alfa Aesar polyimide in NMP and (B) is a representation of the particle size distribution of the polymer solution, determined by dynamic light scattering.
- Fig. 16 is a graph showing the linear relationship between solution concentration and viscosity of a solution of the Alfa-Aesar polyimide in NMP.
- Figure 17 is a graph of termogravimetric analysis of the Alfa Aesar polyimide. The thermal decomposition begins at approx. 450 ° C.
- FIG. 18 shows photographs of an a-AbOs / y-AkOs-supported polyimide or CMS membrane according to the invention in various stages of pyrolysis (as coated, 500 ° C, 600 ° C and 700 ° C) and a size comparison of a tubular a-AhCVy-AI2O3-supported CMS membrane according to the invention after pyrolysis at 700 ° C with a commercially available ballpoint pen,
- Fig. 20 is a schematic representation of membrane separation (Scholes, C, A. et al. » Recent Patents on Chemical Engineering 2008, 52-66, p. 53).
- Fig. 21 is a schematic representation of the three basic separation mechanisms on membranes (Scholes C.A. et al., Op. Cit., P. 54).
- kinetic diameter is understood to mean the smallest diameter that a molecule can present in its environment. It differs from the atomic diameter, which indicates the atomic size as the size of the electron shell and which is generally much smaller than the kinetic diameter.
- atomic diameter indicates the atomic size as the size of the electron shell and which is generally much smaller than the kinetic diameter.
- thermal conductivity There are several types of determination for the kinetic diameter according to the CRS Handbook of Chemistry and Physics, namely from viscosity data, the Van der Waals equation and the thermal conductivity. A calculation from bond angles, bond lengths and the Van der Waals half-knife is also possible the kinetic diameters calculated by the different methods only differ by 2-3%.
- Pi and Pj [mol m 2 s 1 Pa 1 ] are the permeances of components i and j
- Fi [mol s 1 ] represents the flow rate of component i
- a [m 2 ] is the effective membrane area
- DR ⁇ [Pa] is the partial pressure of the component / between the supply and permeate sides of the membrane
- aij is the permeance ratio of component i to component j.
- Gas permeability is the degree of permeability of a solid to a particular substance, i.e. the degree of its permeation. It is influenced
- the gas permeance is often specified in GPU (gas permeance unit).
- Permeanz is the ratio of permeability to membrane thickness.
- Permselectivity is the ratio of permeances.
- Permporosimetry is a technique for determining the pore size of porous materials. With this technique it is possible to determine the pore size in the range of 0.5-50 nm depending on the adsorbent (steam).
- a binary feed mixture consisting of an inert gas (He or N 2 ) and a vapor (water or hexane) is passed through the membrane.
- the steam fills the pores of the membrane and blocks the passage of the less adsorbed gas, ie He or N 2 .
- a remaining N 2 or He flow indicates the presence of defects (larger pores that cannot be completely filled).
- a Kelvin equation is usually used to calculate the pore radius.
- Robeson upper bound indicates the performance limit of a polymer membrane, which suffers from a compromise between selectivity and permeability. Polymer membranes with high permeability show a lower selectivity and vice versa Robeson had this in 1997 and 2008
- Defect means macroscopic defects in the membrane. More specifically, defect means that the pore size of the CMS membrane is larger than the kinetic molecular diameter of the largest molecule that one wants to separate, so that separation due to the molecular size can no longer take place. If, for example, the pore size of the membrane is larger than the kinetic diameter of CO 2 (0.33 nm), no selective separation of H 2 / C0 2 with the corresponding membrane can take place, since both H 2 (kinetic diameter 0.29 nm) as well as C0 2 can diffuse through the correspondingly large pores. Defects in membranes can have a size of approximately 4 nm to 1 pm. A distinction is made between
- Defects (2-50 nm) and macro defects (> 50 nm). Defects result in a low selectivity or no selectivity of the membrane. Since the permeance due to defects is much larger than that of a defect-free membrane, the total membrane permeance can be dominated by the defect flow. Defects can arise as a result of problems with the membrane deposition method and defects in the surface on which the membrane is deposited. Defects can also result from membrane deposits using sol-gel processes Bubbles form during the production of the sol (details on the measurement see S. Chiu, WV et al., Journal of Membrane Science 377 (2011) 182,190)
- Ultrathin means a layer thickness of the CMS membrane of less than 1 gm.
- Thin means a layer thickness of the CMS membrane of approximately 1 to 2 gm
- Layer thickness can be determined by scanning electron microscope of a section.
- the pore size in the CMS membrane can be determined by individual gas permeation measurements of several gases with different kinetic
- Diameters are determined (Fig. 6 and 7). It is defined by "which gases are still allowed to pass " ie by gas permeability. Pore size is understood to mean the average pore diameter.
- the pore size of the intermediate layer (e.g. y-A Oa) is determined by permporosimetry (Fig. 10).
- the pore size of the carrier (e.g. a-A C) is determined by the manufacturer
- crystalline structures of a-AkOa- carrier used in this invention is based on manufacturer information "and the presence of 01-AI2O3 was additionally by
- the intermediate layer according to the invention was also by X-ray diffraction
- the CMS membrane according to the invention is in the form of a film or in the form of hollow fibers, preferably in the form of a film
- the supported CMS membrane according to the invention is provided on a porous support and a mesoporous intermediate layer provided thereon.
- porous support means that the support is a medium one
- Mesoporous intermediate layer generally means that pore sizes are in the range from 2 to 50 nm. According to the invention, however, mesoporous means that the
- Interlayer has an average pore diameter of 3 to 6 nm, preferably 3 to 5 nm, particularly preferably 3.5 to 4.5 nm, measured by
- the CMS membrane according to the invention i.e. in the case of the supported CMS membrane without support and without intermediate layer, preferably has a layer thickness of 300 to 400 nm, preferably about 350 nm, measured by scanning electron microscopy of a section.
- the material of the porous support is preferably selected from a-Al2O3, T1O2, Zr0 2 and a suitable metal, and is particularly preferably a-AbOa.
- the material of the mesoporous intermediate layer is preferably selected from g-Al 2 O 3 or T1O 2 , particularly preferably y-AbC> 3 .
- the CMS membrane is obtained by pyrolysis of a polyimide precursor.
- the known polyimides mentioned above, which are defined in claim 3 are preferred as polyimide.
- the above-mentioned polyimide from Alfa Aesar with the CAS no. 62929-02-6. It can be obtained from the monomers specified in claim 1 by customary experts known
- Processes are prepared, e.g. through acid-catalyzed condensation. It is particularly suitable for the production of CMS membranes due to its high glass transition temperature (Tg) of> 305 ° C and due to its high
- the supported CMS membrane according to the invention is e.g. in the form of a hollow tube or in the form of a flat disc.
- the intermediate layer and the CMS membrane are located inside the tube.
- the carrier tubes preferably have an asymmetrical configuration which has a pore gradient, the pore size decreasing from the outside inwards.
- the pore size specified by the manufacturer is the cut-off specification, i.e. it is the smallest pore size of the respective asymmetric carrier.
- the carrier tubes have the usual dimensions for commercially available
- Ultrafiltration membranes e.g. 10 mm outside diameter / 6 mm inside diameter up to 26 mm outside diameter / 16 mm inside diameter.
- the length is up to 1500 mm, preferably 200 to 400 mm, particularly preferably 300 mm.
- the carrier has e.g. a diameter of approximately 35 to 50 mm, preferably 39 mm, and a thickness of 1 to 3 mm, preferably 2 mm.
- Commercial porous filtration membranes can be used as supports.
- the intermediate layer is produced according to the invention by applying a sol of a suitable precursor and then calcining.
- the intermediate layer is preferably applied by applying a boehmite sol and then calcining.
- Common brine can be used as boehmite sol.
- a boehmite sol which is prepared by the method described by Chen, X. et al., Microporous and Mesoporous Materials 214 (2105) 195-203 is particularly preferably used.
- the concentration of the boehmite sol is usually about 0.5 to 2% by weight, preferably 1-1.3% by weight, the pH is in
- the viscosity is usually 1 to 1.5 mPa s, preferably approx. 1.1 to 1.3 mPa s, and the particle size in the sol is approx.
- a particularly smooth mesoporous intermediate layer with a suitable pore size can be obtained according to the invention.
- the sol can be applied by any known method, for example by dip coating, spray coating, knife coating or the like. It is preferably applied by dip coating.
- the calcination takes place in air at temperatures of approx. 500 to 700 ° C, preferably approx. 600 ° C.
- the heating can take place e.g. at a heating rate of 1 ° C per minute until the desired final temperature is reached. It is then held at this temperature for 2 to 4 hours, preferably for 3 hours, and then cooled to room temperature at the same rate.
- the application and the calcining are preferably repeated once in order to avoid large pores in the intermediate layer.
- the layer thickness of the intermediate layer produced in this way is preferably approximately 4 to 6 pm, particularly preferably approximately 5 pm, determined by scanning electron microscopy (see FIG. 3 c).
- the support thus obtained which is provided with the mesoporous intermediate layer, is also referred to in the present case as a composite support.
- the dip coating of the carrier provided with the intermediate layer for producing the polyimide layer as a precursor of the CMS membrane is preferably carried out as defined in claim 6.
- N, N-dimethylformamide or N-methyl-2-pyrrolidone are suitable.
- N-Methyl-2-pyrrolidone is particularly suitable
- the concentration of the polyimide of about 1 to 3% by weight, preferably 2% by weight, of the solvent N-methyl-2-pyrrolidone (NMP) and the viscosity of the polyimide solution of about 2 to 7 mpa s (see FIG. 16) and the special immersion conditions (immersion speed 5 to 15 m / sec, preferably 10 mm / s and immersion time 10 to 30 sec, preferably 10 s) succeed surprisingly, very thin hydrogen-selective CMS Manufacture membranes reproducibly.
- step iii) a solution of the polyimide with a concentration of 1 to 3% by weight, preferably 2% by weight, in N-methyl-2-pyrrolidone is preferred.
- the film obtained is then dried, for example at 90 ° C. overnight.
- Dip coating and drying are preferably carried out in a clean room of class ISO 5 (according to ISO 14644-1) in order to avoid contamination of the polyimide film with dust.
- the pyrolysis of the polyimide film is preferably carried out as specified in claim 5.
- the heating is preferably carried out in stages with a heating rate of initially 0.5 to 2 ° C./min, preferably 1 ° C./min to 300 to 400 ° C., preferably 350 ° C., then 0.5 to 1.5 hours , preferably 1 h, held at this temperature and then heated to a temperature of 550 ° C. to 750 ° C., preferably 600 ° C. or 700 ° C. at the same heating rate and left at the temperature reached for 1 to 3 hours, preferably 2 hours . Subsequently, preference is given to a heating rate of initially 0.5 to 2 ° C./min, preferably 1 ° C./min to 300 to 400 ° C., preferably 350 ° C., then 0.5 to 1.5 hours , preferably 1 h, held at this temperature and then heated to a temperature of 550 ° C. to 750 ° C., preferably 600 ° C. or 700 ° C. at the same heating rate and left at the temperature reached for 1 to 3 hours, preferably
- All temperature data for calcining the boehmite sol and pyrolysis of the polyimide refer to the temperature of the furnace.
- the temperature of the sample can vary.
- WO 2016/196595 describes a very complex heating protocol with constantly changing heating speeds in the range from 0.25 X / min to 13.3 ° C / min, similar to other documents.
- pyrolysis is often also carried out under an inert gas such as nitrogen, helium or argon.
- an inert gas such as nitrogen, helium or argon.
- a particularly preferred embodiment of the supported CMS membrane according to the invention is one with a porous support made of a-AhOa, a mesoporous intermediate layer made of y-AbOa provided thereon and a CMS membrane which is obtained by pyrolysis of the polyimide with the CAS no. 62929-02-6 was obtained.
- Another embodiment of the invention is a conventional apparatus for membrane separation of gases or liquids, which contains the supported and / or the unsupported CMS membrane according to the invention.
- the membranes according to the invention for the separation of gas mixtures is claimed. These are preferably mixtures of H 2 / CO 2 or of H2 / CH 4 , since particularly good separation results are achieved thereby.
- the two gases to be separated are present in the gas mixtures, for example in a molar ratio of 0.5 / 0.5, preferably 0.65 / 0.35, particularly preferably 0.70 / 0.20.
- the supported and unsupported CMS membranes according to the invention can advantageously be used for the separation of liquids.
- Water / alcohol mixtures are preferably separated, particularly preferred
- Water / methanol or water / ethanol mixtures, water-alcohol starting mixtures with a water content of 5 to 15% by weight, preferably about 10% by weight, are particularly suitable for such separations.
- the CMS membrane according to the invention has the highest H 2 permeance and H2 / CO2 permselectivity of all supported CMS membranes known from the literature
- Turbostratic is understood to mean non-graphitic carbon from layers of hexagonally arranged, sp 2 -hybridized carbon atoms. These layers are stacked approximately in parallel without any three-dimensional long-range order. This material consists of stacks of graphene layers that are twisted and shifted against each other. This arrangement is called turbostratic. The distance between the layers can differ significantly from the layer distance found in graphite.
- the carbon membranes of the invention also have unprecedented separation performance in the dehydration of aqueous alcohol mixtures, even for the more demanding water-methanoi mixture.
- the membranes according to the invention have great potential in the high-temperature hydrogen cleaning and dewatering of aqueous alcohol mixtures.
- polyimide resin polyimide resin, item number 43658
- Alfa Aesar CAS number: 62929-02-6
- NMP N-methyl-2-pyrrolidone
- Ultrafiltration membranes (length: 300 mm, outside diameter. 10 mm, pore size approx. 70 nm), which are sealed at the edges with a glass coating, were obtained from atech innovations GmbH, Germany.
- ct-AbOa discs with a diameter of 39 mm, a thickness of 2 mm and a pore size of approx. 80 nm were supplied by COBRA Technologies BV Netherlands.
- the polymer solution was prepared by mixing 2% by weight Alfa Aesar polyimide polyimide powder in NMP (N-methyl-2-pyrrolidone) and stirring for 10 hours.
- FIG. 10 After calcination, Y-Al2O3 with an average pore diameter of about 4 nm (FIG. 10) was obtained.
- Fig. 10 it can clearly be seen that the pores of the y-A OS layer are completely filled with water for a relative humidity of about 75%. This corresponds to an average pore size of approximately 4 nm according to the Kelvin equation.
- the Y-Al2O3 / CX-Al2O3 composite supports prepared in this way were then dip-coated with the polymer solution prepared as described above as follows and dried at 90 ° C. overnight. During the dip coating process, a polymer layer was applied with a dipping and removal speed of 10 mm / s each with a dipping time of 20 s. The diving and the
- Drying processes were carried out in a clean room of class ISO 5 according to ISO 14644-1 in order to avoid dust contamination.
- the supported polymer membranes thus obtained were then placed in the middle of an oven (Gero HTK 25 Mo / 16-1 G) to be subjected to a heat treatment. Before the carbonization process started, a vacuum of approx. IO -6 mbar was applied. At this pressure, the samples were heated at a rate of
- the thickness of the CMS membrane obtained was approx. 350 nm (FIG. 3), determined by scanning electron microscope image of a section.
- FTIR Fourier transform infrared spectroscopy
- XPS X-ray photoelectron spectroscopy
- water contact angle measurement Various techniques such as Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), water contact angle measurement and scanning electron microscopy were used.
- FTIR Fourier transform infrared spectroscopy
- XPS X-ray photoelectron spectroscopy
- ZnSe mirrors ZnSe mirrors.
- the resolution of the spectrometer was set to 4 cm 1 . All spectra were measured in the range of 600-4000 cm 1 and normalized to the gradient vector for comparison.
- the binding energy was normalized by setting the C1s core level to 285 eV (sp 3 ) and
- Water contact angle measurements were carried out at room temperature using the sessile drop method with a contact angle goniometer equipped with a video camera recording system and with software for drop contour analysis.
- the water drop with a volume of 3 ml was placed at four different locations on the dip-coated membrane surface.
- the contact angle was measured for each and the mean value was determined.
- the surface morphology and the thickness of the supported membranes were examined with a scanning electron microscope (SEM Ultra 55, Carl Zeiss Microscopy GmbH, Jena, Germany). Cross-sectional images were obtained by breaking the sample with a pair of cutting pliers.
- the samples i.e. The membrane surface was coated with a conductive layer consisting of platinum with a thickness of 3-5 nm before the analysis.
- the particle size distribution of polymers in solutions was determined by dynamic light scattering (DLS) at 25 ° C with a HORIBA LB-550 system.
- the polymer solution was prepared by mixing 2% by weight
- the Seher viscosity was measured using a “Physica MCR 301 rheometer” rotary rheometer.
- thermogravimetric analysis (TGA) with a STA-449 F1 Jupiter instrument at a heating rate of 10 ° C / min under argon
- the X-ray diffractometry was carried out as follows: A D4 Endeavor Bruker AXS diffractometer with a Kristallofiex 770 X-ray generator was used for the measurement. A Pawley fit using the "Topas 4.2" software was used to identify the crystalline phases with the powder X-ray database JCPDS-ICD. The PDF cards No. 01-079-1558 for y-AI 2 0 3 and No. 00-005-0172 for (X-AI2O3 were used for comparison.
- Raman spectra were recorded on a Renishaw in Via Raman spectroscope with a pellet-cooled CCD.
- the excitation wavelength was 514 nm (Ar ion laser), focused by a 50 x 0.75 Leica N PLAN EPI lens with a laser energy of 0.075 mV and 20% laser defocus.
- the spectra were recorded at a resolution of 1.0 cm 1 and by 20 scans of 20 s each
- the gas permeability was measured from 200 ° C to 50 ° C with three test samples for each membrane. The measurement was carried out in an in-house development of a dead-end permeation test device with a tubular membrane module made of stainless steel.
- Permeate flow was maintained at atmospheric pressure and the pressure across the membrane was maintained at 2 bar.
- the gas flow on the supply side of the module was controlled by an accurate pressure controller (Bronkhorst differential pressure controller with F-001 valve).
- the gas flow rate on the permeate side was measured using two flow meters with a maximum flow of 7.74 ml min 1 and 209 ml min 1 (Brooks GF40). Before determining the The membranes were each dried at 200 ° C. overnight in a vacuum.
- a commercial cross-flow test unit (Pervatech BV Netherlands) was used to evaluate the pervaporation performance of tubular CMS membranes.
- the feed liquid containing 10% by weight alcohol (methanol or ethanol) was heated to 70 ° C.
- the CMS membrane side faces the supply side (flow rate: 300 l / h and delivery volume 2L), while the permeate side was kept at a pressure of 10 mbar using a vacuum pump.
- the water concentrations in the feed liquid and permeate were determined by Karl Fischer titrations and the refractive index (Mettler Toledo RA510M) under ambient conditions.
- the permeate stream was collected in a vacuum trap with liquid nitrogen.
- the permeation flow J and the separation factor aPa are calculated using formulas (3) and (4).
- J [g] is the weight of the permeate collected during the time of the experiment t [h]
- a [m 2 ] is the effective membrane surface
- X and Y represent the molar fraction of components i and j in feed liquid and permeate, respectively
- Pervaporation results are determined after 1 day of continuous operation, which enables a more precise comparison of the flows and selectivities.
- Fig. 1 (a-c) shows the photos of the a-A Os / y-AbOs-supported polyimide membrane before and after the heat treatment at 700 ° C in a vacuum. After immersing the composite support in the polyimide solution, a homogeneous yellow coating can be seen. The color of the coating changes from yellow to black when annealed at 700 ° C, which indicates a pyrolysis process.
- the intensity of these peaks decreases drastically when the samples are treated at 700 ° C. This indicates that the pyrolysis degradation of the polymer by the
- Transformation of the imide groups is determined.
- the surface morphology and the thickness of the CMS top layer were examined by means of scanning electron microscopy. As can be seen in FIG. 3, a dense, uniform, smooth and crack-free carbon layer was formed with good adhesion to the intermediate layer Y-Al2O3. The thickness of the CMS membrane is due to the
- the surface elemental composition of the polymer and CMS membrane determined by XPS is shown in Table 2 below.
- Table 2 Surface element composition of an a-A Os / y-AbOa-supported polyimide membrane according to the invention before and after heat treatment at 700 ° C.
- the CN binding is also confirmed by a single broad peak at approximately 400.3 eV from N1 s nuclear level spectra (FIG. 10).
- the carbon membrane according to the invention is a mixture of graphitic and amorphous carbon, the latter representing "defects" within or at the edge of the graphitic layers.
- the type or type of (electronic) defects in the graphitic layers of the CMS membrane is investigated using Raman spectroscopy. As shown in Fig. 5, the Raman spectrum of the carbonized sample is adjusted using five Gaussian contributions. The peak centered at 1600 cm 1 is defined as the G band and becomes the
- the D1 band is activated by activating the breathing mode of carbon rings the symmetry A 1g at the edge of graphite planes Raman active.
- the D2 peak at 1635 cm 1 is associated with lattice vibrations as with D1, but involves isolated ones
- Graphene layers D3 and D4 bands generally occur with strongly defective carbon-containing materials.
- the first with 1560 cm 1 is usually wide and is attributed to the amorphous carbon, while the second with 1 150 cm 1 is attributed to the sp 3 impurities.
- Eckmann et al. (Eckmann, A .; Felten, A .; Mishchenko, A .; Britnell, L; Krupke, R .; Novoselov, KS; Casiraghi, C., Probing the Nature of Defects in Graphene by Raman Spectroscopy.
- Nanoengages 2012, 12 (8), 3925-3930 used the intensity ratio of D1 and D2 peaks (ID 1 / ID 2) by means of Raman spectroscopy to investigate the nature of the defects in graphene samples which were caused by fluorination (sp 3 -like defects) and Ar + shelling (vacancy-like
- Defects were introduced. They found an ID 1 / ID 2 ratio of about 13 for defects related to sp 3 hybridization and 7 for vacancies such as defects. According to the invention, the calculated intensity ratio of ID 1 / ID 2 is estimated to be approximately 13.15, which indicates that most of the defects in the carbonized sample according to the invention are sp 3 -like defects. This result is consistent with the XPS analysis, which has shown that 34 at.% Of the total amount of carbon is related to sp 3 hybridization.
- tubular CMS membranes The gas separation performance of tubular CMS membranes was assessed by measuring the permeance of several gases with different kinetic diameters at 200 ° C and an inlet pressure of 2 bar difference. Three membranes from different batches were tested to ensure the reliability of the results (Fig. 13 and table). As shown in Fig. 6, the
- H 2 has the highest permeance, which increases by almost an order of magnitude in the range from 50 to 200 ° C.
- the permselectivity of all Gas pairs also increase with increasing temperature (Fig. 7B).
- the CMS membrane for H2 / CO2, H2 / N2 and H2 / CH4 gas pairs has permselectivities of around 24, 130 and 228, which are far above the corresponding Knudsen coefficients (4.7, 3.7 and 2.8).
- Such excellent permselectivities show the pinhole (defect) freedom of the CMS membranes according to the invention and are attributed to the presence of ultramicropores, which increase the diffusion
- the pore size of the CMS membrane according to the invention is close to the kinetic diameter of CO2, ie 0.33 nm.
- the apparent activation energy E act for the permeation of H2, CO2, N2 and CH 4 through the CMS membrane according to the invention was calculated from the Arrhenius temperature dependence of the permeation.
- the H2 / CO2 separation performance of the carbon membrane according to the invention was further compared with other ultra-modern materials such as MOF (Metal Organic Framework), ZIF 38 (Zeolithic Imidolate Framework), silica-modified zeolite, silica and graphene (FIG. 8).
- MOF Metal Organic Framework
- ZIF 38 Zerolithic Imidolate Framework
- silica-modified zeolite silica and graphene
- Carbon membrane (1, 1 x10 6 mol rrr 2 s -1 Pa 1 ).
- the increased H2 permeance of the carbon membrane according to the invention can be attributed to the presence of sp 3 -like defects in the graphene planes, which enables a faster diffusion of H 2 . From these results it can be concluded that the carbon membrane according to the invention has both a high Hb / CC selectivity and a high H2 permeance, which are important performance parameters for an industrial application.
- CMS-600 Single gas permeation through a CMS membrane heat-treated at 600 ° C (CMS-600) and a CMS membrane at 700 ° C (CMS-700) at different temperatures
- the surface wettability of the membrane surface against water can be easily estimated by measuring the water contact angle.
- the water angle of the polymer membrane before and after the heat treatment is shown in FIG. 9.
- the untreated membrane has a contact angle of approximately 75 ° before pyrolysis, which increases to approximately 90 ° after the heat treatment. This is attributed to the increase in carbon content, which makes the membrane more hydrophobic. It should be noted that water contact angles in the range of 95-100 ° have been given in the literature for graphene. The lower contact angle for the
- CMS membrane according to the invention was measured in comparison to graphene, is due in part to the presence of some oxygen-containing functional groups (7 at.%) on the membrane surface, as mentioned above.
- Table 3 summarizes the pervaporation results for 10% by weight of water-containing binary liquid supplies by the CMS- Membrane together at 70 ° C. Because of their different molecular sizes, methanol and ethanol were used as feed solutions.
- Table 4 compares the pervaporation performance for the methanol dewatering of the carbon membrane according to the invention with NaA zeolite, silicon dioxide and carbon membranes.
- the pervaporation index (PSI) is used as an indicator of the performance of the synthesized membrane.
- the data given in Table 4 were taken from documents a) to f) given below.
- the CMS membrane according to the invention has a lower water flow than the hydrophilic membranes, including NaA-type zeolite and silica membranes, but the highest separation factor and PSI. That means the
- the CMS membrane according to the invention can effectively separate water from aqueous alcohol mixtures based on the molecular sieve mechanism.
Abstract
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