JP6892156B2 - 合成ガスの直接転化に基づく低炭素オレフィンの調製方法 - Google Patents
合成ガスの直接転化に基づく低炭素オレフィンの調製方法 Download PDFInfo
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- JP6892156B2 JP6892156B2 JP2019566832A JP2019566832A JP6892156B2 JP 6892156 B2 JP6892156 B2 JP 6892156B2 JP 2019566832 A JP2019566832 A JP 2019566832A JP 2019566832 A JP2019566832 A JP 2019566832A JP 6892156 B2 JP6892156 B2 JP 6892156B2
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- catalyst
- low carbon
- synthetic gas
- carbon olefin
- catalyst component
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- 238000006243 chemical reaction Methods 0.000 title claims description 49
- 238000000034 method Methods 0.000 title claims description 39
- 229910052799 carbon Inorganic materials 0.000 title claims description 38
- -1 carbon olefin Chemical class 0.000 title claims description 37
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 34
- 239000003054 catalyst Substances 0.000 claims description 131
- 239000007789 gas Substances 0.000 claims description 38
- 229910052760 oxygen Inorganic materials 0.000 claims description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 34
- 239000001301 oxygen Substances 0.000 claims description 34
- 239000002808 molecular sieve Substances 0.000 claims description 29
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 29
- 229910044991 metal oxide Inorganic materials 0.000 claims description 21
- 150000004706 metal oxides Chemical class 0.000 claims description 21
- 239000011148 porous material Substances 0.000 claims description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 239000003245 coal Substances 0.000 claims description 8
- 229910002515 CoAl Inorganic materials 0.000 claims description 7
- 229910015372 FeAl Inorganic materials 0.000 claims description 7
- 229910016583 MnAl Inorganic materials 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 6
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 18
- 150000001336 alkenes Chemical class 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000005530 etching Methods 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 15
- 239000012298 atmosphere Substances 0.000 description 12
- 239000011787 zinc oxide Substances 0.000 description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 description 10
- 239000011261 inert gas Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 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
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052566 spinel group Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000012695 Ce precursor Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000012697 Mn precursor Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000012435 analytical chromatography Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- LMHUKLLZJMVJQZ-UHFFFAOYSA-N but-1-ene;prop-1-ene Chemical compound CC=C.CCC=C LMHUKLLZJMVJQZ-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910001417 caesium ion Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003805 vibration mixing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
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Description
2.多孔質の担体が分子篩を分散させるので、中間体と生成物との間の物質伝達に有利であり、水素化などの副反応の影響が大幅に軽減されて、低炭素オレフィンの高い選択性を維持するとともに、転化率を高めることができる。
3.本発明において、複合触媒の調製過程が簡単で、条件が温和であり、且つ反応プロセスにおける製品収量と選択性が高く、C2−C4低炭素オレフィンの選択率が50−90%に達し、特に、転化率が上向した後であっても、依然として高いアルケン/アルカン比が維持できると共に、副産物であるメタンの選択性が低く(<15%)、触媒の寿命が長く(700時間を超える)、優れた応用見通しがある。
一、触媒Aの調製
(一)エッチング法により極性表面を有するZnO材料を合成する。
(1)Zn(NO3)2・6H2Oを0.446g(1.5mmol)ずつ4部計量して、それぞれ四つの容器に入れ、次に0.300g(7.5mmol)、0.480g(12mmol)、0.720g(18mmol)、1.200g(30mmol)のNaOHを上記の4つの容器に順次に加え、4つの容器それぞれに脱イオン水を30mlずつ加え、0.5時間以上攪拌して、溶液を均一に混合する。温度を160℃に上昇させ、20時間反応させて、沈殿物を酸化亜鉛に分解させる。反応液を室温まで冷却させた後、遠心分離して遠心分離後の沈殿物を回収し、脱イオン水で2回洗浄してZnO酸化物を得る。
上記から得られた生成物を遠心分離し、或はろ過し、脱イオン水で洗浄した後、雰囲気下で、乾燥或は乾燥と還元処理を行う。雰囲気は、不活性ガス、或は不活性ガスと還元性雰囲気の混合ガスであり、不活性ガスは、N2、He、Arのうちの一種或は二種以上であり、還元性雰囲気は、H2、COの一種或は二種である。乾燥還元における混合ガス中の不活性ガスと還元性ガスの体積比は100/10〜0/100であり、乾燥と乾燥還元処理において、処理温度は350℃であり、時間は4hであり、これで表面に豊富な酸素空孔を有するZnO材料を得る。具体的なサンプルとその調製条件を以下の表1に示す。その中、表面酸素空孔は次のように定義する(1−酸素原子のモル量が化学量論比酸素モル量に占める含有量)。
調製プロセスは、上記(一)の(1)が0.480g(12mmol)NaOHの用量に対応する産物と(3)に説明されるものと同じである。異なる処は、Znの前駆体がCeの対応の前駆体に置き換えることである。Ceの対応の前駆体は、硝酸セリウム、塩化セリウム、酢酸セリウムのいずれかであり、本実施例では硝酸セリウムを用いる。
硝酸亜鉛、硝酸アルミニウム、硝酸クロム、硝酸マンガン、硝酸ジルコニウムを前駆体として使用し、尿素と共に室温で水において混合する。前記混合溶液を熟成させた後、取り出し、洗浄、濾過及び乾燥を行い、得られた固体を空気雰囲気で焙焼して、(110)結晶面の方向に成長するスピネル酸化物を得る。サンプルもエッチング法で処理して、大量の表面酸素空孔を有する触媒を合成する。エッチング及び後処理プロセスは、上記の(一)の(2)及び(3)で説明されたのと同じである。該サンプルは大きい比表面積を有し、表面欠陥が多くあり、合成ガス転化における触媒として適用できる。
Cr2O3、Al2O3或はZrO2を担体として、沈殿法によりCr2O3、Al2O3或はZrO2が分散された活性金属酸化物を調製する。分散型ZnO酸化物の調製を例として説明すると、市販のCr2O3、Al2O3或はZrO2担体をベース液に予め分散させた後、硝酸亜鉛を原料として、室温で水酸化ナトリウム沈殿剤と混合して沈殿させる。Zn2+のモル濃度は0.067Mであり、Zn2+と沈殿剤のモル比は1:8である。その後、160℃で24時間熟成させ、Cr2O3、Al2O3或はZrO2を担体として分散されたZnO酸化物を得る(触媒A中の分散剤の含有量がそれぞれ0.1wt%、10wt%、90wt%である)。
前記CHA及びAEI位相構造の分子篩は八元環穴口、3Dチャンネルを備え、チャケージを含む。
酸化物SiO2:Al2O3:H3PO4:R:H2O=1.6:16:32:55:150(質量比)に従って、原材料であるシリカゾル30%(質量濃度)、AlOOH、リン酸、TEA(R)、脱イオン水を取り、室温で混合した後、テンプレート剤の0.5倍モル量の助剤HFを添加し、担体酸化物粉末を添えて、30℃で撹拌しながら2時間老化させた後、熱水釜に移し、200℃で24時間結晶化させる。
必要な割合の触媒Aと触媒Bを容器に加え、これらの材料及び/或は容器の高速移動により生成される押出力、衝撃力、切断力、摩擦力等の一種或は二種以上の作用により、分離、粉砕、混合等の目的を達成する。温度と搬送ガス雰囲気を調整することにより、機械的エネルギー、熱エネルギー、化学エネルギーの転換を実現し、さらに異なる成分間の相互作用を調節する。
固定床反応を例とするが、触媒は移動床反応器にも適する。該装置は、ガス質量流量計とオンライン製品分析クロマトグラフィーを配備している(反応器排気ガスをクロマトグラフィーの定量バルブに直接接続し、定期的な実時間試料分析を行う)。
(付記1)
触媒であって、前記触媒は、触媒成分Aと触媒成分Bを機械的に混合することにより得られる複合触媒A+Bであり、触媒成分Aの活性成分が活性金属酸化物であり、触媒Bは負荷型分子篩であり、その担体は多孔質のAl2O3、SiO2、TiO2、ZrO2、CeO2、MgO、Ga2O3のうちの一種或は二種以上であり、前記分子篩はCHA構造及びAEI構造の一種或は二種であり、前記分子篩の容量が4%−45%wtであり、前記活性金属酸化物がMnO、MnCr2O4、MnAl2O4、MnZrO4、ZnO、ZnCr2O4、ZnAl2O4、CoAl2O4、FeAl2O4のうちの一種或は二種以上である、
ことを特徴とする触媒。
前記触媒成分Bは、多孔質のAl2O3、SiO2、TiO2、ZrO2、CeO2、MgO、Ga2O3のうちの一種或は二種以上を担体とし、比表面積が30〜250m2/gであり、細孔容積が0.25〜0.80ml/gであり、比表面積に基づいて計算すると、メソ細孔が30〜75%を占め、マクロ孔が25〜70%を占め、分子篩は活性成分としてその場成長或は物理的混合により担体の周りに分散される、
ことを特徴とする付記1に記載の触媒。
触媒成分Aは、MnO、MnCr2O4、MnAl2O4、MnZrO4、ZnAl2O4、CoAl2O4、FeAl2O4のうちの一種或は二種以上である、
ことを特徴とする付記1に記載の触媒。
触媒成分A中の活性成分と触媒成分Bの重量比は、0.1〜20倍、好ましくは0.3〜5倍である、
ことを特徴とする付記1に記載の触媒。
前記活性金属酸化物は、大きさが5〜30nmの結晶粒から構成され、結晶粒の表面から結晶粒の内部方向への深さが0.3nmの距離範囲内に大量の酸素空孔が存在し、その中、酸素原子のモル量が化学量論比酸素モル含有量の80%未満を占め、好ましくは80%−10%を占め、より好ましくは60%−10%を占め、最も好ましくは50%−10%を占め、表面酸素空孔は、100%−酸素原子のモル量が化学量論比酸素モル量に占める百分率として定義され、対応の酸素空孔濃度が好ましくは20%−90%であり、より好ましくは40%−90%であり、最も好ましくは50%−90%である、
ことを特徴とする付記1又は4に記載の触媒。
前記触媒成分Aは、Al2O3、SiO2、Cr2O3、ZrO2、TiO2のうちの一種或いは二種を分散剤としてさらに含み、前記活性金属酸化物が分散剤に分散され、分散剤が触媒Aに占める含有量は0.05〜90wt%であり、残りが活性金属酸化物である、
ことを特徴とする付記1に記載の触媒。
合成ガスを反応原料とし、付記1〜6のいずれか一つに記載の触媒を触媒として、固定床或は移動床において転化反応を行い、
その中、前記合成ガスの圧力が0.5〜10MPaであり、反応温度が300〜600℃であり、対気速度が300〜10000h−1であり、前記反応に用いる合成ガスのH2/CO比が0.2〜3.5である、
ことを特徴とする合成ガスの直接転化に基づく低炭素オレフィンの調製方法。
Claims (6)
- 触媒は、触媒成分Aと触媒成分Bを機械的に混合することにより得られる複合触媒A+Bであり、触媒成分Aの活性成分が活性金属酸化物であり、触媒Bは負荷型分子篩であり、その担体は多孔質のAl 2 O 3 、SiO 2 、TiO 2 、ZrO 2 、CeO 2 、MgO、Ga 2 O 3 のうちの一種或は二種以上であり、前記分子篩はCHA構造及びAEI構造の一種或は二種であり、前記分子篩の容量が4%−45%wtであり、前記活性金属酸化物がMnO、MnCr 2 O 4 、MnAl 2 O 4 、MnZrO 4 、ZnO、ZnCr 2 O 4 、ZnAl 2 O 4 、CoAl 2 O 4 、FeAl 2 O 4 のうちの一種或は二種以上であり、
合成ガスを反応原料とし、前記触媒を触媒として、固定床或は移動床において転化反応を行い、
その中、前記合成ガスの圧力が0.5〜10MPaであり、反応温度が300〜600℃であり、対気速度が300〜10000h−1であり、前記反応に用いる合成ガスのH2/CO比が0.2〜3.5である、
ことを特徴とする合成ガスの直接転化に基づく低炭素オレフィンの調製方法。 - 前記触媒成分Bは、多孔質のAl2O3、SiO2、TiO2、ZrO2、CeO2、MgO、Ga2O3のうちの一種或は二種以上を担体とし、比表面積が30〜250m2/gであり、細孔容積が0.25〜0.80ml/gであり、比表面積に基づいて計算すると、メソ細孔が30〜75%を占め、マクロ孔が25〜70%を占め、分子篩は活性成分としてその場成長或は物理的混合により担体の周りに分散される、
ことを特徴とする請求項1に記載の合成ガスの直接転化に基づく低炭素オレフィンの調製方法。 - 触媒成分Aは、MnO、MnCr2O4、MnAl2O4、MnZrO4、ZnAl2O4、CoAl2O4、FeAl2O4のうちの一種或は二種以上である、
ことを特徴とする請求項1に記載の合成ガスの直接転化に基づく低炭素オレフィンの調製方法。 - 触媒成分A中の活性成分と触媒成分Bの重量比は、0.1〜20倍、好ましくは0.3〜5倍である、
ことを特徴とする請求項1に記載の合成ガスの直接転化に基づく低炭素オレフィンの調製方法。 - 前記活性金属酸化物は、大きさが5〜30nmの結晶粒から構成され、結晶粒の表面から結晶粒の内部方向への深さが0.3nmの距離範囲内に大量の酸素空孔が存在し、その中、酸素原子のモル量が化学量論比酸素モル含有量の80%未満を占め、好ましくは80%−10%を占め、より好ましくは60%−10%を占め、最も好ましくは50%−10%を占め、表面酸素空孔は、100%−酸素原子のモル量が化学量論比酸素モル量に占める百分率として定義され、対応の酸素空孔濃度が好ましくは20%−90%であり、より好ましくは40%−90%であり、最も好ましくは50%−90%である、
ことを特徴とする請求項1又は4に記載の合成ガスの直接転化に基づく低炭素オレフィンの調製方法。 - 前記触媒成分Aは、Al2O3、SiO2、Cr2O3、ZrO2、TiO2のうちの一種或いは二種を分散剤としてさらに含み、前記活性金属酸化物が分散剤に分散され、分散剤が触媒Aに占める含有量は0.05〜90wt%であり、残りが活性金属酸化物である、
ことを特徴とする請求項1に記載の合成ガスの直接転化に基づく低炭素オレフィンの調製方法。
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