CN112547054B - Supported methane oxidative coupling catalyst and preparation method and application thereof - Google Patents
Supported methane oxidative coupling catalyst and preparation method and application thereof Download PDFInfo
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- CN112547054B CN112547054B CN202110070026.3A CN202110070026A CN112547054B CN 112547054 B CN112547054 B CN 112547054B CN 202110070026 A CN202110070026 A CN 202110070026A CN 112547054 B CN112547054 B CN 112547054B
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- oxidative coupling
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- coupling catalyst
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000005691 oxidative coupling reaction Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 106
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 69
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 69
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 53
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 39
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 39
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 39
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 239000004480 active ingredient Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 126
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 75
- 239000002244 precipitate Substances 0.000 claims description 53
- 239000003921 oil Substances 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 28
- 239000004530 micro-emulsion Substances 0.000 claims description 28
- 239000004094 surface-active agent Substances 0.000 claims description 28
- 239000012153 distilled water Substances 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 235000012239 silicon dioxide Nutrition 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 22
- 230000007935 neutral effect Effects 0.000 claims description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- 239000011258 core-shell material Substances 0.000 claims description 15
- 239000004064 cosurfactant Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- 150000002910 rare earth metals Chemical class 0.000 claims description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 8
- -1 rare earth metal salt Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 6
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229940071125 manganese acetate Drugs 0.000 claims description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 5
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 229920004890 Triton X-100 Polymers 0.000 claims description 4
- 239000013504 Triton X-100 Substances 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 3
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004914 cyclooctane Substances 0.000 claims description 3
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 claims description 3
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 claims description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000012495 reaction gas Substances 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 5
- 150000003624 transition metals Chemical class 0.000 abstract description 5
- 239000010453 quartz Substances 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000001632 sodium acetate Substances 0.000 description 5
- 235000017281 sodium acetate Nutrition 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- ALCKOTLFXSKGSJ-UHFFFAOYSA-N [Na].[Mn].[W] Chemical compound [Na].[Mn].[W] ALCKOTLFXSKGSJ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Substances [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B01J35/396—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to the field of supported multi-component transition metal methane oxidative coupling catalysts. A supported methane oxidative coupling catalyst, which is prepared from WO3And MnO2As active ingredient, with M1Adding an alkali metal additive M as a structural additive2Active components, structural assistant and alkali metal assistant are loaded on SiO carrier2@Al2O3The composition of the catalyst is M1‑M2‑WO3‑MnO2/SiO2@Al2O3. The invention also relates to a preparation method and application of the supported methane oxidative coupling catalyst.
Description
Technical Field
The invention relates to the field of supported multi-component transition metal methane oxidative coupling catalysts.
Background
The technology for preparing ethylene from natural gas comprises two routes of indirect conversion and direct conversion. The indirect conversion comprises the technology of preparing ethylene from natural gas by Methanol (MTO), the technology of preparing ethylene by a Fischer-Tropsch synthesis route (FTO) and the like; the direct conversion comprises methane anaerobic dehydrogenation technology (MDA) and methane oxidative coupling ethylene preparation technology(OCM), etc. The indirect methane conversion process is complex, and the methane needs to be converted into synthesis gas at high temperature, and then the synthesis gas is subjected to one-step or two-step method to synthesize the ethylene. From the energy point of view, the indirect conversion needs to completely break the C-H bonds which should be partially remained in the product to generate synthesis gas, and then hydrocarbon products are obtained by recombination under the action of a catalyst, so that great waste on energy is caused. The direct conversion of methane has been regarded by the industry and scholars because of the simple process, among which, the anaerobic dehydrogenation technique is difficult to activate methane, the reaction usually requires a high temperature above 1000 ℃, and the products are mainly aromatic hydrocarbons and a small amount of C2 +A hydrocarbon; the reaction temperature for preparing ethylene by Oxidative Coupling (OCM) is relatively low, the important industrial raw material ethylene is taken as a main product, the industrial prospect is wide, and the method is always in a generally good technical route. Although various types of methane-activating catalysts have been developed since the first report of this process in the last 80 th century, the performance of these catalysts has a significant gap from commercial demand. Of these catalysts, the silica-supported sodium tungsten manganese system catalyst exhibits good performance in comparison with other system catalysts, CH4Conversion, C2The hydrocarbon selectivity and yield have significant advantages and are considered to be one of the most potential methane oxidative coupling catalysts. However, the sodium tungsten manganese system catalyst has insufficient stability. For this reason, researchers have endeavored to find suitable solutions to achieve high yields while extending the useful life of the catalyst.
CN1389293A discloses a catalyst for preparing ethylene by methane pressure oxidative coupling using silicon dioxide as a carrier, which can obtain 33.0% of methane conversion rate and 24.1% of C under the pressure condition2 +The yield was found. CN101385982A discloses a method for loading Na by taking mesoporous material SBA-15 as a carrier2WO4And Mn, methane conversion of 30.19%, C under the preferred conditions2 +The hydrocarbon selectivity was 60.43%. CN103657640A discloses a supported catalyst using barium titanate as a carrier, C2 +The hydrocarbon yield can reach 24%. Although these catalysts perform better, there is a clear gap from commercial use, the catalystsThere is still room for improvement in performance. The analysis reason is that the mutual fusion of the components is not tight enough, and the crystal transformation ratio of the carrier silicon dioxide is serious, so that the catalyst has poor heat resistance and poor stability, and is still a negative factor for industrial application. Therefore, there is a need for improved preparation of SiO by addition of auxiliaries2The carrier modification and other modes promote the synergistic effect between the active components and inhibit the deep crystallization of the carrier.
Disclosure of Invention
The invention aims to provide a method for preparing C by oxidative coupling of methane2+A hydrocarbon supported multicomponent transition metal catalyst, a preparation method and an application thereof, which solve the problems of the catalyst.
The technical scheme adopted by the invention is as follows: a supported methane oxidative coupling catalyst, which is prepared from WO3And MnO2As active ingredient, with M1Adding an alkali metal additive M as a structural additive2Active components, structural assistant and alkali metal assistant are loaded on SiO carrier2@Al2O3The composition of the catalyst is M1-M2-WO3-MnO2/SiO2@Al2O3。
Structural assistant M1Is one of rare earth metals La, Ce and Y.
Alkali metal auxiliary M2Is one of Li, Na and K.
In the supported methane oxidative coupling catalyst, an active component WO32.0-20.0% by mass of the carrier, MnO21.0-10.0% of the mass of the rare earth additive M1With active ingredient WO3Molar ratio M1：WO3=0.01 to 0.1: 1.0 alkali metal auxiliary M2The mass of the carrier is 0.1-10.0% of the mass of the carrier, and the carrier is SiO2@Al2O3The mass ratio of the medium silicon dioxide to the alumina is 1: 0.19 to 3.4.
The preparation method of the supported methane oxidative coupling catalyst comprises the following steps
(1) Mixing alumina and absolute ethyl alcohol according to a mass ratio of 1: 10 to 100 in proportionMixing, adjusting the pH value to 8.0-10.0 by using ammonia water after uniformly stirring, continuously stirring until the pH value is 10-120 minutes after uniform dispersion, and then performing ultrasonic treatment according to the molar ratio of TEOS: al (Al)2O3= 1: adding tetraethoxysilane into the mixture according to the proportion of 1-10, and continuously stirring the mixture for 30-120 minutes; coating the step with tetraethoxysilane for 5-20 times, washing the obtained sample to be neutral by using absolute ethyl alcohol, drying, roasting at 500-800 ℃ for 1-12 hours to obtain SiO with a core-shell structure2@Al2O3A carrier;
(2) mixing a surfactant, a cosurfactant and an oil phase according to a mass ratio of 2-4: 1: 1-0.5, and uniformly stirring to form an oil phase solution A;
(3) soluble tungsten-containing salt and manganese salt are mixed according to the mass ratio W: mn = 1: dissolving the mixture in deionized water in a ratio of 0.05-5, stirring the mixture uniformly, and adding citric acid to ensure that the total molar ratio of the citric acid to metal atoms is 3-20: 1, stirring uniformly, adding soluble rare earth metal salt, and continuously stirring uniformly to form a mixed solution B;
(4) dropwise adding the mixed solution B into the oil phase solution A obtained in the step (2) at the speed of 2-20 mL/min, stirring while dropwise adding, and after stirring uniformly, adding the SiO obtained in the step (1)2@Al2O3The carrier is stirred to be uniform to form a microemulsion system;
(5) preparing 0.1-1.0 mol/L alkaline solution, and then dropwise adding the solution to the microemulsion system formed in the step (4) until the pH value is 8.0-11.0;
(6) aging the sample obtained in the step (5) at 25-80 ℃ for 1-24 hours, separating the sample for 5-30 minutes by a centrifuge of 1000-5000 r/min, washing the sample with absolute ethyl alcohol until no obvious oil phase and surfactant exist on the surface of the precipitate, and washing the precipitate with distilled water until the precipitate is neutral;
(7) dissolving soluble alkali metal salt in distilled water with the same volume as the precipitate obtained in the step (6), adding the precipitate obtained in the step (6), stirring into paste, drying, and roasting at 700-900 ℃ for 1-12 hours to obtain M-WO3-MnO2/SiO2@Al2O3A catalyst.
The alumina in the step (1) is activated alumina with the particle size within the range of 5-150 nanometers.
SiO of core-shell structure in step (1)2@Al2O3The carrier is a composite carrier formed by coating a silicon dioxide layer with the thickness of 1.0-10.0 nanometers on the surface of active aluminum oxide within the range of 5-150 nanometers.
The surfactant in the step (2) is one of cetyl trimethyl ammonium bromide CTAB, dioctadecyl dimethyl ammonium chloride DODMAC, polyethylene glycol octyl phenyl ether Triton X-100, dioctyl sodium sulfosuccinate AOT, sodium dodecyl sulfate SDS, sodium dodecyl benzene sulfonate DBS and lauryl polyoxyethylene sodium sulfate AES.
The cosurfactant in the step (2) is one of n-butyl alcohol, n-amyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decyl alcohol and n-dodecyl alcohol.
The oil phase in the step (2) is one of hexane, heptane, octane, cyclohexane, cycloheptane or cyclooctane.
And (4) the soluble tungsten-containing salt in the step (3) is one of sodium tungstate, potassium tungstate or ammonium tungstate.
The soluble manganese salt in the step (3) is one of manganese nitrate, manganese acetate, manganese chloride or manganese sulfate.
The soluble rare earth additive salt in the step (3) is one of soluble lanthanum nitrate, lanthanum acetate, lanthanum chloride, cerium nitrate, ammonium ceric nitrate, cerium acetate, cerium chloride, yttrium nitrate, yttrium acetate and yttrium chloride.
And (5) the alkaline solution is one of sodium carbonate, potassium carbonate or ammonia water.
The soluble alkali metal salt in the step (7) is soluble salt of one of Li, Na and K.
Application of supported methane oxidative coupling catalyst in preparation of C through methane oxidative coupling2+In the hydrocarbon reaction, the conditions applied are: reaction feed gas CH4/O2The ratio is 10.0-2.0, the reaction pressure is normal pressure, the reaction temperature is 700-900 ℃, and the airspeed of the reaction gas is 5000-100000 mL-g-1·h-1。
Compared with the prior art, the invention has the following advantages:
(1) the active component WO can be prepared by adopting a preparation method combining sol-gel and microemulsion3And MnO2The contact at the atomic level is beneficial to the mutual cooperation among atoms, improves the performance of the catalyst, enables the action between the active components and the silicon dioxide to be more compact, delays the loss and sintering of the active phase and prolongs the service life of the catalyst. Meanwhile, the addition of the rare earth metal auxiliary agent further promotes the interaction between the active components and the carrier, so that the catalytic performance can be improved, and the service life of the catalyst can be prolonged.
(2) SiO with core-shell structure formed by supporting silicon dioxide by alumina2@Al2O3On one hand, the alumina can stabilize the structure of the silicon dioxide and inhibit the deep crystallization of the silicon dioxide; on the other hand, the core-shell structure can avoid the exposure of acid sites to alumina and prevent C2Secondary oxidation of hydrocarbons.
(3) Compared with the prior conventional catalyst, the M-WO prepared by adopting the combined method3-MnO2/SiO2@Al2O3The catalyst is added with a small amount of rare earth metal in the sol-gel process, so that the activation temperature is low, the heat resistance is good, the methane oxidative coupling reaction can be carried out in a wider range, and the catalyst has a good application prospect.
Detailed Description
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1:
mixing activated alumina with the particle size of 5nm and absolute ethyl alcohol according to the mass ratio of 1: 100, uniformly stirring, adjusting the pH value to 8.0 by using ammonia water, continuously stirring until the pH value is uniformly dispersed, performing ultrasonic treatment for 10 minutes, and then mixing the components according to the weight ratio of TEOS: al (Al)2O3= 1: 10 (molar ratio), adding tetraethoxysilane, and continuing stirring for 30 minutes; the tetraethyl orthosilicate coating step is repeated for 5 times. Washing the obtained sample with anhydrous ethanol to neutrality, drying, and roasting at 500 deg.C for 12 hr to obtain coreSiO of shell structure2@Al2O3The carrier and the characterization result show that SiO is contained2The thickness of the layer is about 2.5 nm, SiO2With Al2O3The mass ratio of (1): 3.2. and mixing a surfactant CTAB, a cosurfactant n-butanol and oil phase hexane according to the weight ratio of 2: 1: 1 (mass ratio), and uniformly stirring to form an oil phase solution; taking sodium tungstate and manganese nitrate according to WO3：MnO2= 1: 0.05 (mass ratio) is dissolved in deionized water, and after the mixture is stirred to be uniform, the weight ratio of citric acid: total metal atoms = 3: 1 (molar ratio), adding citric acid, stirring uniformly, and adding La: WO3= 0.01: 1.0, adding lanthanum nitrate, and continuously stirring uniformly to form a mixed solution; dripping the solution into the oil phase solution at a speed of 2mL/min while stirring, and after stirring uniformly, adding into a solvent according to WO3And MnO2The SiO obtained above was added in an amount of 20.0% and 1.0% relative to the mass of the support2@Al2O3And stirring uniformly to form a microemulsion system. And (3) preparing 0.1mol/L sodium carbonate solution, and then dropwise adding the solution to the microemulsion system until the pH value is 8.0. The obtained sample is aged for 24 hours at 25 ℃, separated for 30 minutes by a centrifuge of 1000r/min, washed by absolute ethyl alcohol until no obvious oil phase and surface active agent exist on the surface of the precipitate, and then washed by distilled water until the precipitate is neutral. Lithium nitrate is made to correspond to SiO2@Al2O3Dissolving 0.1% (by metal atom mass) of the carrier in distilled water with the same volume as the precipitate, adding the obtained precipitate, stirring to obtain paste, drying, and roasting at 700 deg.C for 12 hr to obtain Li-La-WO3-MnO2/SiO2@Al2O3A catalyst. The oxidative coupling reaction of methane is carried out on a fixed bed quartz tube reactor under the reaction condition of CH4/O2The volume ratio is 2.0, the reaction pressure is normal pressure, the reaction temperature is 850 ℃, and the space velocity is 5000mL g-1·h-1. The reaction results are shown in Table 1.
Example 2:
mixing activated alumina with the particle size of 20nm and absolute ethyl alcohol according to the mass ratio of 1: mixing at a ratio of 50, stirring, and adjusting pH to8.5, continuously stirring until the dispersion is uniform, then carrying out ultrasonic treatment for 30 minutes, and then carrying out ultrasonic treatment according to the weight ratio of TEOS: al (Al)2O3= 1: 10 (molar ratio), adding tetraethoxysilane, and continuing stirring for 60 minutes; the tetraethyl orthosilicate coating step was repeated 20 times. Washing the obtained sample with absolute ethyl alcohol to be neutral, drying, and roasting at 600 ℃ for 6 hours to obtain SiO with a core-shell structure2@Al2O3The carrier and the characterization result show that SiO is contained2The thickness of the layer is about 5.5 nm, SiO2With Al2O3The mass ratio of (1): 0.9. and adding surfactant DODMAC, cosurfactant n-amyl alcohol and oil phase heptane according to the weight ratio of 3: 1: 0.75 (mass ratio), and uniformly stirring to form an oil phase solution; taking potassium tungstate and manganese acetate according to WO3：MnO2= 1: 0.1 (mass ratio) is dissolved in deionized water, and after the mixture is stirred to be uniform, the weight ratio of citric acid: total metal atoms = 5: 1 (molar ratio), adding citric acid, stirring uniformly, and adding La: WO3= 0.02: 1.0, adding lanthanum acetate, and continuously stirring uniformly to form a mixed solution; dripping the solution into the oil phase solution at a speed of 4mL/min while stirring, and after stirring uniformly, adding into a solvent according to WO3And MnO2The SiO obtained above was added in an amount of 20.0% and 2.0% relative to the mass of the support2@Al2O3And stirring uniformly to form a microemulsion system. And (3) preparing 0.2mol/L potassium carbonate solution, and then dropwise adding the solution to the microemulsion system until the pH value is 9.0. The obtained sample is aged for 12 hours at 40 ℃, separated for 20 minutes by a 2000r/min centrifugal machine, washed by absolute ethyl alcohol until no obvious oil phase and surface active agent exist on the surface of the precipitate, and then washed by distilled water until the precipitate is neutral. Sodium nitrate is added to SiO2@Al2O3Dissolving 0.5% (by metal atom mass) of the carrier in distilled water with the same volume as the precipitate, adding the obtained precipitate, stirring to obtain paste, drying, and roasting at 750 deg.C for 8 hr to obtain Na-La-WO3-MnO2/SiO2@Al2O3A catalyst. The oxidative coupling reaction of methane is carried out on a fixed bed quartz tube reactor under the reaction condition of CH4/O2Volume ratio of 3.0 and reaction pressure ofNormal pressure, reaction temperature of 800 deg.c and space velocity of 8000mL g-1·h-1. The reaction results are shown in Table 1.
Example 3:
mixing activated alumina with the particle size of 20nm and absolute ethyl alcohol according to the mass ratio of 1: 50, uniformly stirring, adjusting the pH value to 9.0 by using ammonia water, continuously stirring until the pH value is uniformly dispersed, performing ultrasonic treatment for 60 minutes, and then mixing the components according to the weight ratio of TEOS: al (Al)2O3= 1: 5 (molar ratio), adding tetraethoxysilane, and continuing stirring for 60 minutes; the tetraethyl orthosilicate coating step was repeated 10 times. Washing the obtained sample with absolute ethyl alcohol to be neutral, drying, and roasting at 700 ℃ for 3 hours to obtain SiO with a core-shell structure2@Al2O3The carrier and the characterization result show that SiO is contained2The thickness of the layer is about 4.9 nm, SiO2With Al2O3The mass ratio of (1): 0.88. and adding surfactant Triton X-100, cosurfactant n-hexanol and oil phase octane according to the weight ratio of 3: 1: 0.8 (mass ratio), and uniformly stirring to form an oil phase solution; taking potassium tungstate and manganese acetate according to WO3：MnO2= 1: 0.5 (mass ratio) is dissolved in deionized water, and after the mixture is stirred to be uniform, the weight ratio of citric acid: total metal atoms = 10: 1 (molar ratio), adding citric acid, stirring uniformly, and adding La: WO3= 0.05: 1.0, adding lanthanum chloride, and continuously stirring uniformly to form a mixed solution; dripping the solution into oil phase solution at a rate of 5mL/min while stirring, and stirring uniformly according to WO3And MnO2The SiO obtained above was added in an amount of 10.0% and 5.0% relative to the mass of the support2@Al2O3And stirring uniformly to form a microemulsion system. 0.5mol/L ammonia water is prepared, and then the mixture is dripped into the microemulsion system until the pH value is 9.5. The obtained sample is aged for 12 hours at 50 ℃, is separated for 20 minutes by a centrifuge with 3000r/min, is washed by absolute ethyl alcohol until no obvious oil phase and surface active agent exist on the surface of the precipitate, and is washed by distilled water until the precipitate is neutral. Relative to SiO to potassium nitrate2@Al2O3Dissolving 1.0% (by metal atom mass) of the carrier in distilled water of the same volume as the precipitate, and adding the precipitatePrecipitating, stirring to obtain paste, drying, and calcining at 800 deg.C for 6 hr to obtain K-La-WO3-MnO2/SiO2@Al2O3A catalyst. The oxidative coupling reaction of methane is carried out on a fixed bed quartz tube reactor under the reaction condition of CH4/O2The volume ratio is 5.0, the reaction pressure is normal pressure, the reaction temperature is 800 ℃, and the space velocity is 20000 mL-g-1·h-1. The reaction results are shown in Table 1.
Example 4:
mixing activated alumina with the particle size of 50nm and absolute ethyl alcohol according to the mass ratio of 1: 20, uniformly stirring, adjusting the pH value to 9.5 by using ammonia water, continuously stirring until the pH value is uniformly dispersed, performing ultrasonic treatment for 60 minutes, and then mixing the components according to the weight ratio of TEOS: al (Al)2O3= 1: 4 (molar ratio), adding tetraethoxysilane, and continuing stirring for 90 minutes; the tetraethyl orthosilicate coating step was repeated 10 times. Washing the obtained sample with absolute ethyl alcohol to neutrality, drying, and roasting at 750 ℃ for 2 hours to obtain SiO with a core-shell structure2@Al2O3The carrier and the characterization result show that SiO is contained2The thickness of the layer is about 3.0 nm, SiO2With Al2O3The mass ratio of (1): 0.7. and adding a surfactant AOT, a cosurfactant n-heptanol and oil-phase cyclohexane according to the weight ratio of 4: 1: 0.5 (mass ratio), and uniformly stirring to form an oil phase solution; taking ammonium tungstate and manganese chloride according to WO3：MnO2= 1: 1 (mass ratio) is dissolved in deionized water, and after the mixture is stirred to be uniform, the weight ratio of citric acid: total metal atoms = 10: 1 (molar ratio), adding citric acid, stirring uniformly, and adding Ce: WO3= 0.05: adding cerium nitrate according to the proportion (molar ratio) of 1.0, and continuously stirring uniformly to form a mixed solution; dripping the solution into oil phase solution at a rate of 10mL/min while stirring, and stirring uniformly according to WO3And MnO2SiO obtained as described above was added in an amount of 5.0% and 5.0% with respect to the mass of the support2@Al2O3And stirring uniformly to form a microemulsion system. 1mol/L ammonia water is prepared, and then the ammonia water is dripped into the microemulsion system until the pH value is 10.0. The obtained sample is aged at 60 deg.C for 10 hr, and centrifuged at 3000r/min for 10mAfter in, washing the precipitate with absolute ethyl alcohol until no obvious oil phase and surfactant exist on the surface of the precipitate, and then washing the precipitate with distilled water until the precipitate is neutral. Lithium acetate is made to correspond to SiO2@Al2O3Dissolving 0.2% of the carrier (calculated by metal atom mass) in distilled water with the same volume as the precipitate, adding the obtained precipitate, stirring into paste, drying, and roasting at 800 deg.C for 3 hr to obtain Li-Ce-WO3-MnO2/SiO2@Al2O3A catalyst. The oxidative coupling reaction of methane is carried out on a fixed bed quartz tube reactor under the reaction condition of CH4/O2The volume ratio is 8.0, the reaction pressure is normal pressure, the reaction temperature is 750 ℃, and the space velocity is 50000mL g-1·h-1. The reaction results are shown in Table 1.
Example 5:
mixing active alumina with the particle size of 60nm and absolute ethyl alcohol according to the mass ratio of 1: 100, uniformly stirring, adjusting the pH value to 10.0 by using ammonia water, continuously stirring until the pH value is uniformly dispersed, performing ultrasonic treatment for 120 minutes, and then mixing the components according to the weight ratio of TEOS: al (Al)2O3= 1: 6 (molar ratio), adding tetraethoxysilane, and continuing stirring for 90 minutes; the tetraethyl orthosilicate coating step is repeated for 8 times. Washing the obtained sample with absolute ethyl alcohol to be neutral, drying, and roasting at 800 ℃ for 1 hour to obtain SiO with a core-shell structure2@Al2O3The carrier and the characterization result show that SiO is contained2The thickness of the layer is about 1.6 nm, SiO2With Al2O3The mass ratio of (1): 1.3. and adding a surfactant SDS, a cosurfactant n-octanol and an oil phase cycloheptane into the mixture according to the weight ratio of 4: 1: 0.6 (mass ratio), and uniformly stirring to form an oil phase solution; taking ammonium tungstate and manganese sulfate according to WO3：MnO2= 1: 2 (mass ratio) is dissolved in deionized water, and after the mixture is stirred to be uniform, the mixture is stirred according to the following ratio of citric acid: total metal atoms = 20: 1 (molar ratio), adding citric acid, stirring uniformly, and adding Ce: WO3= 0.05: adding ammonium ceric nitrate in a proportion (molar ratio) of 1.0, and continuously stirring uniformly to form a mixed solution; dripping the solution into the oil phase solution at a rate of 20mL/min while stirring, and stirring uniformly according to WO3And MnO2The SiO obtained above was added in an amount of 3.0% and 6.0% relative to the mass of the support2@Al2O3And stirring uniformly to form a microemulsion system. And preparing 1mol/L sodium carbonate solution, and then dropwise adding the solution to the microemulsion system until the pH value is 10.0. Aging the obtained sample at 80 deg.C for 3 hr, centrifuging at 5000r/min for 5min, washing with anhydrous ethanol until no obvious oil phase and surfactant are on the surface of precipitate, and washing with distilled water to neutrality. Sodium acetate is made to correspond to SiO2@Al2O3Dissolving 0.75% of the carrier (calculated by metal atom mass) in distilled water with the same volume as the precipitate, adding the obtained precipitate, stirring to obtain paste, drying, and roasting at 850 deg.C for 2 hr to obtain Na-Ce-WO3-MnO2/SiO2@Al2O3A catalyst. The oxidative coupling reaction of methane is carried out on a fixed bed quartz tube reactor under the reaction condition of CH4/O2The volume ratio is 2.5, the reaction pressure is normal pressure, the reaction temperature is 700 ℃, and the space velocity is 30000mL g-1·h-1. The reaction results are shown in Table 1.
Example 6:
mixing active alumina with the particle size of 100nm and absolute ethyl alcohol according to the mass ratio of 1: 100, uniformly stirring, adjusting the pH value to 10.0 by using ammonia water, continuously stirring until the pH value is uniformly dispersed, performing ultrasonic treatment for 120 minutes, and then mixing the components according to the weight ratio of TEOS: al (Al)2O3= 1: 2 (molar ratio), adding tetraethoxysilane, and continuing stirring for 120 minutes; the tetraethyl orthosilicate coating step was repeated 20 times. Washing the obtained sample with absolute ethyl alcohol to be neutral, drying, and roasting at 800 ℃ for 1 hour to obtain SiO with a core-shell structure2@Al2O3The carrier and the characterization result show that SiO is contained2The thickness of the layer is about 10.0 nm, SiO2With Al2O3The mass ratio of (1): 0.19. and mixing surfactant DBS, cosurfactant n-decyl alcohol and oil phase cyclooctane according to the weight ratio of 3.6: 1: 0.7 (mass ratio), and uniformly stirring to form an oil phase solution; taking ammonium tungstate and manganese nitrate according to WO3：MnO2= 1: 5 (mass ratio) is dissolved in deionized water, and after the mixture is stirred to be uniform, the weight ratio of citric acid:total metal atoms = 20: 1 (molar ratio), adding citric acid, stirring uniformly, and adding Ce: WO3= 0.01: adding cerium acetate in a proportion (molar ratio) of 1.0, and continuously stirring uniformly to form a mixed solution; dripping the solution into oil phase solution at a rate of 10mL/min while stirring, and stirring uniformly according to WO3And MnO2The SiO obtained above was added at 2.0% and 10.0% with respect to the mass of the support2@Al2O3And stirring uniformly to form a microemulsion system. And (3) preparing 0.5mol/L potassium carbonate solution, and then dropwise adding the solution to the microemulsion system until the pH value is 11.0. Aging the obtained sample at 80 deg.C for 1 hr, centrifuging at 5000r/min for 5min, washing with anhydrous ethanol until no obvious oil phase and surfactant are on the surface of precipitate, and washing with distilled water to neutrality. Relative to SiO, potassium acetate2@Al2O3Dissolving 5% of carrier (calculated by metal atom mass) in distilled water with the same volume as the precipitate, adding the obtained precipitate, stirring to obtain paste, drying, and roasting at 900 deg.C for 1 hr to obtain K-Ce-WO3-MnO2/SiO2@Al2O3A catalyst. The oxidative coupling reaction of methane is carried out on a fixed bed quartz tube reactor under the reaction condition of CH4/O2The volume ratio is 12.0, the reaction pressure is normal pressure, the reaction temperature is 900 ℃, and the space velocity is 60000 mL-g-1·h-1. The reaction results are shown in Table 1.
Example 7:
mixing active alumina with the particle size of 10nm and absolute ethyl alcohol according to the mass ratio of 1: 10, uniformly stirring, adjusting the pH value to 8.5 by using ammonia water, continuously stirring until the pH value is uniformly dispersed, performing ultrasonic treatment for 20 minutes, and then mixing the components according to the weight ratio of TEOS: al (Al)2O3= 1: 2 (molar ratio), adding tetraethoxysilane, and continuing stirring for 30 minutes; the tetraethyl orthosilicate coating step is repeated for 15 times. Washing the obtained sample with absolute ethyl alcohol to be neutral, drying, and roasting at 600 ℃ for 6 hours to obtain SiO with a core-shell structure2@Al2O3The carrier and the characterization result show that SiO is contained2The thickness of the layer is about 6.2 nm, SiO2With Al2O3Quality of (1)The quantity ratio is 1: 0.24. and mixing surfactant AES, cosurfactant n-dodecanol and oil-phase hexane according to the weight ratio of 2: 1: 1 (mass ratio), and uniformly stirring to form an oil phase solution; taking sodium tungstate and manganese acetate according to WO3：MnO2= 1: 0.3 (mass ratio) is dissolved in deionized water, and after the mixture is stirred to be uniform, the weight ratio of citric acid: total metal atoms = 6: 1 (molar ratio), adding citric acid, stirring uniformly, and adding Ce: WO3= 0.02: adding cerium chloride in a proportion (molar ratio) of 1.0, and continuously stirring uniformly to form a mixed solution; dripping the solution into the oil phase solution at a speed of 4mL/min while stirring, and after stirring uniformly, adding into a solvent according to WO3And MnO2SiO obtained as described above was added in an amount of 5.0% and 1.5% relative to the mass of the support2@Al2O3And stirring uniformly to form a microemulsion system. And (3) preparing 0.5mol/L potassium carbonate solution, and then dropwise adding the solution to the microemulsion system until the pH value is 9.0. The obtained sample is aged for 6 hours at 40 ℃, is separated for 10 minutes by a 2500r/min centrifuge, is washed by absolute ethyl alcohol until no obvious oil phase and surfactant exist on the surface of the precipitate, and is washed by distilled water until the precipitate is neutral. Sodium nitrate is added to SiO2@Al2O3Dissolving 0.75% of the carrier (calculated by metal atom mass) in distilled water with the same volume as the precipitate, adding the obtained precipitate, stirring to obtain paste, drying, and roasting at 800 deg.C for 3 hr to obtain Na-Ce-WO3-MnO2/SiO2@Al2O3A catalyst. The oxidative coupling reaction of methane is carried out on a fixed bed quartz tube reactor under the reaction condition of CH4/O2The volume ratio is 3.0, the reaction pressure is normal pressure, the reaction temperature is 800 ℃, and the space velocity is 8000mL g-1·h-1. The reaction results are shown in Table 1.
Example 8:
mixing active alumina with the particle size of 10nm and absolute ethyl alcohol according to the mass ratio of 1: 20, uniformly stirring, adjusting the pH value to 9.0 by using ammonia water, continuously stirring until the pH value is uniformly dispersed, performing ultrasonic treatment for 60 minutes, and then mixing the components according to the weight ratio of TEOS: al (Al)2O3= 1: 5 (molar ratio), adding tetraethoxysilane, and continuing stirring for 60 minutes; heavy loadAnd (4) coating by using tetraethoxysilane for 15 times. Washing the obtained sample with absolute ethyl alcohol to neutrality, drying, and roasting at 700 ℃ for 4 hours to obtain SiO with a core-shell structure2@Al2O3The carrier and the characterization result show that SiO is contained2The thickness of the layer is about 5.1 nm, SiO2With Al2O3The mass ratio of (1): 0.58. and mixing a surfactant CTAB, a cosurfactant n-butanol and oil phase heptane according to the weight ratio of 3.6: 1: 0.7 (mass ratio), and uniformly stirring to form an oil phase solution; taking ammonium tungstate and manganese sulfate according to WO3：MnO2= 1: 0.3 (mass ratio) is dissolved in deionized water, and after the mixture is stirred to be uniform, the weight ratio of citric acid: total metal atoms = 6: 1 (molar ratio), adding citric acid, uniformly stirring, and adding the mixture according to the weight ratio of Y: WO3= 0.02: adding yttrium nitrate according to the proportion (molar ratio) of 1.0, and continuously stirring uniformly to form a mixed solution; dripping the solution into oil phase solution at a rate of 3mL/min while stirring, and stirring uniformly according to WO3And MnO2SiO obtained as described above was added in an amount of 5.0% and 1.5% relative to the mass of the support2@Al2O3And stirring uniformly to form a microemulsion system. And (3) preparing 0.5mol/L sodium carbonate solution, and then dropwise adding the solution to the microemulsion system until the pH value is 9.5. The obtained sample is aged for 6 hours at 60 ℃, is separated for 10 minutes by a 2500r/min centrifuge, is washed by absolute ethyl alcohol until no obvious oil phase and surfactant exist on the surface of the precipitate, and is washed by distilled water until the precipitate is neutral. Sodium acetate is made to correspond to SiO2@Al2O3Dissolving 1.0% (by metal atom mass) of the carrier in distilled water with the same volume as the precipitate, adding the obtained precipitate, stirring to obtain paste, drying, and roasting at 850 deg.C for 3 hr to obtain Na-Y-WO3-MnO2/SiO2@Al2O3A catalyst. The oxidative coupling reaction of methane is carried out on a fixed bed quartz tube reactor under the reaction condition of CH4/O2The volume ratio is 3.0, the reaction pressure is normal pressure, the reaction temperature is 800 ℃, and the space velocity is 8000mL g-1·h-1. The reaction results are shown in Table 1.
Example 9:
mixing active alumina with the particle size of 60nm and absolute ethyl alcohol according to the mass ratio of 1: 60, uniformly stirring, adjusting the pH value to 9.5 by using ammonia water, continuously stirring until the pH value is uniformly dispersed, performing ultrasonic treatment for 90 minutes, and then mixing the components according to the weight ratio of TEOS: al (Al)2O3= 1: 1 (molar ratio), adding tetraethoxysilane, and continuing stirring for 120 minutes; the tetraethyl orthosilicate coating step is repeated for 5 times. Washing the obtained sample with absolute ethyl alcohol to be neutral, drying, and roasting at 550 ℃ for 9 hours to obtain SiO with a core-shell structure2@Al2O3The carrier and the characterization result show that SiO is contained2The thickness of the layer is about 4.8 nm, SiO2With Al2O3The mass ratio of (1): 0.35. and adding surfactant DODMAC, cosurfactant n-amyl alcohol and oil phase octane according to the weight ratio of 4: 1: 1 (mass ratio), and uniformly stirring to form an oil phase solution; taking potassium tungstate and manganese nitrate according to WO3：MnO2= 1: 1 (mass ratio) is dissolved in deionized water, and after the mixture is stirred to be uniform, the weight ratio of citric acid: total metal atoms = 5: 1 (molar ratio) adding citric acid, and uniformly stirring to form a mixed solution; dripping the solution into oil phase solution at a rate of 5mL/min while stirring, and stirring uniformly according to WO3And MnO2The SiO obtained above was added in an amount of 10.0% and 10.0% relative to the mass of the support2@Al2O3Stirring uniformly according to the proportion of Y: WO3= 0.1: adding yttrium acetate in the proportion (molar ratio) of 1.0, and continuously stirring uniformly to form a microemulsion system. 0.1mol/L ammonia water is prepared, and then the mixture is dripped into the microemulsion system until the pH value is 10.0. The obtained sample is aged for 12 hours at 50 ℃, is separated for 10 minutes by a centrifuge with 3000r/min, is washed by absolute ethyl alcohol until no obvious oil phase and surface active agent exist on the surface of the precipitate, and is washed by distilled water until the precipitate is neutral. Sodium nitrate is added to SiO2@Al2O3Dissolving 10.0% (by metal atom mass) of the carrier in distilled water with the same volume as the precipitate, adding the obtained precipitate, stirring to obtain paste, drying, and roasting at 800 deg.C for 6 hr to obtain Na-Y-WO3-MnO2/SiO2@Al2O3A catalyst. Oxidative coupling of methaneThe reaction is carried out on a fixed bed quartz tube reactor under the reaction condition of CH4/O2The volume ratio is 8.0, the reaction pressure is normal pressure, the reaction temperature is 850 ℃, and the space velocity is 100000 mL-g-1·h-1. The reaction results are shown in Table 1.
Example 10:
mixing activated alumina with the particle size of 150nm and absolute ethyl alcohol according to the mass ratio of 1: 100, uniformly stirring, adjusting the pH value to 9.5 by using ammonia water, continuously stirring until the pH value is uniformly dispersed, performing ultrasonic treatment for 120 minutes, and then mixing the components according to the weight ratio of TEOS: al (Al)2O3= 1: 10 (molar ratio), adding tetraethoxysilane, and continuing stirring for 120 minutes; the tetraethyl orthosilicate coating step is repeated for 5 times. Washing the obtained sample with absolute ethyl alcohol to be neutral, drying, and roasting at 550 ℃ for 6 hours to obtain SiO with a core-shell structure2@Al2O3The carrier and the characterization result show that SiO is contained2The thickness of the layer is about 1.0 nm, SiO2With Al2O3The mass ratio of (1): 3.4. and adding surfactant Triton X-100, cosurfactant hexanol and oil-phase cyclohexane according to the weight ratio of 3: 1: 1 (mass ratio), and uniformly stirring to form an oil phase solution; taking sodium tungstate and manganese nitrate according to WO3：MnO2= 1: 0.5 (mass ratio) is dissolved in deionized water, and after the mixture is stirred to be uniform, the weight ratio of citric acid: total metal atoms = 3: 1 (molar ratio), adding citric acid, uniformly stirring, and adding the mixture according to the weight ratio of Y: WO3= 0.075: adding yttrium chloride in a proportion (molar ratio) of 1.0, and continuously stirring uniformly to form a mixed solution; dripping the solution into oil phase solution at a rate of 3mL/min while stirring, and stirring uniformly according to WO3And MnO2The SiO obtained above was added at 2.0% and 1.0% with respect to the mass of the support2@Al2O3And stirring uniformly to form a microemulsion system. 0.5mol/L ammonia water is prepared, and then the mixture is dripped into the microemulsion system until the pH value is 8.0. The obtained sample is aged for 24 hours at 20 ℃, separated for 5 minutes by a centrifuge with the speed of 5000r/min, washed by absolute ethyl alcohol until no obvious oil phase and surface active agent exist on the surface of the precipitate, and then washed by distilled water until the precipitate is neutral. Sodium acetate is made to correspond to SiO2@Al2O3Dissolving 10.0% (by metal atom mass) of the carrier in distilled water with the same volume as the precipitate, adding the obtained precipitate, stirring to obtain paste, drying, and roasting at 850 deg.C for 4 hr to obtain Na-Y-WO3-MnO2/SiO2@Al2O3A catalyst. The oxidative coupling reaction of methane is carried out on a fixed bed quartz tube reactor under the reaction condition of CH4/O2The volume ratio is 3.0, the reaction pressure is normal pressure, the reaction temperature is 800 ℃, and the space velocity is 8000mL g-1·h-1. The reaction results are shown in Table 1.
Comparative example 1:
mixing a surfactant, a cosurfactant and an oil phase according to the weight ratio of 3.6: 1: 0.7 (mass ratio), and uniformly stirring to form an oil phase solution; taking ammonium tungstate and manganese nitrate according to WO3：MnO2= 1: 0.3 (mass ratio) is dissolved in deionized water, and after the mixture is stirred to be uniform, the weight ratio of citric acid: total metal atoms = 6: 1 (molar ratio) adding citric acid, and uniformly stirring to form a mixed solution; dripping the solution into oil phase solution at a rate of 3mL/min while stirring, and stirring uniformly according to WO3And MnO2Adding silicon dioxide with particle size of 10nm into the carrier with a mass ratio of 5.0% and 1.5%, and stirring to obtain microemulsion system. And (3) preparing 0.5mol/L sodium carbonate solution, and then dropwise adding the solution to the microemulsion system until the pH value is 9.5. The obtained sample is aged for 6 hours at 60 ℃, is separated for 10 minutes by a 2500r/min centrifuge, is washed by absolute ethyl alcohol until no obvious oil phase and surfactant exist on the surface of the precipitate, and is washed by distilled water until the precipitate is neutral. Sodium acetate is made to correspond to SiO2@Al2O3Dissolving 1.0% (by metal atom mass) of the carrier in distilled water with the same volume as the precipitate, adding the obtained precipitate, stirring to obtain paste, drying, and roasting at 850 deg.C for 3 hr to obtain Na-WO3-MnO2/SiO2A catalyst. The oxidative coupling reaction of methane is carried out on a fixed bed quartz tube reactor under the reaction condition of CH4/O2The volume ratio is 3.0, the reaction pressure is normal pressure, the reaction temperature is 800 ℃, and the space velocity is 8000mL g-1·h-1. The reaction results are shown in Table 1.
Comparative example 2:
dissolving manganese nitrate and yttrium nitrate in a certain amount of deionized water to ensure that MnO is21.5% by mass of support, Y: WO3= 0.02: 1.0 (molar ratio), isovolumetrically impregnating 60-80 mesh silica, drying, and mixing ammonium tungstate with the mixture3：MnO2= 1: dissolving 0.3 (corresponding oxide mass ratio) in a certain amount of deionized water, soaking the obtained sample twice in equal volume, drying, soaking the twice-soaked sample again in equal volume with sodium acetate according to 1.0% (by metal atom mass) of the carrier mass, drying, and roasting at 850 deg.C for 3 hr to obtain Na-Y-WO prepared by soaking method3-MnO2/SiO2A catalyst. The oxidative coupling reaction of methane is carried out on a fixed bed quartz tube reactor under the reaction condition of CH4/O2The volume ratio is 3.0, the reaction pressure is normal pressure, the reaction temperature is 800 ℃, and the space velocity is 8000mL g-1·h-1. The reaction results are shown in Table 1.
TABLE 1 results of catalyst reaction evaluation
*Containing 3% or less of C3And the above hydrocarbons, the same as below.
As shown in the table, the invention adopts the method of combining the sol-gel and the microemulsion to prepare the supported multi-component transition metal catalyst, and the supported multi-component transition metal catalyst is modified by the rare earth metal to show excellent reaction performance, and CH is added under the optimized condition4Conversion 38.0%, C2+Hydrocarbon selectivity 71.1%, C2+The hydrocarbon yield can reach 27.0 percent (example 8, 800 ℃); comparative example 1, in which the support contained only silica and no alumina, and was not modified with a rare earth metal, methane conversion, C2+The hydrocarbon selectivity is significantly lower than that of example 8, while the performance of the catalyst prepared by the impregnation method in comparative example 2 is much lower than that of the catalyst provided by the invention.
The stability differences between the preferred catalysts provided by the present invention and the catalysts of comparative example 1 were compared by reaction performance evaluation, and the results are shown in table 2.
TABLE 2 evaluation results of preferred catalyst stability
Reaction conditions are as follows: the temperature is 800 ℃, and the space velocity is 8000h-1，CH4/O2=3.0
As shown in the table above, the catalyst provided by the invention has good stability performance and no obvious change in performance at 200 hours on line compared with the catalyst not containing alumina in comparative example 1 due to the inhibition effect of alumina on silica crystal transformation and the promotion effect of rare earth metal.
Claims (15)
1. A supported methane oxidative coupling catalyst, characterized by: with WO3And MnO2As active ingredient, with M1Adding an alkali metal additive M as a structural additive2Active components, structural assistant and alkali metal assistant are loaded on SiO carrier2@Al2O3The composition of the catalyst is M1-M2-WO3-MnO2/SiO2@Al2O3The preparation method comprises the following steps of (1) mixing alumina and absolute ethyl alcohol according to the mass ratio of 1: 10-100, uniformly stirring, adjusting the pH value to 8.0-10.0 by using ammonia water, continuously stirring until the pH value is uniformly dispersed, performing ultrasonic treatment for 10-120 minutes, and then mixing the components in a molar ratio of TEOS: al (Al)2O3= 1: adding tetraethoxysilane into the mixture according to the proportion of 1-10, and continuously stirring the mixture for 30-120 minutes; coating the step with tetraethoxysilane for 5-20 times, washing the obtained sample to be neutral by using absolute ethyl alcohol, drying, roasting at 500-800 ℃ for 1-12 hours to obtain SiO with a core-shell structure2@Al2O3A carrier;
(2) mixing a surfactant, a cosurfactant and an oil phase according to a mass ratio of 2-4: 1: 1-0.5, and uniformly stirring to form an oil phase solution A;
(3) soluble tungsten-containing salt and manganese salt are mixed according to the mass ratio W: mn = 1: dissolving the mixture in deionized water in a ratio of 0.05-5, stirring the mixture uniformly, and adding citric acid to ensure that the total molar ratio of the citric acid to metal atoms is 3-20: 1, stirring uniformly, adding soluble rare earth metal salt, and continuously stirring uniformly to form a mixed solution B;
(4) dropwise adding the mixed solution B into the oil phase solution A obtained in the step (2) at the speed of 2-20 mL/min, stirring while dropwise adding, and after stirring uniformly, adding the SiO obtained in the step (1)2@Al2O3The carrier is stirred to be uniform to form a microemulsion system;
(5) preparing 0.1-1.0 mol/L alkaline solution, and then dropwise adding the solution to the microemulsion system formed in the step (4) until the pH value is 8.0-11.0;
(6) aging the sample obtained in the step (5) at 25-80 ℃ for 1-24 hours, separating the sample for 5-30 minutes by a centrifuge of 1000-5000 r/min, washing the sample with absolute ethyl alcohol until no obvious oil phase and surfactant exist on the surface of the precipitate, and washing the precipitate with distilled water until the precipitate is neutral;
(7) dissolving soluble alkali metal salt in distilled water with the same volume as the precipitate obtained in the step (6), adding the precipitate obtained in the step (6), stirring into paste, drying, and roasting at 700-900 ℃ for 1-12 hours to obtain M-WO3-MnO2/SiO2@Al2O3A catalyst.
2. A supported methane oxidative coupling catalyst according to claim 1, wherein: structural assistant M1Is one of rare earth metals La, Ce and Y.
3. A supported methane oxidative coupling catalyst according to claim 1, wherein: alkali metal auxiliary M2Is one of Li, Na and K.
4. The supported methane oxidative coupling catalyst of claim 1The method is characterized in that: in the supported methane oxidative coupling catalyst, an active component WO32.0-20.0% by mass of the carrier, MnO21.0-10.0% of the mass of the rare earth additive M1With active ingredient WO3Molar ratio M1：WO3=0.01 to 0.1: 1.0 alkali metal auxiliary M2The mass of the carrier is 0.1-10.0% of the mass of the carrier, and the carrier is SiO2@Al2O3The mass ratio of the medium silicon dioxide to the alumina is 1: 0.19 to 3.4.
5. A supported methane oxidative coupling catalyst according to claim 1, wherein: the alumina in the step (1) is activated alumina with the particle size within the range of 5-150 nanometers.
6. A supported methane oxidative coupling catalyst according to claim 1, wherein: SiO of core-shell structure in step (1)2@Al2O3The carrier is a composite carrier formed by coating a silicon dioxide layer with the thickness of 1.0-10.0 nanometers on the surface of active aluminum oxide within the range of 5-150 nanometers.
7. A supported methane oxidative coupling catalyst according to claim 1, wherein: the surfactant in the step (2) is one of cetyl trimethyl ammonium bromide CTAB, dioctadecyl dimethyl ammonium chloride DODMAC, polyethylene glycol octyl phenyl ether Triton X-100, dioctyl sodium sulfosuccinate AOT, sodium dodecyl sulfate SDS, sodium dodecyl benzene sulfonate DBS and lauryl polyoxyethylene sodium sulfate AES.
8. A supported methane oxidative coupling catalyst according to claim 1, wherein: the cosurfactant in the step (2) is one of n-butyl alcohol, n-amyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decyl alcohol and n-dodecyl alcohol.
9. A supported methane oxidative coupling catalyst according to claim 1, wherein: the oil phase in the step (2) is one of hexane, heptane, octane, cyclohexane, cycloheptane or cyclooctane.
10. A supported methane oxidative coupling catalyst according to claim 1, wherein: and (4) the soluble tungsten-containing salt in the step (3) is one of sodium tungstate, potassium tungstate or ammonium tungstate.
11. A supported methane oxidative coupling catalyst according to claim 1, wherein: the soluble manganese salt in the step (3) is one of manganese nitrate, manganese acetate, manganese chloride or manganese sulfate.
12. A supported methane oxidative coupling catalyst according to claim 5, wherein: the soluble rare earth additive salt in the step (3) is one of soluble lanthanum nitrate, lanthanum acetate, lanthanum chloride, cerium nitrate, ammonium ceric nitrate, cerium acetate, cerium chloride, yttrium nitrate, yttrium acetate and yttrium chloride.
13. A supported methane oxidative coupling catalyst according to claim 1, wherein: and (5) the alkaline solution is one of sodium carbonate, potassium carbonate or ammonia water.
14. A supported methane oxidative coupling catalyst according to claim 1, wherein: the soluble alkali metal salt in the step (7) is soluble salt of one of Li, Na and K.
15. A supported methane oxidative coupling catalyst according to claim 1, wherein: for preparing C by oxidative coupling of methane2+In the hydrocarbon reaction, the conditions applied are: reaction feed gas CH4/O2The ratio is 10.0-2.0, the reaction pressure is normal pressure, the reaction temperature is 700-900 ℃, and the airspeed of the reaction gas is 5000-100000 mL-g-1·h-1。
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| CN110035986A (en) * | 2016-10-31 | 2019-07-19 | 沙特基础工业全球技术公司 | The mild oxidation coupling catalyst of methane ethylene and ethane |
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| CN110035986A (en) * | 2016-10-31 | 2019-07-19 | 沙特基础工业全球技术公司 | The mild oxidation coupling catalyst of methane ethylene and ethane |
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