CN112221491A - Isobutane dehydrogenation catalyst with modified spherical mesoporous material as carrier and preparation method and application thereof - Google Patents
Isobutane dehydrogenation catalyst with modified spherical mesoporous material as carrier and preparation method and application thereof Download PDFInfo
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- CN112221491A CN112221491A CN201910581941.1A CN201910581941A CN112221491A CN 112221491 A CN112221491 A CN 112221491A CN 201910581941 A CN201910581941 A CN 201910581941A CN 112221491 A CN112221491 A CN 112221491A
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- mesoporous material
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- spherical mesoporous
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- isobutane
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- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 312
- 239000013335 mesoporous material Substances 0.000 title claims abstract description 241
- 239000001282 iso-butane Substances 0.000 title claims abstract description 156
- 239000003054 catalyst Substances 0.000 title claims abstract description 140
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 68
- 239000002243 precursor Substances 0.000 claims abstract description 60
- 238000000498 ball milling Methods 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 238000001694 spray drying Methods 0.000 claims abstract description 22
- 239000012065 filter cake Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000007598 dipping method Methods 0.000 claims abstract description 12
- 238000007725 thermal activation Methods 0.000 claims abstract description 12
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 106
- 239000011148 porous material Substances 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 238000005470 impregnation Methods 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 24
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000012159 carrier gas Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 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 3
- 230000001681 protective effect Effects 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000011777 magnesium Substances 0.000 description 61
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 59
- 239000010936 titanium Substances 0.000 description 55
- 239000000243 solution Substances 0.000 description 45
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 38
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 235000011147 magnesium chloride Nutrition 0.000 description 19
- 229910001629 magnesium chloride Inorganic materials 0.000 description 18
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 18
- 239000000047 product Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 12
- 238000011068 loading method Methods 0.000 description 12
- 229910052749 magnesium Inorganic materials 0.000 description 12
- -1 polytetrafluoroethylene Polymers 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 238000004876 x-ray fluorescence Methods 0.000 description 10
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 9
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 9
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- 101150116295 CAT2 gene Proteins 0.000 description 7
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 7
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- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
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- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000004231 fluid catalytic cracking Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010183 spectrum analysis Methods 0.000 description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 3
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000009718 spray deposition Methods 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 241001292396 Cirrhitidae Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910017299 Mo—O Inorganic materials 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 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
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- HFTSQAKJLBPKBD-UHFFFAOYSA-N magnesium;butan-1-olate Chemical compound [Mg+2].CCCC[O-].CCCC[O-] HFTSQAKJLBPKBD-UHFFFAOYSA-N 0.000 description 1
- WNJYXPXGUGOGBO-UHFFFAOYSA-N magnesium;propan-1-olate Chemical compound CCCO[Mg]OCCC WNJYXPXGUGOGBO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
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- B01J35/394—
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- B01J35/40—
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- B01J35/51—
-
- B01J35/617—
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- B01J35/635—
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- B01J35/638—
-
- B01J35/647—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
Abstract
The invention relates to the field of catalysts, and discloses an isobutane dehydrogenation catalyst with a modified spherical mesoporous material as a carrier, and a preparation method and application thereof. The method for preparing the isobutane dehydrogenation catalyst with the modified spherical mesoporous material as the carrier comprises the following steps: (a) preparing a mesoporous material filter cake; (b) sequentially carrying out template agent treatment, thermal activation treatment and ball milling treatment on the mesoporous material filter cake to obtain a spherical mesoporous material; (c) carrying out first dipping treatment on the spherical mesoporous material in a solution containing an Mg component precursor and/or a Ti component precursor, and then carrying out spray drying to obtain a modified spherical mesoporous material carrier; (d) and carrying out second dipping treatment on the modified spherical mesoporous material carrier in a solution containing a Pt component precursor and a Zn component precursor, and then sequentially carrying out solvent removal treatment, drying and roasting. The obtained isobutane dehydrogenation catalyst has better catalytic activity and carbon deposition resistance.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a method for preparing an isobutane dehydrogenation catalyst with a modified spherical mesoporous material as a carrier, the isobutane dehydrogenation catalyst with the modified spherical mesoporous material as the carrier prepared by the method and application of the isobutane dehydrogenation catalyst in preparation of isobutene through isobutane dehydrogenation.
Background
Isobutene is an important organic chemical raw material and is mainly used for preparing various organic raw materials and fine chemicals such as methyl tert-butyl ether, butyl rubber, methyl ethyl ketone, polyisobutylene, methyl methacrylate, isoprene, tert-butyl phenol, tert-butyl amine, 1, 4-butanediol, ABS resin and the like. The main sources of isobutene are the by-product C4 fraction from an apparatus for producing ethylene by steam cracking of naphtha, the by-product C4 fraction from a refinery Fluid Catalytic Cracking (FCC) apparatus, and the by-product tert-butyl alcohol (TAB) in the synthesis of propylene oxide by the Halcon method.
In recent years, with the development and utilization of downstream products of isobutene, the demand of isobutene is increased year by year, and the traditional isobutene production cannot meet the huge demand of the chemical industry on isobutene, so the research and development work of a new isobutene production technology becomes a hot spot of the chemical industry. Among the most competitive technologies, isobutane dehydrogenation, n-butene skeletal isomerization and isobutene production by a novel FCC unit are known. Among the methods, the research on the reaction for preparing isobutene by directly dehydrogenating isobutane is early, and the industrial production is realized. China has abundant C4 resources, but the chemical utilization rate of C4 fraction is low in China, most of isobutane is directly used as fuel, and the waste is serious. The reasonable utilization of C4 resource is an urgent task in the petrochemical research field. Therefore, the isobutene prepared by dehydrogenating isobutane has a great development prospect in China.
The catalysts for preparing isobutene by isobutane dehydrogenation mainly comprise two types: oxide catalysts and noble metal catalysts. The oxide catalyst mainly comprises Cr2O3、V2O5、Fe2O3、MoO3ZnO, etc., and a composite oxide thereof, such as V-Sb-O, V-Mo-O, Ni-V-O, V-Nb-O, Cr-Ce-O, molybdate, etc. Compared with noble metal catalysts, oxide catalysts are less expensive. However, the catalyst is easy to deposit carbon, and the catalytic activity, selectivity and stability are low. In addition, most oxide catalysts contain components with high toxicity, which is not favorable for environmental protection. The research on dehydrogenation reactions on noble metal catalysts has a long history, and noble metal catalysts have higher activity, better selectivity, and are more environmentally friendly than other metal oxide catalysts. However, the catalyst cost is high due to the expensive price of noble metals, and the performance of such catalysts has not yet reached a satisfactory level.
In order to improve the reaction performance of the catalyst for preparing isobutene by isobutane dehydrogenation, researchers have done a lot of work. Such as: the catalyst performance is improved by changing the preparation method of the catalyst (industrial catalysis, 2014, 22(2): 148-. However, when the improved isobutane dehydrogenation catalyst commonly used at present is used for catalyzing isobutane to dehydrogenate to prepare isobutene, the catalyst is prone to carbon deposition and deactivation, and the isobutane conversion rate and the isobutene selectivity still need to be further improved.
Therefore, how to improve the diffusion effect of raw materials and products in the reaction process of preparing isobutene by isobutane dehydrogenation and keep the activity of an isobutane dehydrogenation catalyst by a proper means so as to improve the conversion rate of isobutane and the selectivity of isobutene when the isobutane dehydrogenation catalyst catalyzes isobutene prepared by isobutane dehydrogenation is still a problem to be solved in the field of isobutene preparation by isobutane dehydrogenation.
Disclosure of Invention
The invention aims to improve the conversion rate of isobutane, the selectivity of isobutene and the stability of an isobutane dehydrogenation catalyst in the process of preparing isobutene by isobutane dehydrogenation as much as possible, and provides a method for preparing the isobutane dehydrogenation catalyst, the isobutane dehydrogenation catalyst with a modified spherical mesoporous material as a carrier prepared by the method and the application of the isobutane dehydrogenation catalyst in preparing isobutene by isobutane dehydrogenation.
In order to achieve the above object, one aspect of the present invention provides a method of preparing an isobutane dehydrogenation catalyst, the method comprising the steps of:
(a) in the presence of a template agent, contacting tetraethoxysilane with ammonia water, and crystallizing and filtering a mixture obtained after the contact to obtain a mesoporous material filter cake;
(b) sequentially carrying out template agent treatment, thermal activation treatment and ball milling treatment on the mesoporous material filter cake to obtain a spherical mesoporous material;
(c) in the presence of inert gas, carrying out first dipping treatment on the spherical mesoporous material in a solution containing a Mg component precursor and/or a Ti component precursor to obtain a slurry to be sprayed, and then carrying out spray drying on the slurry to be sprayed to obtain a modified spherical mesoporous material carrier;
(d) and carrying out second dipping treatment on the modified spherical mesoporous material carrier in a solution containing a Pt component precursor and a Zn component precursor, and then sequentially carrying out solvent removal treatment, drying and roasting.
The invention provides an isobutane dehydrogenation catalyst with a modified spherical mesoporous material as a carrier, which is prepared by the method.
The third aspect of the invention provides an application of the isobutane dehydrogenation catalyst in preparing isobutene through isobutane dehydrogenation, wherein the method for preparing isobutene through isobutane dehydrogenation comprises the following steps: isobutane was subjected to a dehydrogenation reaction in the presence of a catalyst and hydrogen.
After research, the inventor of the invention finds that the isobutane dehydrogenation catalyst prepared by loading a specific content of platinum-based active component and alkali metal and other auxiliary components has excellent catalytic activity and stability after loading a Mg component and/or a Ti component on a spherical mesoporous material by a spray drying method. The inventor guesses that the spherical mesoporous material synthesized by the high-temperature method has the advantages of nano-micro-scale size and larger specific surface area, adopts a spray drying method to uniformly load Mg components and/or Ti components on the surface of the spherical mesoporous material, modifies the spherical mesoporous material, can dilute the loaded Mg components and/or Ti components, improves the dispersion degree of subsequent active metal components on the spherical mesoporous material, obtains the Mg components and/or Ti components modified spherical mesoporous material carrier, can effectively avoid the aggregation of the active metal components when loading the active Pt components and Zn components, is beneficial to the good dispersion of the active metal components on the surface of the carrier, can also generate a radical effect or a structural effect with the Pt components, increases the activation adsorption center number of Pt, and improves the thermal stability of the Pt in hydrogen flow, the reaction activity of the active metal component for catalyzing the dehydrogenation of the isobutane and the selectivity of the product are improved. In addition, the Mg component can further adjust the acid sites on the surface of the catalyst, so that the occurrence of carbon deposition of the catalyst is further reduced, the Ti component has an empty d orbit to generate strong interaction with isobutene, and compete for isobutene with Pt active sites, so that the isobutene is promoted to be desorbed from the Pt surface, and the yield of the isobutene and the conversion rate of the isobutane are improved. Therefore, the catalyst prepared by the method provided by the invention can obtain better dehydrogenation activity, isobutane conversion rate, isobutene selectivity, stability and carbon deposition resistance under the condition of very low noble metal loading.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an X-ray diffraction pattern of the spherical mesoporous material P1 of example 1;
FIG. 2 is an SEM scanning electron micrograph of the micro-morphology of the modified spherical mesoporous material carrier C1 of example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As previously described, a first aspect of the present invention provides a method for preparing an isobutane dehydrogenation catalyst, the method comprising the steps of:
(a) in the presence of a template agent, contacting tetraethoxysilane with ammonia water, and crystallizing and filtering a mixture obtained after the contact to obtain a mesoporous material filter cake;
(b) sequentially carrying out template agent treatment, thermal activation treatment and ball milling treatment on the mesoporous material filter cake to obtain a spherical mesoporous material;
(c) in the presence of inert gas, carrying out first dipping treatment on the spherical mesoporous material in a solution containing a Mg component precursor and/or a Ti component precursor to obtain a slurry to be sprayed, and then carrying out spray drying on the slurry to be sprayed to obtain a modified spherical mesoporous material carrier;
(d) and carrying out second dipping treatment on the modified spherical mesoporous material carrier in a solution containing a Pt component precursor and a Zn component precursor, and then sequentially carrying out solvent removal treatment, drying and roasting.
According to the invention, the amounts of the individual substances used in step (a) can be selected and adjusted within wide limits. For example, in step (a), the tetraethoxysilane, the template agent, ammonia in ammonia water and water can be used in a molar ratio of 1: 0.1-1: 0.1-5: 100-200, preferably 1: 0.2-0.5: 1.5-3.5: 120-180.
According to the invention, in order to make the obtained mesoporous material filter cake have a two-dimensional hexagonal pore structure, the template agent is preferably cetyl trimethyl ammonium bromide.
According to the invention, the conditions for contacting the ethyl orthosilicate with ammonia water may comprise: the temperature is 25-100 ℃, and the time is 10-72 hours; preferably, the conditions for contacting the tetraethoxysilane and the ammonia solution can comprise: the temperature is 30-100 ℃ and the time is 20-40 hours.
The mode of contacting the template agent, the tetraethoxysilane and the ammonia water is not particularly limited, for example, the template agent, the tetraethoxysilane and the ammonia water solution can be simultaneously mixed, or any two of the template agent, the tetraethoxysilane and the ammonia water solution can be mixed, and other components can be added and uniformly mixed. According to a preferred embodiment, the template agent and the tetraethoxysilane are added into the ammonia water solution together and mixed evenly. The contact mode is that the template agent and the tetraethoxysilane are added into an ammonia water solution and mixed evenly, the obtained mixture is placed into a water bath with the temperature of 25-100 ℃ to be stirred until the mixture is dissolved, then the temperature is kept unchanged, and the mixture is stirred and reacts for 20-40 hours.
According to the present invention, in the step (a), the crystallization conditions may include: the temperature is 30-150 ℃ and the time is 10-72 hours. Preferably, the crystallization conditions include: the temperature is 40-100 ℃ and the time is 20-40 hours. The crystallization is carried out by a hydrothermal crystallization method.
According to the present invention, the process of obtaining a filter cake of mesoporous material having a two-dimensional hexagonal channel structure by filtration in step (a) may comprise: after filtration, repeated washing with deionized water (washing times may be 2 to 10) and suction filtration. Preferably, the washing is such that the pH of the obtained cake of mesoporous material is 7.
According to the present invention, in the step (b), the method for removing the template from the mesoporous material filter cake is preferably a calcination method. The conditions for removing the template agent may include: the temperature is 300-600 ℃, preferably 350-550 ℃, and most preferably 500 ℃; the time is 8-20h, preferably 10-18 h.
According to the present invention, in order to remove hydroxyl groups and residual moisture from the mesoporous material filter cake, the spherical mesoporous material needs to be subjected to a thermal activation treatment, and the conditions of the thermal activation treatment may include: calcining the spherical mesoporous material at the temperature of 300-900 ℃ for 7-10h in the presence of nitrogen.
According to the invention, in the step (b), the specific operation method and conditions of the ball milling treatment are subject to the pore channel structure of the spherical mesoporous material which does not destroy or basically does not destroy the two-dimensional hexagonal pore channel structure of the mesoporous material. One skilled in the art can select various suitable conditions to implement the present invention based on the above principles. Specifically, the ball milling treatment may be performed in a ball mill, wherein the diameter of the milling balls in the ball mill may be 2-3 mm; the number of the grinding balls can be reasonably selected according to the size of the ball milling tank, 20-80 grinding balls can be generally used for the ball milling tank with the size of 50-150mL, and the ball-material ratio can be 10-30: 1; the material of the grinding ball can be agate, polytetrafluoroethylene and the like, and agate is preferred. The ball milling conditions include: the rotation speed of the grinding ball can be 300-500r/min, the temperature in the ball milling tank can be 15-100 ℃, and the ball milling time can be 0.1-100 hours. Preferably, in the step (b), the ball milling treatment is performed under conditions such that the average particle diameter of the spherical mesoporous material obtained by ball milling is 5 to 20 μm.
According to the present invention, in the step (C), the solution containing the Mg component precursor and/or the Ti component precursor used in the first impregnation treatment may be an organic solution containing a magnesium compound and/or a titanium compound, and the organic solvent in the organic solution may be an electron donor solvent, for example, the organic solvent may be selected from alkyl esters, aliphatic ethers, and cyclic ethers of aliphatic or aromatic carboxylic acids, preferably at least one of alkyl esters of C1 to C4 saturated aliphatic carboxylic acids, alkyl esters of C7 to C8 aromatic carboxylic acids, C2 to C6 aliphatic ethers, and C3 to C4 cyclic ethers; more preferably at least one of methyl formate, ethyl acetate, butyl acetate, diethyl ether, hexyl ether and Tetrahydrofuran (THF); further preferred is tetrahydrofuran.
According to the present invention, in the step (c), when the first impregnation treatment is performed, the Mg component and/or the Ti component loaded on the spherical mesoporous material may be introduced into the pore channels of the spherical mesoporous material by using an impregnation method, depending on capillary pressure of the pore channel structure of the spherical mesoporous material, and the Mg component and/or the Ti component may be adsorbed on the surface of the spherical mesoporous material until the Mg component and/or the Ti component reaches adsorption equilibrium on the surface of the spherical mesoporous material. When the spherical mesoporous material is loaded with the Mg component and the Ti component, the first impregnation treatment can be co-impregnation treatment or step-by-step impregnation treatment. The first impregnation treatment is preferably a co-impregnation treatment; further preferably, the conditions of the first impregnation treatment include: the first dipping treatment temperature is 25-100 ℃, preferably 40-80 ℃; the first impregnation treatment time is 0.1 to 5 hours, preferably 1 to 4 hours.
According to the present invention, in the step (c), the spherical mesoporous material, the Mg component precursor and the Ti component precursor are preferably used in such amounts that the spherical mesoporous material is contained in the prepared modified spherical mesoporous material support in an amount of 20 to 90 wt%, based on the total weight of the modified spherical mesoporous material support, the Mg component is calculated as magnesium element, the Ti component is calculated as titanium element, and the Mg component and/or the Ti component is contained in the modified spherical mesoporous material support in an amount of 1 to 50 wt%.
Preferably, the spherical mesoporous material, the Mg component precursor and the Ti component precursor are used in amounts such that the content of the spherical mesoporous material in the prepared modified spherical mesoporous material carrier is 30-70 wt%, based on the total weight of the modified spherical mesoporous material carrier, the Mg component is calculated as magnesium element, the Ti component is calculated as titanium element, and the content of the Mg component and/or the Ti component is 1-30 wt%.
According to the present invention, when the spherical mesoporous material is subjected to the first impregnation treatment in the solution containing only the Mg component precursor, the spherical mesoporous material and the Mg component precursor are preferably used in amounts such that the content of the spherical mesoporous material in the prepared modified spherical mesoporous material support is 20 to 90 wt% and the content of the Mg component is 1 to 50 wt%, preferably 1 to 30 wt%, based on the total weight of the modified spherical mesoporous material support; when the spherical mesoporous material is subjected to the first impregnation treatment in the solution containing only the Ti component precursor, the spherical mesoporous material and the Ti component precursor are preferably used in amounts such that the content of the spherical mesoporous material in the prepared modified spherical mesoporous material carrier is 20 to 90 wt%, and the content of the Ti component is 1 to 50 wt%, preferably 1 to 15 wt%, based on the total weight of the modified spherical mesoporous material carrier.
According to a preferred embodiment of the present invention, in the step (c), the spherical mesoporous material, the Mg component precursor and the Ti component precursor are preferably used in such amounts that the spherical mesoporous material is contained in the prepared modified spherical mesoporous material support in an amount of 20 to 90 wt%, based on the total weight of the modified spherical mesoporous material support, the Mg component is calculated as magnesium, the Ti component is calculated as titanium, and the sum of the contents of the Mg component and the Ti component is 10 to 30 wt%.
Preferably, in the step (c), the spherical mesoporous material and the solution containing the Mg component precursor and/or the Ti component precursor may be used in a weight ratio of 1: 50 to 150, preferably 1: 75-120.
Preferably, in the step (c), the spherical mesoporous material obtained in the step (b) is subjected to a first impregnation treatment in a solution containing a Mg component precursor and a Ti component precursor, wherein the Mg component precursor and the Ti component precursor are used in such amounts that the molar ratio of the content of the Mg component in terms of Mg element to the content of the Ti component in terms of Ti element in the prepared modified spherical mesoporous material carrier is 0.5 to 50: 1, preferably 5 to 18: 1.
in the invention, the content of each element in the modified spherical mesoporous material carrier component can be measured by adopting an X-ray fluorescence spectrum analysis method.
According to the present invention, the Mg component precursor may be of the general formula Mg (OR)1)mX2-mWherein R is1Is a hydrocarbon group having 2 to 20 carbon atoms, X is a halogen atom, 0. ltoreq. m.ltoreq.2, and for example, the precursor of the Mg component may be at least one of diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, dioctoxymagnesium, and magnesium chloride.
According to the invention, the Ti component precursor may be of the general formula Ti (OR)2)nX4-nWherein R is2Is a hydrocarbon group having 2 to 20 carbon atoms, X is a halogen atom, 0. ltoreq. n.ltoreq.4, and for example, the precursor of the Ti component may be at least one of tetraethyl titanate, tetrabutyl titanate, tetraisopropyl titanate, titanium trichloride and titanium tetrachloride.
Preferably, the Mg component precursor is one or more of magnesium chloride, magnesium sulfate, magnesium nitrate and magnesium bromide, more preferably magnesium chloride; the precursor of the Ti component is titanium tetrachloride and/or titanium trichloride, and titanium tetrachloride is more preferable.
According to the present invention, the concentration of the Mg component precursor may be 0.1 to 1mol/L, and the concentration of the Ti component precursor may be 0.01 to 0.2 mol/L.
In the invention, the content of each element in the modified spherical mesoporous material carrier can be measured by adopting an X-ray fluorescence spectrum analysis method.
According to the present invention, in the step (c), the inert gas is a gas which does not react with the raw materials and the products during the first impregnation treatment, and may be, for example, at least one of nitrogen gas or a group zero element gas in the periodic table, which is conventional in the art, and is preferably nitrogen gas.
According to the present invention, in step (c), the spray drying may be carried out according to a conventional method. May be at least one selected from the group consisting of a pressure spray drying method, a centrifugal spray drying method and a pneumatic spray drying method. According to a preferred embodiment of the present invention, the spray drying is an air-flow spray drying method. The spray drying may be carried out in an atomizer. The conditions of the spray drying may include: the process is carried out in a nitrogen protective atmosphere, the temperature of an air inlet is 100-150 ℃, the temperature of an air outlet is 25-90 ℃, and the flow rate of carrier gas is 10-50L/s. The above conditions impart a relatively high viscosity to the slurry to be sprayed, making it suitable for spray forming operations, and also impart good mechanical strength to the sprayed particles. Preferably, the spray drying conditions are such that the average particle diameter of the prepared modified spherical mesoporous material support is 6-22 μm.
According to a preferred embodiment of the present invention, the step (c) comprises: adding electron donor solvent Tetrahydrofuran (THF) into a reactor with a stirrer in the presence of inert gas, controlling the temperature of the reactor to be 25-40 ℃, quickly adding magnesium chloride and titanium tetrachloride when the stirrer is started, adjusting the temperature of the system to 60-75 ℃, and reacting for 1-5 hours at constant temperature until the magnesium chloride and the titanium tetrachloride are completely dissolved to obtain an organic solution containing the magnesium chloride and the titanium tetrachloride. Mixing the organic solution containing magnesium chloride and titanium tetrachloride with the spherical mesoporous material obtained in the step (b) to perform first impregnation treatment, controlling the proportion of the components to 1mol of titanium element, wherein the content of magnesium element is 0.5-50 mol, preferably 1-10 mol, the content of electron donor solvent Tetrahydrofuran (THF) is 0.5-200 mol, preferably 20-200 mol, the temperature of the reactor is controlled to be 60-75 ℃, and stirring reaction is performed for 0.1-5 hours to prepare slurry to be sprayed, wherein the concentration of the slurry is uniform. The amount of the spherical mesoporous material to be added should be sufficient to form a slurry liquid suitable for spray forming, i.e., the content of the spherical mesoporous material in the slurry to be sprayed is 20 to 90% by weight, preferably 30 to 70% by weight, and the sum of the contents of the magnesium chloride and titanium tetrachloride in terms of magnesium element and titanium element, respectively, is 1 to 50% by weight, preferably 1 to 30% by weight. The resulting slurry to be sprayed is then introduced into a spray dryer at N2Under protection, the temperature of the air inlet of the spray dryer is controlled to be 100-150 ℃, the temperature of the air outlet is controlled to be 25-90 ℃, and the flow rate of the carrier gas is controlled to be 10-20L/s, so that spherical particles with the average particle size of 6-22 mu m are obtained, preferablySpherical particles of 7-21 μm are selected.
According to the invention, in the step (d), when the second impregnation treatment is performed, the Pt component and the Zn component can enter the pore channel of the modified spherical mesoporous material carrier by using the capillary pressure of the pore channel structure of the modified spherical mesoporous material carrier, and at the same time, the Pt component and the Zn component can be adsorbed on the surface of the modified spherical mesoporous material carrier until the Pt component and the Zn component reach adsorption balance on the surface of the modified spherical mesoporous material carrier. The second impregnation treatment may be a co-impregnation treatment or a step-wise impregnation treatment. Since the Zn component is beneficial to further improving the uniform dispersion degree of the Pt component and is also beneficial to desorption of isobutene from the Pt surface when the Pt component is contacted with the Zn component, the second impregnation treatment is preferably a co-impregnation treatment in order to save the preparation cost and simplify the experimental process; further preferably, the conditions of the second impregnation treatment include: and mixing and contacting the Mg component and/or Ti component modified spherical mesoporous material carrier in a solution containing a Pt component precursor and a Zn component precursor, wherein the second impregnation temperature can be 25-50 ℃, and the second impregnation time can be 2-6 h.
According to the present invention, in the step (d), the Pt component precursor is preferably H2PtCl6The Zn component precursor is preferably Zn (NO)3)2。
The concentration of the solution containing the Pt component precursor and the Zn component precursor is not particularly limited in the present invention, and may be conventionally selected in the art, for example, the concentration of the Pt component precursor may be 0.001 to 0.003mol/L, and the concentration of the Zn component precursor may be 0.015 to 0.1 mol/L.
According to the present invention, in the step (d), the solvent removing treatment may be carried out by a method conventional in the art, for example, a rotary evaporator may be used to remove the solvent in the system.
According to the present invention, in the step (d), the drying may be performed in a drying oven, and the firing may be performed in a muffle furnace. The drying conditions may include: the temperature is 110-150 ℃ and the time is 3-6 h; the conditions for the firing may include: the temperature is 600 ℃ and 650 ℃, and the time is 5-8 h.
According to the invention, in the step (d), in the second dipping treatment process, the modified spherical mesoporous material carrier, the Pt component precursor and the Zn component precursor are used in amounts such that, in the prepared isobutane dehydrogenation catalyst, based on the total weight of the isobutane dehydrogenation catalyst, the content of the modified spherical mesoporous material carrier is 98-99.4 wt%, the content of the Pt component calculated by Pt element is 0.1-0.5 wt%, and the content of the Zn component calculated by Zn element is 0.5-1.5 wt%.
Preferably, the modified spherical mesoporous material carrier, the Pt component precursor and the Zn component precursor are used in amounts such that, in the prepared isobutane dehydrogenation catalyst, based on the total weight of the isobutane dehydrogenation catalyst, the content of the modified spherical mesoporous material carrier is 98.4 to 99 wt%, the content of the Pt component calculated by the Pt element is 0.2 to 0.4 wt%, and the content of the Zn component calculated by the Zn element is 0.8 to 1.2 wt%.
The invention provides an isobutane dehydrogenation catalyst with a modified spherical mesoporous material as a carrier, which is prepared by the method.
According to the invention, the isobutane dehydrogenation catalyst comprises a carrier, and a Pt component and a Zn component which are loaded on the carrier, wherein the carrier is a modified spherical mesoporous material carrier, the modified spherical mesoporous material carrier contains a spherical mesoporous material and a Mg component and/or a Ti component which are loaded on the spherical mesoporous material, and the content of the spherical mesoporous material is 20-90 wt%, preferably 30-70 wt% based on the total weight of the modified spherical mesoporous material carrier; the Mg component is calculated by Mg element, the Ti component is calculated by Ti element, and the content of the Mg component and/or the Ti component is 1-50 wt%, preferably 1-30 wt%.
Preferably, the modified spherical mesoporous material comprises a spherical mesoporous material and a Mg component and a Ti component which are loaded on the spherical mesoporous material, and the molar ratio of the content of the Mg component to the content of the Ti component in terms of magnesium element to the content of titanium element is 0.5-50: 1, preferably 5 to 18: 1.
according to the invention, the spherical mesoporous material in the modified spherical mesoporous material has a two-dimensional hexagonal pore channel structure, the average particle diameter of the spherical mesoporous material is 5-20 mu m, and the specific surface area is 700-1200m2Per g, pore volume of 0.2-1.5mL/g, average pore diameter of 1.5-10 nm.
According to the invention, the spherical mesoporous material has a special two-dimensional hexagonal pore channel distribution structure, the unique framework structure breaks through the limitation of one-dimensional pore channels on molecular transmission, the mesoporous material has the spherical shape characteristic, the mesoporous pore channel structure is uniform in distribution, proper in pore size, large in pore volume, good in mechanical strength and good in structural stability, and the metal components can be favorably dispersed in the pore channels and on the surface of the mesoporous material. The preparation method comprises the steps of uniformly loading an Mg component and/or a Ti component on the surface of the spherical mesoporous material by adopting a spray drying method, modifying the spherical mesoporous material, wherein the loaded Mg component and/or Ti component can play a role in dilution, improving the dispersion degree of a subsequent active metal component on the spherical mesoporous material, and obtaining the modified spherical mesoporous material carrier. In addition, the Mg component can further adjust the acid sites on the surface of the catalyst, so that the occurrence of carbon deposition of the isobutane dehydrogenation catalyst is further reduced, the carbon deposition resistance of the obtained isobutane dehydrogenation catalyst is improved, the Ti component has an empty d orbit to generate strong interaction with isobutene, and compete for isobutene with Pt active sites, so that isobutene is desorbed from the surface of Pt, the yield of isobutene and the conversion rate of isobutane are improved, and the isobutane dehydrogenation catalyst prepared by the method can achieve better dehydrogenation activity, selectivity, stability and carbon deposition resistance under the condition of very low noble metal loading.
According to the invention, the average particle diameter of the spherical mesoporous material is measured by a laser particle size distribution instrument, and the specific surface area, the pore volume and the average pore diameter are measured by a nitrogen adsorption method. In the present invention, the average particle diameter refers to the particle size of the raw material particles, and since the morphology of the spherical mesoporous material is a hexagonal structure, the particle diameter of the spherical mesoporous material is represented by the diagonal distance of the cross section thereof.
According to the invention, the spherical mesoporous material is ensured not to be easily agglomerated by controlling the structural parameters of the spherical mesoporous material within the range, and the conversion rate of the reaction raw material in the reaction process of preparing isobutene by isobutane dehydrogenation can be improved by the prepared supported catalyst. When the specific surface area of the spherical mesoporous material is less than 700m2When the volume/g and/or pore volume is less than 0.2mL/g, the catalytic activity of the supported catalyst prepared by using the supported catalyst is remarkably reduced; when the specific surface area of the spherical mesoporous material is more than 1200m2When the volume/g and/or the pore volume is more than 1.5mL/g, the supported catalyst prepared by using the supported catalyst as the carrier is easy to agglomerate in the reaction process of preparing isobutene by isobutane dehydrogenation, so that the conversion rate of the reaction raw material in the reaction process of preparing isobutene by isobutane dehydrogenation is influenced.
Preferably, the spherical mesoporous material has an average pore diameter of 1.5 to 10nm, such as 1.5nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm and 10nm, and an average pore diameter between any two ranges of the average pore diameters, and a specific surface area of 800-1100m2The pore volume is 0.5-1.2mL/g, and the average particle diameter is 6-18 mu m, so that the spherical mesoporous material has the advantages of larger pore diameter, larger pore volume and larger specific surface area, and is more favorable for the good dispersion of the modified metal component and the active metal component on the surface of the spherical mesoporous material, and further the isobutane dehydrogenation catalyst prepared by the spherical mesoporous material can be ensured to haveHas excellent catalytic performance, and thus has the advantages of high isobutane conversion rate, high isobutene selectivity and good carbon deposition resistance.
Preferably, the spherical mesoporous material is an MCM molecular sieve material.
Preferably, the average particle diameter of the isobutane dehydrogenation catalyst is 8-23 mu m, and the specific surface area is 650-1100m2Per g, pore volume of 0.4-1.1mL/g, average pore diameter of 1.5-8 nm.
According to the invention, the average particle size of the isobutane dehydrogenation catalyst is measured by using a laser particle size distribution instrument, and the specific surface area, the pore volume and the average pore diameter are measured by using a nitrogen adsorption method.
According to the invention, in the isobutane dehydrogenation catalyst, the content of the carrier is 98-99.4 wt%, the content of the Pt component calculated by Pt element is 0.1-0.5 wt%, and the content of the Zn component calculated by Zn element is 0.5-1.5 wt%, based on the total weight of the isobutane dehydrogenation catalyst.
Preferably, the content of the carrier is 98.4-99 wt%, the content of the Pt component calculated by Pt element is 0.2-0.4 wt%, and the content of the Zn component calculated by Zn element is 0.8-1.2 wt%, based on the total weight of the isobutane dehydrogenation catalyst.
In the invention, the content of each element in the isobutane dehydrogenation catalyst component can be measured by adopting an X-ray fluorescence spectrum analysis method.
As described above, the third aspect of the present invention provides a use of the aforementioned isobutane dehydrogenation catalyst in preparing isobutene through isobutane dehydrogenation, wherein the method for preparing isobutene through isobutane dehydrogenation comprises: isobutane was subjected to a dehydrogenation reaction in the presence of a catalyst and hydrogen.
When the isobutane dehydrogenation catalyst prepared by the method provided by the invention is used for catalyzing isobutane to dehydrogenate to prepare isobutene, the conversion rate of isobutane and the selectivity of isobutene can be greatly improved.
According to the present invention, in order to increase the isobutane conversion rate and prevent the catalyst from coking, it is preferable that the molar ratio of the amount of isobutane to the amount of hydrogen is 0.5 to 1.5: 1.
the conditions for the dehydrogenation reaction in the present invention are not particularly limited and may be conventionally selected in the art, and for example, the conditions for the dehydrogenation reaction may include: the reaction temperature is 550-650 ℃, the reaction pressure is 0.05-0.2MPa, and the mass space velocity of the isobutane is 2-5h-1。
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, X-ray diffraction analysis was carried out on an X-ray diffractometer, model D8Advance, available from Bruker AXS, Germany; scanning electron microscopy analysis was performed on a scanning electron microscope, model XL-30, available from FEI, USA; pore structure parameter analysis was performed on an ASAP2020-M + C type adsorber, available from Micromeritics, USA, and BET method was used for the specific surface area and pore volume calculation of the sample; the rotary evaporator is produced by German IKA company, and the model is RV10 digital; the active component loading of the isobutane dehydrogenation catalyst was measured on a wavelength dispersive X-ray fluorescence spectrometer, available from parnacco, netherlands, model No. Axios-Advanced; spray drying was carried out on a spray dryer model B-290, commercially available from Buchi corporation, Switzerland; analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under model 7890A.
In the following experimental examples and experimental comparative examples, the conversion (%) of isobutane was equal to the amount of isobutane consumed by the reaction/initial amount of isobutane × 100%;
the selectivity (%) of isobutylene was defined as the amount of isobutane consumed for producing isobutylene/total consumption of isobutane × 100%.
Example 1
This example is illustrative of an isobutane dehydrogenation catalyst and a method for preparing the same.
(1) Preparation of spherical mesoporous material
Adding hexadecyl trimethyl ammonium bromide and ethyl orthosilicate into an ammonia water solution with the concentration of 25 weight percent, wherein the adding amount of the ethyl orthosilicate is 1g, and the mol ratio of ammonia to water in the ethyl orthosilicate, the hexadecyl trimethyl ammonium bromide and the ammonia water is 1: 0.37: 2.8: 142 and stirring for 24 hours at the temperature of 80 ℃, then transferring the obtained solution to a reaction kettle with a polytetrafluoroethylene lining, crystallizing for 24 hours at the temperature of 90 ℃, then filtering and washing for 4 times by using deionized water until the pH value of the solution is 7, and then carrying out suction filtration to obtain a filter cake of the mesoporous material with the two-dimensional hexagonal pore channel structure. And then calcining the filter cake in a muffle furnace at 500 ℃ for 15 hours, and removing the template agent to obtain a template agent-removed mesoporous material product A1. Then calcining the mesoporous material product A1 without the template agent at 400 ℃ for 10h under the protection of nitrogen for thermal activation treatment, and removing hydroxyl and residual moisture of the mesoporous material product A1 to obtain a thermally activated mesoporous material product B1; taking 10g of the thermally activated mesoporous material product B1, and putting the thermally activated mesoporous material product B1 into a 100ml ball milling tank, wherein the ball milling tank is made of polytetrafluoroethylene, grinding balls are made of agate, the diameter of the grinding balls is 3-15mm, the number of the grinding balls is 30, and the ball-to-material ratio is 20: 1, the rotating speed is 400r/min, the ball milling tank is closed, and ball milling is carried out in the ball milling tank for 12 hours at the temperature of 25 ℃ to obtain 10g of spherical mesoporous material P1 with the average grain diameter of 5-20 mu m.
(2) Preparation of modified spherical mesoporous material carrier
To pass through N2Blowing and holding N2Adding 130mL of tetrahydrofuran electron donor solvent into a reactor with a stirring device in the atmosphere, controlling the temperature of the reactor to be 30 ℃, quickly adding 5.3g of magnesium chloride and 1mL of titanium tetrachloride when stirring and starting, adjusting the temperature of the system to 70 ℃, and reacting for 4 hours at constant temperature to obtain a solution containing magnesium chloride and titanium tetrachloride. Cooling the solution to 50 ℃, adding 6g of the ball-milled spherical mesoporous material P1 into the solution containing magnesium chloride and titanium tetrachloride, carrying out first impregnation treatment, and stirring for reacting for 2 hours to obtain the slurry to be sprayed with uniform concentration. The resulting slurry to be sprayed is then introduced into a spray dryer at N2Under protection, the temperature of the air inlet of the spray dryer is controlled to be 120 ℃, the temperature of the air outlet is controlled to be 70 ℃, and the carrier gas flow is controlled to be 15L/s, spray drying is carried out to obtain a modified spherical mesoporous material carrier C1 (obtained by X-ray fluorescence analysis, in the modified spherical mesoporous material carrier C1 obtained in the embodiment, the total weight of the modified spherical mesoporous material carrier C1 is taken as a reference,the content of magnesium element was 12.8 wt% and the content of titanium element was 2.56 wt% in terms of element).
(3) Preparation of isobutane dehydrogenation catalyst
H is to be2PtCl6·6H2O and Zn (NO)3)2·6H2Dissolving O in deionized water to obtain a mixture solution, adding the modified spherical mesoporous material carrier C1 obtained in the step (2) into the mixture solution, carrying out second impregnation treatment at 25 ℃ for 5h, evaporating solvent water in a system by using a rotary evaporator to obtain a solid product, and placing the solid product in a drying box at 120 ℃ for drying for 3 h. Then roasting the mixture for 6 hours in a muffle furnace at the temperature of 600 ℃ to obtain an isobutane dehydrogenation catalyst Cat-1, and controlling H2PtCl6·6H2O、Zn(NO3)2·6H2The O and the modified spherical mesoporous material carrier C1 are used in an amount such that in the prepared isobutane dehydrogenation catalyst Cat-1, the content of the Pt component calculated by the Pt element is 0.3 wt% and the content of the Zn component calculated by the Zn element is 1 wt% based on the total weight of the isobutane dehydrogenation catalyst Cat-1.
Characterizing the spherical mesoporous material P1, the modified spherical mesoporous material carrier C1 and the isobutane dehydrogenation catalyst Cat-1 by using an XRD, a scanning electron microscope and an ASAP2020-M + C type adsorption instrument;
FIG. 1 is an X-ray diffraction pattern of the spherical mesoporous material P1, wherein the abscissa is 2 θ and the ordinate is intensity, and the spherical mesoporous material P1 has a 2D hexagonal channel structure specific to the mesoporous material, as can be seen from a small-angle spectrum peak appearing in an XRD spectrum;
fig. 2 is an SEM scanning electron micrograph of the modified spherical mesoporous material carrier C1, which shows that the modified spherical mesoporous material carrier C1 has a spherical shape and a micron-sized particle size.
Table 1 shows the pore structure parameters of the spherical mesoporous material P1 and the isobutane dehydrogenation catalyst Cat-1.
TABLE 1
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) | Average pore diameter (nm) | Particle size (. mu.m) |
| Spherical mesoporous material P1 | 800 | 0.8 | 2 | 5-20 |
| Catalyst Cat-1 | 759 | 0.6 | 1.5 | 7-21 |
As can be seen from the data in table 1, after the spherical mesoporous material P1 is modified and loaded with the Pt component and the Zn component, the specific surface area and the pore volume are reduced, which indicates that the Mg component, the Ti component, the Pt component and the Zn component enter the inside of the pore channel of the spherical mesoporous material P1 during the modification and loading of the active component.
Example 2
This example is illustrative of an isobutane dehydrogenation catalyst and a method for preparing the same.
(1) Preparation of spherical mesoporous material
Adding hexadecyl trimethyl ammonium bromide and ethyl orthosilicate into an ammonia water solution with the concentration of 25 weight percent, wherein the adding amount of the ethyl orthosilicate is 1g, and the mol ratio of ammonia to water in the ethyl orthosilicate, the hexadecyl trimethyl ammonium bromide and the ammonia water is 1: 0.3: 2.5: 150, stirring for 36 hours at the temperature of 80 ℃, then transferring the obtained solution to a reaction kettle with a polytetrafluoroethylene lining, crystallizing for 28 hours at the temperature of 90 ℃, then filtering and washing for 5 times by using deionized water until the pH value of the solution is 7, and then carrying out suction filtration to obtain a filter cake of the mesoporous material with the two-dimensional hexagonal pore channel structure. Then calcining the filter cake in a muffle furnace at 550 ℃ for 13 hours, and removing the template agent to obtain a mesoporous material product A2 with the template agent removed; then calcining the mesoporous material product A2 without the template agent at 600 ℃ for 8h under the protection of nitrogen for thermal activation treatment, and removing hydroxyl and residual moisture of the spherical mesoporous material A2 to obtain a thermally activated spherical mesoporous material B2; taking 10g of the spherical mesoporous material B2 after thermal activation, and putting the spherical mesoporous material B2 into a 100ml ball milling tank, wherein the ball milling tank is made of polytetrafluoroethylene, the grinding balls are made of agate, the diameter of the grinding balls is 3-15mm, the number of the grinding balls is 30, and the ball-to-material ratio is 27: 1, the rotating speed is 300r/min, the ball milling tank is closed, and ball milling is carried out in the ball milling tank for 11 hours at the temperature of 35 ℃ to obtain 10g of spherical mesoporous material P2 with the average grain diameter of 7-20 mu m.
(2) Preparation of modified spherical mesoporous material carrier
To pass through N2Blowing and holding N2Adding 130mL of tetrahydrofuran electron donor solvent into a reactor with a stirring device in the atmosphere, controlling the temperature of the reactor to be 35 ℃, quickly adding 5.3g of magnesium chloride and 1mL of titanium tetrachloride when stirring and starting, adjusting the temperature of a system to 65 ℃, and reacting for 3 hours at constant temperature to obtain a solution containing magnesium chloride and titanium tetrachloride. And cooling the solution to 50 ℃, adding 3g of the ball-milled spherical mesoporous material P2 into the solution containing magnesium chloride and titanium tetrachloride, carrying out first impregnation treatment, and stirring for reacting for 2 hours to obtain the slurry to be sprayed with uniform concentration. The resulting slurry to be sprayed is then introduced into a spray dryer at N2Under protection, the temperature of an air inlet of the spray dryer is controlled to be 140 ℃, the temperature of an air outlet is controlled to be 80 ℃, the flow rate of carrier gas is controlled to be 20L/s, and spray drying is carried out to obtain the modified spherical mesoporous materialThe carrier C2 (obtained by X-ray fluorescence analysis, in the modified spherical mesoporous material carrier C2 obtained in this example, the content of magnesium element was 17.2 wt% and the content of titanium element was 3.15 wt% in terms of elements based on the total weight of the modified spherical mesoporous material carrier C2).
(3) Preparation of isobutane dehydrogenation catalyst
H is to be2PtCl6·6H2O and Zn (NO)3)2·6H2Dissolving O in deionized water to obtain a mixture solution, adding the modified spherical mesoporous material carrier C2 obtained in the step (2) into the mixture solution, carrying out second impregnation treatment at 35 ℃ for 3.5h, evaporating solvent water in a system by using a rotary evaporator to obtain a solid product, and placing the solid product in a drying oven at 125 ℃ for drying for 4 h. Then roasting the mixture for 6 hours in a muffle furnace at the temperature of 620 ℃ to obtain an isobutane dehydrogenation catalyst Cat-2, and controlling H2PtCl6·6H2O、Zn(NO3)2·6H2The O and the modified spherical mesoporous material carrier C2 are used in an amount such that in the prepared isobutane dehydrogenation catalyst Cat-2, the content of the Pt component calculated by the Pt element is 0.3 wt% and the content of the Zn component calculated by the Zn element is 1.2 wt% based on the total weight of the isobutane dehydrogenation catalyst Cat-2.
Characterizing the spherical mesoporous material P2 and the isobutane dehydrogenation catalyst Cat-2 by using an XRD, a scanning electron microscope and an ASAP2020-M + C type adsorption instrument;
table 2 shows the pore structure parameters of the spherical mesoporous material P2 and the isobutane dehydrogenation catalyst Cat-2.
TABLE 2
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) | Average pore diameter (nm) | Particle size (. mu.m) |
| Spherical mesoporous material P2 | 1050 | 1.1 | 4.2 | 8-18 |
| Catalyst Cat-2 | 895 | 0.8 | 3.1 | 10-20 |
As can be seen from the data in table 2, after the spherical mesoporous material P2 is modified and loaded with the Pt component and the Zn component, the specific surface area and the pore volume are reduced, which indicates that the Mg component, the Ti component, the Pt component and the Zn component enter the inside of the pore channel of the spherical mesoporous material P2 during the modification and loading of the active component.
Example 3
This example is illustrative of an isobutane dehydrogenation catalyst and a method for preparing the same.
(1) Preparation of spherical mesoporous material
Adding hexadecyl trimethyl ammonium bromide and ethyl orthosilicate into an ammonia water solution with the concentration of 25 weight percent, wherein the adding amount of the ethyl orthosilicate is 1g, and the mol ratio of ammonia to water in the ethyl orthosilicate, the hexadecyl trimethyl ammonium bromide and the ammonia water is 1: 0.4: 3.5: 120, stirring for 20 hours at 70 ℃, then transferring the obtained solution to a reaction kettle with a polytetrafluoroethylene lining, crystallizing for 25 hours at 90 ℃, then filtering and washing for 6 times by deionized water until the pH value of the solution is 7, and then performing suction filtration to obtain a filter cake of the mesoporous material with the two-dimensional hexagonal pore channel structure. Then calcining the filter cake in a muffle furnace at 520 ℃ for 18 hours, and removing the template agent to obtain a mesoporous material product A3 with the template agent removed; then calcining the product spherical mesoporous material A3 without the template agent at 650 ℃ for 8h under the protection of nitrogen for thermal activation treatment to remove hydroxyl and residual moisture of the spherical mesoporous material A3, and obtaining a thermally activated spherical mesoporous material B3; taking 10g of the spherical mesoporous material B3 after thermal activation, and putting the spherical mesoporous material B3 into a 100ml ball milling tank, wherein the ball milling tank is made of polytetrafluoroethylene, the grinding balls are made of agate, the diameter of the grinding balls is 3-12mm, the number of the grinding balls is 70, and the ball-to-material ratio is 21: 1, the rotation speed is 550r/min, the ball milling tank is closed, and ball milling is carried out in the ball milling tank for 18 hours at the temperature of 25 ℃ to obtain 10g of spherical mesoporous material P3 with the average grain diameter of 7.5-18 mu m.
(2) Preparation of modified spherical mesoporous material carrier
To pass through N2Blowing and holding N2Adding 130mL of tetrahydrofuran electron donor solvent into a reactor with a stirring device in the atmosphere, controlling the temperature of the reactor to be 25 ℃, quickly adding 5.3g of magnesium chloride and 1mL of titanium tetrachloride when stirring and starting, adjusting the temperature of the system to 75 ℃, and reacting for 2 hours at constant temperature to obtain a solution containing magnesium chloride and titanium tetrachloride. Cooling the solution to 35 ℃, adding 4.5g of the ball-milled spherical mesoporous material P3 into the solution containing magnesium chloride and titanium tetrachloride, carrying out first impregnation treatment, and stirring for reacting for 2 hours to obtain the slurry to be sprayed with uniform concentration. The resulting slurry to be sprayed is then introduced into a spray dryer at N2Under protection, the temperature of the air inlet of the spray dryer is controlled to be 130 ℃, the temperature of the air outlet is controlled to be 60 ℃, and the flow rate of the carrier gas is controlled to be 13L/s, and spray drying is performed to obtain a modified spherical mesoporous material carrier C3 (obtained through X-ray fluorescence analysis, in the modified spherical mesoporous material carrier C3 obtained in this embodiment, the content of magnesium element is 15.3 wt% and the content of titanium element is 2.75 wt% based on the total weight of the modified spherical mesoporous material carrier C3).
(3) Preparation of isobutane dehydrogenation catalyst
H is to be2PtCl6·6H2O and Zn (NO)3)2·6H2Dissolving O in deionized water to obtain a mixture solution, adding the modified spherical mesoporous material carrier C3 obtained in the step (2) into the mixture solution, carrying out second impregnation treatment at 30 ℃ for 4h, evaporating solvent water in a system by using a rotary evaporator to obtain a solid product, and placing the solid product in a drying box at the temperature of 110 ℃ for drying for 3.5 h. Then roasting the mixture for 5.5 hours in a muffle furnace at the temperature of 630 ℃ to obtain an isobutane dehydrogenation catalyst Cat-3, and controlling H2PtCl6·6H2O、Zn(NO3)2·6H2The O and the modified spherical mesoporous material carrier C3 are used in an amount such that in the prepared isobutane dehydrogenation catalyst Cat-3, the content of the Pt component calculated by the Pt element is 0.3 wt% and the content of the Zn component calculated by the Zn element is 0.8 wt% based on the total weight of the isobutane dehydrogenation catalyst Cat-3.
Characterizing the spherical mesoporous material P3 and the isobutane dehydrogenation catalyst Cat-3 by using an XRD, a scanning electron microscope and an ASAP2020-M + C type adsorption instrument;
table 3 shows the pore structure parameters of the spherical mesoporous material P3 and the isobutane dehydrogenation catalyst Cat-3.
TABLE 3
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) | Average pore diameter (nm) | Particle size (. mu.m) |
| Spherical mesoporous material P3 | 992 | 0.9 | 6.4 | 8-18 |
| Catalyst Cat-3 | 917 | 0.5 | 3.3 | 10.5-20.3 |
As can be seen from the data in table 3, after the spherical mesoporous material P3 is modified and loaded with the Pt component and the Zn component, the specific surface area and the pore volume are reduced, which indicates that the Mg component, the Ti component, the Pt component and the Zn component enter the inside of the pore channel of the spherical mesoporous material P3 during the modification and loading of the active component.
Example 4
This example is illustrative of an isobutane dehydrogenation catalyst and a method for preparing the same.
An isobutane dehydrogenation catalyst Cat-4 was prepared by the procedure of example 2, except that 6.87g of diethoxymagnesium was used as the magnesium component precursor instead of 5.3g of magnesium dichloride, 1.4g of titanium trichloride was used as the Ti component precursor instead of 1mL of titanium tetrachloride, the spherical mesoporous material P4 was modified to obtain a catalyst carrier C4 containing a modified spherical mesoporous material and a catalyst Cat-4 containing isobutane dehydrogenation (obtained by X-ray fluorescence analysis, in the modified spherical mesoporous material carrier C4 obtained in this example, the content of magnesium element was 22.46 wt% and the content of titanium element was 1.5 wt% in terms of elements, and in the isobutane dehydrogenation catalyst Cat-4 obtained in this example, the content of Pt component in terms of Pt element was 0.3 wt% and the content of Zn component in terms of Zn element was 1.2 wt% in terms of the total weight of the isobutane dehydrogenation catalyst Cat-4).
The spherical mesoporous material P4 and the isobutane dehydrogenation catalyst Cat-4 are characterized by XRD, a scanning electron microscope and a nitrogen adsorption instrument.
Table 4 shows the pore structure parameters of the spherical mesoporous material P4 and the isobutane dehydrogenation catalyst Cat-4.
TABLE 4
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) | Average pore diameter (nm) | Particle size (. mu.m) |
| Spherical mesoporous material P4 | 1050 | 1.1 | 4.2 | 8-18 |
| Catalyst Cat-4 | 864 | 0.6 | 3 | 11.3-21.2 |
As can be seen from the data in table 4, after the spherical mesoporous material P4 is modified and loaded with the Pt component and the Zn component, the specific surface area and the pore volume are reduced, which indicates that the Mg component, the Ti component, the Pt component and the Zn component enter the inside of the pore channel of the spherical mesoporous material P4 during the modification and loading of the active component.
Example 5
This example is illustrative of an isobutane dehydrogenation catalyst and a method for preparing the same.
The isobutane dehydrogenation catalyst Cat-5 was prepared according to the method of example 2, except that a magnesium chloride solution was not added during the modification of the spherical mesoporous material, so as to obtain a modified spherical mesoporous material carrier C5 containing a Ti component and an isobutane dehydrogenation catalyst Cat-5 (obtained by X-ray fluorescence analysis, in the modified spherical mesoporous material carrier C5 containing a Ti component obtained in this example, the content of the Ti element was 2.58 wt% in terms of elements, and in the isobutane dehydrogenation catalyst Cat-5 obtained in this example, the content of the Pt component in terms of the Pt element was 0.3 wt% and the content of the Zn component in terms of the Zn element was 1.2 wt% in terms of the total weight of the isobutane dehydrogenation catalyst Cat-5).
Characterizing the spherical mesoporous material P5 and the isobutane dehydrogenation catalyst Cat-5 by using an XRD, a scanning electron microscope and an ASAP2020-M + C type adsorption instrument;
table 5 shows the pore structure parameters of the spherical mesoporous material P5 and the isobutane dehydrogenation catalyst Cat-5.
TABLE 5
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) | Average pore diameter (nm) | Particle size (. mu.m) |
| Spherical mesoporous material P5 | 1050 | 1.1 | 4.2 | 8-18 |
| Catalyst Cat-5 | 931 | 1 | 3.7 | 8.4-18.7 |
As can be seen from the data in table 5, the specific surface area and the pore volume are reduced after the spherical mesoporous material P5 is modified and loaded with the Pt component and the Zn component, which indicates that the Ti component, the Pt component and the Zn component enter the inside of the pore channel of the spherical mesoporous material P5 during the modification and loading of the active component.
Comparative example 1
This comparative example serves to illustrate a reference isobutane dehydrogenation catalyst and a process for its preparation.
The carrier and the isobutane dehydrogenation catalyst were prepared according to the method of example 1, except that the spherical mesoporous material P1 was not modified with the Mg component and/or the Ti component in the process of preparing the carrier, thereby preparing the carrier D1 and the isobutane dehydrogenation catalyst Cat-D-1, respectively.
In the isobutane dehydrogenation catalyst Cat-D-1, the content of a Pt component calculated by a Pt element is 0.3 wt% and the content of a Zn component calculated by a Zn element is 1 wt% based on the total weight of the isobutane dehydrogenation catalyst Cat-D-1.
Comparative example 2
This comparative example serves to illustrate a reference isobutane dehydrogenation catalyst and a process for its preparation.
The modified carrier and the isobutane dehydrogenation catalyst were prepared according to the method of example 1, except that in the process of preparing the modified spherical mesoporous material carrier, spray drying and ball milling treatment were not adopted, but after the first impregnation treatment, direct filtration was performed, washing was performed with n-hexane for 4 times, and drying was performed at 75 ℃ to prepare the modified spherical mesoporous material carrier D2, and the modified spherical mesoporous material carrier D2 in the same weight part was adopted to replace the modified spherical mesoporous material carrier C1 to perform the second impregnation treatment to load the Pt component and the Zn component, thereby obtaining the isobutane dehydrogenation catalyst Cat-D-2.
As a result of X-ray fluorescence analysis, in the modified spherical mesoporous material support D2 obtained in this comparative example, the content of magnesium element was 13.6 wt% and the content of titanium element was 1.5 wt% in terms of elements, based on the total weight of the modified spherical mesoporous material support D2. In the isobutane dehydrogenation catalyst Cat-D-2, based on the total weight of the isobutane dehydrogenation catalyst Cat-D-32, the content of a Pt component calculated by a Pt element is 0.3 wt%, and the content of a Zn component calculated by a Zn element is 1 wt%.
Experimental example 1
This example is intended to illustrate the preparation of isobutene using the isobutane dehydrogenation catalyst of the present invention
0.5g of isobutane dehydrogenation catalyst Cat-1 was loaded into a fixed bed quartz reactor, the reaction temperature was controlled at 590 ℃, the reaction pressure was 0.1MPa, and the isobutane: the molar ratio of hydrogen is 1: 1, the mass space velocity of isobutane is 4h-1. By Al2O3The reaction product separated by the S molecular sieve column was directly fed into an Agilent 7890A gas chromatograph equipped with a hydrogen flame detector (FID) for on-line analysis, and the isobutane conversion and isobutene selectivity were obtained as shown in Table 6.
Experimental examples 2 to 5
Isobutene is prepared by isobutane dehydrogenation according to the method of the experimental example 1, except that isobutane dehydrogenation catalysts Cat-2 to Cat-5 are respectively adopted to replace the isobutane dehydrogenation catalyst Cat-1. Isobutane conversion and isobutene selectivity are shown in table 6.
Experimental comparative examples 1 to 2
Isobutene is prepared by isobutane dehydrogenation according to the method of the experimental example 1, except that isobutane dehydrogenation catalysts Cat-D-1 to Cat-D-2 are respectively adopted to replace the isobutane dehydrogenation catalyst Cat-1. Isobutane conversion and isobutene selectivity are shown in table 6.
TABLE 6
As can be seen from table 6, when the modified spherical mesoporous material prepared by the method of the present invention is used as a carrier, and the isobutane dehydrogenation catalyst loaded with an active Pt component and a Zn component is used in the reaction of preparing isobutene by isobutane dehydrogenation, after 6 hours of reaction, the isobutane conversion rate and the isobutene selectivity are still high, which indicates that the isobutane dehydrogenation catalyst of the present invention has not only good catalytic performance, but also good stability, and can maintain activity for a long time.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A method for preparing an isobutane dehydrogenation catalyst with a modified spherical mesoporous material as a carrier is characterized by comprising the following steps:
(a) in the presence of a template agent, contacting tetraethoxysilane with ammonia water, and crystallizing and filtering a mixture obtained after the contact to obtain a mesoporous material filter cake;
(b) sequentially carrying out template agent treatment, thermal activation treatment and ball milling treatment on the mesoporous material filter cake to obtain a spherical mesoporous material;
(c) in the presence of inert gas, carrying out first dipping treatment on the spherical mesoporous material in a solution containing a Mg component precursor and/or a Ti component precursor to obtain a slurry to be sprayed, and then carrying out spray drying on the slurry to be sprayed to obtain a modified spherical mesoporous material carrier;
(d) and carrying out second dipping treatment on the modified spherical mesoporous material carrier in a solution containing a Pt component precursor and a Zn component precursor, and then sequentially carrying out solvent removal treatment, drying and roasting.
2. The method of claim 1, wherein in the step (a), the ethyl orthosilicate, the template, ammonia in ammonia water and water are used in a molar ratio of 1: 0.1-1: 0.1-5: 100-200, preferably 1: 0.2-0.5: 1.5-3.5: 120-180;
preferably, the template agent is cetyl trimethyl ammonium bromide;
further preferably, the conditions under which the ethyl orthosilicate is contacted with ammonia water include: the temperature is 25-100 ℃, and the time is 10-72 hours;
still more preferably, the crystallization conditions include: the temperature is 30-150 ℃ and the time is 10-72 hours.
3. The method of claim 1 wherein in step (b) the stripper plate agent treatment process comprises: calcining the mesoporous material filter cake for 8-20h at the temperature of 300-600 ℃; the conditions of thermal activation include: the temperature is 300-900 ℃ and the time is 7-10 h;
the conditions of the ball milling treatment comprise: the rotation speed of the grinding ball is 300-.
4. The method of claim 1, wherein in step (c), the conditions of the first impregnation comprise: the first dipping temperature is 25-100 ℃, and the first dipping time is 0.1-5 h;
the dosage of the spherical mesoporous material and the solution containing the Mg component precursor and/or the Ti component precursor is such that the content of the spherical mesoporous material in the prepared modified spherical mesoporous material carrier is 20-90 wt%, preferably 30-70 wt%, based on the total weight of the modified spherical mesoporous material carrier; the Mg component is calculated by Mg element, the Ti component is calculated by Ti element, and the content of the Mg component and/or the Ti component is 1-50 wt%, preferably 1-30 wt%;
the conditions of the spray drying include: the process is carried out in a nitrogen protective atmosphere, the temperature of an air inlet is 100-150 ℃, the temperature of an air outlet is 25-90 ℃, and the flow rate of carrier gas is 10-50L/s.
5. The method of claim 1, wherein in step (d), the conditions of the second impregnation process comprise: the temperature is 25-50 ℃, the time is 2-6h, the consumption of the modified spherical mesoporous material carrier, the Pt component precursor and the Zn component precursor enables the content of the modified spherical mesoporous material carrier to be 98-99.4 wt%, the content of the Pt component calculated by Pt element is 0.1-0.5 wt%, and the content of the Zn component calculated by Zn element is 0.5-1.5 wt% in the prepared isobutane dehydrogenation catalyst based on the total weight of the isobutane dehydrogenation catalyst.
6. The isobutane dehydrogenation catalyst with the modified spherical mesoporous material as the carrier prepared by the method of any one of claims 1 to 5.
7. The isobutane dehydrogenation catalyst according to claim 6, wherein the isobutane dehydrogenation catalyst comprises a carrier and a Pt component and a Zn component supported on the carrier, wherein the carrier is a modified spherical mesoporous material carrier containing a spherical mesoporous material and a Mg component and/or a Ti component supported on the spherical mesoporous material, wherein the content of the spherical mesoporous material is 20-90 wt%, preferably 30-70 wt%, based on the total weight of the modified spherical mesoporous material carrier; the Mg component is calculated by Mg element, the Ti component is calculated by Ti element, and the content of the Mg component and/or the Ti component is 1-50 wt%, preferably 1-30 wt%.
8. The isobutane dehydrogenation catalyst according to claim 7, wherein the spherical mesoporous materials in the modified spherical mesoporous material support have a two-dimensional hexagonal pore distribution structure, the average particle diameter of the spherical mesoporous materials is 5-20 μm, and the specific surface area is700-1200m2Per gram, pore volume of 0.2-1.5mL/g, average pore diameter of 1.5-10 nm;
preferably, the average particle diameter of the spherical mesoporous material is 6-18 μm, and the specific surface area is 800-1100m2Per gram, pore volume of 0.5-1.2mL/g, average pore diameter of 1.5-8 nm;
preferably, the spherical mesoporous material is an MCM molecular sieve material.
9. The isobutane dehydrogenation catalyst according to claim 7, wherein the content of the modified spherical mesoporous material support is 98-99.4 wt%, the content of the Pt component calculated as Pt element is 0.1-0.5 wt%, and the content of the Zn component calculated as Zn element is 0.5-1.5 wt%, based on the total weight of the isobutane dehydrogenation catalyst.
10. Use of the isobutane dehydrogenation catalyst according to any one of claims 6 to 9 for preparing isobutene by the dehydrogenation of isobutane, wherein the method for preparing isobutene by the dehydrogenation of isobutane comprises: isobutane was subjected to a dehydrogenation reaction in the presence of a catalyst and hydrogen.
11. Use according to claim 10, wherein the molar ratio of the amount of isobutane to the amount of hydrogen is 0.5-1.5: 1;
preferably, the dehydrogenation reaction conditions include: the reaction temperature is 550-650 ℃, the reaction pressure is 0.05-0.2MPa, and the mass space velocity of the isobutane is 2-5h-1。
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