CN116532148A - Spherical isobutane dehydrogenation catalyst and preparation method and application thereof - Google Patents
Spherical isobutane dehydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- CN116532148A CN116532148A CN202210090085.1A CN202210090085A CN116532148A CN 116532148 A CN116532148 A CN 116532148A CN 202210090085 A CN202210090085 A CN 202210090085A CN 116532148 A CN116532148 A CN 116532148A
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- spherical
- catalyst
- composite carrier
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- alumina
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- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 236
- 239000003054 catalyst Substances 0.000 title claims abstract description 190
- 239000001282 iso-butane Substances 0.000 title claims abstract description 116
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 claims abstract description 113
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000002808 molecular sieve Substances 0.000 claims abstract description 50
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 50
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 34
- 239000010703 silicon Substances 0.000 claims abstract description 34
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 26
- 239000011148 porous material Substances 0.000 claims abstract description 19
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 14
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 62
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 50
- 239000003921 oil Substances 0.000 claims description 41
- 238000000498 ball milling Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 229910021529 ammonia Inorganic materials 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 21
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000012702 metal oxide precursor Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 229920000428 triblock copolymer Polymers 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 238000004073 vulcanization Methods 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 229940024546 aluminum hydroxide gel Drugs 0.000 claims description 2
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 229910001679 gibbsite Inorganic materials 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 229940057995 liquid paraffin Drugs 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 23
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 230000008569 process Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 238000000227 grinding Methods 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 239000011651 chromium Substances 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000012265 solid product Substances 0.000 description 8
- 230000005484 gravity Effects 0.000 description 7
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
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- 230000007613 environmental effect Effects 0.000 description 3
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- 238000011156 evaluation Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
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- 229910001873 dinitrogen Inorganic materials 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
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- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 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
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
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- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
-
- B01J35/40—
-
- B01J35/51—
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- B01J35/615—
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- B01J35/617—
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- B01J35/633—
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- B01J35/635—
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/20—Sulfiding
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
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Abstract
The invention relates to the field of catalysts, and discloses a spherical isobutane dehydrogenation catalyst and a preparation method and application thereof. The catalyst packageComprises a spherical composite carrier, and non-noble metal oxide and non-metal loaded on the spherical composite carrier, wherein the spherical composite carrier comprises alumina and all-silicon beta molecular sieve, and the specific surface area of the spherical composite carrier is 300-800m 2 Per gram, the pore volume is 0.3-0.9mL/g, the average diameter of the particles is 1-3mm, and the average strength of the particles is 20-80N. The spherical isobutane dehydrogenation catalyst provided by the invention can achieve better isobutane dehydrogenation activity, isobutene selectivity and stability under the condition of not using noble metals and serious pollution metal components.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a spherical isobutane dehydrogenation catalyst, and a preparation method and application thereof.
Background
Isobutene is an important basic petrochemical raw material, has wide application, and can be used for synthesizing various organic raw materials and fine chemicals such as methyl tertiary butyl ether, ethyl tertiary butyl ether, butyl rubber, polyisobutylene, methacrylate, methyl methacrylate, isoprene, tertiary butylphenol, tertiary butylamine, 1, 4-butanediol, ABS resin and the like. However, isobutene has no natural source and is mainly derived from C in catalytically cracked liquefied petroleum gas 4 Component and byproduct C in ethylene preparation by naphtha steam cracking 4 C in olefins and natural gas 4 The components are as follows. In the above background, the dehydrogenation of isobutane to isobutene is one of the important ways to increase the isobutene source.
At present, three reaction pathways developed in the research field of preparing isobutene by isobutane dehydrogenation are mainly: (1) direct dehydrogenation of isobutane; (2) oxidative dehydrogenation of isobutane; (3) membrane-catalyzed reaction dehydrogenation of isobutane.
The technology for preparing isobutene by direct catalytic dehydrogenation of isobutane has realized industrial production in the 90 th century, and the main technologies comprise a Catofin process developed by ABB Lummes company, an Oleflex process developed by UOP company, a Star process developed by Phillips company, an FBD-4 process developed by Snamprogetti-Yarstez company and a Linde process developed by Linde company. The five processes described above all employ catalysts of the Pt (Oleflex and Star processes) or Cr (Catofin, FBD-4 and Linde processes). The activity of the noble metal catalyst is higher,better selectivity and more environmental friendliness. However, pt-based catalysts have the disadvantages of complicated operation process, high operation requirements, and high cost. Relatively speaking, cr-based catalysts are low in price, but the catalysts are easy to accumulate carbon and quick in deactivation, need frequent regeneration, cause environmental pollution once leaked and generate cancerogenic substances Cr 6+ Is not beneficial to environmental protection.
Therefore, for various processes for preparing isobutene by isobutane dehydrogenation, the development of a catalyst which does not use nonmetallic components with serious environmental pollution, has higher dehydrogenation catalytic activity and better stability is a main technical problem to be solved at present.
In order to improve various performance indexes of Cr-based dehydrogenation catalysts, researchers have made many efforts. Such as: the catalytic performance of the Cr catalyst is improved by adding an auxiliary agent (CN 104549220A), the addition of Cr components is avoided by developing a multicomponent catalyst formula (CN 102451677B, CN 104607168A), and the reactivity of the non-noble metal dehydrogenation catalyst is improved by improving the catalyst preparation method (ACS catalyst.2015, 5, 3494-3503). Although the prior art improves the Cr-based catalyst for industrial application to a certain extent, the problems of complex catalyst components, complicated preparation process and further improvement of catalyst performance still exist.
Disclosure of Invention
The invention aims to overcome the defects of high cost or easiness in causing environmental pollution of the existing isobutane dehydrogenation catalyst, and provides a spherical isobutane dehydrogenation catalyst and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a spherical isobutane dehydrogenation catalyst, wherein the catalyst comprises a spherical composite support and a non-noble metal oxide and a non-metal supported on the spherical composite support, wherein the spherical composite support comprises alumina and an all-silica beta molecular sieve, and the ratio table of the spherical composite supportThe area is 300-800m 2 Per gram, the pore volume is 0.3-0.9mL/g, the average diameter of the particles is 1-3mm, and the average strength of the particles is 20-80N.
The second aspect of the invention provides a preparation method of a spherical isobutane dehydrogenation catalyst, wherein the preparation method comprises the following steps:
(Z1) under the ultrasonic auxiliary condition, carrying out contact reaction on a solution containing a non-noble metal oxide precursor and a spherical composite carrier, and removing a solvent, drying and roasting to obtain an initial catalyst; wherein the spherical composite carrier comprises alumina and an all-silicon beta molecular sieve;
(Z2) vulcanizing the initial catalyst by sulfur-containing gas to obtain the spherical isobutane dehydrogenation catalyst.
In a third aspect, the present invention provides a spherical isobutane dehydrogenation catalyst prepared by the aforementioned preparation method.
The fourth aspect of the invention provides an application of the spherical isobutane dehydrogenation catalyst in the reaction of preparing isobutene by isobutane dehydrogenation.
Through the technical scheme, the technical scheme of the invention has the following advantages:
(1) The spherical isobutane dehydrogenation catalyst does not contain noble metal, so that the preparation cost of the isobutane dehydrogenation catalyst can be effectively reduced; the spherical isobutane dehydrogenation catalyst disclosed by the invention does not contain chromium element and is environment-friendly.
(2) The spherical isobutane dehydrogenation catalyst provided by the invention is a molded catalyst product, and the mechanical strength can meet the requirements of industrial production.
(3) The spherical isobutane dehydrogenation catalyst has good catalytic performance, high isobutane conversion rate, high isobutene selectivity and good catalyst stability when being used for the reaction of preparing isobutene by isobutane dehydrogenation.
(4) The preparation method of the spherical isobutane dehydrogenation catalyst has the advantages of simple process, easy control of conditions and good product repeatability.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is an XRD spectrum of a spherical alumina-beta composite carrier A prepared in example 1;
FIG. 2 is a photograph of a spherical alumina-. Beta.composite support A prepared in example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a spherical isobutane dehydrogenation catalyst, wherein the catalyst comprises a spherical composite support and a non-noble metal oxide and a non-metal supported on the spherical composite support, wherein the spherical composite support comprises alumina and an all-silica beta molecular sieve, and the specific surface area of the spherical composite support is 300 to 800m 2 Per gram, the pore volume is 0.3-0.9mL/g, the average diameter of the particles is 1-3mm, and the average strength of the particles is 20-80N.
In the present invention, the spherical composite support may be represented as a spherical alumina-beta composite support.
The inventors of the present invention have found when conducting a study of preparation of an isobutane dehydrogenation catalyst: in the prior art, the Cr-based catalyst has lower cost than the Pt-based dehydrogenation catalyst, but the Cr-based catalyst has poor stability and serious pollution. Based on this, in order to maintain low catalyst cost while considering environmental requirements, the dehydrogenation catalyst is prepared by using a non-noble metal element instead of Cr in the prior art. The research of the alternative catalyst has been continued for almost twenty years, but the performance of the alternative catalyst still cannot completely reach the level of the Cr-series catalyst, and the performance is mainly represented by low selectivity, poor stability and the like. For the non-noble metal catalyst, if the oxidized metal component is deeply reduced in the reducing atmosphere of the isobutane dehydrogenation reaction, a pure metal component is easily formed, and the pure metal component has very strong dehydrogenation performance, resulting in deep dehydrogenation or hydrogenolysis of isobutane, and the selectivity of isobutene is severely reduced.
Further, the present inventors have found that, when conducting a study of preparing an isobutane dehydrogenation catalyst, the prior art uses gamma-alumina or silica as a carrier to support a non-noble metal component to prepare a spherical isobutane dehydrogenation catalyst, and the present invention has disadvantages of poor olefin selectivity and poor stability. Although the commercial alumina carrier or silica carrier is low in cost, the pore size distribution is uneven, the crystal phase structure is not regular enough, and the uniform dispersion of active metal components on the carrier surface is not facilitated. The all-silicon beta molecular sieve has a three-dimensional twelve-ring BEA structure, the pore size is between 0.55 and 0.7nm, the specific surface area is large, and the crystal phase structure is regular. The isobutane dehydrogenation catalyst is prepared by taking the all-silicon beta molecular sieve as a carrier and loading active metal components, so that the reaction performance of the catalyst can be greatly improved. However, all-silicon beta molecular sieves have somewhat poor adhesion and less strength after molding, which would limit their industrial application. The inventor of the invention discovers that by utilizing the advantage of good cohesiveness of alumina, the structural characteristics of alumina and all-silicon beta molecular sieve are combined to prepare a formed spherical composite carrier (spherical alumina-beta composite carrier), and further prepare a spherical isobutane dehydrogenation catalyst, so that the current situation that the performance of the spherical isobutane dehydrogenation catalyst in the prior art is poor can be effectively improved.
Further, the inventors of the present invention found that, with the sulfidation treatment, the S element is combined with the active metal component to form sulfide in the reducing atmosphere of the dehydrogenation reaction, and a certain amount of the S element can be present on the catalyst surface. In addition, the existence of nonmetallic sulfur elements can effectively avoid the deep reduction of metal components, thereby reducing pure metal components on the surface of the catalyst and obviously inhibiting the occurrence of side reactions such as hydrogenolysis and the like. The selectivity and stability of the dehydrogenation catalyst after vulcanization treatment in the reaction of preparing isobutene by dehydrogenating isobutane are obviously improved.
According to the present invention, the spherical composite support preferably has a specific surface area of 450 to 650m 2 Per gram, the pore volume is 0.4-0.8mL/g, the average diameter of the particles is 1.3-2.8mm, and the average strength of the particles is 25-70N; more preferably, the specific surface area of the spherical composite carrier is 531-615m 2 Per gram, the pore volume is 0.49-0.72mL/g, the average diameter of the particles is 1.5-2.6mm, and the average strength of the particles is 28.9-57.2N;
according to the invention, the content of the alumina is 55-90 wt% and the content of the all-silicon beta molecular sieve is 10-45 wt% based on the total weight of the spherical composite carrier; preferably, the content of the alumina is 65-80 wt% and the content of the all-silicon beta molecular sieve is 20-35 wt%, based on the total weight of the spherical composite carrier.
According to the present invention, the non-noble metal oxide is selected from one or more of iron oxide, zinc oxide, tin oxide, nickel oxide, tungsten oxide, and manganese oxide; preferably, the non-noble metal oxide is selected from one or more of iron oxide, zinc oxide, tin oxide and nickel oxide.
According to the invention, the nonmetallic component is an S element.
According to the invention, the content of the non-noble metal oxide is 5-30 wt%, the content of the non-metal component is 0.2-3 wt% and the content of the spherical composite carrier is 67-95 wt% based on the total weight of the catalyst; preferably, the content of the non-noble metal oxide is 8-25 wt%, the content of the non-metal component is 0.3-2 wt%, and the content of the spherical composite carrier is 73-92 wt%, based on the total weight of the catalyst; more preferably, the content of the non-noble metal oxide is 9.8 to 17.5 wt%, the content of the non-metal component is 0.6 to 1.3 wt%, and the content of the spherical composite carrier is 81.2 to 89.6 wt%, based on the total weight of the catalyst. In the invention, the contents of the non-noble metal oxide, the non-metal component and the spherical composite carrier are limited to be within the range, so that the active components of the catalyst can be uniformly dispersed, and the pore channel structure is beneficial to the diffusion of reactants and products.
According to the invention, the preparation method of the spherical composite carrier comprises the following steps:
(1) Mixing an alumina precursor with a full-silica beta molecular sieve for ball milling, mixing powder obtained after ball milling with an acidic aqueous solution to prepare sol, dripping the sol into an oil ammonia column forming device, and performing ball forming and aging treatment to obtain a spherical precursor;
(2) And washing, drying and roasting the spherical precursor to obtain the spherical composite carrier.
The inventors of the present invention have also found that if ball milling is performed during the mixing of the alumina precursor with the all-silica beta molecular sieve, the particle crush strength of the resulting spherical composite support can be significantly improved, and the surface is more uniform and smooth.
According to the invention, in step (1), the ball milling is carried out in a ball mill, wherein the diameter of the grinding balls in the ball mill may be 2-3mm; the number of grinding balls can be reasonably selected according to the size of the ball milling tank, and for the ball milling tank with the size of 100-300mL, 4 grinding balls can be generally used; the material of the grinding ball can be agate and/or polytetrafluoroethylene, and agate is preferred. The ball milling conditions include: the rotating speed of the grinding balls can be 300-500r/min, the temperature in the ball milling tank can be 30-80 ℃, and the ball milling time can be 2-30h.
According to the invention, in the step (1), the alumina precursor is selected from one or more of pseudo-boehmite, aluminum hydroxide gel, alumina sol, gibbsite and boehmite; preferably, the alumina precursor is pseudo-boehmite. In the present invention, the alumina precursor is commercially available, and specifically, the pseudo-boehmite is preferably: pseudo-boehmite powder (produced by Shandong aluminum Co., ltd., specific surface area of 249 m) having a model of P-DF-07-LSi 2 Per g, pore volume of 0.82 mL/g), pseudo-boehmite powder of type P-DF-09-LSi (manufactured by Shandong aluminum Co., ltd., specific surface area of 286 m) 2 Per g, pore volume of 1.08 mL/g), pseudo-boehmite powder (manufactured by Bobo constant Ji Fen New Material Co., ltd., specific surface area of 327 m) of type PB-0104 2 /g, pore volume of 1.02 mL/g).
According to the invention, in step (1), the alumina precursor, the all-silica beta molecular sieve and the acidic aqueous solution are used in a weight ratio of 1: (0.03-0.8): (1-5), preferably 1: (0.1-0.5): (2-4).
According to the present invention, in the step (1), the acidic aqueous solution is an aqueous organic acid solution or an aqueous inorganic acid solution, preferably one or more of an aqueous formic acid solution, an aqueous acetic acid solution, an aqueous citric acid solution, an aqueous nitric acid solution and an aqueous hydrochloric acid solution, more preferably an aqueous nitric acid solution or an aqueous citric acid solution; the mass concentration of the acidic aqueous solution is 0.2-10%, preferably 0.5-5%.
According to the invention, in the oil ammonia column forming device, an oil ammonia column is arranged in the oil ammonia column forming device, and the oil ammonia column forming device is a carrier forming device which utilizes the surface tension of liquid to shrink sol into balls in an oil layer and dehydrate and shape in an alkaline water layer. In the invention, the oil ammonia column forming device is an XF1616 type oil ammonia column forming test device manufactured by Sichuan research technology Co.
According to the invention, the oil phase of the oil ammonia column forming device is one or more selected from transformer oil, silicone oil, vacuum pump oil, liquid paraffin, white oil and petroleum ether; preferably one or more of transformer oil, vacuum pump oil and silicone oil.
According to the invention, the aqueous phase of the oil ammonia column forming device is an ammonia water solution containing a nonionic surfactant and low-carbon alcohol.
In the invention, the nonionic surfactant is selected from one or more of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether and polyoxyethylene-polypropylene oxide-polyoxyethylene triblock copolymer; preferably, the nonionic surfactant is selected from peregal O-25 (fatty alcohol polyoxyethylene ether, formula C) 62～68 H 126～138 O 26 ) P123 (a triblock copolymer, collectively: a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer having the formula: PEO-PPO-PEO, the specific molecular formula is: EO (ethylene oxide) film 20 PO 70 EO 20 Molecular weight 5800), F108 (a triblock copolymer, collectively: ring collectorAn ethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer having the formula: PEO-PPO-PEO, the specific molecular formula is: EO (ethylene oxide) film 133 PO 50 EO 133 Molecular weight 14600).
In the invention, the lower alcohol is C 1 -C 4 Monohydric alcohol, C 1 -C 4 Diols and C 1 -C 4 Preferably one or more of ethanol, ethylene glycol and isopropanol.
According to the present invention, in step (1), the conditions for the dropping include: the dropping rate is 10 to 300 drops/min, preferably 30 to 150 drops/min.
According to the present invention, in step (1), the conditions for the balling include: the temperature of the oil ammonia column is 20-120 ℃, preferably 30-90 ℃.
According to the invention, in step (1), the aging conditions include: the temperature is 20-120deg.C, preferably 30-90deg.C; the time is 1-20h, preferably 3-12h.
According to the present invention, in the step (2), the washing method is not particularly limited, and the spherical product may be washed with deionized water a plurality of times to a pH of 7 of the eluate. Preferably, the number of washes with deionized water is from 5 to 10.
According to the present invention, in step (2), the drying conditions may include: the temperature is 70-150deg.C, preferably 100-130deg.C; the time is 2-20h, preferably 3-16h.
According to the present invention, in the step (2), the conditions of the firing may include: the temperature is 400-700 ℃, preferably 500-650 ℃; the time is 2-24 hours, preferably 5-12 hours.
The second aspect of the invention provides a preparation method of a spherical isobutane dehydrogenation catalyst, wherein the preparation method comprises the following steps:
(Z1) under the ultrasonic auxiliary condition, carrying out contact reaction on a solution containing a non-noble metal oxide precursor and a spherical composite carrier, and removing a solvent, drying and roasting to obtain an initial catalyst; wherein the spherical composite carrier comprises alumina and an all-silicon beta molecular sieve;
(Z2) vulcanizing the initial catalyst by sulfur-containing gas to obtain the spherical isobutane dehydrogenation catalyst.
The inventor of the invention also discovers that the ultrasonic auxiliary method is introduced in the preparation process of the spherical isobutane dehydrogenation catalyst, so that the active components can be promoted to be better dispersed on the surface of a molded carrier, and the spherical isobutane dehydrogenation catalyst with better catalytic activity can be obtained.
According to the invention, the ultrasound-assisted conditions include: the temperature is 10-100deg.C, the time is 10-180min, and the power is 100-300W; preferably, the ultrasound-assisted conditions include: the temperature is 20-80 ℃, the time is 30-120min, and the power is 150-250W.
According to the invention, the solution containing the non-noble metal oxide precursor is an aqueous solution containing the non-noble metal oxide precursor; the mass concentration of the solution is 0.5-10%; the non-noble metal oxide precursor is selected from one or more of nitrate, sulfate, sulfite or metal chloride containing iron, zinc, tin, nickel, tungsten and manganese; preferably, the non-noble metal oxide precursor is selected from one or more of nitrate or sulfate containing iron, zinc, tin, nickel, tungsten, manganese elements.
The method for removing the solvent according to the present invention is not particularly limited, and may be a method known in the art, such as: the solvent is removed by evaporation using a rotary evaporator or by heating and stirring.
According to the invention, the drying conditions include: the temperature is 60-150deg.C, preferably 80-130deg.C; the time is 1-20h, preferably 3-15h.
According to the invention, the conditions of the calcination include: the temperature is 400-700 ℃, preferably 500-650 ℃; the time is 2-15 hours, preferably 3-10 hours.
According to the invention, the sulfur-containing gas is nitrogen, helium or argon containing hydrogen sulfide; the volume content of the hydrogen sulfide in the sulfur-containing gas is 0.1 to 5% by volume, preferably 0.3 to 2% by volume.
According to the present invention, in step (Z1), the contact reaction conditions include: the temperature is 20-100deg.C, and the time is 0.5-10h.
According to the invention, in step (Z2), the processing conditions include: the temperature is 400-700 ℃ and the time is 1-15h; preferably, the processing conditions include: the temperature is 450-650 ℃ and the time is 2-8h.
In a third aspect, the present invention provides a spherical isobutane dehydrogenation catalyst prepared by the aforementioned preparation method.
The fourth aspect of the invention provides an application of the spherical isobutane dehydrogenation catalyst in the reaction of preparing isobutene by isobutane dehydrogenation.
According to the invention, the reaction comprises: the reaction raw material isobutane is contacted with a spherical isobutane dehydrogenation catalyst.
According to the invention, the conditions of the contact include: the contact temperature can be 500-650 ℃, the partial pressure of raw material gas is 0.02-0.5MPa, and the mass airspeed of isobutane is 0.5-10.0h -1 。
The present invention will be described in detail by examples.
In the following examples and comparative examples:
XRD testing of the samples was performed on an X' Pert MPD X-ray powder diffractometer, philips company, netherlands, cu ka target, scan range 2θ=5-90 °.
The pore structure parameter analysis of the samples was performed on an ASAP2020-M+C type adsorber available from Micromeritics, inc. The sample was degassed under vacuum at 350 ℃ for 4 hours prior to measurement, the specific surface area of the sample was calculated by BET method, and the pore volume was calculated by BJH model.
Elemental analysis experiments of the samples were performed on an Eagle III energy dispersive X-ray fluorescence spectrometer manufactured by EDAX, inc. of America.
The ultrasonic generator is a KQ-300GTDV high-frequency constant-temperature numerical control ultrasonic cleaner manufactured by Kunshan ultrasonic instrument Co., ltd, the ultrasonic frequency is 80kHz, and the working voltage is 220V.
The rotary evaporator is manufactured by IKA corporation of Germany and has the model RV10 digital.
The drying oven is manufactured by Shanghai-Heng scientific instrument Co., ltd, and the model is DHG-9030A.
The muffle furnace is available from CARBOLITE company under the model CWF1100.
The oil ammonia column forming device is an XF1616 type oil ammonia column forming test device manufactured by Sichuan research technology Co.
All-silicon beta molecular sieves were purchased from Nanjing Xianfeng nanomaterials technologies Inc.
The other reagents used in the examples and comparative examples were purchased from national pharmaceutical chemicals, inc., and the purity of the reagents was analytically pure.
Example 1
This example is intended to illustrate a spherical isobutane dehydrogenation catalyst prepared in accordance with the present invention.
(1) Preparation of spherical composite Carrier (spherical alumina-beta composite Carrier)
100g of pseudo-boehmite with the model of P-DF-07-LSi and 30g of all-silicon beta molecular sieve are mixed and transferred to a 200mL ball milling tank, and 4 agate grinding balls with the diameter of 2mm are put into the ball milling tank to start ball milling. The temperature in the ball milling tank is controlled to be 60 ℃, the rotating speed of the grinding balls is 400r/min, and the ball milling time is 16h. The powder obtained after ball milling was mixed with 270g of dilute nitric acid with a concentration of 1.5%, and stirred for 8 hours to prepare a sol. The sol is dripped into an oil ammonia column forming device, the speed of the sol dripping ball is 90 drops/min, the oil phase of the oil ammonia column forming device is transformer oil, the water phase is ammonia water solution containing peregal O-25 and ethanol, and the temperature of the oil ammonia column is 60 ℃. After the completion of the sol dripping, the sol is aged for 8 hours at 60 ℃ to obtain a spherical precursor. Washing the spherical precursor with deionized water for 8 times, drying at 110 ℃ for 12 hours, and roasting at 600 ℃ for 8 hours to obtain the spherical alumina-beta composite carrier A.
The content of alumina is 70 wt% and the content of all-silicon beta molecular sieve is 30 wt%, based on the total weight of the spherical alumina-beta composite carrier A.
The spherical alumina-beta composite support A was characterized and its structural parameters are shown in Table 1.
FIG. 1 is an XRD spectrum of a spherical alumina-. Beta.composite support A prepared in example 1 of the present invention, and it is shown from FIG. 1 that the x-ray diffraction angle of the sample is mainly: 2θ=7.7°, 13.1 °, 22.5 °, 25.0 °, 37.5 °,39.3 °, 45.7 ° and 66.6 °, wherein the four diffraction signals at 2θ=7.7 °, 13.1 °, 22.5 °, 25.0 ° coincide with the full-silica beta molecular sieve diffraction pattern; four diffraction signals and γ -Al at 2θ=37.5°, 39.3 °, 45.7 ° and 66.6 ° 2 O 3 The diffraction patterns are identical, which shows that the spherical composite carrier A has no obvious change of crystalline phase of the all-silicon beta molecular sieve after being roasted at 600 ℃, and the pseudo-boehmite shows typical gamma-Al after being dehydrated 2 O 3 A crystalline phase.
Fig. 2 is a photograph of a spherical alumina-beta composite carrier a prepared in example 1 of the present invention, and it can be seen from fig. 2 that the spherical carrier is white, smooth in surface and uniform in size.
(2) Spherical isobutane dehydrogenation catalyst preparation
8.0g of ferric nitrate nonahydrate is dissolved in 100g of deionized water, mixed with 10g of spherical alumina-beta composite carrier A, and stirred and reacted for 60 minutes at 50 ℃ under the assistance of ultrasonic waves with the power of 200W. And after the reaction is finished, evaporating solvent ethanol in the system by using a rotary evaporator to obtain a solid product. The solid product was placed in a drying oven at 100℃and dried for 5 hours. Then, the mixture was calcined in a muffle furnace at 550℃for 5 hours to obtain an initial catalyst A.
10g of the initial catalyst A was taken and used in H 2 The spherical isobutane dehydrogenation catalyst A was obtained by treating at 550℃for 4 hours in a nitrogen stream having an S content of 1.5%.
The specific gravity of each component of the spherical isobutane dehydrogenation catalyst A is as follows: 13.2% by weight of ferric oxide (calculated as iron oxide content), 0.9% by weight of elemental sulphur and the balance being a carrier.
(3) Evaluation of catalyst Performance in the reaction of producing isobutene by dehydrogenation of isobutane
The reactivity of the catalyst was evaluated on a fixed bed reactor. 2.0 g of catalyst A is filled into a fixed bed quartz reactor, the reaction temperature is controlled to 590 ℃, the reaction pressure is 0.1MPa, and the isobutane is prepared: the molar ratio of helium is 1:1, isobutane mass space velocity of 2.0h -1 The reaction time was 6h. Through Al 2 O 3 The reaction product separated by the S molecular sieve column directly enters the catalyst system and is provided with hydrogenAgilent 7890A gas chromatograph of flame detector (FID) was analyzed on-line. The reaction results are shown in Table 2. The isobutane conversion and the isobutene selectivity were calculated from the reaction data, and the stability of the catalyst was judged from the magnitudes of the isobutane conversion and the isobutene selectivity gradually decreasing with the extension of the reaction time during the reaction.
Example 2
This example is intended to illustrate a spherical isobutane dehydrogenation catalyst prepared in accordance with the present invention.
(1) Preparation of spherical alumina-beta composite carrier
130g of pseudo-boehmite with the model of P-DF-09-LSi and 50g of all-silicon beta molecular sieve are mixed and transferred to a 200mL ball milling tank, and 3 agate grinding balls with the diameter of 2mm are put into the ball milling tank to start ball milling. The temperature in the ball milling tank is controlled to be 30 ℃, the rotating speed of the grinding balls is 500r/min, and the ball milling time is 6h. The powder obtained after ball milling is mixed with 360g of citric acid with the concentration of 2 percent and stirred for 12 hours to prepare sol. The sol is dripped into an oil ammonia column forming device, the speed of the sol dripping ball is 150 drops/min, the oil phase of the oil ammonia column forming device is silicone oil, the water phase is ammonia water solution containing F108 and isopropanol, and the temperature of the oil ammonia column is 90 ℃. After the completion of the sol dripping, the sol is aged for 3 hours at 90 ℃ to obtain a spherical precursor. Washing the spherical precursor with deionized water for 6 times, drying at 100 ℃ for 16 hours, and roasting at 650 ℃ for 5 hours to obtain the spherical alumina-beta composite carrier B. The spherical alumina-beta composite carrier B is white, has smooth surface, uniform particles and uniform size.
The content of alumina is 65% by weight and the content of all-silicon beta molecular sieve is 35% by weight based on the total weight of the spherical alumina-beta composite carrier B.
The spherical alumina-beta composite support B was characterized and its structural parameters are shown in Table 1.
(2) Spherical isobutane dehydrogenation catalyst preparation
7.8g of zinc nitrate hexahydrate was dissolved in 150mL of deionized water, mixed with 10g of spherical alumina-beta composite carrier B, and reacted for 30 minutes with stirring at 80℃under the assistance of ultrasonic waves having a power of 250W. After the reaction is finished, water in the system is distilled off by a rotary evaporator, and a solid product is obtained. The solid product was placed in a drying oven at 80℃and dried for 15 hours. Then, the mixture was calcined in a muffle furnace at 650℃for 3 hours to obtain an initial catalyst B.
10g of the initial catalyst B was taken and reacted in H 2 The spherical isobutane dehydrogenation catalyst B is obtained by treating the mixture for 8 hours at 450 ℃ in a nitrogen gas stream with the S content of 2.0 percent.
The specific gravity of each component of the spherical isobutane dehydrogenation catalyst B is as follows: 17.5% by weight of zinc oxide, 1.3% by weight of elemental sulfur and the balance of a carrier.
(3) Evaluation of catalyst Performance in the reaction of producing isobutene by dehydrogenation of isobutane
The test of the reaction performance of catalyst B in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in the step (3) of example 1, and the reaction results are shown in Table 3.
Example 3
This example is intended to illustrate a spherical isobutane dehydrogenation catalyst prepared in accordance with the present invention.
(1) Preparation of spherical alumina-beta composite carrier
100g of pseudo-boehmite with the model PB-0104 and 18g of all-silicon beta molecular sieve are mixed and transferred to a 200mL ball milling tank, and 4 agate grinding balls with the diameter of 3mm are placed into the ball milling tank to start ball milling. The temperature in the ball milling tank is controlled to be 80 ℃, the rotating speed of the grinding balls is 300r/min, and the ball milling time is 10h. The powder obtained after ball milling is mixed with 220g of dilute nitric acid with the concentration of 0.5 percent and stirred for 16 hours to prepare sol. The sol is dripped into an oil ammonia column forming device, the speed of the sol dripping ball is 30 drops/min, the oil phase of the oil ammonia column forming device is vacuum pump oil, the water phase is an ammonia water solution containing P123 and ethanol, and the temperature of the oil ammonia column is 30 ℃. After the completion of the sol dripping, the sol is aged for 12 hours at 30 ℃ to obtain a spherical precursor. Washing the spherical precursor with deionized water for 5 times, drying at 130 ℃ for 3 hours, and roasting at 500 ℃ for 12 hours to obtain the spherical alumina-beta composite carrier C. The spherical alumina-beta composite carrier C is white, smooth in surface, uniform in particles and uniform in size.
The content of alumina is 80% by weight and the content of all-silicon beta molecular sieve is 20% by weight based on the total weight of the spherical alumina-beta composite carrier C.
The spherical alumina-beta composite support C was characterized and its structural parameters are shown in Table 1.
(2) Spherical isobutane dehydrogenation catalyst preparation
4.3g of nickel nitrate hexahydrate was dissolved in 100mL of deionized water, mixed with 10g of spherical alumina-beta composite carrier C, and reacted for 120 minutes with stirring at 20℃under the assistance of ultrasonic waves having a power of 150W. After the reaction is finished, water in the system is distilled off by a rotary evaporator, and a solid product is obtained. The solid product was placed in a drying oven at 130 ℃ and dried for 3 hours. Then, the catalyst was calcined in a muffle furnace at 500℃for 10 hours to obtain an initial catalyst C.
10g of the initial catalyst C was taken and reacted in H 2 The spherical isobutane dehydrogenation catalyst C is obtained by treating the mixture for 2 hours at 650 ℃ in a nitrogen gas stream with the S content of 1.0 percent.
The specific gravity of each component of the spherical isobutane dehydrogenation catalyst C is as follows: 9.8 wt% nickel oxide, 0.6 wt% elemental sulfur, and the balance being a support.
(3) Evaluation of catalyst Performance in the reaction of producing isobutene by dehydrogenation of isobutane
The test of the reaction performance of catalyst C in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in the step (3) of example 1, and the reaction results are shown in Table 2.
Example 4
This example is intended to illustrate a spherical isobutane dehydrogenation catalyst prepared in accordance with the present invention.
Spherical isobutane dehydrogenation catalyst D was prepared in the same manner as in example 1 except that: in the preparation of the spherical alumina-beta composite carrier (1), 100g of pseudo-boehmite with the model of P-DF-07-LSi and 30g of all-silicon beta molecular sieve are replaced by 110g of pseudo-boehmite with the model of P-DF-07-LSi and 23g of all-silicon beta molecular sieve; and preparing the spherical alumina-beta composite carrier D.
The content of alumina is 77 wt% and the content of all-silicon beta molecular sieve is 23 wt%, based on the total weight of the spherical alumina-beta composite carrier D.
The spherical alumina-beta composite support D was characterized and its structural parameters are shown in Table 1.
In the preparation of the spherical isobutane dehydrogenation catalyst (2), 8.0g of ferric nitrate nonahydrate is dissolved in 100g of deionized water, mixed with 10g of spherical alumina-beta composite carrier A, replaced by 5.0g of ferric nitrate nonahydrate is dissolved in 100g of deionized water, and mixed with 10g of spherical alumina-beta composite carrier D; will be "at H 2 The treatment at 550℃for 4 hours in a nitrogen stream with an S content of 1.5% was "replaced" with H 2 The spherical isobutane dehydrogenation catalyst D was obtained by treating the mixture at 550℃for 2 hours in a nitrogen stream having an S content of 1.0%.
The specific gravity of each component of the spherical isobutane dehydrogenation catalyst D is as follows: 8.3% by weight of iron oxide, 0.5% by weight of elemental sulphur and the balance of carrier.
The test of the reaction performance of catalyst D in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in the step (3) of example 1, and the reaction results are shown in Table 2.
Example 5
This example is intended to illustrate a spherical isobutane dehydrogenation catalyst prepared in accordance with the present invention.
Spherical isobutane dehydrogenation catalyst E was prepared in the same manner as in example 3 except that: in the preparation of the spherical alumina-beta composite carrier (1), 100g of pseudo-boehmite with the model PB-0104 and 18g of all-silicon beta molecular sieve are replaced by 84g of pseudo-boehmite with the model PB-0104 and 30g of all-silicon beta molecular sieve; and preparing the spherical alumina-beta composite carrier E.
The alumina content was 68% by weight and the total silica beta molecular sieve content was 32% by weight, based on the total weight of the spherical alumina-beta composite carrier E.
The spherical alumina-beta composite support E was characterized and its structural parameters are shown in Table 1.
In the preparation of the spherical isobutane dehydrogenation catalyst (2), the preparation method comprises the steps of dissolving 4.3g of nickel nitrate hexahydrate in 100mL of deionized water, mixing with 10g of spherical alumina-beta composite carrier C, replacing the step of dissolving 8.5g of nickel nitrate hexahydrate in 100mL of deionized water, and mixing with 10g of spherical alumina-beta composite carrier E; will be "at H 2 The treatment at 650℃for 5 hours in a nitrogen stream with S content of 2.0% was "replaced" with H 2 Treating at 550 ℃ for 2 hours "in a nitrogen stream with an S content of 1.0%; spherical isobutane dehydrogenation catalyst E was obtained.
The specific gravity of each component of the spherical isobutane dehydrogenation catalyst E is as follows: 22.1% by weight of nickel oxide, 1.6% by weight of elemental sulfur and the balance of support.
The test of the reaction performance of catalyst E in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in the step (3) of example 1, and the reaction results are shown in Table 2.
Example 6
This example is intended to illustrate a spherical isobutane dehydrogenation catalyst prepared in accordance with the present invention.
A spherical isobutane dehydrogenation catalyst F was prepared in the same manner as in example 2 except that: in the preparation of the spherical alumina-beta composite carrier (1), the process of mixing 130g of pseudo-boehmite with the model of P-DF-09-LSi with 50g of all-silicon beta molecular sieve is replaced by mixing 120g of pseudo-boehmite with the model of P-DF-09-LSi with 58g of all-silicon beta molecular sieve; the spherical alumina-beta composite carrier F is prepared.
The alumina content was 59% by weight and the total silica beta molecular sieve content was 41% by weight, based on the total weight of the spherical alumina-beta composite carrier F.
The spherical alumina-beta composite support F was characterized and its structural parameters are shown in Table 1.
In the preparation of the spherical isobutane dehydrogenation catalyst (2), the preparation method comprises the steps of dissolving 7.8g of zinc nitrate hexahydrate in 150mL of deionized water, mixing with 10g of spherical alumina-beta composite carrier B, replacing the preparation method with dissolving 2.7g of zinc nitrate hexahydrate in 150mL of deionized water, and mixing with 10g of spherical alumina-beta composite carrier F; will be "at H 2 The treatment at 450℃for 8 hours in a nitrogen stream with S content of 2.0% was "replaced" with H 2 Treating at 400 ℃ for 2 hours "in a nitrogen stream with an S content of 0.5%; spherical isobutane dehydrogenation catalyst F was obtained.
The specific gravity of each component of the spherical isobutane dehydrogenation catalyst F is as follows: 6.8 wt% zinc oxide, 0.2 wt% elemental sulphur and the balance being a carrier.
The test of the reaction performance of catalyst F in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in step (3) of example 1, and the reaction results are shown in Table 2.
Example 7
This example is intended to illustrate a spherical isobutane dehydrogenation catalyst prepared in accordance with the present invention.
Spherical isobutane dehydrogenation catalyst G was prepared in the same manner as in example 1 except that: in the preparation of the spherical alumina-beta composite carrier (1), 100g of pseudo-boehmite with the model of P-DF-07-LSi and 30g of all-silicon beta molecular sieve are replaced by 120g of pseudo-boehmite with the model of P-DF-07-LSi and 14g of all-silicon beta molecular sieve; the spherical alumina-beta composite carrier G is prepared.
The content of alumina is 86% by weight and the content of all-silica beta molecular sieve is 14% by weight, based on the total weight of the spherical alumina-beta composite carrier G.
The spherical alumina-beta composite support G was characterized and its structural parameters are shown in Table 1.
In the preparation of the spherical isobutane dehydrogenation catalyst (2), 8.0G of ferric nitrate nonahydrate is dissolved in 100G of deionized water, mixed with 10G of spherical alumina-beta composite carrier A, replaced by 19.8G of ferric nitrate nonahydrate is dissolved in 100G of deionized water, and mixed with 10G of spherical alumina-beta composite carrier G; will be "at H 2 The treatment at 550℃for 4 hours in a nitrogen stream with an S content of 1.5% was "replaced" with H 2 Treating at 600 ℃ for 10 hours "in a nitrogen stream with an S content of 2.5%; spherical isobutane dehydrogenation catalyst G was obtained.
The specific gravity of each component of the spherical isobutane dehydrogenation catalyst G is as follows: 27.3 wt% of iron oxide, 2.5 wt% of elemental sulfur, and the balance being a carrier.
The test of the reaction performance of catalyst G in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in step (3) of example 1, and the reaction results are shown in Table 2.
TABLE 1
Comparative example 1
This comparative example is to illustrate the differences in vectors.
A spherical isobutane dehydrogenation catalyst D1 was prepared in the same manner as in example 1 except that: catalyst D1 was prepared by the method of step (2) in example 1, except that "commercially available alumina" was used as the catalyst support instead of "spherical alumina-. Beta.composite support A"; wherein the specific surface area of the commercial alumina is 224m 2 Per gram, the pore volume was 0.69mL/g, the average particle diameter was 1.5mm, and the particle crush strength was 12.6N.
13.2% by weight of ferric oxide, 0.9% by weight of elemental sulfur and the balance of the carrier, based on the total weight of catalyst D1.
The test of the reaction performance of catalyst D1 in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in step (3) of example 1, and the reaction results are shown in Table 2.
Comparative example 2
This comparative example is to illustrate the different preparation conditions and thus the different catalyst components.
Spherical alumina-beta composite carrier A was prepared by the method of step (1) in example 1. Catalyst D2 was prepared according to the procedure of step (2) in example 1, and the catalyst preparation conditions, specifically:
2.1g of ferric nitrate nonahydrate is dissolved in 100g of deionized water, mixed with 10g of spherical alumina-beta composite carrier A, and stirred and reacted for 60 minutes at 50 ℃ under the assistance of ultrasonic waves with the power of 200W. And after the reaction is finished, evaporating solvent ethanol in the system by using a rotary evaporator to obtain a solid product. The solid product was placed in a drying oven at 100℃and dried for 5 hours. Then, the mixture was calcined in a muffle furnace at 550℃for 5 hours to obtain an initial catalyst D2.
10g of the initial catalyst D2 were taken and reacted in H 2 The spherical isobutane dehydrogenation catalyst D2 was obtained by treating at 650℃for 8 hours in a nitrogen stream having an S content of 3.0%.
3.9% by weight of ferric oxide, 3.2% by weight of elemental sulfur and the balance of the carrier, based on the total weight of catalyst D2.
The test of the reaction performance of catalyst D2 in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in step (3) of example 1, and the reaction results are shown in Table 2.
Comparative example 3
This comparative example is intended to illustrate a vulcanization-free treatment process.
Spherical alumina-beta composite carrier A was prepared by the method of step (1) in example 1. Catalyst D3 was prepared by the method of step (2) in example 1, and the sulfiding treatment of the initial catalyst was omitted so that 13.2% by weight of ferric oxide, based on the total weight of catalyst D3, and the balance was a carrier.
The test of the reaction performance of catalyst D3 in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in step (3) of example 1, and the reaction results are shown in Table 2.
Comparative example 4
This comparative example is to illustrate the differences in vectors.
A spherical isobutane dehydrogenation catalyst D4 was prepared in the same manner as in example 1 except that: catalyst D4 was prepared by the method of step (2) in example 1, except that "all-silica beta molecular sieve" was used as the catalyst support instead of "spherical alumina-beta composite support A" except that step (1) in example 1 was omitted.
13.2% by weight of ferric oxide, 0.9% by weight of elemental sulfur and the balance of the carrier, based on the total weight of catalyst D4.
The test of the reaction performance of catalyst D4 in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in step (3) of example 1, and the reaction results are shown in Table 2.
Comparative example 5
This comparative example is to illustrate the difference in component content in the spherical composite carrier.
A spherical isobutane dehydrogenation catalyst D5 was prepared in the same manner as in example 1 except that: in the preparation of the spherical composite carrier, 100g of pseudo-boehmite with the model of P-DF-07-LSi and 30g of all-silicon beta molecular sieve are replaced by 50g of pseudo-boehmite with the model of P-DF-07-LSi and 65g of all-silicon beta molecular sieve; the spherical alumina-beta composite carrier D5 is prepared.
The result was that the alumina content was 35% by weight and the total silica beta molecular sieve content was 65% by weight based on the total weight of the spherical alumina-beta composite carrier D5.
Wherein, the specific surface area of the spherical alumina-beta composite carrier D5 is 437m 2 Per gram, pore volume was 0.35mL/g, average particle diameter was 2.2mm, and particle crush strength was 17.6N.
Catalyst D5 was prepared according to the procedure of step (2) in example 1.
13.2% by weight of ferric oxide, 0.9% by weight of elemental sulfur and the balance of the carrier, based on the total weight of catalyst D5.
The test of the reaction performance of catalyst D5 in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in step (3) of example 1, and the reaction results are shown in Table 2.
Comparative example 6
This comparative example is to illustrate the difference in the preparation method of the spherical composite carrier.
A spherical isobutane dehydrogenation catalyst D6 was prepared in the same manner as in example 1 except that: in the preparation of the spherical composite carrier in the step (1), the ball milling process is canceled; the spherical alumina-beta composite carrier D6 is prepared.
The result was that the alumina content was 70% by weight and the total silica beta molecular sieve content was 30% by weight based on the total weight of the spherical alumina-beta composite carrier D6.
Wherein, the specific surface area of the spherical alumina-beta composite carrier D6 is 557m 2 Per gram, pore volume was 0.62mL/g, average particle diameter was 2.1mm, and particle crush strength was 31.8N.
Catalyst D6 was prepared according to the procedure of step (2) in example 1.
13.2% by weight of ferric oxide, 0.9% by weight of elemental sulfur and the balance of the carrier, based on the total weight of catalyst D6.
The test of the reaction performance of catalyst D6 in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in step (3) of example 1, and the reaction results are shown in Table 2.
TABLE 2
As can be seen from Table 2, the spherical isobutane dehydrogenation catalyst prepared by the method of the present invention has excellent performance when used in the reaction of preparing isobutene by dehydrogenation of isobutane.
The experimental results of comparative example 1 and comparative example 1 revealed that the catalyst a prepared using the spherical alumina-beta composite carrier had significantly better performance than the catalyst D1 prepared using the commercially available alumina as the carrier, and that the alkane conversion, the alkene selectivity, and the catalyst stability were significantly improved. The above results show that the spherical alumina-beta composite carrier is more favorable for the reaction of preparing isobutene by dehydrogenating isobutane.
The results of the experiments of comparative examples 1 and 2 revealed that the D2 catalyst having the contents of the respective components outside the specific ranges of the present invention was inferior in performance (isobutane conversion, isobutylene selectivity and catalyst stability), indicating that the propane dehydrogenation catalyst excellent in performance could be obtained only by the active components and the auxiliary agent supported on the carrier within the specific contents of the present invention.
The experimental results of the comparative example 1 and the comparative example 3 show that the performance of the catalyst A after the vulcanization treatment is obviously better than that of the catalyst D3 without sulfur, and the conversion rate of the isobutene and the selectivity of the isobutene are obviously improved; the performance of catalyst a was hardly degraded during the 6 hours reaction, while the isobutane conversion and the isobutene selectivity of the D3 catalyst were significantly reduced. The above results demonstrate that the presence of the S element on the catalyst surface can effectively improve the dehydrogenation activity of the catalyst, the selectivity of the target olefin, and the stability of the catalyst.
The experimental results of comparative example 1 and comparative example 4 revealed that the catalyst could not be industrially applied regardless of the catalyst performance, using all-silica molecular sieves instead of spherical alumina-beta composite carriers as catalyst carriers. Because all-silicon beta molecular sieve is powder, the powder cannot be molded without the help of a binder. The catalysts used in industry are all shaped samples.
The experimental results of comparative examples 1 and 5 show that the proportion of alumina and all-silica beta molecular sieve in the spherical alumina-beta composite carrier D5 is not within the specific range of the invention, the shape of the prepared molded carrier is not regular enough, the particle strength is poor, and the dispersion of the internal components is not uniform enough. The uniform dispersion of the active ingredient is also affected after the active ingredient is supported as a carrier. Therefore, the performance of catalyst D5 is inferior to that of catalyst a.
The experimental results of comparative examples 1 and 6 revealed that the spherical composite carrier prepared by omitting the ball milling process had insufficient uniform dispersion of the components, and the diffusion of the raw material molecules and the product molecules was affected during the reaction, resulting in lower catalyst conversion and selectivity.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (14)
1. A spherical isobutane dehydrogenation catalyst, which is characterized by comprising a spherical composite carrier, and a non-noble metal oxide and a non-metal supported on the spherical composite carrier, wherein the spherical composite carrier comprises alumina and an all-silicon beta molecular sieve, and the specific surface area of the spherical composite carrier is 300-800m 2 Per gram, the pore volume is 0.3-0.9mL/g, the average diameter of the particles is 1-3mm, and the average strength of the particles is 20-80N.
2. The catalyst according to claim 1, wherein the specific surface area of the spherical composite carrier is 450-650m 2 Per gram, the pore volume is 0.4-0.8mL/g, the average diameter of the particles is 1.3-2.8mm, and the average strength of the particles is 25-70N;
preferablyThe specific surface area of the spherical composite carrier is 531-615m 2 Per gram, the pore volume is 0.49-0.72mL/g, the average diameter of the particles is 1.5-2.6mm, and the average strength of the particles is 28.9-57.2N;
and/or, the content of the alumina is 55-90 wt% based on the total weight of the spherical composite carrier, and the content of the all-silicon beta molecular sieve is 10-45 wt%;
preferably, the content of the alumina is 65-80 wt% and the content of the all-silicon beta molecular sieve is 20-35 wt%, based on the total weight of the spherical composite carrier.
3. The catalyst of claim 1 or 2, wherein the non-noble metal oxide is selected from one or more of iron oxide, zinc oxide, tin oxide, nickel oxide, tungsten oxide, and manganese oxide;
and/or, the nonmetallic component is S element.
4. A catalyst according to any one of claims 1 to 3, wherein the content of the non-noble metal oxide is 5 to 30% by weight, the content of the non-metal component is 0.2 to 3% by weight, and the content of the spherical composite carrier is 67 to 95% by weight, based on the total weight of the catalyst;
preferably, the content of the non-noble metal oxide is 8-25 wt%, the content of the non-metal component is 0.3-2 wt%, and the content of the spherical composite carrier is 73-92 wt%, based on the total weight of the catalyst;
more preferably, the content of the non-noble metal oxide is 9.8 to 17.5 wt%, the content of the non-metal component is 0.6 to 1.3 wt%, and the content of the spherical composite carrier is 81.2 to 89.6 wt%, based on the total weight of the catalyst.
5. The catalyst according to any one of claims 1 to 4, wherein the preparation method of the spherical composite carrier comprises:
(1) Mixing an alumina precursor with a full-silica beta molecular sieve for ball milling, mixing powder obtained after ball milling with an acidic aqueous solution to prepare sol, dripping the sol into an oil ammonia column forming device, and performing ball forming and aging treatment to obtain a spherical precursor;
(2) And washing, drying and roasting the spherical precursor to obtain the spherical composite carrier.
6. The catalyst of claim 5, wherein the alumina precursor is selected from one or more of pseudo-boehmite, aluminum hydroxide gel, aluminum sol, gibbsite, and boehmite;
and/or the weight ratio of the usage amount of the alumina precursor, the all-silicon beta molecular sieve and the acidic aqueous solution is 1: (0.03-0.8): (1-5), preferably 1: (0.1-0.5): (2-4).
7. The catalyst of claim 5, wherein the oil phase of the oil ammonia column forming device is selected from one or more of transformer oil, silicone oil, vacuum pump oil, liquid paraffin, white oil, and petroleum ether;
and/or the water phase of the oil ammonia column forming device is an ammonia water solution containing nonionic surfactant and low-carbon alcohol;
preferably, the nonionic surfactant is selected from one or more of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, and polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.
8. The catalyst according to claim 5, wherein the conditions of the dropping include: the dropping rate is 10 to 300 drops/min, preferably 30 to 150 drops/min;
and/or, the balling conditions include: the temperature of the oil ammonia column is 20-120 ℃;
and/or, the aging conditions include: the temperature is 20-120 ℃ and the time is 1-20h;
and/or, the drying conditions include: the temperature is 70-150 ℃ and the time is 2-20h;
and/or, the roasting conditions include: the temperature is 400-700 ℃ and the time is 2-24h.
9. The preparation method of the spherical isobutane dehydrogenation catalyst is characterized by comprising the following steps:
(Z1) under the ultrasonic auxiliary condition, carrying out contact reaction on a solution containing a non-noble metal oxide precursor and a spherical composite carrier, and removing a solvent, drying and roasting to obtain an initial catalyst; wherein the spherical composite carrier comprises alumina and an all-silicon beta molecular sieve;
(Z2) vulcanizing the initial catalyst by sulfur-containing gas to obtain the spherical isobutane dehydrogenation catalyst.
10. The method of preparation of claim 9, wherein the ultrasound-assisted conditions comprise: the temperature is 10-100deg.C, the time is 10-180min, and the power is 100-300W;
Preferably, the ultrasound-assisted conditions include: the temperature is 20-80 ℃, the time is 30-120min, and the power is 150-250W.
11. The production method according to claim 9, wherein the solution containing the non-noble metal oxide precursor is an aqueous solution containing the non-noble metal oxide precursor;
and/or the mass concentration of the solution is 0.5-10%;
and/or the non-noble metal oxide precursor is selected from one or more of nitrate, sulfate, sulfite or metal chloride containing iron, zinc, tin, nickel, tungsten and manganese elements;
preferably, the non-noble metal oxide precursor is selected from one or more of nitrate or sulfate containing iron, zinc, tin, nickel, tungsten, manganese elements.
12. The production method according to claim 9, wherein the sulfur-containing gas is nitrogen, helium or argon containing hydrogen sulfide;
and/or the volume content of the hydrogen sulfide in the sulfur-containing gas is 0.1 to 5% by volume, preferably 0.3 to 2% by volume;
and/or, in step (Z1), the conditions of the firing include: the temperature is 400-700 ℃, preferably 500-650 ℃; the time is 2-15h, preferably 3-10h;
and/or, in step (Z1), the contacting reaction conditions include: the temperature is 20-100 ℃ and the time is 0.5-10h;
And/or, in step (Z2), the vulcanization treatment conditions include: the temperature is 400-700 ℃ and the time is 1-15h; preferably, the processing conditions include: the temperature is 450-650 ℃ and the time is 2-8h.
13. A spherical isobutane dehydrogenation catalyst prepared by the preparation method according to any one of claims 9 to 13.
14. Use of the spherical isobutane dehydrogenation catalyst according to any one of claims 1-8 in a reaction for producing isobutene by dehydrogenation of isobutane.
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