CN110614097A - Isobutane dehydrogenation catalyst with carrier being composite material containing silica gel and hexagonal mesoporous material, and preparation method and application thereof - Google Patents
Isobutane dehydrogenation catalyst with carrier being composite material containing silica gel and hexagonal mesoporous material, and preparation method and application thereof Download PDFInfo
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- CN110614097A CN110614097A CN201810638932.7A CN201810638932A CN110614097A CN 110614097 A CN110614097 A CN 110614097A CN 201810638932 A CN201810638932 A CN 201810638932A CN 110614097 A CN110614097 A CN 110614097A
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- Prior art keywords
- mesoporous material
- hexagonal mesoporous
- isobutane
- silica gel
- dehydrogenation catalyst
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- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 260
- 239000001282 iso-butane Substances 0.000 title claims abstract description 130
- 239000013335 mesoporous material Substances 0.000 title claims abstract description 121
- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 110
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000000741 silica gel Substances 0.000 title claims abstract description 72
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 50
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000005470 impregnation Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 9
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 82
- 239000011148 porous material Substances 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 25
- 238000007725 thermal activation Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 9
- 235000011151 potassium sulphates Nutrition 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
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- 239000013078 crystal Substances 0.000 claims description 3
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- 230000035484 reaction time Effects 0.000 claims description 3
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052710 silicon Inorganic materials 0.000 abstract description 10
- 239000010703 silicon Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000003213 activating effect Effects 0.000 abstract 1
- 230000004913 activation Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229910000510 noble metal Inorganic materials 0.000 description 10
- 239000002994 raw material Substances 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
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 9
- 230000008021 deposition Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000012265 solid product Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
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- 101150116295 CAT2 gene Proteins 0.000 description 4
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 4
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 4
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000004231 fluid catalytic cracking Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 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
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-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
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 241001292396 Cirrhitidae Species 0.000 description 1
- 102100021202 Desmocollin-1 Human genes 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
- 101000968043 Homo sapiens Desmocollin-1 Proteins 0.000 description 1
- 101000880960 Homo sapiens Desmocollin-3 Proteins 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000002431 hydrogen Chemical class 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000000967 suction filtration 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
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/618—
-
- B01J35/635—
-
- 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
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/02—Impregnation, coating or precipitation
-
- 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
- B01J37/08—Heat treatment
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/60—Platinum group metals with zinc, cadmium or mercury
Abstract
The invention relates to the field of catalysts, and discloses an isobutane dehydrogenation catalyst with a composite material containing silica gel and a hexagonal mesoporous material as a carrier, and a preparation method and application thereof. The method comprises the following steps: (a) preparing hexagonal mesoporous material raw powder; (b) preparing a hexagonal mesoporous material; (c) activating the hexagonal mesoporous material; (d) the carrier is subjected to activation treatment, then impregnation treatment is carried out in a solution containing a Pt component precursor and a Zn component precursor, and then solvent removal treatment, drying and roasting are sequentially carried out. The method can synthesize the isobutane dehydrogenation catalyst with high catalytic activity by utilizing the silicon source with low cost.
Description
Technical Field
The invention relates to the field of catalysts, in particular to an isobutane dehydrogenation catalyst with a carrier made of a composite material containing silica gel and a hexagonal mesoporous material, a preparation method of the isobutane dehydrogenation catalyst, the isobutane dehydrogenation catalyst 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, the specific surface area of the currently used carrier is small, which is not beneficial to the dispersion of the active metal component on the surface of the carrier, and is also not beneficial to the diffusion of raw materials and products in the reaction process.
Therefore, how to improve the reaction performance of the isobutane dehydrogenation catalyst is a problem to be solved in the field of preparing isobutene by isobutane dehydrogenation.
Disclosure of Invention
The invention aims to overcome the defects of uneven dispersion of noble metal active components and poor catalytic activity and stability of the existing isobutane dehydrogenation catalyst, and provides an isobutane dehydrogenation catalyst with a carrier made of a composite material containing silica gel and a hexagonal mesoporous material, a preparation method of the isobutane dehydrogenation catalyst, the isobutane dehydrogenation catalyst prepared by the method and application of the isobutane dehydrogenation catalyst in preparation of isobutene through isobutane dehydrogenation.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing an isobutane dehydrogenation catalyst, the method comprising the steps of:
(a) mixing and contacting a template agent, potassium sulfate, an acid agent and tetraethoxysilane, and crystallizing and filtering the obtained mixture to obtain hexagonal mesoporous material raw powder;
(b) carrying out demoulding agent treatment on the hexagonal mesoporous material raw powder to obtain a hexagonal mesoporous material;
(c) carrying out first thermal activation treatment on the hexagonal mesoporous material, and mixing the hexagonal mesoporous material subjected to the first thermal activation with silica gel;
(d) and carrying out second thermal activation treatment on the composite material carrier containing the silica gel and the hexagonal mesoporous material, then carrying out immersion treatment in a solution containing a Pt component precursor and a Zn component precursor, and then sequentially carrying out solvent removal treatment, drying and roasting.
A second aspect of the invention provides an isobutane dehydrogenation catalyst prepared by the aforementioned process.
The third aspect of the invention provides an application of the isobutane dehydrogenation catalyst prepared by the method 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 intensive research, the inventor of the invention finds that the carrier structure (including physical structures such as specific surface area, pore volume and pore size distribution, and chemical structures such as surface acid sites and electronic properties) of the noble metal catalyst not only has important influence on the dispersion degree of active metal components, but also directly influences mass transfer and diffusion in the reaction process. Thus, the catalytic properties of heterogeneous catalysts, such as activity, selectivity and stability, depend both on the catalytic characteristics of the active component and on the characteristics of the catalyst support. In order to reduce the content of noble metal in the catalyst as much as possible and improve the activity and stability of the catalyst at the same time, the preparation process of the carrier is of great importance. Most commercially available activated alumina has too many surface hydroxyl groups and too strong acidity. When the aluminum oxide is used as a carrier to prepare the dehydrogenation catalyst, the surface of the catalyst is easy to deposit carbon in the reaction process, and the rapid inactivation is caused.
Compared with the prior art, the isobutane dehydrogenation catalyst prepared by the method provided by the invention has the following advantages:
(1) the method for preparing the isobutane dehydrogenation catalyst provided by the invention has the advantages of simple preparation process, easily controlled conditions and good product repeatability;
(2) the isobutane dehydrogenation catalyst prepared by the method provided by the invention can achieve better dehydrogenation activity, selectivity, stability and carbon deposition resistance under the condition of low loading of main active components (namely noble metals), and can effectively reduce the preparation cost of the isobutane dehydrogenation catalyst;
(3) in the isobutane dehydrogenation catalyst prepared by the method provided by the invention, the stability of a Zn center with an oxidized structure under a high-temperature reduction condition is very high, the inactivation of a single Pt component loaded on a carrier can be inhibited, carbon deposition is reduced, a strong acid center on the surface of the carrier is effectively neutralized, the surface of the carrier is free from acidity, and the dispersion degree of the Pt component is improved through a geometric effect, so that the carbon deposition risk in the reaction process of preparing isobutene by anaerobic dehydrogenation of isobutane can be remarkably reduced, the selectivity of a target product is improved, and the stability of the isobutane dehydrogenation catalyst is improved;
(4) the mesoporous molecular sieve material with the spherical shape, the larger specific surface area and the larger pore volume is synthesized by utilizing the silicon source with low cost, which is beneficial to the good dispersion of the noble metal component on the surface of the carrier, thereby ensuring that the isobutane catalyst is not easy to be inactivated due to the agglomeration of active metal particles in the reaction process;
(5) the isobutane dehydrogenation catalyst prepared by the method provided by the invention shows good catalytic performance when used for preparing isobutene by anaerobic dehydrogenation of isobutane, and has the advantages of high isobutane conversion rate, high isobutene selectivity, good catalyst stability and low carbon deposition.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is an X-ray diffraction pattern of the hexagonal mesoporous material of example 1;
FIG. 2A is a nitrogen adsorption-desorption graph of the hexagonal mesoporous material of example 1;
FIG. 2B is a pore size distribution diagram of the hexagonal mesoporous material of example 1;
FIG. 3 is a TEM transmission electron micrograph of the micro-morphology of the hexagonal mesoporous material of example 1;
FIG. 4 is an SEM scanning electron micrograph of the microstructure of the hexagonal mesoporous material 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 indicated previously, a first aspect of the present invention provides a process for the preparation of an isobutane dehydrogenation catalyst, the process comprising the steps of:
(a) mixing and contacting a template agent, potassium sulfate, an acid agent and tetraethoxysilane, and crystallizing and filtering the obtained mixture to obtain hexagonal mesoporous material raw powder;
(b) carrying out demoulding agent treatment on the hexagonal mesoporous material raw powder to obtain a hexagonal mesoporous material;
(c) carrying out first thermal activation treatment on the hexagonal mesoporous material, and mixing the hexagonal mesoporous material subjected to the first thermal activation with silica gel;
(d) and carrying out second thermal activation treatment on the composite material carrier containing the silica gel and the hexagonal mesoporous material, then carrying out immersion treatment 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 present invention, in the step (a), the process of preparing the hexagonal mesoporous material raw powder may include: mixing and contacting a template agent, potassium sulfate, an acid agent and a silicon source, and crystallizing and filtering the obtained mixture. The order of the mixing and contacting is not particularly limited, and the template agent, the potassium sulfate, the acid agent and the silicon source may be mixed at the same time, or any two or three of them may be mixed, and then the other components may be added and mixed uniformly. According to a preferred embodiment, the template agent, the potassium sulfate and the acid agent are mixed uniformly, and then the silicon source is added and mixed uniformly.
In the present invention, the amount of the template, potassium sulfate and silicon source may vary within a wide range, for example, the molar ratio of the template, potassium sulfate and silicon source may be 1: (100-800): (20-200), preferably 1: (150-700): (80-180), more preferably 1: (200-400): (100-150).
In the present invention, the templating agent may be various templating agents that are conventional in the art. For example, the templating agent may be a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene, which may be prepared by methods known to those skilled in the art, or may be obtained commercially, for example, from Fuka under the trade name Synperonic F108, formula EO132PO60EO132Average molecular weight Mn14600. Wherein the number of moles of polyoxyethylene-polyoxypropylene-polyoxyethylene is calculated from the average molecular weight of polyoxyethylene-polyoxypropylene-polyoxyethylene.
In the present invention, the silicon source may be various silicon sources conventionally used in the art, and preferably the silicon source is at least one of tetraethoxysilane, methyl orthosilicate, propyl orthosilicate, sodium orthosilicate and silica sol, and more preferably tetraethoxysilane.
In the present invention, the acid agent may be various acidic aqueous solutions conventionally used in the art, and for example, may be at least one aqueous solution of hydrochloric acid, sulfuric acid, nitric acid and hydrobromic acid, preferably an aqueous hydrochloric acid solution.
The amount of the acid agent is not particularly limited, and may be varied within a wide range, and it is preferable that the pH value of the mixing contact is 1 to 7.
The conditions of the mixing and contacting are not particularly limited in the present invention, and for example, the conditions of the mixing and contacting may include: the temperature is 25-60 deg.C, the time is 10-72h, and the pH value is 1-7. In order to further facilitate uniform mixing between the substances, according to a preferred embodiment of the invention, the mixing contact is carried out under stirring conditions.
In the present invention, the crystallization conditions are not particularly limited, and for example, the crystallization conditions may include: the temperature is 30-150 ℃, preferably 90-150 ℃; the time is 10-72h, preferably 10-40 h. According to a preferred embodiment, the crystallization is carried out by hydrothermal crystallization.
In the present invention, in the above process for preparing a hexagonal mesoporous material, the process for obtaining a raw powder of the hexagonal mesoporous material by filtration may include: after filtration, repeated washing with deionized water (washing times may be 2 to 10) and suction filtration.
In the present invention, in step (b), the method for removing the template is generally a calcination method. The conditions for removing the template agent may be selected conventionally in the art, and for example, the conditions for removing the template agent include: the temperature can be 300-600 ℃, and the calcination time can be 8-20 h.
In the present invention, in the step (c), the hexagonal mesoporous material is subjected to a first thermal activation treatment, and the conditions of the first thermal activation include: the temperature is 300-900 ℃ and the time is 7-10 h; the hexagonal mesoporous material and the silica gel are mixed mechanically. The hexagonal mesoporous material and the silica gel can be well mixed and dispersed by adopting a mechanical blending mode, so that the hexagonal mesoporous material and the silica gel are mutually dispersed into the space occupied by each other, the initial distribution condition of the space occupied by the hexagonal mesoporous material and the silica gel is changed, the particle sizes of the hexagonal mesoporous material and the silica gel are reduced, and the dispersion of molecular degree is achieved in an extreme case.
In the present invention, there is no particular limitation on the kind of the silica gel as long as the silica gel has the structural requirements as set forth in the foregoing first aspect of the present invention, and preferably, the silica gel is commercially available ES955 silica Gel (GRACE).
According to the present invention, in step (d), in order to remove hydroxyl groups and residual moisture from the raw powder containing silica gel and hexagonal mesoporous material obtained in step (c), a second thermal activation treatment is required before the raw powder containing silica gel and hexagonal mesoporous material supports a metal component, and the conditions of the second thermal activation treatment may include: in the presence of nitrogen, the carrier is calcined at the temperature of 300-900 ℃ for 7-10 h.
According to the invention, the composite material loaded with the metal component containing the silica gel and the hexagonal mesoporous material can adopt an impregnation mode, the metal component enters the pore channel of the composite material containing the silica gel and the hexagonal mesoporous material by virtue of capillary pressure of the pore channel structure of the composite material containing the silica gel and the hexagonal mesoporous material, and meanwhile, the metal component can be adsorbed on the surface of the composite material containing the silica gel and the hexagonal mesoporous material until the metal component reaches adsorption equilibrium on the surface of the composite material containing the silica gel and the hexagonal mesoporous material. Preferably, the impregnation treatment is performed after the composite material containing the silica gel and the hexagonal mesoporous material is subjected to the second thermal activation treatment, and the impregnation treatment may be co-impregnation treatment or step-by-step impregnation treatment. In order to save the preparation cost and simplify the experimental process, the dipping treatment is preferably co-dipping treatment; further preferably, the conditions of the co-impregnation treatment include: and mixing and contacting the composite material containing the silica gel and the hexagonal mesoporous material after the second thermal activation in a solution containing a Pt component precursor and a Zn component precursor, wherein the impregnation temperature can be 25-50 ℃, and the impregnation time can be 2-6 h.
According to the bookIn the present invention, the solutions of the Pt component precursor and the Zn component precursor are not particularly limited, and may be selected conventionally in the art as long as they are water-soluble. For example, the Pt component precursor can be H2PtCl6The Zn component precursor may be 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, the solvent removal treatment can be carried out by a method conventional in the art, for example, a rotary evaporator can 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 conditions for the drying and firing are also not particularly limited in the present invention, and may be conventionally selected in the art, for example, the conditions for the drying 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.
Preferably, in the step (d), the composite material carrier containing the silica gel and the hexagonal mesoporous material, the Pt component precursor and the Zn component precursor are used in amounts such that, in the prepared isobutane dehydrogenation catalyst, the content of the carrier is 98-99.4 wt%, the content of the Pt component calculated by the Pt element is 0.1-0.5 wt%, and the content of the Zn component calculated by the Zn element is 0.5-1.5 wt%, based on the total weight of the isobutane dehydrogenation catalyst.
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 composite material containing silica gel and a hexagonal mesoporous material, the crystal structure of the hexagonal mesoporous material has a cubic-centered Im3m structure, the average pore diameter of the hexagonal mesoporous material is 4-15nm, and the specific surface area of the hexagonal mesoporous material is 550-650 m-2Per g, pore volume of 05-1.5mL/g, with an average particle size of 30-50 μm; the specific surface area of the silica gel is 200-300m2Per g, pore volume of 1-2mL/g, average pore diameter of 10-30nm, and average particle diameter of 20-100 μm.
According to the invention, the average particle size of the silica gel and the hexagonal 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 particle diameter means the particle size of the raw material particles, and when the raw material particles are spherical, the particle size is represented by the diameter of the sphere, when the raw material particles are cubic, the particle size is represented by the side length of the cube, and when the raw material particles are irregularly shaped, the particle size is represented by the mesh size of the screen mesh that is just capable of screening out the raw material particles.
According to the invention, the structural parameters of the silica gel and the hexagonal mesoporous material in the composite material are controlled within the range, so that the composite material is not easy to agglomerate, and the conversion rate of reaction raw materials in the reaction process of preparing propylene by dehydrogenating isobutane can be improved by using the supported catalyst prepared by using the composite material as a carrier. When the specific surface area of the hexagonal mesoporous material is less than 550m2When the volume/g and/or pore volume is less than 0.5mL/g, the catalytic activity of the supported catalyst prepared by using the supported catalyst is remarkably reduced; when the specific surface area of the hexagonal mesoporous material is more than 650m2When 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 propylene by isobutane dehydrogenation, so that the conversion rate of the reaction raw material in the reaction process of preparing propylene by isobutane dehydrogenation is influenced.
Preferably, in the composite material, the average pore diameter of the hexagonal mesoporous material is 4-12nm, and the specific surface area is 580-620m2Per gram, pore volume of 0.5-1mL/g, average particle size of 35-45 μm; the specific surface area of the silica gel is 230-280m2Per g, pore volume of 1.2-1.8mL/g, average pore diameter of 12-18nm, and average particle diameter of 30-70 μm;
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 Pt component is an active metal component, and the Zn component is a metal auxiliary agent.
According to the invention, based on the total weight of 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%.
According to the present invention, it is preferable that the content of the support is 98.5 to 99.3 wt%, the content of the Pt component is 0.2 to 0.5 wt% in terms of Pt element, and the content of the Zn component is 0.6 to 1.2 wt% in terms of Zn element, based on the total weight of the isobutane dehydrogenation catalyst.
Preferably, the content weight ratio of the hexagonal mesoporous material to the silica gel is (1.2-10): 1;
preferably, the silica gel is 955 silica gel.
The hexagonal mesoporous material in the composite material containing the silica gel and the hexagonal mesoporous material has an ultrahigh specific surface area, and also has the advantages of stable structure and large pore volume, and the hexagonal mesoporous material is compounded with the silica gel to be applied, so that the dispersion degree of metal components in the catalyst is favorably improved, and the catalyst formed by the composite material containing the hexagonal mesoporous material and the silica gel has more excellent catalytic performance in the process of catalyzing isobutane to dehydrogenate to prepare hydrogen, and the beneficial effects of high propane conversion rate and high propylene selectivity are obtained.
The third aspect of the invention provides an application of the isobutane dehydrogenation catalyst prepared by the method 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.
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 (0.5-1.5): 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, the reaction time is 20-40h, and the mass space velocity of 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, ES955 silica gel was obtained from GRACE; polyoxyethylene-polyoxypropylene-polyoxyethylene commercially available from Fuka under the trade name Synperonic F108, having the formula EO132PO60EO132Average molecular weight Mn＝14600。
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 particle size distribution of the sample is carried out on a Malvern laser particle sizer; 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; analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under model 7890A;
the drying box is produced by Shanghai-Hengchun scientific instruments Co., Ltd, and is of a type DHG-9030A;
the muffle furnace is manufactured by CARBOLITE corporation, and is of a model CWF 1100;
the ultrasonic generator is a KQ-300GTDV high-frequency constant-temperature numerical control ultrasonic cleaner produced by ultrasonic instruments Limited in Kunshan, the ultrasonic frequency is 80kHz, and the working voltage is 220V;
the nitrogen adsorption and desorption experiments of the samples were carried out on a full-automatic physicochemical adsorption analyzer model ASAP 2020M + C manufactured by Micromeritics, USA. The samples were degassed at 350 ℃ for 4 hours under vacuum prior to assay. The BET method is adopted to calculate the specific surface area of the sample, and the BJH model is adopted to calculate the pore volume and the average pore diameter.
The NH3-TPD experiment of the sample was carried out on an AUTOCHEM2920 full-automatic chemisorption instrument, manufactured by Micromeritics, USA. The sample was first reduced at 480 ℃ in an atmosphere of 10% H2-90% Ar for 1 hour. Then heating to 700 ℃ in He atmosphere, staying for 1 hour, cooling to 40 ℃ and adsorbing ammonia gas until saturation. After purging for 1h in He gas atmosphere, the temperature was raised from 40 ℃ to 700 ℃ at a rate of 10 ℃/min, while the ammonia desorption data was recorded using a TCD detector.
The content of each metal component in the prepared dehydrogenation catalyst is determined by calculating raw material feeding during preparation;
the isobutane conversion was calculated as follows:
isobutane conversion rate ═ amount of isobutane consumed by reaction/initial amount of isobutane × 100%;
the isobutene selectivity was calculated as follows:
isobutene selectivity is the amount of isobutane consumed for the production of isobutene/total consumption of isobutane × 100%;
the isobutene yield was calculated as follows:
the isobutene yield is isobutane conversion × isobutene selectivity × 100%.
Example 1
This example is illustrative of an isobutane dehydrogenation catalyst and a method for preparing the same.
(1) Preparation of the support
2g (1.4X 10)-4mol) template F108, 5.24g (0.03mol) of K2SO4Stirring with 60g hydrochloric acid solution with 2(2N) equivalent concentration at 38 deg.C until F108 is completely dissolved;
adding 4.2g (0.02mol) of tetraethoxysilane into the solution, stirring at 38 ℃ for 15min, and standing at 38 ℃ for 24 h;
adding 100 g of deionized water for dilution, filtering, washing and drying to obtain a raw powder mesoporous material;
calcining the original powder mesoporous material at 400 ℃ for 10 hours, and removing the template agent to obtain a hexagonal mesoporous material;
calcining the hexagonal mesoporous material for 10 hours at 400 ℃ under the protection of nitrogen (first thermal activation), and removing hydroxyl and residual moisture to obtain the hexagonal mesoporous material subjected to the first thermal activation;
the composite material is a composite material formed by mechanically blending a hexagonal mesoporous material and industrial 955 silica gel, wherein the mass ratio of 955 silica gel to the hexagonal mesoporous material is 1: 2, a composite material F1 was obtained as a support.
(2) Preparation of isobutane dehydrogenation catalyst
And (2) calcining 30g of the composite material C1 containing the silica gel and the hexagonal mesoporous material obtained in the step (1) at 400 ℃ for 10h under the protection of nitrogen, and performing second thermal activation treatment to remove hydroxyl and residual moisture of the composite material C1 containing the silica gel and the hexagonal mesoporous material.
0.080g H2PtCl6·6H2O and 0.457g Zn (NO)3)2·6H2Dissolving O in 100ml of deionized water to obtain a mixture solution, soaking 10g of the composite material C1 containing the silica gel and the hexagonal mesoporous material, which is prepared in the step (1), in the mixture solution 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 oven at 120 ℃ for drying for 3 h. And then roasting the mixture in a muffle furnace at the temperature of 600 ℃ for 6 hours to obtain the isobutane dehydrogenation catalyst Cat-1 (based on the total weight of the isobutane dehydrogenation catalyst Cat-1, the content of a Pt component in terms of Pt is 0.3 wt%, the content of a Zn component in terms of Zn is 1 wt%, and the balance is a carrier).
The hexagonal mesoporous material A1 and the isobutane dehydrogenation catalyst Cat-1 are characterized by an XRD, a scanning electron microscope and an ASAP2020-M + C type adsorption instrument;
fig. 1 is an X-ray diffraction pattern of the hexagonal mesoporous material a1, wherein the abscissa is 2 θ and the ordinate is intensity, and it is apparent from the XRD pattern that the hexagonal mesoporous material a1 has 1 diffraction peak (2 θ ═ 0.6 °) of the (110) plane and a diffraction shoulder (2 θ ═ 1.2 °) of the (200) plane in accordance with the cube center Im3m in the small angle region. (110) The diffraction peak intensity of the surface is high, the peak shape is narrow, which indicates that the hexagonal mesoporous material A1 has a good long-range ordered structure, and the result is consistent with the mesoporous material XRD spectrogram reported in the literature (Chengzhong Yu, Bozhi Tian, Jie Fan, Galen D. Stucky, Dongyuman Zao, J.Am.Chem.Soc.2002,124,4556-4557), and in addition, the position of the diffraction shoulder peak (2 theta is 1.2 degrees) of the (200) surface is completely different from the hexagonal or lamellar structure;
FIG. 2A is a graph showing the nitrogen adsorption-desorption curve (relative pressure in p/p on the abscissa) of hexagonal mesoporous material A10) Fig. 2B is a pore size distribution diagram (abscissa is pore size, unit is 0.1nm) of the hexagonal mesoporous material a1, from the pore size distribution diagram, it can be seen that the hexagonal mesoporous material a1 has a narrow pore size distribution and very uniform pore channels, and a nitrogen adsorption desorption isotherm in fig. 2A indicates that the hexagonal mesoporous material a1 is a typical IUPAC-defined class IV adsorption-desorption isotherm, and a sample has a hysteresis loop of H2, which proves that the hexagonal mesoporous material a1 has a mesoporous structure with a characteristic cubic cage structure reported in literature. Desorption branches between 0.4 and 0.5 relative partial pressure also indicate that the material has a cage-like cavity structure;
FIG. 3 is a TEM image of the micro-morphology of the hexagonal mesoporous material A1, and the shapes of the pores in the (100) crystal plane of the hexagonal mesoporous material A1 can be clearly seen from FIG. 3, and the samples are all shown to have a cubic-centered Im3m structure;
FIG. 4 is an SEM scanning electron micrograph of the micro-morphology of the hexagonal mesoporous material A1, which shows that the micro-morphology of the hexagonal mesoporous material A1 is hexagonal and the particle size is in micron order.
Table 1 shows the pore structure parameters of the hexagonal mesoporous material A1 and the isobutane dehydrogenation catalyst Cat-1.
Comparative example 1
This comparative example serves to illustrate a reference isobutane dehydrogenation catalyst and a process for its preparation.
A support and an isobutane dehydrogenation catalyst were prepared according to the method of example 1, except that the same weight of alumina support was used instead of the composite material C1 containing silica gel and hexagonal mesoporous material in the preparation of the support, thereby preparing a support D1 and an isobutane dehydrogenation catalyst Cat-D-1, respectively.
Comparative example 2
A support and an isobutane dehydrogenation catalyst were prepared according to the method of example 1, except that commercially available ES955 silica gel (GRACE company) was used as the support D2 instead of the composite material C1 containing silica gel and hexagonal mesoporous material in the preparation of the support, thereby preparing a support D2 and an isobutane dehydrogenation catalyst Cat-D-2, respectively.
Comparative example 3
A carrier and an isobutane dehydrogenation catalyst were prepared according to the method of example 1, except that Zn (NO) was not added during the impregnation process for preparing the isobutane dehydrogenation type catalyst3)2·6H2O, addition of only 0.080g H2PtCl6·6H2And O, only loading a single Pt component on the composite material which is used as the carrier and contains silica gel and the hexagonal mesoporous material by a co-impregnation method, thereby preparing the isobutane dehydrogenation catalyst Cat-D-3, wherein the content of the Pt component is 0.3 wt% calculated by Pt element and the balance is the carrier by taking the total weight of the isobutane dehydrogenation catalyst Cat-D-3 as the reference.
Example 2
This example is illustrative of an isobutane dehydrogenation catalyst and a method for preparing the same.
(1) Preparation of the support
1.46g (1X 10)-4mol) template F108, 6.96g (0.04mol) of K2SO4Stirring with 60g hydrochloric acid solution with 2(2N) equivalent concentration at 38 deg.C until F108 is completely dissolved;
adding 3.1g (0.015mol) of tetraethoxysilane into the solution, stirring for 15min at 38 ℃, and standing for 24h at 38 ℃;
adding 100 g of deionized water for dilution, filtering, washing and drying to obtain a raw powder mesoporous material;
calcining the original powder mesoporous material at 400 ℃ for 10 hours, and removing the template agent to obtain a hexagonal mesoporous material;
calcining the hexagonal mesoporous material for 10 hours at 400 ℃ under the protection of nitrogen (first thermal activation), and removing hydroxyl and residual moisture to obtain the hexagonal mesoporous material subjected to the first thermal activation;
30g of hexagonal mesoporous material A2 was mechanically blended with 10g of ES955 silica gel B (see Table 1 for relevant parameters, available from Grace, USA) at 25 ℃ to obtain composite material F2 as a carrier.
The XRD structural diagram and the SEM micro-topography diagram of the hexagonal mesoporous material A2 are respectively similar to those of the hexagonal mesoporous material A1, and the SEM micro-topography diagram of ES955 silica gel B is similar to that of ES955 silica gel A.
The pore structure parameters of the hexagonal mesoporous material a2 and ES955 silica gel B are shown in table 1.
(2) Preparation of isobutane dehydrogenation catalyst
And (2) calcining 30g of the composite material C2 containing the silica gel and the hexagonal mesoporous material obtained in the step (1) at 400 ℃ for 10h under the protection of nitrogen, and performing second thermal activation treatment to remove hydroxyl and residual moisture of the composite material C2 containing the silica gel and the hexagonal mesoporous material.
0.080g H2PtCl6·6H2O and 0.457g Zn (NO)3)2·6H2Dissolving O in 100ml of deionized water to obtain a mixture solution, soaking 10g of the composite material C2 containing silica gel and a hexagonal mesoporous material, which is prepared in the step (1), in the mixture solution for 5 hours at 25 ℃, evaporating solvent water in a system by using a rotary evaporator to obtain a solid product, placing the solid product in a drying box at 120 ℃, drying for 3 hours, then placing the dried solid product in a muffle furnace at 600 ℃, and roasting for 6 hours to obtain the isobutane dehydrogenation catalyst Cat-2 (based on the total weight of the isobutane dehydrogenation catalyst Cat-2, the content of the Pt component is 0.3 wt% calculated by the Pt element, the content of the Zn component is 1 wt% calculated by the Zn element, and the balance is a carrier).
Example 3
This example is illustrative of an isobutane dehydrogenation catalyst and a method for preparing the same.
(1) Preparation of the support
Preparing a composite material F3 containing a hexagonal mesoporous material A1 and ES955 silica gel B
First, a hexagonal mesoporous material a1 was prepared in the same manner as in preparation example 1.
Then, 20g of hexagonal mesoporous material A1 and 10g of ES955 silica gel B were mechanically blended at 25 ℃ to obtain a composite material F3 as a carrier.
(2) Preparation of isobutane removal catalyst
And (2) calcining 30g of the composite material C3 containing the silica gel and the hexagonal mesoporous material obtained in the step (1) at 400 ℃ for 10h under the protection of nitrogen, and performing second thermal activation treatment to remove hydroxyl and residual moisture of the composite material C3 containing the silica gel and the hexagonal mesoporous material.
0.080g H2PtCl6·6H2O and 0.457g Zn (NO)3)2·6H2Dissolving O in 100ml of deionized water to obtain a mixture solution, soaking 10g of the composite material C3 containing silica gel and a hexagonal mesoporous material, which is prepared in the step (1), in the mixture solution for 5 hours at 25 ℃, evaporating solvent water in a system by using a rotary evaporator to obtain a solid product, placing the solid product in a drying box at 120 ℃, drying for 3 hours, then placing the dried product in a muffle furnace at 600 ℃, and roasting for 6 hours to obtain the isobutane dehydrogenation catalyst Cat-3 (based on the total weight of the isobutane dehydrogenation catalyst Cat-3, the content of the Pt component in terms of Pt element is 0.3 wt%, the content of the Zn component in terms of Zn element is 1 wt%, and the balance is a carrier).
TABLE 1
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) | Average pore diameter*(nm) | Particle size (. mu.m) |
| Hexagonal mesoporous material A1 | 598 | 0.7 | 5 | 35-40 |
| Hexagonal mesoporous material A2 | 560 | 1.3 | 9 | 35-45 |
| ES955 silica gel A | 250 | 1.5 | 15 | 20-50 |
| ES955 silica gel B | 230 | 1.5 | 16 | 30-55 |
As can be seen from the data in table 1, the specific surface area and the pore volume of the hexagonal mesoporous material are reduced after the main active component Pt and the metal assistant Zn are loaded, which indicates that the main active component Pt and the metal assistant Zn enter the interior of the hexagonal mesoporous material during the loading reaction.
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 reaction time is 24 hours, and the mass space velocity of the isobutane is 4 hours-1. By Al2O3The reaction product separated by the S molecular sieve column directly enters an Agilent 7890A gas chromatograph equipped with a hydrogen flame detector (FID) for on-line analysis, and the obtained isobutane conversion rate and isobutene selectivity are shown in Table 2. After the reaction, the amount of carbon deposition in the isobutane dehydrogenation catalyst Cat-1 was measured using a TGA/DSC1 thermogravimetric analyzer from METTLER-TOLEDO, as shown in table 2.
Experimental examples 2 to 3
Isobutene was prepared by dehydrogenation of isobutane according to the method of experimental example 1, except that isobutane dehydrogenation catalyst Cat-2 and isobutane dehydrogenation catalyst Cat-3 were used instead of isobutane dehydrogenation catalyst Cat-1, respectively. The isobutane conversion, isobutene selectivity and carbon deposition amount of the isobutane dehydrogenation catalyst are shown in table 2.
Experimental comparative examples 1 to 3
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-3 are respectively adopted to replace the isobutane dehydrogenation catalyst Cat-1. The isobutane conversion, isobutene selectivity and carbon deposition amount of the isobutane dehydrogenation catalyst are shown in table 2.
TABLE 2
| Dehydrogenation catalyst | Isobutane conversion rate | Selectivity to isobutene | Amount of carbon deposition | |
| Experimental example 1 | Cat-1 | 25％ | 96％ | 1.15wt％ |
| Experimental example 2 | Cat-2 | 24％ | 95％ | 1.3wt％ |
| Experimental example 3 | Cat-3 | 23％ | 94％ | 1.2wt％ |
| Experimental comparative example 1 | Cat-D-1 | 12.5％ | 71.3％ | 5.3wt％ |
| Experimental comparative example 2 | Cat-D-2 | 17.2％ | 20.5％ | 6.2wt％ |
| Experimental comparative example 3 | Cat-D-3 | 24.5％ | 55.6％ | 3.1wt％ |
As can be seen from Table 2, when the isobutane dehydrogenation catalyst prepared by the method of the invention is used in the reaction of preparing isobutene by isobutane dehydrogenation, a higher isobutane conversion rate and isobutene selectivity can still be obtained after 24 hours of reaction, which shows that the isobutane dehydrogenation catalyst of the invention not only has better dehydrogenation activity and high selectivity, but also has excellent stability and low carbon deposition. In addition, the method for preparing the isobutane dehydrogenation catalyst provided by the invention has the advantages of simple preparation process and lower cost.
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, characterized in that the method comprises the following steps:
(a) mixing and contacting a template agent, potassium sulfate, an acid agent and tetraethoxysilane, and crystallizing and filtering the obtained mixture to obtain hexagonal mesoporous material raw powder;
(b) carrying out demoulding agent treatment on the hexagonal mesoporous material raw powder to obtain a hexagonal mesoporous material;
(c) carrying out first thermal activation treatment on the hexagonal mesoporous material, and mixing the hexagonal mesoporous material subjected to the first thermal activation with silica gel;
(d) and carrying out second thermal activation treatment on the composite material carrier containing the silica gel and the hexagonal mesoporous material, then carrying out immersion treatment 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 step (a), the molar ratio of the templating agent, potassium sulfate, and ethyl orthosilicate is 1: (100-800): (20-200);
more preferably, the templating agent is a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene; the acid agent is hydrochloric acid;
further preferably, the conditions of the mixing contact include: the temperature is 25-60 ℃, the time is 10-72h, and the pH value is 1-7; the crystallization conditions include: the temperature is 30-150 ℃, and the time is 10-72 h; the process of the stripper plate agent treatment comprises: calcining the hexagonal mesoporous material raw powder for 8-20h at the temperature of 300-600 ℃.
3. The method of claim 1, wherein in step (b), the conditions for removing the templating agent comprise: the temperature is 300 ℃ and 600 ℃, and the time is 8-20 hours.
4. The method of claim 1, wherein in step (c), the first thermally-activated conditions comprise: the temperature is 300 ℃ and 900 ℃ and the time is 7-10 h.
5. The method according to claim 1, wherein in the step (d), the composite material carrier containing the silica gel and the hexagonal mesoporous material, the Pt component precursor and the Zn component precursor are used in amounts such that the content of the carrier in the prepared isobutane dehydrogenation catalyst is 98-99.4 wt%, the content of the Pt component in terms of Pt element is 0.1-0.5 wt%, and the content of the Zn component in terms of Zn element is 0.5-1.5 wt%, based on the total weight of the isobutane dehydrogenation catalyst;
preferably, the second heat-activated conditions include: the temperature is 300-900 ℃ and the time is 7-10 h; the conditions of the impregnation treatment include: the temperature is 25-50 ℃ and the time is 2-6 h.
6. An isobutane dehydrogenation catalyst produced by the process of any one of claims 1-5.
7. Isobutane dehydrogenation catalyst according to claim 6, wherein the isobutane dehydrogenation catalystComprises a carrier, a Pt component and a Zn component which are loaded on the carrier, wherein the carrier is a composite material containing silica gel and a hexagonal mesoporous material, the crystal structure of the hexagonal mesoporous material has a cubic-centered Im3m structure, the average pore diameter of the hexagonal mesoporous material is 4-15nm, and the specific surface area is 550-650 m-2Per gram, pore volume of 0.5-1.5mL/g, average particle size of 30-50 μm; the specific surface area of the silica gel is 200-300m2Per g, pore volume of 1-2mL/g, average pore diameter of 10-30nm, and average particle diameter of 20-100 μm.
8. An isobutane dehydrogenation catalyst according to claim 6 or 7, wherein the average pore diameter of said hexagonal mesoporous material is 4-12nm, the specific surface area is 580-620m2Per gram, pore volume of 0.5-1mL/g, average particle size of 35-45 μm; the specific surface area of the silica gel is 230-280m2Per g, pore volume of 1.2-1.8mL/g, average pore diameter of 12-18nm, and average particle diameter of 30-70 μm;
preferably, the content weight ratio of the hexagonal mesoporous material to the silica gel is (1.2-10): 1;
preferably, the silica gel is 955 silica gel.
9. An isobutane dehydrogenation catalyst according to claim 7, wherein the carrier is present in an amount of 98-99.4 wt%, the Pt component is present in an amount of 0.1-0.5 wt% calculated as Pt element, and the Zn component is present in an amount of 0.5-1.5 wt% calculated as Zn element, 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 in the production of isobutene by the dehydrogenation of isobutane, wherein the method for producing 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, the reaction time is 20-40h, and the mass space velocity of isobutane is 2-5h-1。
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