CN114570415A - Pt @ hierarchical pore zeolite catalyst for preparing propylene by propane dehydrogenation and preparation method thereof - Google Patents
Pt @ hierarchical pore zeolite catalyst for preparing propylene by propane dehydrogenation and preparation method thereof Download PDFInfo
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- CN114570415A CN114570415A CN202210309262.0A CN202210309262A CN114570415A CN 114570415 A CN114570415 A CN 114570415A CN 202210309262 A CN202210309262 A CN 202210309262A CN 114570415 A CN114570415 A CN 114570415A
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- zeolite
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- hierarchical pore
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- propane
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 89
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000010457 zeolite Substances 0.000 title claims abstract description 83
- 239000001294 propane Substances 0.000 title claims abstract description 58
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 38
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000000956 alloy Substances 0.000 claims abstract description 3
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 3
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- -1 polytetrafluoroethylene Polymers 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012690 zeolite precursor Substances 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 4
- 229910005267 GaCl3 Inorganic materials 0.000 claims description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 239000011686 zinc sulphate Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Inorganic materials [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000373 gallium sulfate Inorganic materials 0.000 claims description 2
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910009112 xH2O Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052799 carbon Inorganic materials 0.000 abstract description 20
- 230000008021 deposition Effects 0.000 abstract description 18
- 239000000376 reactant Substances 0.000 abstract description 14
- 238000012546 transfer Methods 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 7
- 230000002779 inactivation Effects 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 238000005580 one pot reaction Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 239000002243 precursor Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 2
- 229910002846 Pt–Sn Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
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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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
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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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/22—Noble metals
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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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7476—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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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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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a Pt @ hierarchical pore zeolite catalyst for preparing propylene by propane dehydrogenation and a preparation method thereof, and the catalyst is characterized in that: pure silicon hierarchical pore zeolite is used as a carrier; the active component is Pt, wherein the Pt exists in micropores of the zeolite in the form of clusters; the promoter metal is Sn, Zn or Ge, and the promoter metal and Pt interact to form an alloy. According to the invention, the Pt @ hierarchical pore zeolite catalyst packaged by the hierarchical pore zeolite is synthesized by a one-pot method under the action of the mesoporous template, and the excellent mass transfer performance of the mesoporous template obviously improves the transmission rate of reactants and products in a pore channel, so that the utilization rate of Pt is improved to the maximum extent, and the carbon deposition inactivation rate of the catalyst is reduced. The catalyst is applied to propane dehydrogenation catalytic reaction and shows performance far exceeding that of other zeolite catalysts.
Description
Technical Field
The invention relates to the field of preparation of catalysts, in particular to a Pt @ hierarchical pore zeolite catalyst for preparing propylene by propane dehydrogenation and a preparation method thereof.
Background
Propylene is an important petrochemical basic raw material, is mainly used for producing chemicals such as polypropylene, propylene oxide, acrylonitrile, butanol and octanol, and is widely applied to the fields of coatings, rubber, cosmetics, plastics, fibers and the like. At present, over half of propylene production in the petrochemical field is realized by the traditional petroleum cracking technology, however, with the continuous increase of propylene demand in China and the world, the technology is not enough to meet the actual demand in China, so that the propylene market in China has demand gaps, and the propylene market in China can only rely on a large number of imports to meet the actual demand; therefore, various countries in the world, especially our country, are working on developing novel technology for producing propylene.
The method for preparing the propylene by using the shale gas, the natural gas, the coal bed gas, the refinery gas and the like rich in the propane as the raw materials can greatly relieve the supply-demand contradiction of the propylene market, and is an important way for realizing the diversification of the raw materials for producing the propylene. Compared with other propylene production routes, the method for preparing propylene by propane dehydrogenation has the following obvious advantages: 1) the raw material propane has wide source and low price; 2) the technical process is relatively simple, and the investment of the device is relatively small; 3) the yield of propylene is high, and about 1.2 tons of propane can produce 1 ton of propylene. Therefore, the technology for preparing propylene by propane dehydrogenation has obvious cost advantage and is a very competitive route for expanding the production capacity of propylene at present.
Alumina-supported Pt-based catalysts developed by UOP corporation are used in over 80% of all propane dehydrogenation plants worldwide. However, the catalyst has low Pt dispersity, so that Pt cannot be fully utilized; in addition, in the operation, due to carbon deposition and sintering of Pt particles, the catalyst is deactivated quickly, and the regeneration is carried out for 5 to 7 days. Therefore, the invention of the Pt-based catalyst with high activity and high stability is an urgent key problem to be solved for breaking through the existing propane dehydrogenation technology and developing a new generation propane dehydrogenation technology.
In recent years, the development of zeolite-encapsulated Pt catalyst Pt @ zeolite based on the zeolite channel confinement effect has attracted a wide range of attention for propane dehydrogenation (CN 110479353A). The Pt @ Zeolite catalyst created based on the specific micropore confinement effect of zeolite not only solves the problem of high dispersity of Pt (Pt sub-nano clusters are highly dispersed in micropores), but also can solve the problem of sintering of Pt nano particles (the Pt sub-nano clusters in the micropores are not agglomerated at high temperature), and is a propane dehydrogenation catalyst with research value and application prospect. However, propane dehydrogenation Pt @ zeolite catalysts still face two major technical problems in future applications: (1) the diffusion in the microporous zeolite belongs to typical configuration diffusion, the diffusion coefficient of the microporous zeolite is far lower than Knudsen diffusion in mesopores and macropores, and the phi value of the microporous zeolite is generally far larger than 1. Thus, there is a concentration gradient within the zeolite crystallites, the concentration of the reactants within the crystallitesCDistance from surfaceLIs reduced, and thus the effective utilization of active sites within the zeolite channelsη(approximately equal to tanh (Φ)/Φ) is lower than 1. It can be seen that the improvement in the stability performance of the Pt @ zeolite catalyst is achieved at the expense of activity, which in turn reduces the effective utilization rate for the Pt noble metal. (2) Since the propylene product cannot be rapidly removed from the reactorThe pores diffuse out, and polymerization inevitably occurs in the slow diffusion of the micropores to generate carbon deposit. When the amount of carbon deposition reaches a certain level, the carbon deposition causes the complete blockage of the pore channels, and the catalyst is deactivated. In addition, during the roasting and regeneration process of the catalyst, carbon deposition is difficult to completely burn off due to the limitation of micropore mass transfer and heat transfer. The two problems restrict the overall utilization efficiency of the noble metal Pt and seriously affect the economical efficiency of the practical application of the Pt @ Zeolite catalyst.
In order to effectively solve the problems that the existing Pt @ Zeolite catalyst is low in catalytic efficiency and easy to form carbon in the propane dehydrogenation reaction, the invention provides a method for introducing mesopores into conventional zeolite to construct hierarchical pore zeolite so as to strengthen mass transfer, realize the coordination of diffusion and reaction and construct a high-performance propane dehydrogenation catalyst.
CN107303497A and CN 112619690A report a hierarchical pore dehydrogenation catalyst and a preparation method thereof, and disclose a catalyst which takes hierarchical pore ZSM-5 zeolite as a carrier, Pt as an active component, Sn and the like as auxiliaries. The catalyst prepared by the method has high propane conversion rate and propylene selectivity. The method synthesizes the Pt catalyst loaded by the hierarchical pore zeolite through a multi-step method, namely, synthesizing the conventional ZSM-5 zeolite, obtaining the hierarchical pore zeolite through alkali or ammonium treatment, and finally impregnating components such as Pt and the like on the zeolite. This approach has significant disadvantages: 1. the multistep synthesis process is complex and is not economical; 2. impregnation does not disperse the Pt component well into the hierarchical pores of the zeolite, with the Pt component on the surface of the zeolite crystals.
The invention synthesizes the Pt @ hierarchical pore zeolite catalyst packaged by the hierarchical pore zeolite by using the mesoporous template through an in-situ one-pot method, the process is simple, and the Pt can be dispersed into the micro-channels of the zeolite. The catalyst obviously improves the transmission rate of reactants and products in a pore channel by utilizing the excellent mass transfer performance of the mesopores, thereby improving the utilization rate of Pt to the maximum extent and reducing the carbon deposition inactivation rate of the catalyst.
Disclosure of Invention
According to the invention, the Pt @ hierarchical pore zeolite catalyst packaged by the hierarchical pore zeolite is synthesized by adopting a mesoporous mold one-pot method, and the excellent mass transfer performance of mesopores obviously improves the transmission rate of reactants and products in pore channels, so that the utilization rate of Pt is improved to the maximum extent, and the carbon deposition inactivation rate of the catalyst is reduced. The catalyst is applied to propane dehydrogenation catalytic reaction and shows far better activity and stability than zeolite catalysts.
In order to achieve the purpose, the invention adopts the following technical scheme:
a Pt @ hierarchical pore zeolite catalyst for preparing propylene by propane dehydrogenation and a preparation method thereof are disclosed: the catalyst prepared by the method mainly comprises three components, namely the hierarchical pore zeolite, a main active component loaded on a carrier and an auxiliary agent. The catalyst is synthesized by adopting a mesoporous template one-pot method, the main active component loaded on zeolite is Pt, and the auxiliary agent is mainly Zn, Ga or Sn and other components. The preparation method of the catalyst is mainly a hydrothermal synthesis method. The method has the advantages of simple process, wide application range and excellent catalyst performance.
A Pt @ hierarchical pore zeolite catalyst for preparing propylene by propane dehydrogenation takes pure silicon hierarchical pore zeolite as a carrier; the active component is Pt, wherein the Pt exists in micropores of the zeolite in the form of clusters; the promoter metal is Sn, Zn or Ge, and the promoter metal and Pt interact to form an alloy, wherein the loading capacity of the active component Pt is 0.20-0.30wt% and the loading capacity of the promoter metal is 0.20-0.50wt% on the basis of the catalyst; in the pure silicon hierarchical pore zeolite, the size of the mesopores is 10-30nm, and the volume of the mesopores is 0.30-0.50 cm3(ii) in terms of/g. The pure silicon hierarchical pore zeolite is one of ZSM-5 zeolite, MCM-22 zeolite, beta zeolite and mordenite with a hierarchical pore structure.
A preparation method of a Pt @ hierarchical pore zeolite catalyst for preparing propylene by propane dehydrogenation specifically comprises the following steps:
(1) uniformly mixing a silicon source, a mesoporous template agent, a structure directing agent and water, then fully stirring overnight to obtain a zeolite precursor, adding a Pt compound and an auxiliary metal compound into the zeolite precursor, and fully stirring;
(2) transferring the solution prepared in the step (1) to a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a reaction kettle, and then putting the polytetrafluoroethylene lining into an oven for crystallization reaction;
(3) after the crystallization process is finished, cooling and opening the reaction kettle, filtering and washing the generated zeolite product for multiple times, and then drying to obtain the zeolite containing the auxiliary agent;
(4) grinding the zeolite solid containing the auxiliary agent obtained in the step (3) into powder, and then placing the powder into a muffle furnace for high-temperature roasting to remove the mesoporous template agent and the structure directing agent;
(5) the catalyst precursor prepared in the step (4) is put in H at a certain temperature2Reducing in the atmosphere to obtain the Pt @ hierarchical pore zeolite catalyst for preparing propylene by propane dehydrogenation.
Further, the molar ratio of each substance in the mixture in the step synthesis satisfies the following conditions:
structure directing agent (microporous template): silicon source = 0.05-0.30: 1;
a mesoporous template: silicon source = 0.05-0.10: 1;
metal salts of Pt: auxiliary agent metal salt: SiO 22=0 .015 ~ 0 .030：0 .015 ~ 0 .090：1；
H2O：SiO2=10 ~ 60：1；
Wherein the mole number of the silicon source is SiO2In terms of moles; the number of moles of the template is calculated by the number of moles of the template itself; the moles of the Pt metal salt and the promoter metal salt are based on the moles of the metal element.
Further, the silicon source is white carbon black, tetraethoxysilane or silica sol; the structure directing agent is any one of tetrapropylammonium hydroxide, tetraethylammonium hydroxide and hexamethyleneimine; pt organometallic compounds including Pt (HACAC)2、Pt(COD)Cl2And Pt (COD) (Me)2、H2PtCl6·6H2O or the like; the adjuvant metal compound comprises HSnBu3、Sn(HAC)2、HSnPh3And GaCl3、Ga(NO3)3·xH2O、Ga2(SO4)3·18H2O and Zn (NO)3)2·6H2O、ZnSO4·7H2O、ZnCl2Any ofOne kind of the material is selected; the mesoporous template agent is any one of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), polydiallyldimethylammonium chloride (PDDA) and polyvinyl alcohol.
Further, the temperature of the crystallization reaction in the step (2) is 140-170 ℃, and the crystallization reaction time is 2-7 days.
Further, in the high-temperature roasting process in the step (4), the roasting temperature is 500-600 ℃, and the roasting time is 3-5 hours.
Further, step (5) is H2The technological parameters of the reduction reaction in the atmosphere are as follows: the temperature used for reduction is 500-630 ℃, and the reduction time is 4-8 h.
The application comprises the following steps: the Pt @ hierarchical pore zeolite catalyst is used for the reaction of preparing propylene by propane dehydrogenation, the reaction temperature is 570-600 ℃, and the mass airspeed WHSV of propane is 5.3 h-1The propane dehydrogenation reaction is carried out in a fixed bed reactor.
The invention has the beneficial effects that:
the Pt @ hierarchical pore zeolite catalyst is synthesized by a simple one-pot method, and the method is simple in process, easy to amplify and good in economy. The catalyst utilizes the excellent mass transfer performance of mesopores to obviously improve the transmission rate of reactants and products in pore channels, thereby improving the utilization rate of Pt to the maximum extent and reducing the carbon deposition inactivation rate of the catalyst.
Drawings
FIG. 1 is a STEM chart of the catalyst obtained in example 1; it can be seen from the figure that the Pt metal clusters and nanoparticles are highly dispersed in the microporous channels of the zeolite.
Detailed Description
For a further understanding of the details of the invention, reference is made to the following detailed description and accompanying drawings, which are incorporated in and constitute a part of this specification, but not limiting the scope of the invention.
Example 1
27.10g TEOS were weighed into a 250ml beaker, 11.60g deionized water was added and stirred at room temperature for 1h, after which 10.5g PDDA was added and stirred for 2 h. 24g of tetrapropylammonium hydroxide are weighed into a 200ml beaker and addedAnd adding 24g of deionized water for dilution, adding the diluted solution into the solution, and stirring the prepared transparent solution at room temperature overnight to completely hydrolyze the transparent solution so as to synthesize the precursor of the ZSM-5. Thereafter 0.1075g Zn (NO) is weighed out3)2·6H2O and 0.0550g H2PtCl6·6H2Adding O into the zeolite precursor, stirring thoroughly, transferring to 200ml polytetrafluoroethylene lining, and crystallizing at 170 deg.C for 3 days in a reaction kettle. After crystallization is finished, the generated white solid is washed clean by distilled water and dried at 120 ℃, then calcined at 550 ℃ for 4h, and then reduced by hydrogen at 550 ℃ for 4h to prepare the Pt-Zn @ hierarchical pore ZSM-5 zeolite catalyst (the load of Pt is 0.25wt%, and the load of Zn is 0.30 wt%). The catalyst has a mesopore size of 25 nm and a mesopore volume of 0.40cm3/g。
In a fixed-bed tubular reactor packed with 200mg of the catalyst prepared in example 1, the dehydrogenation reactant was propane, the reaction temperature was 570 ℃ and the mass space velocity WHSV of propane was 5.3 h-1Under the condition that the reaction pressure is normal pressure, the initial conversion rate of propane is 50%, the selectivity of propylene is 99.5%, the conversion rate of the catalyst after 72 hours of reaction is 49.5%, and the carbon deposition amount is 0.4%.
Example 2
7.35g of white carbon black are weighed into a 250ml beaker, 11.60g of deionized water are added and stirred at room temperature for 1 hour, after which 2.8g P123 is added and stirred for 2 hours. 24g of tetraethylammonium hydroxide is weighed in a 200ml beaker, and 24g of deionized water is added for dilution and then added into the solution, and the prepared transparent solution is stirred at room temperature overnight to be completely hydrolyzed, thereby synthesizing the precursor of the ZSM-5. Thereafter 0.0440g Pt (HACAC) were weighed2And 0.0864g Sn (HAC)2Adding into zeolite precursor, stirring, transferring to 200ml polytetrafluoroethylene lining, and crystallizing at 140 deg.C for 4 days. After crystallization, the generated white solid is washed clean by distilled water and dried at 100 ℃, then calcined at 550 ℃ for 4h, and then reduced by hydrogen at 600 ℃ for 4h, thus obtaining the Pt-Sn @ hierarchical pore Beta zeolite catalyst (the load of Pt is 0.30wt%, and the load of Sn is 0.39 wt%). The catalyst has a mesopore size of 20 nm and a mesopore volume of 0.50 cm3/g。
In-suit clothesIn a fixed bed tubular reactor packed with 200mg of the catalyst prepared in example 2, the dehydrogenation reactant was propane, the reaction temperature was 565 ℃ and the mass space velocity WHSV of propane was 5.3 h-1Under the condition that the reaction pressure is normal pressure, the conversion rate of propane is 46%, the selectivity of propylene is 99.3%, the conversion rate of the catalyst after 72 hours of reaction is 45.5%, and the carbon deposition amount is 0.3%.
Example 3
25.20g of silica Sol (SiO) was weighed2 Content 40%) in a 250ml beaker, 13.80g of deionized water are added and stirred at room temperature for 1h, after which 2g of polyvinyl alcohol are added and stirred for 2 h. 3g of hexamethyleneimine is weighed in a 200ml beaker and added with 32g of deionized water for dilution, then the mixture is added into the solution, and the prepared transparent solution is stirred at room temperature for one night to be completely hydrolyzed so as to synthesize the precursor of the zeolite. Thereafter 0.0555g of Pt (COD) Cl were weighed out2And 0.1335g GaCl3Adding into precursor of zeolite, stirring, transferring to 200ml polytetrafluoroethylene lining, and crystallizing at 120 deg.C for 4 days. After crystallization, the generated white solid is washed clean by distilled water and dried at 120 ℃, then calcined at 550 ℃ for 4h, and then reduced by hydrogen at 600 ℃ for 6h to prepare the Pt-Ga @ hierarchical pore MCM-22 catalyst (the load of Pt is 0.30wt%, and the load of Ga is 0.50 wt%). The catalyst has a mesopore size of 25 nm and a mesopore volume of 0.55 cm3/g。
In a fixed-bed tubular reactor packed with 200mg of the catalyst prepared in example 3, the dehydrogenation reactant was propane, the reaction temperature was 575 ℃ and the mass space velocity WHSV of propane was 5.3 h-1Under the condition that the reaction pressure is normal pressure, the conversion rate of propane is 42%, the selectivity of propylene is 99%, the conversion rate of the catalyst after 72 hours of reaction is 41.5%, and the carbon deposition amount is 0.3%.
Example 4
29.10g of silica sol are weighed into a 250ml beaker, 11.60g of deionized water are added and stirred for 1h at room temperature, after which 1.8g of polyvinyl alcohol are added and stirred for 4 h. ZSM-5 was synthesized by weighing 28g of TPAOH in a 200ml beaker, diluting with 28g of deionized water, adding to the solution, and stirring the resulting clear solution overnight at room temperature to complete the hydrolysisA precursor. Then 0.0600g Pt (COD) (Me) was weighed2And 0.1854g Ga (NO)3)3·xH2Adding O into ZSM-5 precursor, stirring, transferring to 200ml polytetrafluoroethylene lining, and crystallizing at 170 deg.C for 7 days. After crystallization, the generated white solid is washed clean by distilled water and dried at 120 ℃, then calcined at 550 ℃ for 4h, and then reduced by hydrogen at 550 ℃ for 7h, thus obtaining the Pt-Ga @ hierarchical pore ZSM-5 zeolite catalyst (the load of Pt is 0.29wt%, and the load of Ga is 0.42 wt%). The size of the mesopores of the catalyst is 30nm, and the volume of the mesopores is 0.50 cm3/g。
In a fixed-bed tubular reactor packed with 200mg of the catalyst prepared in example 4, the dehydrogenation reactant was propane, the reaction temperature was 560 ℃ and the mass space velocity WHSV of propane was 5.3 h-1Under the condition that the reaction pressure is normal pressure, the conversion rate of propane is 42%, the selectivity of propylene is 98.5%, the conversion rate of the catalyst after 72 hours of reaction is 41.7%, and the carbon deposition amount is 0.4%.
Example 5
4.72g of white carbon black are weighed into a 250ml beaker, 11.60g of deionized water are added and stirred at room temperature for 1h, after which 18.6g of PDDA are added and stirred for 4 h. Weighing 36g of tetraethylammonium hydroxide in a 200ml beaker, adding 36g of deionized water for dilution, adding the diluted solution into the solution, and stirring the prepared transparent solution at room temperature overnight to completely hydrolyze the solution so as to synthesize the precursor of the ZSM-5. 0.025g of Pt (COD) Cl was then weighed2And 0.0645g Zn (NO)3)2·6H2Adding O into the zeolite precursor, stirring thoroughly, transferring to 200ml polytetrafluoroethylene lining, and crystallizing at 150 deg.C for 6 days. After crystallization, the generated white solid is washed clean by distilled water and dried at 100 ℃, then calcined at 550 ℃ for 4h, and then reduced by hydrogen at 500 ℃ for 8h, thus obtaining the Pt-Zn @ hierarchical pore Beta zeolite catalyst (the load of Pt is 0.27wt%, and the load of Zn is 0.30 wt%). The size of the mesopores of the catalyst is 30nm, and the volume of the mesopores is 0.56 cm3/g。
In a fixed bed tubular reactor packed with 200mg of the catalyst prepared in example 5, the reactant for the dehydrogenation reaction was propane and the reaction temperature was set atThe mass space velocity WHSV of the propane is 5.3 h at 580 DEG C-1Under the condition that the reaction pressure is normal pressure, the conversion rate of propane is 41%, the selectivity of propylene is 99.6%, the conversion rate of the catalyst after 72 hours of reaction is 40.7%, and the carbon deposition amount is 0.5%.
Example 6
25.6g TEOS was weighed into a 250ml beaker, 16.60g deionized water was added and stirred at room temperature for 1h, after which 3.3g P123 was added and stirred for 6 h. 3g of hexamethyleneimine is weighed in a 200ml beaker and added with 22g of deionized water for dilution, then the mixture is added into the solution, and the prepared transparent solution is stirred at room temperature overnight to be completely hydrolyzed, thereby synthesizing the precursor of the ZSM-5. Then 0.0572g of anhydrous SnCl is weighed4Adding into zeolite precursor, stirring, transferring to 200ml polytetrafluoroethylene lining, placing into reaction kettle, crystallizing at 120 deg.C for 2 days, and crystallizing at 150 deg.C for 3 days. After the crystallization is finished, the white solid generated is washed clean by distilled water and dried at 110 ℃, and then calcined in a muffle furnace at 560 ℃ for 6 h. 0.038g H2PtCl6·6H2Adding the O solid into 56.40g of ethanol to prepare an impregnation solution, impregnating according to the proportion of adding 1g of zeolite catalyst into 3.2g of impregnation solution, standing for a period of time, drying at 110 ℃, calcining at 550 ℃ for 4h, and reducing by hydrogen at 630 ℃ for 4h to prepare the Pt-Sn @ hierarchical porous MCM-22 zeolite catalyst (the load of Pt is 0.20wt%, and the load of Sn is 0.34 wt%). The catalyst has a mesopore size of 25 nm and a mesopore volume of 0.50 cm3/g。
In a fixed-bed tubular reactor packed with 200mg of the catalyst prepared in example 6, the dehydrogenation reactant was propane, the reaction temperature was 560 ℃ and the mass space velocity WHSV of propane was 5.3 h-1Under the condition that the reaction pressure is normal pressure, the conversion rate of propane is 43 percent, the selectivity of propylene is 98.5 percent, the conversion rate of the catalyst after 72 hours of reaction is 42.7 percent, and the carbon deposition amount is 0.3 percent.
Comparative catalyst 1: (without adding mesoporous template)
27.10g TEOS were weighed into a 250ml beaker, 11.60g deionized water was added and stirred at room temperature for 1 h. 24g of tetrapropylammonium hydroxide was weighed into a 200ml beaker and diluted with 24g of deionized water and added to the solutionThe prepared transparent solution is stirred at room temperature overnight to be completely hydrolyzed, so that a ZSM-5 precursor is synthesized. Then 0.1075g of ZnSO was weighed4·7H2O and 0.055g H2PtCl6·6H2And O is added into the zeolite precursor, fully stirred and then transferred to a 200ml polytetrafluoroethylene lining to be placed into a reaction kettle to be crystallized for 72 hours at 170 ℃. After crystallization is finished, the generated white solid is washed clean by distilled water and dried at 120 ℃, then calcined for 4 hours at 550 ℃ in a muffle furnace, and then reduced for 4 hours at 550 ℃ by hydrogen to prepare the microporous zeolite-encapsulated Pt-Zn @ ZSM-5 zeolite catalyst (the load of Pt is 0.25wt%, and the load of Zn is 0.30 wt%). The catalyst has a mesopore size of 7 nm and a mesopore volume of 0.04 cm3(g), the content of mesopores is low.
In a fixed bed tubular reactor filled with 200mg of the prepared catalyst, the reactant of the dehydrogenation reaction is propane, the reaction temperature is 570 ℃, and the mass space velocity WHSV of the propane is 5.3 h-1Under the condition that the reaction pressure is normal pressure, the initial conversion rate of propane is 35%, the selectivity of propylene is 90.5%, the conversion rate of the catalyst after 72 hours of reaction is 25.5%, and the carbon deposition amount is 2.4%.
Comparative catalyst 2: (supporting the Metal component by impregnation)
27.10g TEOS were weighed into a 250ml beaker, 11.60g deionized water was added and stirred at room temperature for 1 h. 24g of tetrapropylammonium hydroxide is weighed in a 200ml beaker, and is added with 24g of deionized water for dilution, and then the solution is added, and the prepared transparent solution is stirred at room temperature overnight for complete hydrolysis, thereby synthesizing the precursor of the ZSM-5 zeolite. The mixed solution is fully stirred and then transferred to a 200ml polytetrafluoroethylene lining to be put into a reaction kettle to be crystallized for 72 hours at 170 ℃. After crystallization, the white solid generated is washed clean by distilled water and dried at 120 ℃, then calcined at 550 ℃ for 4h, and then reduced by hydrogen at 550 ℃ for 4h to prepare ZSM-5 zeolite (the load of Pt is 0.25wt%, and the load of Zn is 0.30 wt%). The zeolite has a mesopore size of 25 nm and a mesopore volume of 0.25 cm3/g。
Treating the prepared ZSM-5 zeolite with 0.10M NaOH at room temperature for 24 hours to obtain mesoporous ZSM-5, and then carrying out impregnation to obtain the zeolite containing 0.1075g of ZnSO4·7H2O and 0.055g H2PtCl6·6H2And loading the mixed solution of O on ZSM-5 zeolite to obtain the Pt-Zn @ ZSM-5 zeolite catalyst.
In a fixed bed tubular reactor filled with 200mg of the prepared catalyst, the reactant of the dehydrogenation reaction is propane, the reaction temperature is 570 ℃, and the mass space velocity WHSV of the propane is 5.3 h-1Under the condition that the reaction pressure is normal pressure, the initial conversion rate of propane is 33%, the selectivity of propylene is 87.5%, the conversion rate of the catalyst after 72 hours of reaction is 22.5%, and the carbon deposition amount is 3.1%.
As can be seen from the comparative data of the catalyst, the catalyst prepared by the invention contains a large amount of mesopores, and the volume of the mesopores can be increased to 0.40cm3More than g. The synthesized catalyst has the advantages of high activity, low inactivation rate, less carbon deposition and the like in the propane dehydrogenation reaction, so the catalyst has better industrial application potential. The excellent performance of the catalyst mainly utilizes the excellent mass transfer property of mesopores, and can obviously improve the transmission rate of reactants and products in a pore channel, thereby improving the utilization rate of Pt to the maximum extent and reducing the carbon deposition inactivation rate of the catalyst.
The above-mentioned embodiments are merely preferred embodiments of the present invention, and all changes and modifications made according to the claims of the present invention shall fall within the scope of the present invention.
Claims (10)
1. A Pt @ hierarchical pore zeolite catalyst for preparing propylene by propane dehydrogenation is characterized in that: the Pt @ hierarchical pore zeolite catalyst takes pure silicon hierarchical pore zeolite as a carrier; the active component is Pt, wherein the Pt exists in micropores of the zeolite in the form of clusters; the auxiliary metal is Sn, Zn or Ge, and the auxiliary metal and Pt interact to form an alloy, wherein the load of the active component Pt is 0.20-0.30wt%, and the load of the auxiliary metal is 0.20-0.50 wt%; in the pure silicon hierarchical pore zeolite, the size of the mesopores is 10-30nm, and the volume of the mesopores is 0.30-0.50 cm3/g。
2. The Pt @ multiwell zeolite catalyst of claim 1, wherein: the pure silicon hierarchical pore zeolite is one of ZSM-5 zeolite, MCM-22 zeolite, beta zeolite and mordenite with a hierarchical pore structure.
3. The process of claim 1 for preparing a Pt @ multiwell zeolite catalyst for propane dehydrogenation to propylene, wherein: the method specifically comprises the following steps:
(1) uniformly mixing a silicon source, a mesoporous template agent, a structure directing agent and water, then fully stirring overnight to obtain a zeolite precursor, adding a Pt compound and an auxiliary metal compound into the zeolite precursor, and fully stirring;
(2) transferring the solution prepared in the step (1) to a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a reaction kettle, and then putting the polytetrafluoroethylene lining into an oven for crystallization reaction;
(3) after the crystallization process is finished, cooling and opening the reaction kettle, filtering and washing the generated zeolite product for multiple times, and then drying to obtain the zeolite containing the auxiliary agent;
(4) grinding the zeolite solid containing the auxiliary agent obtained in the step (3) into powder, and then placing the powder into a muffle furnace for high-temperature roasting to remove the mesoporous template agent and the structure directing agent;
(5) the catalyst precursor prepared in the step (4) is put in H at a certain temperature2Reducing in the atmosphere to obtain the Pt @ hierarchical pore zeolite catalyst for preparing propylene by propane dehydrogenation.
4. The method according to claim 3, wherein the molar ratio of each substance in the mixture in step synthesis satisfies the following condition:
structure directing agent: silicon source = 0.05-0.30: 1
A mesoporous template: silicon source = 0.05-0.10: 1;
pt compound: auxiliary metal compound: SiO 22=0 .015 ~ 0 .030：0 .015 ~ 0 .090：1；
H2O：SiO2=10 ~ 60：1；
Wherein the mole number of the silicon source is SiO2Number of moles ofCounting; the number of moles of the template is calculated by the number of moles of the template itself; the moles of the Pt compound and the promoter metal compound are based on the moles of the metal element.
5. The method according to claim 3, wherein the silicon source used is white carbon black, tetraethyl orthosilicate or silica sol; the structure directing agent is any one of tetrapropylammonium hydroxide, tetraethylammonium hydroxide and hexamethyleneimine; the Pt compound comprises Pt (HACAC)2、Pt(COD)Cl2And Pt (COD) (Me)2、H2PtCl6·6H2O or the like; the adjuvant metal compound comprises HSnBu3、Sn(HAC)2、HSnPh3And GaCl3、Ga(NO3)3·xH2O、Ga2(SO4)3·18H2O and Zn (NO)3)2·6H2O、ZnSO4·7H2O、ZnCl2Any one of them.
6. The production method according to claim 3, characterized in that: the mesoporous template agent is any one of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123, polydiallyldimethylammonium chloride PDDA and polyvinyl alcohol.
7. The production method according to claim 3, characterized in that: the temperature of the crystallization reaction in the step (2) is 140-170 ℃, and the crystallization reaction time is 2-7 days.
8. The production method according to claim 3, characterized in that: in the high-temperature roasting process in the step (4), the roasting temperature is 500-600 ℃, and the roasting time is 3-5 hours.
9. The production method according to claim 3, characterized in that: step (5) H2The technological parameters of the reduction reaction in the atmosphere are as follows: the temperature used for reduction is 500-630 ℃, and the reduction is carried out at the time of reductionThe time is 4-8 h.
10. Use of a Pt @ multiwell zeolite catalyst according to claim 1, wherein: the Pt @ hierarchical pore zeolite catalyst is used for the reaction of preparing propylene by propane dehydrogenation, the reaction temperature is 570-600 ℃, and the mass airspeed WHSV of propane is 5.3 h-1The propane dehydrogenation reaction is carried out in a fixed bed reactor.
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| CN115582139A (en) * | 2022-10-19 | 2023-01-10 | 天津大学 | Transition metal oxide cluster anchoring noble metal catalyst, preparation method and application thereof |
| CN115779974A (en) * | 2022-11-15 | 2023-03-14 | 宁夏大学 | Propane dehydrogenation-hydrogen combustion catalyst and preparation method and application thereof |
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| CN115582139B (en) * | 2022-10-19 | 2023-10-27 | 天津大学 | Transition metal oxide cluster anchored noble metal catalyst, preparation method and application thereof |
| CN115779974A (en) * | 2022-11-15 | 2023-03-14 | 宁夏大学 | Propane dehydrogenation-hydrogen combustion catalyst and preparation method and application thereof |
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