CN114570415B - 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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- 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 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002149 hierarchical pore Substances 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
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 229910052718 tin 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
- 238000006243 chemical reaction Methods 0.000 claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- -1 polytetrafluoroethylene Polymers 0.000 claims description 17
- 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 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 239000012690 zeolite precursor Substances 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 238000006722 reduction reaction Methods 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000000843 powder Substances 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
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 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
- 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
- 229910052733 gallium Inorganic materials 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
- 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 19
- 229910052799 carbon Inorganic materials 0.000 abstract description 19
- 230000008021 deposition Effects 0.000 abstract description 17
- 239000000376 reactant Substances 0.000 abstract description 14
- 238000012546 transfer Methods 0.000 abstract description 8
- 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
- 238000010790 dilution Methods 0.000 description 8
- 239000012895 dilution Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 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
- 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
- 230000003321 amplification Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 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
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- 238000004821 distillation Methods 0.000 description 1
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- 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
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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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
- B01J29/40—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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- 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
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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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- 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
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- 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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- 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, wherein the catalyst is characterized in that: pure silicon hierarchical pore zeolite is used as a carrier; the active component is Pt, wherein 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 alloy. According to the invention, the Pt @ hierarchical pore zeolite catalyst packaged by the hierarchical pore zeolite is synthesized by using the action of the mesoporous template through a one-pot method, and the excellent mass transfer performance of the mesopores 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 propylene production capacity 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 zeolite-encapsulated Pt catalyst Pt @ zeolite developed on the basis of the zeolite channel confinement effect has attracted a wide 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, the propane dehydrogenation Pt @ zeolite catalyst still faces two major technical problems in the future application: (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 greater than 1. Thus, there is a concentration gradient within the zeolite crystallites, the concentration of the reactants within the crystallitesCDistance from surfaceLIs increased and decreased, thereforeEffective utilization rate of active sites in zeolite channelsη(approximately equal to tanh (Φ)/Φ) is lower than 1. It follows that the improvement in the stability performance of a 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 diffuse out of the micropores rapidly, it inevitably undergoes polymerization to produce carbon deposits during the slow diffusion of the micropores. When the amount of carbon deposition reaches a certain level, the channels are completely blocked, 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 limitations 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 of low catalytic efficiency and easy carbon formation of the existing Pt @ zeolite catalyst in the propane dehydrogenation reaction, the invention provides a method for introducing mesoporous built hierarchical pore zeolite into conventional zeolite to strengthen mass transfer, realize the coordination of diffusion and reaction and build a high-performance propane dehydrogenation catalyst.
CN107303497A and CN 112619690A report multi-level pore dehydrogenation catalysts and preparation methods thereof, and disclose a catalyst which takes multi-level 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 utilizes the mesoporous template to synthesize the hierarchical pore zeolite catalyst encapsulated by the hierarchical pore zeolite by an in-situ one-pot method, the process is simple, and the Pt can be dispersed in 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 due to the excellent mass transfer performance of mesopores, the transmission rate of reactants and products in pore channels is remarkably improved, 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 higher activity and stability than zeolite catalysts thereof.
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 as follows: the catalyst prepared by the method mainly comprises three components, namely the multi-stage 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, 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% based on 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 cm 3 (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 temperature 2 The reduction is carried out in the atmosphere to obtain the Pt @ hierarchical pore zeolite catalyst for preparing the 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 2 2 =0 .015 ~ 0 .030：0 .015 ~ 0 .090：1；
H 2 O：SiO 2 =10 ~ 60：1；
Wherein the mole number of the silicon source is SiO 2 In 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; the Pt metal organic compound comprises Pt (HACAC) 2 、Pt(COD)Cl 2 And Pt (COD) (Me) 2 、H 2 PtCl 6 ·6H 2 O or the like; adjuvant metalThe compound comprises HSnBu 3 、Sn(HAC) 2 、HSnPh 3 And GaCl 3 、Ga(NO 3 ) 3 ·xH 2 O、Ga 2 (SO 4 ) 3 ·18H 2 O and Zn (NO) 3 ) 2 ·6H 2 O、ZnSO 4 ·7H 2 O、ZnCl 2 Any one of the above; 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 3-5h.
Further, step (5) is H 2 The 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 space velocity WHSV of propane is 5.3 h -1 The propane dehydrogenation reaction is carried out in a fixed bed reactor.
The invention has the beneficial effects that:
the invention synthesizes the Pt @ hierarchical pore zeolite catalyst by a simple one-pot method, and has the advantages of simple process, easy amplification and good economy. 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.
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 was 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 2h. 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, so as to synthesize a precursor of ZSM-5. Thereafter 0.1075g Zn (NO) is weighed out 3 ) 2 ·6H 2 O and 0.0550g H 2 PtCl 6 ·6H 2 Adding 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, 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 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 0.40cm 3 /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 -1 Under 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 silica were weighed into a 250ml beaker, 11.60g of deionized water were added and stirred at room temperature for 1h, after which 2.8g of P123 were added and stirred for 2h. 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 of Pt (HACAC) was weighed 2 And 0.0864g Sn (HAC) 2 Adding the mixture into a zeolite precursor, fully stirring, transferring the mixture into a 200ml polytetrafluoroethylene lining, and placing the lining into a reaction kettle for crystallization for 4 days at 140 ℃. By distillation after crystallizationWashing the generated white solid with water, drying at 100 ℃, calcining at 550 ℃ for 4h, and reducing with hydrogen at 600 ℃ for 4h to obtain 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 cm 3 /g。
In 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 propane mass space velocity WHSV was 5.3 h -1 Under 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) were weighed 2 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 2h. 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. Then 0.0555g of Pt (COD) Cl was weighed 2 And 0.1335g GaCl 3 Adding into precursor of zeolite, stirring, transferring to 200ml polytetrafluoroethylene lining, and crystallizing at 120 deg.C for 4 days. After crystallization is finished, the generated white solid is washed clean by distilled water and dried at 120 ℃, then calcined for 4h at 550 ℃, and then reduced for 6h at 600 ℃ by hydrogen 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 cm 3 /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 -1 Under 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 at room temperature for 1h, after which 1.8g of polyvinyl alcohol are added and stirred for 4h. 28g of TPAOH is weighed in a 200ml beaker, 28g of deionized water is added for dilution, then the solution is added, and the prepared transparent solution is stirred at room temperature overnight for complete hydrolysis, so that a precursor of ZSM-5 is synthesized. Then 0.0600g Pt (COD) (Me) is weighed 2 And 0.1854g Ga (NO) 3 ) 3 ·xH 2 Adding O into ZSM-5 precursor, stirring thoroughly, transferring to 200ml polytetrafluoroethylene lining, and crystallizing at 170 deg.C for 7 days. 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 7h, thus obtaining the Pt-Ga @ hierarchical pore ZSM-5 zeolite catalyst (the loading capacity of Pt is 0.29wt%, and the loading capacity 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 cm 3 /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 -1 Under 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 4h. 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. Then 0.025g of Pt (COD) Cl was weighed 2 And 0.0645g Zn (NO) 3 ) 2 ·6H 2 Adding O into the zeolite precursor, stirring thoroughly, transferring to 200ml polytetrafluoroethylene lining, and crystallizing at 150 deg.C for 6 days. After crystallization, the 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 8hThus, a Pt-Zn @ hierarchical pore zeolite Beta catalyst (Pt supported 0.27wt%, zn supported 0.30 wt%) was prepared. The catalyst has a mesopore size of 30nm and a mesopore volume of 0.56 cm 3 /g。
In a fixed-bed tubular reactor packed with 200mg of the catalyst prepared in example 5, the dehydrogenation reactant was propane, the reaction temperature was 580 ℃ and the mass space velocity WHSV of propane was 5.3 h -1 Under 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 6h. 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 weighed 4 Adding the mixture into a zeolite precursor, fully stirring, transferring the mixture to 200ml of a polytetrafluoroethylene lining, placing the lining into a reaction kettle, crystallizing for 2 days at 120 ℃, and crystallizing for 3 days at 150 ℃. After crystallization, the white solid was washed with distilled water and dried at 110 ℃ before being calcined in a muffle furnace at 560 ℃ for 6h. 0.038g of H 2 PtCl 6 ·6H 2 Adding 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 pore 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 cm 3 /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 -1 Under 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, and the catalyst isAfter 72 hours of reaction, the conversion rate was 42.7%, and the carbon deposition amount was 0.3%.
Comparative catalyst 1: (without adding mesoporous template)
27.10g TEOS was weighed into a 250ml beaker, 11.60g deionized water was added and stirred at room temperature for 1h. 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, so as to synthesize a precursor of ZSM-5. Then 0.1075g of ZnSO was weighed 4 ·7H 2 O and 0.055g H 2 PtCl 6 ·6H 2 And O is added into the zeolite precursor, 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 ℃. And after crystallization is finished, washing the generated white solid with distilled water, drying at 120 ℃, calcining for 4 hours at 550 ℃ in a muffle furnace, and reducing for 4 hours at 550 ℃ by using hydrogen to prepare the microporous zeolite-encapsulated Pt-Zn @ ZSM-5 zeolite catalyst (the loading capacity of Pt is 0.25wt%, and the loading capacity of Zn is 0.30 wt%). The catalyst has a mesopore size of 7 nm and a mesopore volume of 0.04 cm 3 (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 -1 Under 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 Metal component by impregnation)
27.10g TEOS was weighed into a 250ml beaker, 11.60g deionized water was added and stirred at room temperature for 1h. 24g of tetrapropylammonium hydroxide is weighed in a 200ml beaker, 24g of deionized water is added for dilution, the diluted solution is added into the solution, and the prepared transparent solution is stirred at room temperature overnight to be completely hydrolyzed, so that the precursor of the ZSM-5 zeolite is synthesized. 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 the temperature of 170 ℃. After crystallization, the white solid is washed clean with distilled water and dried at 120 ℃ and then at 550 DEG CCalcining for 4h, and then reducing for 4h at 550 ℃ by hydrogen to obtain the 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 cm 3 /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 ZnSO 4 ·7H 2 O and 0.055g H 2 PtCl 6 ·6H 2 And loading the mixed solution of O on the 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 -1 Under 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 0.40cm 3 More 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 of mesopores, and can 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.
The above-described 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 (8)
1. A preparation method of Pt @ hierarchical pore zeolite catalyst for preparing propylene by propane dehydrogenation is characterized by comprising the following steps: 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 temperature 2 Reducing in the atmosphere to obtain a Pt @ hierarchical pore zeolite catalyst for preparing propylene by propane dehydrogenation;
the molar ratio of each substance in the synthesis of the steps is as follows:
structure directing agent: silicon source = 0.05-0.30: 1;
mesoporous template agent: silicon source = 0.05-0.10: 1;
pt compound: auxiliary metal compound: siO 2 2 =0 .015 ~ 0 .030：0 .015 ~ 0 .090：1；
H 2 O：SiO 2 =10 ~ 60：1；
Wherein the mole number of the silicon source is SiO 2 The number of moles of (a); 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 calculated by the moles of the metal element;
the structure directing agent is any one of tetrapropylammonium hydroxide, tetraethylammonium hydroxide and hexamethyleneimine; the mesoporous template agent is any one of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123, polydiallyl dimethyl ammonium chloride PDDA and polyvinyl alcohol; the adjuvant metal compound comprises HSnBu 3 、Sn(HAC) 2 、HSnPh 3 、GaCl 3 、Ga(NO 3 ) 3 ·xH 2 O、Ga 2 (SO 4 ) 3 ·18H 2 O、Zn(NO 3 ) 2 ·6H 2 O、ZnSO 4 ·7H 2 O、ZnCl 2 Any one of them.
2. The method according to claim 1, wherein the silicon source used is white carbon black, tetraethyl orthosilicate or silica sol; the Pt compound includes Pt (HACAC) 2 、Pt(COD)Cl 2 、Pt(COD)(Me) 2 、H 2 PtCl 6 ·6H 2 Any one of O.
3. The production method according to claim 1, 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.
4. The production method according to claim 1, characterized in that: in the high-temperature roasting process in the step (4), the roasting temperature is 500-600 ℃, and the roasting time is 3-5h.
5. The method of claim 1, wherein: step (5) H 2 The 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.
6. A Pt @ porous zeolite catalyst for propane dehydrogenation to propylene, prepared by the preparation method according to any one of claims 1 to 5, characterized in that: the Pt @ hierarchical pore zeolite catalyst takes pure silicon hierarchical pore zeolite as a carrier; the active component is Pt, wherein 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 0.20-0.50wt%; 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 cm 3 /g。
7. The Pt @ multi-pore zeolite catalyst of claim 6, 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.
8. Use of a Pt @ hierarchical pore zeolite catalyst according to claim 6, wherein: the Pt @ porous zeolite catalyst is used for the reaction of preparing propylene by propane dehydrogenation, the reaction temperature is 570-600 ℃, and the mass space velocity WHSV of propane is 5.3 h -1 The propane dehydrogenation reaction is carried out in a fixed bed reactor.
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