CN114749202B - Core-shell type SAPO-34@ZSM-5 molecular sieve catalyst and preparation method thereof - Google Patents
Core-shell type SAPO-34@ZSM-5 molecular sieve catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000011258 core-shell material Substances 0.000 title claims abstract description 28
- 239000002808 molecular sieve Substances 0.000 title description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 56
- 239000010457 zeolite Substances 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000013078 crystal Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004005 microsphere Substances 0.000 claims abstract description 15
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000012153 distilled water Substances 0.000 claims description 27
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- 239000010703 silicon Substances 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 20
- 230000003197 catalytic effect Effects 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 229910001220 stainless steel Inorganic materials 0.000 claims description 17
- 239000010935 stainless steel Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 12
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 12
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 10
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- 239000006012 monoammonium phosphate Substances 0.000 claims description 6
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000693 micelle Substances 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- -1 polytetrafluoroethylene Polymers 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 239000012467 final product Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000004075 alteration Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000012690 zeolite precursor Substances 0.000 description 1
Classifications
-
- 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
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- 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
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The invention provides a core-shell type SAPO-34@ZSM-5 zeolite catalyst and a preparation method thereof, wherein SAPO-34 microspheres (2 mu m) formed by stacking nano polycrystalline aggregates are taken as cores, a layer of MCM-41 material is deposited on the outer surfaces of the SAPO-34 microspheres, and then a traditional hydrothermal synthesis method is utilized to induce shell MCM-41 to perform in-situ zeolitization by adding ZSM-5 seed crystal precursor solution so as to form ZSM-5 zeolite particles (150 nm). The core-shell type SAPO-34@ZSM-5 zeolite catalyst prepared by the invention utilizes deposited MCM-41 to modify the surface of the SAPO-34, thereby effectively overcoming the problem that the SAPO-34 crystals are destroyed in an alkaline environment system for synthesizing the SAPO-34@ZSM-5. The preparation method has the advantages of easily obtained raw materials, simple process, relatively mild conditions and the like, can realize industrial application, and has wide application prospect in solving the problem of energy shortage.
Description
Technical Field
The invention belongs to the field of inorganic materials, and particularly relates to a core-shell type SAPO-34@ZSM-5 molecular sieve catalyst and a preparation method thereof.
Background
Zeolite molecular sieve is a kind of crystal material with skeleton structure, and has unique microporous structure, adjustable acidity, excellent heat/water heat stability and chemical stability, and is used widely in catalysis, adsorption separation, biotechnology and other fields. Wherein, the SAPO-34 molecular sieve is one of important members in the SAPO series, and the SAPO-34 has the CHA topological structureThe structure is made of SiO 4 ,AlO 4 And PO (PO) 4 The tetrahedra are connected with each other through an oxygen bridge bond to form a three-dimensional cross-channel structure. Has higher selectivity to ethylene and propylene in MTO catalytic reaction. However, the conventional SAPO-34 zeolite severely limits mass transfer and diffusion of product molecules in micropores due to narrow micropore channels (-0.38, nm), greatly increases the probability of polymerization, cyclization and hydrogen transfer of olefin molecules, thereby accelerating the generation of carbon deposition precursors, and thus leads to rapid deactivation of the catalyst. The most common approach to solve the problem of catalyst deactivation is to construct hierarchical pores in zeolite molecular sieves.
The methods reported in the current literature mainly comprise a post-treatment method and a mesoporous template adding method. The method adopts a post-treatment method (acid or alkali treatment) to extract aluminum or silicon atoms in the zeolite framework so as to cause lattice defects, thus generating intragranular mesopores in zeolite crystals, but the method is easy to cause the damage of the crystals, reduces the crystallinity of the zeolite, and the removed amorphous silicon and aluminum species easily block micropore channels. The adoption of mesoporous template agent and small molecular organic amine (structure directing agent) easily causes incompatibility between the template agents in the zeolite growth process, and easily causes two-phase separation or mixed crystal. In addition, a large amount of exhaust gas generated in the process of removing the template agent easily causes environmental pollution. Whichever method is used weakens the backbone acid center of the catalyst, so that the catalytic active sites of the catalyst in the reaction are greatly reduced, thereby further affecting the reaction performance of the catalyst. Moreover, complex synthetic procedures, mesoporous templates are expensive and time consuming, severely limiting industrial applications.
Disclosure of Invention
Aiming at the situation, the invention aims to provide a core-shell type SAPO-34@ZSM-5 molecular sieve catalyst and a preparation method thereof, and in the MTO reaction, the catalyst has higher olefin selectivity while the service life of the catalyst is prolonged through the synergistic effect of the SAPO-34 (core) and the ZSM-5 (shell).
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: provides a core-shell SAPO-34@ZSM-5 molecular sieve catalyst and a preparation method thereof.
A core-shell type SAPO-34@ZSM-5 zeolite catalyst is prepared by taking SAPO-34 microspheres (2 mu m) formed by stacking nano polycrystalline aggregates as cores, depositing a layer of MCM-41 material on the outer surfaces of the SAPO-34 microspheres, and then adding ZSM-5 seed crystal precursor solution to induce shell MCM-41 to perform in-situ zeolitization to form ZSM-5 zeolite particles (150 nm) by using a traditional hydrothermal synthesis method.
The preparation method of the core-shell SAPO-34@ZSM-5 comprises the following steps:
(1) Preparation of SAPO-34 polycrystalline aggregates: the traditional microporous template agent is used as a Structure Directing Agent (SDA), and the mole components for preparing the SAPO-34 zeolite are as follows: al (Al) 2 O 3 :SiO 2 :P 2 O 5 :SDA:H 2 O=1.00:0.45-1.93:1.00-4.14:0.72-5.17:100.34-300.76; an aluminum source, SDA, a silicon source, and a phosphorus source were sequentially added to the aqueous solution. Stirring uniformly, then placing the mixture into a baking oven, and carrying out hydrothermal crystallization at 160-200 ℃ for 24-96 h. Washing the crystallized sample to neutrality, and drying overnight to obtain solid powder;
(2) Preparation of SAPO-34@MCM-41: adding the SAPO-34 powder synthesized in the step (1) into distilled water, and stirring to form a uniform milky solution, wherein the surfactant comprises organic alcohol and organic base: the silicon source is water=1.00: 100.34-600.25:20.30-150.12:1.51-9.85: 1253.41-3000.23, surfactant, organic alcohol, organic alkali and the silicon source are sequentially added into the aqueous solution and stirred to form uniform solution, then the uniform solution is put into a water bath kettle to hydrolyze for 1-5 hours at the temperature of 30-80 ℃, and the hydrolyzed product is washed and dried to obtain solid powder;
(3) Preparation of ZSM-5 seed crystal precursor solution: according to the mole ratio of silicon source to aluminum source to tetrapropylammonium hydroxide to absolute ethyl alcohol of water= 120.20-300:1.02-3.04:8.34-62.45:450.02-1200.00:1000.14-3000.56, dissolving the silicon source, aluminum source, tetrapropylammonium hydroxide and absolute ethyl alcohol in water, stirring and dissolving, and the crystallization temperature is 100-180 ℃;
(4) Preparation of SAPO-34@ZSM-5: adding the SAPO-34@MCM-41 powder synthesized in the step (2) into a ZSM-5 precursor solution (solid/liquid mass ratio=1-7), fully and uniformly stirring, then placing the mixture into a stainless steel autoclave for hydrothermal crystallization at 100-180 ℃ for 24-72 h, washing the crystallized sample to be neutral, and drying overnight to obtain solid powder.
Further, the aluminum source used for synthesizing the SAPO-34 zeolite molecular sieve is aluminum isopropoxide, pseudo-boehmite, aluminum hydroxide or gamma-Al 2 O 3 One of the following; the silicon source is one of fumed silica, tetraethoxysilane or silica sol; the phosphorus source is one of phosphoric acid, monoammonium phosphate or monoammonium phosphate; the structure directing agent is one of tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide or diethylamine.
Further, the organic alcohol used for synthesizing the SAPO-34@MCM-41 is one of n-propanol, isopropanol, ethanol or n-butanol; the surfactant is one of hexadecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide or dodecyl trimethyl ammonium bromide; the organic base is NH 3 .H 2 One of O, triethylamine, diethylamine or n-butylamine; the silicon source is one of ethyl orthosilicate, propyl orthosilicate, silica sol or sodium silicate.
Further, the silicon source used for synthesizing the ZSM-5 precursor solution is ethyl orthosilicate, sodium silicate, silica sol or gas phase SiO 2 One of the following; the aluminum source is one of aluminum hydroxide, sodium aluminate or aluminum isopropoxide.
Further, the crystallization time of the ZSM-5 precursor solution is 24-96 hours.
The SAPO-34 microsphere of the nano polycrystalline aggregate prepared by the invention is taken as a core, and the ZSM-5 zeolite (-150 nm) is taken as a core-shell type SAPO-34@ZSM-5 zeolite catalytic material.
According to the invention, a surface modification method is adopted, firstly, spherical SAPO-34 nano polycrystalline aggregate is prepared under the condition of no secondary template agent, then SAPO-34 is used as a core, under the condition of organic alkali and surfactant, a silicon source is hydrolyzed on the surface of SAPO-34, so that the directional assembly of silicon hydroxyl on the surface of the organic template agent micelle surfactant is realized to form a highly ordered MCM-41 material with a two-dimensional hexagonal mesoporous structure, thus obtaining the SAPO-34@MCM-41 with a core-shell structure, and finally, in a hydrothermal crystallization system, a pre-prepared ZSM-5 seed crystal precursor solution is added to induce shell MCM-41 in-situ boiling petrochemical, thereby obtaining the SAPO-34@ZSM-5 zeolite catalytic material.
The beneficial effects of the invention are as follows: the core-shell type SAPO-34@ZSM-5 zeolite catalyst prepared by the invention utilizes deposited MCM-41 to modify the surface of the SAPO-34, thereby effectively overcoming the problem that the SAPO-34 crystals are destroyed in an alkaline environment system for synthesizing the SAPO-34@ZSM-5. In addition, MCM-41 forms shell ZSM-5 zeolite crystal grains after in-situ zeolitization, so that the problem of two-phase separation is effectively avoided. The invention obviously improves the service life of the catalyst in the MTO catalytic reaction, and simultaneously obtains higher low-carbon olefin selectivity. The preparation method has the advantages of easily obtained raw materials, simple process, relatively mild conditions and the like, can realize industrial application, and has wide application prospect in solving the problem of energy shortage.
Drawings
FIG. 1 is a flow chart of a process for preparing a material according to an embodiment of the present invention;
FIG. 2 is a wide angle XRD pattern (a) of the SAPO-34@ZSM-5 catalytic material prepared by the invention;
FIG. 3 is a small angle XRD pattern (b) of the SAPO-34@ZSM-5 catalytic material prepared by the invention;
FIG. 4 is a SEM image (c and d) of SAPO-34 pattern (a), SAPO-34@MCM-41 pattern (b) and SAPO-34@ZSM-5 material prepared by the invention;
FIG. 5 is a graph showing the change trend of the methanol conversion rate of the SAPO-34@ZSM-5 catalytic material prepared by the invention along with the reaction time.
FIG. 6 is a graph showing the trend of the reaction time of the light olefins (ethylene and propylene) of the SAPO-34@ZSM-5 catalytic material prepared by the invention.
Detailed Description
The following describes the invention in further detail with reference to examples. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention. Various changes, modifications, substitutions and alterations may be made by those skilled in the art without departing from the principles and spirit of the invention, and it is intended that the invention encompass all such changes, modifications and alterations as fall within the scope of the invention.
Example 1: preparation of SAPO-34@ZSM-5
(1) 6.12g of aluminum isopropoxide is weighed and dissolved in 30.3mL of distilled water and 35.3mL of tetrapropylammonium hydroxide, stirred until the aluminum isopropoxide is completely dissolved, and then 3.6mL of tetraethoxysilane and 4.0mL of phosphoric acid are sequentially added; after being uniformly mixed, the mixture is transferred into a stainless steel reaction kettle with the volume of 100mL, and the mixture is subjected to hydrothermal crystallization at 180 ℃ for 3 days; washing the crystallized sample to neutrality, and drying at 80 deg.c overnight to obtain solid powder;
(2) 160g of distilled water, 1.6g of cetyl trimethyl ammonium bromide, 40mL of isopropanol, 1mL of ammonia water, 1.6mL of tetraethoxysilane and 2g of the SAPO-34 molecular sieve obtained in the step (1) are placed into the distilled water, the mixture is stirred for 3 hours at 30 ℃, the final product is washed by the distilled water, and the mixture is dried overnight at 80 ℃ to obtain the core-shell type SAPO-34@MCM-41;
(3) 10.98g of tetraethoxysilane, 10.37g of tetrapropylammonium hydroxide, 0.06g of aluminum isopropoxide, 15g of water and 9.11g of absolute ethyl alcohol are weighed, stirred for 4 hours, and the mixed solution is put into a stainless steel autoclave with a polytetrafluoroethylene lining to be crystallized for 3 days at 100 ℃ to obtain a precursor solution of ZSM-5 zeolite seed crystal;
(4) Mixing and stirring the SAPO-34@MCM-41 obtained in the step (2) and the precursor solution of the ZSM-5 zeolite seed crystal obtained in the step (3) uniformly according to the solid/liquid (mass ratio) =1:2, then placing the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, crystallizing at 180 ℃ for 3 days, washing the obtained product with distilled water, and drying at 80 ℃ overnight to obtain the SAPO-34@ZSM-5 zeolite catalytic material.
Example 2
Preparation of SAPO-34@ZSM-5, step (1), 7.01g of monoammonium phosphate was obtained, and the rest was the same as in example 1.
Example 3
Preparation of SAPO-34@ZSM-5, step (1), 4.23g of monoammonium phosphate, the remainder being as in example 1.
Example 4
Preparation of SAPO-34@ZSM-5, in step (1), hydrothermal crystallization at 160℃was performed, and the rest was the same as in example 1.
Example 5
Preparation of SAPO-34@ZSM-5:
(1) 5.08g of pseudo-boehmite is weighed and dissolved in 30.3mL of distilled water and 35.3mL of tetrapropylammonium hydroxide, stirred until the pseudo-boehmite is completely dissolved, and then 3.6mL of silica sol and 4.0mL of phosphoric acid are sequentially added; after being uniformly mixed, the mixture is transferred into a stainless steel reaction kettle with the volume of 100mL, and the mixture is subjected to hydrothermal crystallization at 180 ℃ for 3 days; washing the crystallized sample to neutrality, and drying at 60 deg.c overnight to obtain solid powder;
(2) 160g of distilled water, 1.6g of tetradecyl trimethyl ammonium bromide, 40mL of n-propanol, 1mL of n-butylamine and 2g of propyl orthosilicate, putting the SAPO-34 molecular sieve obtained in the step (1) into the distilled water, stirring the mixture for 3 hours at 30 ℃, washing the final product with distilled water, and drying the product at 80 ℃ overnight to obtain the core-shell SAPO-34@MCM-41;
(3) 10.98g of tetraethoxysilane, 10.37g of tetrapropylammonium hydroxide, 0.06g of aluminum isopropoxide, 15g of water and 9.71g of absolute ethyl alcohol are weighed, stirred for 4 hours, and the mixed solution is put into a stainless steel autoclave with a polytetrafluoroethylene lining for crystallization for 3 days at 120 ℃ to obtain a precursor solution of ZSM-5 zeolite seed crystal;
(4) Mixing and stirring the SAPO-34@MCM-41 obtained in the step (2) and the precursor solution of the ZSM-5 zeolite seed crystal obtained in the step (3) uniformly according to the solid/liquid (mass ratio) =1:4, then placing the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, crystallizing at 180 ℃ for 3 days, washing the obtained product with distilled water, drying at 80 ℃ overnight, and roasting the obtained sample at 550 ℃ for 6 hours to obtain the SAPO-34@ZSM-5 zeolite catalytic material.
Example 6
Preparation of SAPO-34@ZSM-5
(1) 6.08g of aluminum hydroxide stone was weighed out and dissolved in a solution of 30.3mL of distilled water and 25.3mL of tetraethylammonium hydroxide, stirred until completely dissolved, then 3.6mL of silica sol and 4.0mL of phosphoric acid were added sequentially. After being evenly mixed, the mixture is transferred into a stainless steel reaction kettle with the volume of 100mL, and the mixture is subjected to hydrothermal crystallization at 180 ℃ for 3 days. Washing the crystallized sample to neutrality, and drying at 60 deg.c overnight to obtain solid powder. Roasting at 550 ℃ for 6 hours to obtain the SAPO-34 molecular sieve with the spherical morphology of the nano polycrystalline aggregate;
(2) 160g of distilled water, 1.6g of dodecyl trimethyl ammonium bromide, 40mL of n-propanol, 1mL of ammonia water and 2g of propyl orthosilicate are put into the distilled water, the SAPO-34 molecular sieve obtained in the step (1) is stirred for 3 hours at 30 ℃, and the final product is washed by distilled water and dried overnight at 80 ℃ to obtain the core-shell SAPO-34@MCM-41;
(3) 10.98g of ethyl orthosilicate, 10.37g of tetrapropylammonium hydroxide and 0.06g of gamma-Al are weighed out 2 O 3 15g of water and 9.71g of absolute ethyl alcohol, stirring for 4 hours, and putting the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining for crystallization for 3 days at 140 ℃ to obtain a precursor solution of ZSM-5 zeolite seed crystal;
(4) Mixing and stirring the SAPO-34@MCM-41 obtained in the step (2) and the precursor solution of the ZSM-5 zeolite seed crystal obtained in the step (3) uniformly according to the solid/liquid (mass ratio) =1:4, then placing the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, crystallizing at 180 ℃ for 3 days, washing the obtained product with distilled water, drying at 80 ℃ overnight, and roasting the obtained sample at 550 ℃ for 6 hours to obtain the SAPO-34@ZSM-5 zeolite catalytic material.
Example 7
Preparation of SAPO-34@ZSM-5
(1) 6.08g of aluminum isopropoxide is weighed and dissolved in a solution of 30.3mL of distilled water and 25.3mL of tetrabutylammonium hydroxide, stirred until completely dissolved, then 3.6mL of silica sol and 4.0mL of phosphoric acid are added sequentially. After being evenly mixed, the mixture is transferred into a stainless steel reaction kettle with the volume of 100mL, and the mixture is subjected to hydrothermal crystallization at 180 ℃ for 3 days. Washing the crystallized sample to neutrality, and drying at 60 deg.c overnight to obtain solid powder. Roasting at 550 ℃ for 6 hours to obtain the SAPO-34 molecular sieve with the spherical morphology of the nano polycrystalline aggregate;
(2) 160g of distilled water, 1.6g of dodecyl trimethyl ammonium bromide, 40mL of ethanol, 1mL of ammonia water and 2g of propyl orthosilicate, putting the SAPO-34 molecular sieve obtained in the step (1) into the distilled water, stirring the mixture for 5 hours at 30 ℃, washing the final product with distilled water, and drying the product at 90 ℃ overnight to obtain the core-shell SAPO-34@MCM-41 catalytic material;
(3) 10.98g of ethyl orthosilicate, 10.37g of tetrabutylammonium hydroxide and 0.06g of gamma-Al are weighed out 2 O 3 ，15Stirring water and 9.71g of absolute ethyl alcohol for 4 hours, and putting the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining for crystallization at 140 ℃ for 3 days to obtain a precursor solution of ZSM-5 zeolite seed crystal;
(4) Mixing and stirring the SAPO-34@MCM-41 obtained in the step (2) and the precursor solution of the ZSM-5 zeolite seed crystal obtained in the step (3) uniformly according to the solid/liquid (mass ratio) =1:2, then placing the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, crystallizing at 180 ℃ for 3 days, washing the obtained product with distilled water, drying at 80 ℃ overnight, and roasting the obtained sample at 550 ℃ for 8 hours to obtain the SAPO-34@ZSM-5 zeolite catalytic material.
Example 8
Preparation of SAPO-34@ZSM-5
(1) 6.08g of aluminum isopropoxide is weighed and dissolved in 30.3mL of distilled water and 25.3mL of tetrabutylammonium hydroxide solution, stirred until the aluminum isopropoxide is completely dissolved, and then 3.6mL of silica sol and 4.0mL of phosphoric acid are sequentially added; after being uniformly mixed, the mixture is transferred into a stainless steel reaction kettle with the volume of 100mL, and the mixture is subjected to hydrothermal crystallization at 180 ℃ for 3 days; washing the crystallized sample to neutrality, and drying at 60 deg.c overnight to obtain solid powder. Roasting at 550 ℃ for 6 hours to obtain the SAPO-34 molecular sieve with the spherical morphology of the nano polycrystalline aggregate;
(2) 160g of distilled water, 1.6g of dodecyl trimethyl ammonium bromide, 40mL of ethanol, 1mL of diethylamine and 2g of propyl orthosilicate, putting the SAPO-34 molecular sieve obtained in the step (1) into the distilled water, stirring the mixture for 5 hours at 30 ℃, washing the final product with distilled water, and drying the product at 90 ℃ overnight to obtain the core-shell SAPO-34@MCM-41;
(3) 10.98g of silica sol, 10.37g of tetrapropylammonium hydroxide, 0.10g of gamma-Al are weighed out 2 O 3 15g of water and 9.71g of absolute ethyl alcohol, stirring for 4 hours, putting the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining
Crystallizing at 140 deg.c for 3 days to obtain the precursor solution of ZSM-5 zeolite seed crystal;
(4) Mixing and stirring the SAPO-34@MCM-41 obtained in the step (2) and the precursor solution of the ZSM-5 zeolite seed crystal obtained in the step (3) uniformly according to the solid/liquid (mass ratio) =1:5, then placing the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, crystallizing at 180 ℃ for 3 days, washing the obtained product with distilled water, drying at 80 ℃ overnight, and roasting the obtained sample at 550 ℃ for 4 hours to obtain the SAPO-34@ZSM-5 zeolite catalytic material.
The preparation method of the core-shell SAPO-34@ZSM-5 zeolite catalyst utilizes the raw materials synthesized by the traditional zeolite. Under the condition of not adding a secondary template agent, the spherical SAPO-34 zeolite microspheres of the nano polycrystalline aggregate are synthesized. And then modifying the surface of the SAPO-34, and directionally assembling the surface of the SAPO-34 zeolite by utilizing a hydrolyzed silicon source under the action of a surfactant micelle to obtain the core-shell type SAPO-34@MCM-41 material. Finally, seed crystal ZSM-5 zeolite precursor solution is utilized to induce the in-situ zeolitization of the surface shell MCM-41, and the core-shell type SAPO-34@ZSM-5 zeolite is formed.
As shown in FIG. 1, the preparation process flow diagram of the SAPO-34@ZSM-5 zeolite catalytic material prepared by the invention is that polycrystalline aggregate SAPO-34 zeolite microspheres are prepared first, MCM-41 is uniformly laminated on the surfaces of the SAPO-34 microspheres, and then shell MCM-41 is subjected to in-situ zeolitization to form the SAPO-34@ZSM-5 zeolite catalytic material.
Figures 2 and 3 are X-ray diffraction patterns (XRD) of the SAPO-34@zsm-5 material prepared by the invention, and from figure 2, it can be seen that the prepared material belongs to typical SAPO-34 characteristic diffraction peaks, and also can be seen that the characteristic diffraction peaks of ZSM-5, and from figure 3, the sample shows a characteristic diffraction peak at 2θ=2.5, and the MCM-41 material with ordered mesoporous channels is proved.
FIG. 4 is a Scanning Electron Microscope (SEM) image of the SAPO-34@ZSM-5 catalytic material obtained in example 1, and it can be seen from FIG. 4 (a) that the average diameter of the SAPO-34 zeolite microspheres formed by stacking nano-crystals of the prepared material is 2 μm, and from FIG. 4 (b), it can be seen that the surfaces of SAP0-34 are covered with a layer of MCM-41 material, so that the surfaces thereof become smooth; as can be seen in FIGS. 4 (c and d), ZSM-5 particles (-150 nm) are uniformly coated on the surface of the SAPO-34 zeolite microspheres, so that the SAPO-34@ZSM-5 zeolite catalytic material taking the SAPO-34 as a core and the ZSM-5 as a shell is formed.
The samples prepared above were used as catalysts for MTO reactions, and the catalytic performance of the catalysts was examined.
Catalytic reaction Performance was evaluated inThe reaction was carried out in a micro fixed bed reactor at normal pressure, and 0.79g of catalyst was charged into the reactor. Firstly, introducing N with the flow rate of 50mL/min into a reactor 2 And the temperature was raised from room temperature to the reaction temperature (400 ℃ C.) at a heating rate of 5 ℃ C./min, the catalyst was activated for 1 hour, and N was maintained 2 The flow rate was then controlled to 1mL/h by feeding methanol with a micro metering pump, and the product after the reaction was analyzed on a gas chromatograph equipped with a hydrogen Flame Ionization Detector (FID).
The catalytic results in fig. 5 and 6 show that, compared with the SAPO-34 and mechanically mixed SAPO-34+ZSM-5 catalyst, the conversion rate of methanol of the SAPO-34@ZSM-5 catalyst material after 60 hours of reaction can still reach more than 60%, and the selectivity of ethylene and propylene is maintained at more than 50%, which indicates that the catalyst material has very high methanol reaction activity, stability and low carbon olefin selectivity.
Claims (7)
1. A core-shell type SAPO-34@ZSM-5 zeolite catalyst is characterized in that: in particular to a core-shell type SAPO-34@ZSM-5 zeolite catalyst which takes SAPO-34 microspheres of nano polycrystalline aggregate as cores and ZSM-5 zeolite as shells;
the zeolite catalyst takes SAPO-34 microspheres formed by stacking nanometer polycrystalline aggregates as cores, a layer of MCM-41 material is deposited on the outer surfaces of the SAPO-34 microspheres, and then a traditional hydrothermal synthesis method is utilized, and a ZSM-5 seed crystal precursor solution is added to induce shell MCM-41 to perform in-situ zeolitization to form ZSM-5 zeolite particles;
the MCM-41 material is deposited on the outer surface of the SAPO-34 microsphere, specifically, the SAPO-34 is used as a core, a silicon source is hydrolyzed on the surface of the SAPO-34 under the condition of organic alkali and a surfactant, and silicon hydroxyl groups are directionally assembled on the organic template micelle surfactant to form the MCM-41 material with a highly ordered two-dimensional hexagonal mesoporous structure.
2. The core-shell SAPO-34@zsm-5 zeolite catalyst of claim 1, wherein: the thickness of the shell MCM-41 is 50-100 nm.
3. A preparation method of a core-shell type SAPO-34@ZSM-5 zeolite catalyst is characterized by comprising the following steps of: the method specifically comprises the following steps:
(1) Preparation of SAPO-34 zeolite microspheres: according to Al 2 O 3 :SiO 2 :P 2 O 5 :SDA:H 2 O=1.00:0.45-1.93:1.00-4.14:0.72-5.17:100.34-300.76, and sequentially adding an aluminum source, a structure directing agent SDA, a silicon source and a phosphorus source into the aqueous solution; uniformly stirring, then placing the mixture into a baking oven for hydrothermal crystallization, wherein the crystallization temperature is 160-200 ℃ and the crystallization time is 24-96 hours; washing the crystallized sample to be neutral, and drying overnight to obtain SAPO-34 powder;
(2) Preparation of SAPO-34@MCM-41: 1g to 3g of the synthesized SAPO-34 powder is weighed and added into distilled water to be stirred to form a uniform milky white solution, and the surfactant comprises organic alcohol and organic alkali: the silicon source is water=1.00: 100.34-600.25:20.30-150.12:1.51-9.85:1253.41-3000.23, surfactant, organic alcohol, organic alkali and silicon source are sequentially added and stirred to form a uniform solution, then the uniform solution is put into a water bath kettle to hydrolyze for 1-5 hours at the temperature of 30-80 ℃, and the hydrolyzed product is washed and dried to obtain SAPO-34@MCM-41 powder;
(3) Preparation of ZSM-5 seed crystal precursor solution: according to the mole ratio of silicon source to aluminum source to tetrapropylammonium hydroxide to absolute ethyl alcohol of water= 120.20-300.00:1.02-3.04:8.34-62.45:450.02-1200.00:1000.14-3000.56, dissolving the silicon source, aluminum source, tetrapropylammonium hydroxide and absolute ethyl alcohol in water, stirring and dissolving, carrying out hydrothermal crystallization, and carrying out crystallization at the temperature of 100-180 ℃ for 24-96 h;
(4) Preparation of SAPO-34@ZSM-5: adding the synthesized SAPO-34@MCM-41 powder into a ZSM-5 precursor solution, wherein the solid/liquid mass ratio=1-7; fully and uniformly stirring, and then placing the mixture into a stainless steel autoclave for hydrothermal crystallization at 100-180 ℃; washing the crystallized sample to neutrality, and drying overnight; and then roasting the obtained sample at 550 ℃ to obtain the SAPO-34@ZSM-5 zeolite catalytic material.
4. The method for preparing the core-shell SAPO-34@ZSM-5 zeolite catalyst according to claim 3, wherein the method is characterized by comprising the following steps of: in the step (1), the aluminum source is aluminum isopropoxide, pseudo-boehmite or oxyhydrogenAluminium or gamma-Al 2 O 3 Any one of them; the silicon source is any one of fumed silica, tetraethoxysilane or silica sol; the phosphorus source is any one of phosphoric acid, monoammonium phosphate or monoammonium phosphate; the structure directing agent is any one of tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide or diethylamine.
5. The method for preparing the core-shell SAPO-34@ZSM-5 zeolite catalyst according to claim 3, wherein the method is characterized by comprising the following steps of: in the step (2), the surfactant is any one of hexadecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide or dodecyl trimethyl ammonium bromide; the organic alcohol is one of n-propanol, isopropanol, ethanol or n-butanol; the silicon source is any one of ethyl orthosilicate, propyl orthosilicate, silica sol or sodium silicate.
6. The method for preparing the core-shell SAPO-34@ZSM-5 zeolite catalyst according to claim 3, wherein the method is characterized by comprising the following steps of: in the preparation of the ZSM-5 precursor solution in the step (3), the silicon source is ethyl orthosilicate, sodium silicate, silica sol or gas phase SiO 2 One of the following; the aluminum source is one of aluminum hydroxide, sodium aluminate or aluminum isopropoxide.
7. The method for preparing the core-shell SAPO-34@ZSM-5 zeolite catalyst according to claim 3, wherein the method is characterized by comprising the following steps of: the roasting time of the SAPO-34@ZSM-5 zeolite is 4 to 8 hours.
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| WO2008019586A1 (en) * | 2006-08-08 | 2008-02-21 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | An insitu synthesis method of a microsphere catalyst used for converting oxygen compound to olefine |
| CN106268933A (en) * | 2016-07-21 | 2017-01-04 | 中国科学院广州能源研究所 | Application in hud typed ZSM 5/SAPO 5 composite molecular sieve film and preparation method thereof and biomass gas purifying |
| CN109174174A (en) * | 2018-08-20 | 2019-01-11 | 太原理工大学 | A kind of HZSM-5/SAPO-5 core-shell molecular sieve and its preparation method and application |
| CN113385215A (en) * | 2021-06-11 | 2021-09-14 | 洛阳市科创石化科技开发有限公司 | Preparation method and application of catalyst for preparing propane by hydro-upgrading |
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| WO2008019586A1 (en) * | 2006-08-08 | 2008-02-21 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | An insitu synthesis method of a microsphere catalyst used for converting oxygen compound to olefine |
| CN106268933A (en) * | 2016-07-21 | 2017-01-04 | 中国科学院广州能源研究所 | Application in hud typed ZSM 5/SAPO 5 composite molecular sieve film and preparation method thereof and biomass gas purifying |
| CN109174174A (en) * | 2018-08-20 | 2019-01-11 | 太原理工大学 | A kind of HZSM-5/SAPO-5 core-shell molecular sieve and its preparation method and application |
| CN113385215A (en) * | 2021-06-11 | 2021-09-14 | 洛阳市科创石化科技开发有限公司 | Preparation method and application of catalyst for preparing propane by hydro-upgrading |
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