CN115490243B - Short b-axis HZSM-5 zeolite molecular sieve and preparation method and application thereof - Google Patents
Short b-axis HZSM-5 zeolite molecular sieve and preparation method and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 89
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 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 73
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 72
- 239000010457 zeolite Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 239000000725 suspension Substances 0.000 claims abstract description 36
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 23
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 17
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 95
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 74
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 32
- 238000002425 crystallisation Methods 0.000 claims description 30
- 230000008025 crystallization Effects 0.000 claims description 30
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical group [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 22
- 235000019270 ammonium chloride Nutrition 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 20
- 238000003786 synthesis reaction Methods 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 13
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 239000012495 reaction gas Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 11
- 239000012528 membrane Substances 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
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 241000628997 Flos Species 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims 1
- 241001388119 Anisotremus surinamensis Species 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000013341 scale-up Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- 239000002131 composite material Substances 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 21
- -1 polytetrafluoroethylene Polymers 0.000 description 21
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 21
- 239000004810 polytetrafluoroethylene Substances 0.000 description 21
- 229910001220 stainless steel Inorganic materials 0.000 description 20
- 239000010935 stainless steel Substances 0.000 description 20
- 238000001354 calcination Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 11
- 239000004570 mortar (masonry) Substances 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 238000007873 sieving Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
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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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- 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
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
A short b-axis HZSM-5 zeolite molecular sieve is in the shape of pompon, the thickness of b-axis is 80-400 nm, and the relative thickness ratio of b-axis and c-axis is 0.03-0.1. The synthesis method comprises the following steps: preparing Silicalite-1 seed crystal suspension; preparing a precursor liquid; xerogel; carrying out hydrothermal crystallization; and preparing H-shaped ZSM-5 to obtain the short b-axis HZSM 5 zeolite molecular sieve. The short b-axis HZSM-5 zeolite molecular sieve and the metal oxide are compounded in a mass ratio of 2:1, and are applied to the reaction of preparing aromatic hydrocarbon from synthetic gas, and carbon monoxide and hydrogen are used as reaction raw materials to realize the aromatic hydrocarbon selectivity higher than 80%, and the light aromatic hydrocarbon accounts for more than 70%. The catalyst has the advantages of simple preparation process, good repeatability, easy scale-up production, low price, good performance and wide industrial application prospect.
Description
Technical Field
The invention relates to the field of catalytic materials, in particular to a short b-axis HZSM-5 zeolite molecular sieve, a preparation method thereof and application thereof in preparing aromatic hydrocarbon from synthetic gas.
Background
Zeolite molecular sieve is an inorganic solid with porous, regular and specific pore structure, and its pore size is generallyThe ZSM-5 zeolite molecular sieve is one of the most common zeolite molecular sieves, has excellent ion exchange and separation adsorption performance, and has excellent shape-selective catalytic performance due to a unique cross pore structure, adjustable acidity and hydrothermal stability, and is widely applied to the fields of petrochemical industry, coal chemical industry, fine chemical industry, environmental protection and the like. In recent years, ZSM-5 zeolite molecular sieves are widely used in catalytic reactions such as aromatic hydrocarbon production from methanol, aromatic hydrocarbon production from synthesis gas and carbon dioxide conversion.
The traditional ZSM-5 zeolite molecular sieve is in micron level, has long micropore channels, and limits the diffusion efficiency of reactant and product molecules in a pore structure. As in the synthesis gas to aromatics, the long channels of ZSM-5 zeolite molecular sieves result in heavy hydrocarbons that are difficult to diffuse out of the micropores of the zeolite. In addition, these hydrocarbons undergo further polymerization reactions within the long microporous channels of conventional ZSM-5, eventually depositing coke to plug the microporous channels, resulting in deactivation of the zeolite. Therefore, the morphology and the channel length of the ZSM-5 molecular sieve need to be designed and changed, side reactions are reduced, and the selectivity and the stability of the product are improved. ZSM-5 molecular sieves are known to have a unique framework structure in which two sets of 10-membered ring channels intersect, one set being Z-shaped channels parallel to the a-axis and one set being linear channels parallel to the b-axis. It is generally believed that the diffusion rate of molecules of a substance in a linear channel is faster than in a zigzag channel. Therefore, the design purpose can be achieved by shortening the length of the b axis. CN110467198A discloses a preparation method of hierarchical pore ZSM-5 nano aggregate microsphere, but it needs a large amount of template agent, and also needs to use biological alcohol as molecular sieve template agent or double solvent to regulate and control molecular sieve size, which does not conform to the concept of sustainable development. CN113072079a discloses a synthesis method of a twist strong acid ZSM-5 zeolite containing mesoporous structure assembled by nano square conical particles, which only needs to use a small amount of small molecular template agent and does not need to be prepared by a traditional hydrothermal method, but has the problems of high price of introducing high molecular template agent, difficult accurate control of synthesized molecular sieve acidity, and the like. CN113184875a discloses a method for preparing a full-silica short b-axis ZSM-5 zeolite molecular sieve, which inhibits the growth of b-axis by adding urea, and compared with aluminosilicate zeolite, silicate zeolite has higher thermal stability and hydrophobicity. The lack of aluminum-related acid centers also inhibits side reactions, such as coking, but the introduction of urea during its synthesis is prone to environmental problems.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the HZSM-5 molecular sieve with the characteristic of short b axis and a preparation method thereof, wherein the short b axis HZSM-5 zeolite molecular sieve is in a pompon flower shape, the thickness of the b axis is 80-400 nm, and the relative thickness ratio of the b axis to the c axis is 0.03-0.1. The short b-axis HZSM-5 zeolite molecular sieve and Zr-Zn metal oxide are ground and mixed to be applied to the synthesis gas to prepare aromatic hydrocarbon, so that the aromatic hydrocarbon selectivity is improved.
The preparation method of the short b-axis HZSM-5 zeolite molecular sieve comprises the following steps:
1) Preparation of Silicalite-1 seed suspension: weighing and putting the metered tetraethyl orthosilicate, tetrapropylammonium hydroxide and pure water into a beaker, and stirring at the temperature of 30-50 ℃ to form a uniform solution; and then placing the solution into a polytetrafluoroethylene liner, and loading the solution into a high-pressure stainless steel water heating reaction kettle. And (3) placing the high-pressure reaction kettle in a baking oven with the temperature of 50-100 ℃ for constant-temperature aging for 6-96 hours to obtain Silicalite-1 seed crystal suspension.
2) Preparing a precursor liquid: weighing a metered amount of alkali and aluminum sources, putting the alkali and aluminum sources into a beaker, adding a template agent, pure water and Silicalite-1 seed crystal suspension, and stirring for 1-2 h at room temperature to fully dissolve the mixture to obtain a solution I. And then dissolving the silicon source in pure water to obtain a diluted silicon solution, namely solution II. And adding the solution II into the solution I, and stirring and mixing to obtain the precursor solution.
3) Preparation of xerogel: and (2) placing the precursor liquid obtained in the step (2) into a glass reactor, stirring for 1-2 h at 20-45 ℃, heating to 70-90 ℃ and continuously stirring for 1-2 h. And then press-filtering for 1-2 times by a membrane press filter to obtain a xerogel product.
4) And (3) hydrothermal crystallization: placing the xerogel obtained in the step 3) into a polytetrafluoroethylene beaker, and then placing the polytetrafluoroethylene beaker into a high-pressure stainless steel water thermal reaction kettle filled with a small amount of pure water for sealing. Placing the high-pressure reaction kettle in a homogeneous reactor at 100-180 ℃ for standing and crystallizing for 6-60 h.
5) Preparation of Na-type ZSM-5: taking out the precipitate after the crystallization in the step 4), filtering to be neutral, drying in an oven at 70-120 ℃ for 3-8 h, and then placing the precipitate in a muffle furnace for roasting at 400-600 ℃ for 4-8 h to obtain the Na-type ZSM-5 molecular sieve.
6) Preparing H-type ZSM-5: after roasting, the obtained Na-type ZSM-5 zeolite molecular sieve is placed in an ammonium chloride solution with the concentration of 1mol/L, stirred in a water bath with the temperature of 80-90 ℃ and subjected to ammonium exchange for 2-3 hours. The ammonium exchange step was repeated 3 times. And after the ammonium exchange is finished, filtering, washing and placing the mixture in a muffle furnace for roasting, wherein the roasting temperature is 400-600 ℃, and the roasting time is 4-8 hours, so that the H-type ZSM-5 molecular sieve is obtained.
In the invention, the mol ratio of tetraethyl orthosilicate, tetrapropylammonium hydroxide and pure water added into the Silicalite-1 seed crystal suspension in the step 1) is 1 (0.3-0.5) and 8-50.
In the invention, the mol ratio of alkali, template agent, aluminum source and pure water in the precursor liquid in the step 2) is (0.13-0.65): (0.5-1): (0.0033-0.02): (15-50); in the silicon source water solution, the mol ratio of the silicon source to the pure water is 1 (15-50); the mass ratio of the silicon source to the Silicalite-1 seed crystal suspension in the step 1) is 5-50 wt%.
In the invention, the silicon source in the step 2) is at least one of silica sol, sodium silicate and tetraethyl orthosilicate; the alkali is at least one of sodium hydroxide, sodium bicarbonate and sodium carbonate; the template agent is a dual-template agent, wherein one of the template agent is ammonium fluoride, hydrofluoric acid or sodium fluoride, the other template agent is tetrapropylammonium bromide, and the ratio of the template agent to the tetrapropylammonium bromide is (0.5-1): 1; the aluminum source is at least one of sodium aluminate, aluminum isopropoxide, aluminum sulfate and aluminum nitrate.
The application of the short b-axis HZSM-5 molecular sieve in the field of preparing aromatic hydrocarbon by a one-step method of synthesis gas is characterized in that Zr-Zn metal oxide and the short b-axis HZSM-5 zeolite molecular sieve are selected according to the weight ratio of 1:2, are placed in a mortar for grinding and mixing for 5-10 min, and are subjected to granulating and molding by a 40-60-mesh sieve, so that a composite catalyst is obtained; 0.5g of complexThe catalyst is placed in a fixed bed reactor to carry out the reaction for preparing aromatic hydrocarbon by synthesis gas, the reaction condition is that the reaction pressure is 40-50 bar, the reaction temperature is 410 ℃, and H 2 The volume ratio of the catalyst to CO is 2:1, and the space velocity of the reaction gas is 1000-50000 mL h -1 g -1 。
Compared with the prior art, the invention has the following remarkable effects:
1. the short b-axis HZSM-5 molecular sieve has a short b-axis, the thickness of the b-axis is 80-400 nm, the relative thickness ratio of the b-axis to the c-axis is 0.03-0.1, the length distribution is uniform, and the molecular sieve presents a unique petal-shaped shape of the pompon;
2. in the preparation process, two template agents of tetrapropylammonium bromide and ammonium fluoride are adopted, so that the molecular sieve can be restrained from growing along the b-axis direction, and is induced to generate a lamellar structure, and then a cross floss ball flower shape is formed;
3. the short b-axis HZSM-5 molecular sieve and Zr-Zn metal oxide are ground and mixed to be applied to preparing aromatic hydrocarbon from synthetic gas, and the molecular sieve has the unique morphology of a shorter b-axis, so that the mass transfer of reactants and products is facilitated, the further aromatization of the light aromatic hydrocarbon of the products is inhibited, the catalyst has better catalytic performance, the aromatic hydrocarbon selectivity is higher than 80%, and the light aromatic hydrocarbon accounts for more than 70%;
4. the template agent, the silicon source and other reagents used by the short b-axis HZSM-5 molecular sieve are low in price, low in cost, simple in preparation process, high in repeatability and easy to carry out large-scale production.
Drawings
FIG. 1 is XRD patterns of the products of example 1, comparative example 1 and comparative example 2;
FIG. 2 is a scanning electron microscope image of the product of example 1;
FIG. 3 is a scanning electron microscope image of the product of comparative example 1;
FIG. 4 is a scanning electron microscope image of the product of comparative example 2.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
Example 1
50g of tetraethyl orthosilicate, 30g of pure water, 43.75g of tetrapropylammonium hydroxide (40 wt% aqueous solution) were added to a 200mL beaker, and stirred at 35 ℃ for 2 hours and then heated to 45 ℃ and stirred for 1 hour to make it a uniform solution; the solution is placed in a polytetrafluoroethylene liner and is filled into a high-pressure stainless steel water heating reaction kettle. Placing the high-pressure reaction kettle in a 70 ℃ oven for constant-temperature crystallization for 12 hours; the resulting suspension after crystallization was collected directly and used as a Silicalite-1 seed suspension.
0.75g sodium hydroxide, 0.031g sodium aluminate were weighed into a 200mL beaker, then 19.97g tetrapropylammonium bromide (TPABr), 1.389g ammonium fluoride, 20mL pure water, 0.78g Silicalite-1 seed crystal suspension were added and stirred at room temperature for 1h to dissolve thoroughly to give solution I. 15g of silica sol (30 wt%) was dissolved in 30g of pure water to obtain a solution II, and the solution I was added to the solution II to obtain a precursor solution. And (3) placing the precursor liquid into a glass reactor, stirring for 1h at 35 ℃, heating to 80 ℃ and stirring for 1h, and then performing filter pressing for 1 time by a membrane filter press to obtain a xerogel product. The obtained xerogel was placed in a polytetrafluoroethylene beaker, and then placed in a high-pressure stainless steel hot reaction kettle filled with 50mL of pure water for sealing. And placing the high-pressure reaction kettle in a 180 ℃ homogeneous reactor, standing and crystallizing for 12 hours. Taking out the precipitate after crystallization, filtering to neutrality, and roasting in a muffle furnace at 600 ℃ for 8h. After the completion of the calcination, the obtained Na-type ZSM-5 zeolite molecular sieve was placed in a 1mol/L ammonium chloride solution, and stirred in a water bath at 80℃for 3 hours in a ratio of 1.0g of ZSM-5 zeolite molecular sieve to 50mL of ammonium chloride solution. The ammonium exchange step was repeated 3 times. And after the ammonium exchange is finished, filtering, washing and placing the mixture in a muffle furnace for roasting, wherein the roasting temperature is 550 ℃, and the roasting time is 4 hours. After calcination, a short b-axis HZSM-5 zeolite molecular sieve in the form of a pompon flower, labeled sbx-H-ZSM-5-200 (5 wt% Si-12H), was obtained.
As shown in FIG. 1, the prepared product exhibited an XRD diffraction peak of ZSM-5 (labeled sbx-H-ZSM-5-200 (5 wt% Si-12H)), indicating successful synthesis of a ZSM-5 zeolite molecular sieve. As shown in FIG. 2, which is an SEM image of the obtained product, it can be clearly observed from the image that the b-axis length of the synthesized H-ZSM-5 molecular sieve material is about 80nm, wherein the b/c relative length is about 0.068, and the whole product has the shape of a pompon.
Putting Zr-Zn metal oxide and short b-axis HZSM-5 zeolite molecular sieve in a weight ratio of 1:2 into a mortar for grinding and mixing for 5min, and then sieving with a 40-60 mesh sieve for granulating and forming to obtain a composite catalyst; taking 0.5g of composite catalyst to carry out reaction evaluation of preparing aromatic hydrocarbon from synthesis gas in a fixed bed reactor, wherein the reaction conditions are as follows: the reaction pressure was 50bar, the reaction temperature was 410℃and H 2 The volume ratio of the catalyst to CO is 2:1, and the space velocity of the reaction gas is 3000mL h -1 g -1 . The results of the performance evaluation are shown in Table 1.
Example 2
50g of tetraethyl orthosilicate, 30g of pure water, 43.75g of tetrapropylammonium hydroxide (40 wt% aqueous solution) were added to a 200mL beaker, and stirred at 35 ℃ for 2 hours and then heated to 45 ℃ and stirred for 1 hour to make it a uniform solution; the solution is placed in a polytetrafluoroethylene liner and is filled into a high-pressure stainless steel water heating reaction kettle. Placing the high-pressure reaction kettle in a 70 ℃ oven for constant-temperature crystallization for 12 hours; the resulting suspension after crystallization was collected directly and used as a Silicalite-1 seed suspension.
0.75g sodium hydroxide, 0.123g sodium aluminate were weighed into a 200mL beaker, followed by addition of 19.97g tetrapropylammonium bromide (TPABr), 1.389g ammonium fluoride, 20mL pure water, 0.78g Silicalite-1 seed crystal suspension and stirring at room temperature for 1h to allow sufficient dissolution to give solution I. 15g of silica sol (30 wt%) was dissolved in 30g of pure water to obtain a solution II, and the solution I was added to the solution II to obtain a precursor solution. And (3) placing the precursor liquid into a glass reactor, stirring for 1h at 35 ℃, heating to 80 ℃ and stirring for 1h, and then performing filter pressing for 1 time by a membrane filter press to obtain a xerogel product. The obtained xerogel was placed in a polytetrafluoroethylene beaker, and then placed in a high-pressure stainless steel hot reaction kettle filled with 50mL of pure water for sealing. And placing the high-pressure reaction kettle in a 180 ℃ homogeneous reactor, standing and crystallizing for 12 hours. Taking out the precipitate after crystallization, filtering to neutrality, and roasting in a muffle furnace at 600 ℃ for 8h. After the completion of the calcination, the obtained Na-type ZSM-5 zeolite molecular sieve was placed in a 1mol/L ammonium chloride solution, and stirred in a water bath at 80℃for 3 hours in a ratio of 1.0g of ZSM-5 zeolite molecular sieve to 50mL of ammonium chloride solution. The ammonium exchange step was repeated 3 times. And after the ammonium exchange is finished, filtering, washing and placing the mixture in a muffle furnace for roasting, wherein the roasting temperature is 550 ℃, and the roasting time is 4 hours. After calcination, a short b-axis HZSM-5 zeolite molecular sieve in the form of a pompon flower, labeled sbx-H-ZSM-5-50 (5 wt% Si-12H), was obtained.
Putting Zr-Zn metal oxide and the short b-axis HZSM-5 zeolite molecular sieve in a weight ratio of 1:2 into a mortar for grinding and mixing for 5min, and then sieving with a 40-60 mesh sieve for granulating and forming to obtain a composite catalyst; taking 0.5g of composite catalyst to carry out reaction evaluation of preparing aromatic hydrocarbon from synthesis gas in a fixed bed reactor, wherein the reaction conditions are as follows: the reaction pressure was 50bar, the reaction temperature was 410℃and H 2 The volume ratio of the catalyst to CO is 2:1, and the space velocity of the reaction gas is 3000mL h -1 g -1 . The results of the performance evaluation are shown in Table 1.
Example 3
50g of tetraethyl orthosilicate, 30g of pure water, 43.75g of tetrapropylammonium hydroxide (40 wt% aqueous solution) were added to a 200mL beaker, and stirred at 35 ℃ for 2 hours and then heated to 45 ℃ and stirred for 1 hour to make it a uniform solution; the solution is placed in a polytetrafluoroethylene liner and is filled into a high-pressure stainless steel water heating reaction kettle. Placing the high-pressure reaction kettle in a 70 ℃ oven for constant-temperature crystallization for 12 hours; the resulting suspension after crystallization was collected directly and used as a Silicalite-1 seed suspension.
0.75g sodium hydroxide, 0.061g sodium aluminate were weighed into a 200mL beaker, then 19.97g tetrapropylammonium bromide (TPABr), 1.389g ammonium fluoride, 20mL pure water, 0.78g Silicalite-1 seed crystal suspension were added and stirred at room temperature for 1h to dissolve thoroughly to give solution I. 15g of silica sol (30 wt%) was dissolved in 30g of pure water to obtain a solution II, and the solution I was added to the solution II to obtain a precursor solution. And (3) placing the precursor liquid into a glass reactor, stirring for 1h at 35 ℃, heating to 80 ℃ and stirring for 1h, and then performing filter pressing for 1 time by a membrane filter press to obtain a xerogel product. The obtained xerogel was placed in a polytetrafluoroethylene beaker, and then placed in a high-pressure stainless steel hot reaction kettle filled with 50mL of pure water for sealing. And placing the high-pressure reaction kettle in a 180 ℃ homogeneous reactor, standing and crystallizing for 12 hours. Taking out the precipitate after crystallization, filtering to neutrality, and roasting in a muffle furnace at 600 ℃ for 8h. After the completion of the calcination, the obtained Na-type ZSM-5 zeolite molecular sieve was placed in a 1mol/L ammonium chloride solution, and stirred in a water bath at 80℃for 3 hours in a ratio of 1.0g of ZSM-5 zeolite molecular sieve to 50mL of ammonium chloride solution. The ammonium exchange step was repeated 3 times. And after the ammonium exchange is finished, filtering, washing and placing the mixture in a muffle furnace for roasting, wherein the roasting temperature is 550 ℃, and the roasting time is 4 hours. After calcination, a short b-axis HZSM-5 zeolite molecular sieve in the form of a pompon flower, labeled sbx-H-ZSM-5-100 (5 wt% Si-12H), was obtained.
Putting Zr-Zn metal oxide and the short b-axis HZSM-5 zeolite molecular sieve in a weight ratio of 1:2 into a mortar for grinding and mixing for 5min, and then sieving with a 40-60 mesh sieve for granulating and forming to obtain a composite catalyst; taking 0.5g of composite catalyst to carry out reaction evaluation of preparing aromatic hydrocarbon from synthesis gas in a fixed bed reactor, wherein the reaction conditions are as follows: the reaction pressure was 50bar, the reaction temperature was 410℃and H 2 The volume ratio of the catalyst to CO is 2:1, and the space velocity of the reaction gas is 3000mL h -1 g -1 . The results of the performance evaluation are shown in Table 1.
Example 4
50g of tetraethyl orthosilicate, 30g of pure water, 43.75g of tetrapropylammonium hydroxide (40 wt% aqueous solution) were added to a 200mL beaker, and stirred at 35 ℃ for 2 hours and then heated to 45 ℃ and stirred for 1 hour to make it a uniform solution; the solution is placed in a polytetrafluoroethylene liner and is filled into a high-pressure stainless steel water heating reaction kettle. Placing the high-pressure reaction kettle in a 70 ℃ oven for constant-temperature crystallization for 12 hours; the resulting suspension after crystallization was collected directly and used as a Silicalite-1 seed suspension.
0.75g sodium hydroxide, 0.041g sodium aluminate were weighed into a 200mL beaker, followed by the addition of 19.97g tetrapropylammonium bromide (TPABr), 1.389g ammonium fluoride, 20mL pure water, 0.78g Silicalite-1 seed crystal suspension and stirring at room temperature for 1h to allow sufficient dissolution to give solution I. 15g of silica sol (30 wt%) was dissolved in 30g of pure water to obtain a solution II, and the solution I was added to the solution II to obtain a precursor solution. And (3) placing the precursor liquid into a glass reactor, stirring for 1h at 35 ℃, heating to 80 ℃ and stirring for 1h, and then performing filter pressing for 1 time by a membrane filter press to obtain a xerogel product. The obtained xerogel was placed in a polytetrafluoroethylene beaker, and then placed in a high-pressure stainless steel hot reaction kettle filled with 50mL of pure water for sealing. And placing the high-pressure reaction kettle in a 180 ℃ homogeneous reactor, standing and crystallizing for 12 hours. Taking out the precipitate after crystallization, filtering to neutrality, and roasting in a muffle furnace at 600 ℃ for 8h. After the completion of the calcination, the obtained Na-type ZSM-5 zeolite molecular sieve was placed in a 1mol/L ammonium chloride solution, and stirred in a water bath at 80℃for 3 hours in a ratio of 1.0g of ZSM-5 zeolite molecular sieve to 50mL of ammonium chloride solution. The ammonium exchange step was repeated 3 times. And after the ammonium exchange is finished, filtering, washing and placing the mixture in a muffle furnace for roasting, wherein the roasting temperature is 550 ℃, and the roasting time is 4 hours. After calcination, a short b-axis HZSM-5 zeolite molecular sieve in the form of a pompon flower, labeled sbx-H-ZSM-5-150 (5 wt% Si-12H), was obtained.
Putting Zr-Zn metal oxide and the short b-axis HZSM-5 zeolite molecular sieve in a weight ratio of 1:2 into a mortar for grinding and mixing for 5min, and then sieving with a 40-60 mesh sieve for granulating and forming to obtain a composite catalyst; taking 0.5g of composite catalyst to carry out reaction evaluation of preparing aromatic hydrocarbon from synthesis gas in a fixed bed reactor, wherein the reaction conditions are as follows: the reaction pressure was 50bar, the reaction temperature was 410℃and H 2 The volume ratio of the catalyst to CO is 2:1, and the space velocity of the reaction gas is 3000mL h -1 g -1 . The results of the performance evaluation are shown in Table 1.
Example 5
50g of tetraethyl orthosilicate, 30g of pure water, 43.75g of tetrapropylammonium hydroxide (40 wt% aqueous solution) were added to a 200mL beaker, and stirred at 35 ℃ for 2 hours and then heated to 45 ℃ and stirred for 1 hour to make it a uniform solution; the solution is placed in a polytetrafluoroethylene liner and is filled into a high-pressure stainless steel water heating reaction kettle. Placing the high-pressure reaction kettle in a 70 ℃ oven for constant-temperature crystallization for 12 hours; the resulting suspension after crystallization was collected directly and used as a Silicalite-1 seed suspension.
0.75g sodium hydroxide, 0.021g sodium aluminate were weighed into a 200mL beaker, then 19.97g tetrapropylammonium bromide (TPABr), 1.389g ammonium fluoride, 20mL pure water, 0.78g Silicalite-1 seed crystal suspension were added and stirred at room temperature for 1h to dissolve thoroughly to give solution I. 15g of silica sol (30 wt%) was dissolved in 30g of pure water to obtain a solution II, and the solution I was added to the solution II to obtain a precursor solution. And (3) placing the precursor liquid into a glass reactor, stirring for 1h at 35 ℃, heating to 80 ℃ and stirring for 1h, and then performing filter pressing for 1 time by a membrane filter press to obtain a xerogel product. The obtained xerogel was placed in a polytetrafluoroethylene beaker, and then placed in a high-pressure stainless steel hot reaction kettle filled with 50mL of pure water for sealing. And placing the high-pressure reaction kettle in a 180 ℃ homogeneous reactor, standing and crystallizing for 12 hours. Taking out the precipitate after crystallization, filtering to neutrality, and roasting in a muffle furnace at 600 ℃ for 8h. After the completion of the calcination, the obtained Na-type ZSM-5 zeolite molecular sieve was placed in a 1mol/L ammonium chloride solution, and stirred in a water bath at 80℃for 3 hours in a ratio of 1.0g of ZSM-5 zeolite molecular sieve to 50mL of ammonium chloride solution. The ammonium exchange step was repeated 3 times. And after the ammonium exchange is finished, filtering, washing and placing the mixture in a muffle furnace for roasting, wherein the roasting temperature is 550 ℃, and the roasting time is 4 hours. After calcination, a short b-axis HZSM-5 zeolite molecular sieve in the form of a pompon flower, labeled sbx-H-ZSM-5-300 (5 wt% Si-12H), was obtained.
Putting Zr-Zn metal oxide and the short b-axis HZSM-5 zeolite molecular sieve in a weight ratio of 1:2 into a mortar for grinding and mixing for 5min, and then sieving with a 40-60 mesh sieve for granulating and forming to obtain a composite catalyst; taking 0.5g of composite catalyst to carry out reaction evaluation of preparing aromatic hydrocarbon from synthesis gas in a fixed bed reactor, wherein the reaction conditions are as follows: the reaction pressure was 50bar, the reaction temperature was 410℃and H 2 The volume ratio of the catalyst to CO is 2:1, and the space velocity of the reaction gas is 3000mL h -1 g -1 . The results of the performance evaluation are shown in Table 1.
Example 6
50g of tetraethyl orthosilicate, 30g of pure water, 43.75g of tetrapropylammonium hydroxide (40 wt% aqueous solution) were added to a 200mL beaker, and stirred at 35 ℃ for 2 hours and then heated to 45 ℃ and stirred for 1 hour to make it a uniform solution; the solution is placed in a polytetrafluoroethylene liner and is filled into a high-pressure stainless steel water heating reaction kettle. Placing the high-pressure reaction kettle in a 70 ℃ oven for constant-temperature crystallization for 12 hours; the resulting suspension after crystallization was collected directly and used as a Silicalite-1 seed suspension.
0.75g sodium hydroxide, 0.031g sodium aluminate were weighed into a 200mL beaker, then 19.97g tetrapropylammonium bromide (TPABr), 1.389g ammonium fluoride, 20mL pure water, 3.12g Silicalite-1 seed crystal suspension were added and stirred at room temperature for 1h to dissolve thoroughly to give solution I. 15g of silica sol (30 wt%) was dissolved in 30g of pure water to obtain a solution II, and the solution I was added to the solution II to obtain a precursor solution. And (3) placing the precursor liquid into a glass reactor, stirring for 1h at 35 ℃, heating to 80 ℃ and stirring for 1h, and then performing filter pressing for 1 time by a membrane filter press to obtain a xerogel product. The obtained xerogel was placed in a polytetrafluoroethylene beaker, and then placed in a high-pressure stainless steel hot reaction kettle filled with 50mL of pure water for sealing. And placing the high-pressure reaction kettle in a 180 ℃ homogeneous reactor, standing and crystallizing for 12 hours. Taking out the precipitate after crystallization, filtering to neutrality, and roasting in a muffle furnace at 600 ℃ for 8h. After the completion of the calcination, the obtained Na-type ZSM-5 zeolite molecular sieve was placed in a 1mol/L ammonium chloride solution, and stirred in a water bath at 80℃for 3 hours in a ratio of 1.0g of ZSM-5 zeolite molecular sieve to 50mL of ammonium chloride solution. The ammonium exchange step was repeated 3 times. And after the ammonium exchange is finished, filtering, washing and placing the mixture in a muffle furnace for roasting, wherein the roasting temperature is 550 ℃, and the roasting time is 4 hours. After calcination, a short b-axis HZSM-5 zeolite molecular sieve in the form of a pompon flower, labeled sbx-H-ZSM-5-200 (20 wt% Si-12H), was obtained.
Putting Zr-Zn metal oxide and the short b-axis HZSM-5 zeolite molecular sieve in a weight ratio of 1:2 into a mortar for grinding and mixing for 5min, and then sieving with a 40-60 mesh sieve for granulating and forming to obtain a composite catalyst; taking 0.5g of composite catalyst to carry out reaction evaluation of preparing aromatic hydrocarbon from synthesis gas in a fixed bed reactor, wherein the reaction conditions are as follows: the reaction pressure was 50bar, the reaction temperature was 410℃and H 2 The volume ratio of the catalyst to CO is 2:1, and the space velocity of the reaction gas is 3000mL h -1 g -1 . The results of the performance evaluation are shown in Table 1.
Example 7
50g of tetraethyl orthosilicate, 30g of pure water, 43.75g of tetrapropylammonium hydroxide (40 wt% aqueous solution) were added to a 200mL beaker, and stirred at 35 ℃ for 2 hours and then heated to 45 ℃ and stirred for 1 hour to make it a uniform solution; the solution is placed in a polytetrafluoroethylene liner and is filled into a high-pressure stainless steel water heating reaction kettle. Placing the high-pressure reaction kettle in a 70 ℃ oven for constant-temperature crystallization for 60 hours; the resulting suspension after crystallization was collected directly and used as a Silicalite-1 seed suspension.
0.75g sodium hydroxide, 0.031g sodium aluminate were weighed into a 200mL beaker, then 19.97g tetrapropylammonium bromide (TPABr), 1.389g ammonium fluoride, 20mL pure water, 0.78g Silicalite-1 seed crystal suspension were added and stirred at room temperature for 1h to dissolve thoroughly to give solution I. 15g of silica sol (30 wt%) was dissolved in 30g of pure water to obtain a solution II, and the solution I was added to the solution II to obtain a precursor solution. And (3) placing the precursor liquid into a glass reactor, stirring for 1h at 35 ℃, heating to 80 ℃ and stirring for 1h, and then performing filter pressing for 1 time by a membrane filter press to obtain a xerogel product. The obtained xerogel was placed in a polytetrafluoroethylene beaker, and then placed in a high-pressure stainless steel hot reaction kettle filled with 50mL of pure water for sealing. And placing the high-pressure reaction kettle in a 180 ℃ homogeneous reactor, standing and crystallizing for 12 hours. Taking out the precipitate after crystallization, filtering to neutrality, and roasting in a muffle furnace at 600 ℃ for 8h. After the completion of the calcination, the obtained Na-type ZSM-5 zeolite molecular sieve was placed in a 1mol/L ammonium chloride solution, and stirred in a water bath at 80℃for 3 hours in a ratio of 1.0g of ZSM-5 zeolite molecular sieve to 50mL of ammonium chloride solution. The ammonium exchange step was repeated 3 times. And after the ammonium exchange is finished, filtering, washing and placing the mixture in a muffle furnace for roasting, wherein the roasting temperature is 550 ℃, and the roasting time is 4 hours. After calcination, a short b-axis HZSM-5 zeolite molecular sieve in the form of a pompon flower, labeled sbx-H-ZSM-5-200 (5 wt% Si-60H), was obtained.
Putting Zr-Zn metal oxide and the short b-axis HZSM-5 zeolite molecular sieve in a weight ratio of 1:2 into a mortar for grinding and mixing for 5min, and then sieving with a 40-60 mesh sieve for granulating and forming to obtain a composite catalyst; taking 0.5g of composite catalyst to carry out reaction evaluation of preparing aromatic hydrocarbon from synthesis gas in a fixed bed reactor, wherein the reaction conditions are as follows: the reaction pressure was 50bar, the reaction temperature was 410℃and H 2 The volume ratio of the catalyst to CO is 2:1, and the space velocity of the reaction gas is 3000mL h -1 g -1 . The results of the performance evaluation are shown in Table 1.
Example 8
50g of tetraethyl orthosilicate, 30g of pure water, 43.75g of tetrapropylammonium hydroxide (40 wt% aqueous solution) were added to a 200mL beaker, and stirred at 35 ℃ for 2 hours and then heated to 45 ℃ and stirred for 1 hour to make it a uniform solution; the solution is placed in a polytetrafluoroethylene liner and is filled into a high-pressure stainless steel water heating reaction kettle. Placing the high-pressure reaction kettle in a 70 ℃ oven for constant-temperature crystallization for 60 hours; the resulting suspension after crystallization was collected directly and used as a Silicalite-1 seed suspension.
0.75g sodium hydroxide, 0.031g sodium aluminate were weighed into a 200mL beaker, then 19.97g tetrapropylammonium bromide (TPABr), 1.389g ammonium fluoride, 20mL pure water, 3.12g Silicalite-1 seed crystal suspension were added and stirred at room temperature for 1h to dissolve thoroughly to give solution I. 15g of silica sol (30 wt%) was dissolved in 30g of pure water to obtain a solution II, and the solution I was added to the solution II to obtain a precursor solution. And (3) placing the precursor liquid into a glass reactor, stirring for 1h at 35 ℃, heating to 80 ℃ and stirring for 1h, and then performing filter pressing for 1 time by a membrane filter press to obtain a xerogel product. The obtained xerogel was placed in a polytetrafluoroethylene beaker, and then placed in a high-pressure stainless steel hot reaction kettle filled with 50mL of pure water for sealing. And placing the high-pressure reaction kettle in a 180 ℃ homogeneous reactor, standing and crystallizing for 12 hours. Taking out the precipitate after crystallization, filtering to neutrality, and roasting in a muffle furnace at 600 ℃ for 8h. After the completion of the calcination, the obtained Na-type ZSM-5 zeolite molecular sieve was placed in a 1mol/L ammonium chloride solution, and stirred in a water bath at 80℃for 3 hours in a ratio of 1.0g of ZSM-5 zeolite molecular sieve to 50mL of ammonium chloride solution. The ammonium exchange step was repeated 3 times. And after the ammonium exchange is finished, filtering, washing and placing the mixture in a muffle furnace for roasting, wherein the roasting temperature is 550 ℃, and the roasting time is 4 hours. After calcination, a short b-axis HZSM-5 zeolite molecular sieve in the form of a pompon flower, labeled sbx-H-ZSM-5-200 (20 wt% Si-60H), was obtained.
Putting Zr-Zn metal oxide and the short b-axis HZSM-5 zeolite molecular sieve in a weight ratio of 1:2 into a mortar for grinding and mixing for 5min, and then sieving with a 40-60 mesh sieve for granulating and forming to obtain a composite catalyst; taking 0.5g of composite catalyst to carry out reaction evaluation of preparing aromatic hydrocarbon from synthesis gas in a fixed bed reactor, wherein the reaction conditions are as follows: the reaction pressure is 50bar, and the reaction temperature is 410 DEG C，H 2 The volume ratio of the catalyst to CO is 2:1, and the space velocity of the reaction gas is 3000mL h -1 g -1 . The results of the performance evaluation are shown in Table 1.
Comparative example 1
HZSM-5 molecular sieve of Shanghai Fuxu molecular sieve Co., ltd was purchased as the molecular sieve. As shown in FIG. 1, the commercial product exhibited XRD diffraction peaks for ZSM-5 (labeled C-H-ZSM-5-200). As shown in fig. 3, which is an SEM scanning electron microscope image of the commercial product, the molecular sieve can be clearly observed to be in a cluster shape and an irregular block shape.
Putting Zr-Zn metal oxide and the commercial HZSM-5 zeolite molecular sieve in a weight ratio of 1:2 into a mortar for grinding and mixing for 5min, and then sieving with a 40-60 mesh sieve for granulating and forming to obtain a composite catalyst; taking 0.5g of composite catalyst to carry out reaction evaluation of preparing aromatic hydrocarbon from synthesis gas in a fixed bed reactor, wherein the reaction conditions are as follows: the reaction pressure was 50bar, the reaction temperature was 410℃and H 2 The volume ratio of the catalyst to CO is 2:1, and the space velocity of the reaction gas is 3000mL h -1 g -1 . The results of the performance evaluation are shown in Table 1.
Comparative example 2
50g of tetraethyl orthosilicate, 30g of pure water, 43.75g of tetrapropylammonium hydroxide (40 wt% aqueous solution) were added to a 200mL beaker, and stirred at 35 ℃ for 2 hours and then heated to 45 ℃ and stirred for 1 hour to make it a uniform solution; the solution is placed in a polytetrafluoroethylene liner and is filled into a high-pressure stainless steel water heating reaction kettle. Placing the high-pressure reaction kettle in a 70 ℃ oven for constant-temperature crystallization for 60 hours; the resulting suspension after crystallization was collected directly and used as a Silicalite-1 seed suspension.
0.75g sodium hydroxide, 0.031g sodium aluminate were weighed into a 200mL beaker, followed by the addition of 19.97g tetrapropylammonium bromide, 20mL pure water, 3.12g Silicalite-1 seed suspension and stirring at room temperature for 1h to allow sufficient dissolution to give solution I. 15g of silica sol (30 wt%) is dissolved in 30g of deionized water to obtain solution II, and solution I is added into solution II to obtain a precursor solution. And (3) placing the precursor liquid into a glass reactor, stirring for 1h at 35 ℃, heating to 80 ℃ and stirring for 1h, and then performing filter pressing for 1 time by a membrane filter press to obtain a xerogel product. The obtained xerogel was placed in a polytetrafluoroethylene beaker, and then placed in a high-pressure stainless steel hot reaction kettle filled with 50mL of pure water for sealing. And placing the high-pressure reaction kettle in a 180 ℃ homogeneous reactor, standing and crystallizing for 12 hours. Taking out the precipitate after crystallization, filtering to neutrality, and roasting in a muffle furnace at 600 ℃ for 8h. After the completion of the calcination, the obtained Na-type ZSM-5 zeolite molecular sieve was placed in a 1mol/L ammonium chloride solution, and stirred in a water bath at 80℃for 3 hours in a ratio of 1.0g of ZSM-5 zeolite molecular sieve to 50mL of ammonium chloride solution. And after the ammonium exchange is finished, filtering, washing and placing the mixture in a muffle furnace for roasting, wherein the roasting temperature is 550 ℃, and the roasting time is 4 hours. The ammonium exchange step was repeated 3 times. The flaky HZSM-5 zeolite molecular sieve is obtained after roasting.
As shown in FIG. 1, the prepared product shows XRD diffraction peaks of ZSM-5 (marked as H-ZSM-5-200), which indicates that the ZSM-5 zeolite molecular sieve is successfully synthesized. As shown in FIG. 4, the SEM image of the obtained product shows clearly that the synthesized H-ZSM-5 molecular sieve material is in a flake form.
Putting Zr-Zn metal oxide and the HZSM-5 zeolite molecular sieve in a weight ratio of 1:2 into a mortar for grinding and mixing for 5min, and then sieving with a 40-60 mesh sieve for granulating and forming to obtain a composite catalyst; taking 0.5g of composite catalyst to carry out reaction evaluation of preparing aromatic hydrocarbon from synthesis gas in a fixed bed reactor, wherein the reaction conditions are as follows: the reaction pressure was 50bar, the reaction temperature was 410℃and H 2 The volume ratio of the catalyst to CO is 2:1, and the space velocity of the reaction gas is 3000mL h -1 g -1 . The results of the performance evaluation are shown in Table 1.
Table 1 evaluation results of aromatic hydrocarbon production Performance from Synthesis gas in examples 1 to 8 and comparative examples 1 to 2
In the preparation process, two template agents of tetrapropylammonium bromide and ammonium fluoride are adopted, so that the molecular sieve can be restrained from growing along the b-axis direction, and is induced to generate a lamellar structure, and then a cross floss ball flower shape is formed; in comparative example 2, only one template agent tetrapropylammonium bromide was used, and the formed structure did not show a cross-pompon pattern; the short b-axis HZSM-5 molecular sieve and Zr-Zn metal oxide are ground and mixed to be applied to the preparation of aromatic hydrocarbon from synthetic gas, so that the mass transfer of reactants and products is facilitated, the further aromatization of the light aromatic hydrocarbon of the products is inhibited, the catalyst has better catalytic performance, the aromatic hydrocarbon selectivity is higher than 80%, and the light aromatic hydrocarbon accounts for more than 70%.
Claims (8)
1. A short b-axis HZSM-5 zeolite molecular sieve, characterized by: the short b-axis HZSM-5 zeolite molecular sieve is in a floss ball flower shape, the thickness of the b-axis is 80-400 nm, and the relative thickness ratio of the b-axis to the c-axis is 0.03-0.1;
the preparation method of the short b-axis HZSM-5 zeolite molecular sieve comprises the following steps:
1) Preparation of Silicalite-1 seed suspension: tetraethyl orthosilicate, tetrapropylammonium hydroxide and pure water are mixed and stirred, and then placed in a high-pressure reaction kettle for constant-temperature aging;
2) Preparing a precursor liquid: weighing a metered amount of alkali and aluminum source in a container, then adding a template agent, pure water and Silicalite-1 seed crystal suspension, finally adding a silicon source aqueous solution, and stirring and mixing to obtain a precursor solution; wherein the molar ratio of the alkali to the template agent to the aluminum source to the pure water is (0.13-0.65): (0.5-1): (0.0033-0.02): (15-50); in the silicon source water solution, the molar ratio of the silicon source to the pure water is 1 (15-50); the mass ratio of the silicon source to the Silicalite-1 seed crystal suspension is 5-wt wt% -50 wt%; the template agent is a dual-template agent, wherein one of the template agent is ammonium fluoride, hydrofluoric acid or sodium fluoride, the other template agent is tetrapropylammonium bromide, and the ratio of the template agent to the tetrapropylammonium bromide is (0.5-1) 1;
3) Preparation of xerogel: heating and stirring the precursor liquid obtained in the step 2), and then carrying out filter pressing through a membrane filter press to obtain a xerogel product;
4) And (3) hydrothermal crystallization: placing the xerogel obtained in the step 3) into a high-pressure reaction kettle containing a small amount of pure water for standing and crystallization;
5) Preparation of Na-type ZSM-5: filtering the crystallized product of the step 4) to be neutral, drying and roasting to obtain Na-type ZSM-5;
6) Preparing H-type ZSM-5: and placing the Na-type ZSM-5 in an ammonium chloride solution, stirring under water bath to perform ammonium exchange, and then performing suction filtration, washing and roasting to obtain the H-type ZSM-5.
2. A short b-axis HZSM-5 zeolite molecular sieve as set forth in claim 1, further characterized in that: in the step 1), the mol ratio of tetraethyl orthosilicate, tetrapropylammonium hydroxide and pure water is 1 (0.3-0.5) to 8-50; the constant temperature aging condition is 50-100 ℃, 6-96 h.
3. A short b-axis HZSM-5 zeolite molecular sieve as set forth in claim 1, further characterized in that: in the step 2), the silicon source is at least one of silica sol, sodium silicate and tetraethyl orthosilicate; the aluminum source is at least one of sodium aluminate, aluminum isopropoxide, aluminum sulfate and aluminum nitrate; the alkali is at least one of sodium hydroxide, sodium bicarbonate and sodium carbonate.
4. A short b-axis HZSM-5 zeolite molecular sieve as set forth in claim 1, characterized in that in step 3), the conditions of heating and stirring are: firstly stirring for 1-2 hours at 20-45 ℃, then heating to 70-90 ℃ and continuing stirring for 1-2 hours; in the step 4), the conditions of standing and crystallization are as follows: and standing and crystallizing for 6-60 h in a homogeneous reactor at the temperature of 100-180 ℃.
5. A short b-axis HZSM-5 zeolite molecular sieve as set forth in claim 1, further characterized in that: in the step 5) and the step 6), the roasting temperature is 400-600 ℃ and the time is 4-8 hours; in the step 6), the water bath temperature is 80-90 ℃.
6. The use of a short b-axis HZSM-5 zeolite molecular sieve as claimed in any one of claims 1-5, characterized in that: is used for preparing aromatic hydrocarbon by a one-step method of synthesis gas.
7. The use according to claim 6, wherein: grinding and mixing Zr-Zn metal oxide and short b-axis HZSM-5 zeolite molecular sieve, granulating and forming, and then placing in a fixed bed reactor for reaction of preparing aromatic hydrocarbon from synthetic gas.
8. The use according to claim 7, wherein: the weight ratio of Zr-Zn metal oxide to short b axis HZSM-5 zeolite molecular sieve is 1:2; the reaction conditions for preparing aromatic hydrocarbon from the synthesis gas are as follows: the pressure is 20-60 bar, the temperature is 350-450 ℃, and H 2 The volume ratio of the catalyst to CO is (0.5-3) 1, and the space velocity of the reaction gas is 1000-50000 mL h -1 g -1 。
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