CN115490243A - 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 90
- 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 90
- 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 71
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 70
- 239000010457 zeolite Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 239000000725 suspension Substances 0.000 claims abstract description 36
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 24
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 17
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 241001388119 Anisotremus surinamensis Species 0.000 claims abstract description 7
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims abstract 4
- 239000000243 solution Substances 0.000 claims description 107
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- 238000003756 stirring Methods 0.000 claims description 50
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 31
- 238000002425 crystallisation Methods 0.000 claims description 31
- 230000008025 crystallization Effects 0.000 claims description 31
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 22
- 235000019270 ammonium chloride Nutrition 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 11
- 238000003825 pressing Methods 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
- 238000000967 suction filtration Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000000034 method 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
- 238000002156 mixing Methods 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 6
- 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
- 230000032683 aging Effects 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
- 238000001035 drying Methods 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
- 238000001914 filtration Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 239000012495 reaction gas Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 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
- 239000000047 product Substances 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 21
- 238000001027 hydrothermal synthesis Methods 0.000 description 21
- -1 polytetrafluoroethylene Polymers 0.000 description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 20
- 239000004810 polytetrafluoroethylene Substances 0.000 description 20
- 229910001220 stainless steel Inorganic materials 0.000 description 20
- 239000010935 stainless steel Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- 239000002244 precipitate Substances 0.000 description 19
- 238000001354 calcination Methods 0.000 description 17
- 239000002131 composite material Substances 0.000 description 17
- 239000004570 mortar (masonry) Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 230000003197 catalytic effect Effects 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
- 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
- 238000004519 manufacturing process 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
- 239000004411 aluminium Substances 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
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004005 microsphere Substances 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
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- 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
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- 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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- 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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- C01P2004/30—Particle morphology extending in three dimensions
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Abstract
A short b-axis HZSM-5 zeolite molecular sieve is in the shape of pompon, the thickness of the b-axis is 80-400nm, and the relative thickness ratio of the b-axis to the c-axis is 0.03-0.1. The synthesis method comprises the following steps: preparing a Silicalite-1 seed crystal suspension; preparing a precursor solution; a xerogel; performing hydrothermal crystallization; preparing H-type 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 according to the mass ratio of 2 to 1, the zeolite molecular sieve is applied to the reaction of preparing aromatic hydrocarbon from synthesis gas, carbon monoxide and hydrogen are used as reaction raw materials, the selectivity of the aromatic hydrocarbon is higher than 80%, and the ratio of light aromatic hydrocarbon is higher than 70%. The catalyst has the advantages of simple preparation process, good repeatability, easy large-scale 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 preparation of aromatic hydrocarbon from synthesis gas.
Background
The zeolite molecular sieve is an inorganic solid with a porous, regular and specific pore structure, and the pore size is generally the same
The ZSM-5 zeolite molecular sieve is one of the most common zeolite molecular sieves, has excellent ion exchange and separation adsorption performance, has excellent shape-selective catalytic performance due to the unique cross pore channel 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 preparation of aromatic hydrocarbons from methanol, preparation of aromatic hydrocarbons from synthesis gas and preparation of aromatic hydrocarbons from carbon dioxide conversion.
Most of the traditional ZSM-5 zeolite molecular sieves belong to the micron grade, and the micropore channels are long, so that the diffusion efficiency of reactant and product molecules in a pore structure is limited. The long channels of ZSM-5 zeolite molecular sieves make it difficult for heavy hydrocarbons to diffuse out of the micropores of the zeolite, as in the production of aromatics from synthesis gas. In addition, these hydrocarbons undergo further polymerization within the long microporous channels of conventional ZSM-5, eventually depositing coke that plugs the microporous channels, resulting in deactivation of the zeolite. Therefore, the ZSM-5 molecular sieve morphology and the channel length need to be designed and changed, side reactions are reduced, and the product selectivity and stability are improved. It is known that ZSM-5 molecular sieves have a unique framework structure, with two groups of 10-membered ring channels intersecting, one group being zigzag channels parallel to the a-axis and one group being linear channels parallel to the b-axis. It is believed that the diffusion rate of the substance molecules in the linear channels is faster than in the zigzag channels. Therefore, the design objective can be achieved by shortening the b-axis length. CN110467198A discloses a preparation method of a hierarchical pore ZSM-5 nano aggregate microsphere, but the preparation method needs a large amount of template agents, and biological alcohol is also needed to be used as a molecular sieve template agent or a double solvent to regulate the size of a molecular sieve, which is not in accordance with the concept of continuous development. CN113072079A discloses a synthesis method of a twist-shaped strong acid ZSM-5 zeolite containing a mesoporous structure assembled by nano square conical particles, which only needs to adopt 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 due to the introduction of a high molecular template agent, difficulty in accurately controlling the acidity of the synthesized molecular sieve and the like. CN113184875A discloses a preparation method of an all-silicon type short b-axis ZSM-5 zeolite molecular sieve, which inhibits the growth of a b axis by adding urea, and compared with aluminosilicate zeolite, the silicate zeolite has higher thermal stability and hydrophobicity. The lack of aluminium-related acid sites also inhibits the occurrence of side reactions, such as coking, but the introduction of urea during its synthesis is likely to cause environmental problems.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the HZSM-5 molecular sieve with the characteristic of short b axis and the preparation method thereof, the HZSM-5 zeolite molecular sieve with the short b axis is in a pompon shape, the thickness of the b axis is 80-400nm, 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 the Zr-Zn metal oxide are ground and mixed to be applied to preparing aromatic hydrocarbon from synthesis gas, so that the selectivity of the aromatic hydrocarbon is improved.
The invention relates to a short b-axis HZSM-5 zeolite molecular sieve, which comprises the following steps:
1) Preparation of a Silicalite-1 seed suspension: weighing and putting measured tetraethyl orthosilicate, tetrapropylammonium hydroxide and pure water into a beaker, and stirring at the temperature of 30-50 ℃ to form a uniform solution; then the solution is put into a polytetrafluoroethylene liner and is put into a high-pressure stainless steel hydrothermal reaction kettle. And (3) placing the high-pressure reaction kettle in an oven with the temperature of 50-100 ℃ for constant-temperature aging for 6-96 hours to obtain the Silicalite-1 seed crystal suspension.
2) Preparing a precursor solution: weighing and putting metered alkali and aluminum source into a beaker, adding a template agent, pure water and a Silicalite-1 seed crystal suspension, and stirring at room temperature for 1-2 h to fully dissolve the alkali and aluminum source to obtain a solution I. And then dissolving a silicon source in pure water to obtain a diluted silicon solution, namely a solution II. And adding the solution II into the solution I, and stirring and mixing to obtain a precursor solution.
3) Preparation of xerogel: putting the precursor solution obtained in the step 2) into a glass reactor, stirring for 1-2 h at 20-45 ℃, then heating to 70-90 ℃, and continuing stirring for 1-2 h. Then filter-pressing for 1-2 times by a membrane filter press to obtain a xerogel product.
4) Hydrothermal crystallization: and (3) placing the xerogel obtained in the step 3) into a polytetrafluoroethylene beaker, and then placing the beaker into a high-pressure stainless steel hydrothermal reaction kettle filled with a small amount of pure water for sealing. The high-pressure reaction kettle is placed in a homogeneous reactor at the temperature of 100-180 ℃ for standing and crystallization for 6-60 h.
5) Preparation of Na-type ZSM-5: and 4) taking out the precipitate after crystallization, performing suction filtration to neutrality, drying in an oven at 70-120 ℃ for 3-8 h, and roasting in a muffle furnace at 400-600 ℃ for 4-8 h to obtain the Na-type ZSM-5 molecular sieve.
6) Preparation of H-type ZSM-5: after roasting, the obtained Na-type ZSM-5 zeolite molecular sieve is placed in 1mol/L ammonium chloride solution, stirred in water bath at the temperature of 80-90 ℃ and subjected to ammonium exchange for 2-3 h. The ammonium exchange step was repeated 3 times. After the ammonium exchange is finished, the mixture is filtered, washed and placed in a muffle furnace to be roasted, the roasting temperature is 400-600 ℃, and the roasting time is 4-8H, 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) to 8-50.
In the invention, the molar ratio of alkali, template agent, aluminum source and pure water in the precursor solution in the step 2) is (0.13-0.65), (0.5-1), (0.0033-0.02) and (15-50); in the silicon source water solution, the molar ratio of the silicon source to 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 double template agent, wherein one of the double template agents is ammonium fluoride, hydrofluoric acid or sodium fluoride, and the other one of the double template agents is tetrapropyl ammonium bromide, and the ratio of the ammonium fluoride to the hydrofluoric acid to the tetrapropyl ammonium 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 aromatic hydrocarbon preparation by a synthesis gas one-step method 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 to 2, are placed in a mortar for 5 to 10min for grinding and mixing, and then are sieved by a 40 to 60-mesh sieve for granulation and molding, so that the composite catalyst is obtained; taking 0.5g of composite catalyst to be placed in a fixed bed reactor to carry out the reaction of preparing the aromatic hydrocarbon by the synthesis gas, wherein the reaction conditions are that the reaction pressure is 40-50 bar, the reaction temperature is 410 ℃, and the reaction temperature is H 2 The volume ratio of the catalyst to CO is 2 -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 80-400nm, the relative thickness ratio of the b-axis to the c-axis is 0.03-0.1, the length distribution is uniform, and the short b-axis HZSM-5 molecular sieve presents a unique pompon petal-shaped appearance;
2. in the preparation process, two templates, namely tetrapropylammonium bromide and ammonium fluoride, are adopted, so that the molecular sieve can be inhibited from growing along the direction of the b axis, the molecular sieve is induced to generate a lamellar structure, and then a cross pompon shape is formed;
3. the short b-axis HZSM-5 molecular sieve and the Zr-Zn metal oxide are ground, mixed and applied to preparing aromatic hydrocarbon from synthesis gas, and the molecular sieve has the unique appearance of a short b-axis, so that mass transfer of reactants and products is facilitated, further aromatization of light aromatic hydrocarbon is inhibited, the catalytic performance is good, the aromatic hydrocarbon selectivity is higher than 80%, and the light aromatic hydrocarbon proportion is higher than 70%;
4. the short b-axis HZSM-5 molecular sieve has the advantages of low price of reagents such as a template agent, a silicon source and the like, low cost, simple preparation process, high repeatability and easy large-scale production.
Drawings
FIG. 1 is an XRD spectrum of the products of example 1, comparative example 1 and comparative example 2;
FIG. 2 is a scanning electron micrograph of the product of example 1;
FIG. 3 is a scanning electron micrograph of the product of comparative example 1;
FIG. 4 is a scanning electron micrograph of the product of comparative example 2.
Detailed Description
For a further understanding of the present invention, reference will now be made to the following preferred embodiments of the invention in conjunction with the examples, but it is to be understood that the description is intended to further illustrate the features and advantages of the invention and is not intended to limit the scope of the claims which follow.
Example 1
Adding 50g of tetraethyl orthosilicate, 30g of pure water and 43.75g of tetrapropylammonium hydroxide (40 wt% aqueous solution) into a 200mL beaker, stirring at 35 ℃ for 2h, then heating to 45 ℃ and stirring for 1h to obtain a uniform solution; the solution is placed in a polytetrafluoroethylene liner and is filled into a high-pressure stainless steel hydrothermal reaction kettle. Placing the high-pressure reaction kettle in a 70 ℃ oven for constant-temperature crystallization for 12 hours; the suspension obtained after crystallization is directly collected and used as the Silicalite-1 seed crystal suspension.
0.75g of sodium hydroxide and 0.031g of sodium aluminate are weighed into a 200mL beaker, and then 19.97g of tetrapropylammonium bromide (TPABr), 1.389g of ammonium fluoride, 20mL of pure water, and 0.78g of a Silicalite-1 seed suspension are added and stirred at room temperature for 1 hour to dissolve sufficiently to obtain a 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) putting the precursor solution into a glass reactor, stirring for 1h at 35 ℃, heating to 80 ℃, stirring for 1h, and then performing filter pressing for 1 time by a membrane filter press to obtain a xerogel product. The obtained xerogel is placed in a polytetrafluoroethylene beaker and then is placed in a high-pressure stainless steel hydrothermal reaction kettle filled with 50mL of pure water for sealing. And (3) placing the high-pressure reaction kettle in a homogeneous reactor at 180 ℃ for standing and crystallizing for 12 hours. And after crystallization is finished, taking out the precipitate, performing suction filtration to neutrality, and placing the precipitate in a muffle furnace for roasting at the roasting temperature of 600 ℃ for 8 hours. After the calcination, the obtained Na-type ZSM-5 zeolite molecular sieve is placed in 1mol/L ammonium chloride solution, and according to the proportion of 1.0g of ZSM-5 zeolite molecular sieve to 50mL of ammonium chloride solution, the mixture is stirred in water bath at 80 ℃ and ammonium exchange is carried out for 3 hours. The ammonium exchange step was repeated 3 times. After the ammonium exchange is finished, the mixture is filtered, washed and placed in a muffle furnace for roasting, wherein the roasting temperature is 550 ℃, and the roasting time is 4 hours. Calcination gave a pompon-like short b-axis HZSM-5 zeolite molecular sieve, labeled sbx-H-ZSM-5-200 (5 wt% Si-12H).
As shown in FIG. 1, the prepared product exhibited the XRD diffraction peak of ZSM-5 (labeled as sbx-H-ZSM-5-200 (5 wt% Si-12H)), indicating that the ZSM-5 zeolite molecular sieve was successfully synthesized. As shown in the SEM scanning electron micrograph of the obtained product in figure 2, the b-axis length of the synthesized H-ZSM-5 molecular sieve material is about 80nm, wherein the relative b/c length is about 0.068, and the whole of the synthesized H-ZSM-5 molecular sieve material is in a shape of a pompon.
Putting Zr-Zn metal oxide and a short b-axis HZSM-5 zeolite molecular sieve in a mortar according to the weight ratio of 1; taking 0.5g of composite catalyst to perform 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, the reaction temperature is 410 ℃, and H 2 The volume ratio of the catalyst to CO is 2 -1 g -1 . The results of the performance evaluation are shown in Table 1.
Example 2
Adding 50g of tetraethyl orthosilicate, 30g of pure water and 43.75g of tetrapropylammonium hydroxide (40 wt% aqueous solution) into a 200mL beaker, stirring at 35 ℃ for 2 hours, then heating to 45 ℃ and stirring for 1 hour to obtain a uniform solution; the solution is placed in a polytetrafluoroethylene liner and is filled into a high-pressure stainless steel hydrothermal reaction kettle. Placing the high-pressure reaction kettle in a 70 ℃ oven for constant-temperature crystallization for 12 hours; the suspension obtained after the crystallization is finished is directly collected and used as a Silicalite-1 seed suspension.
0.75g of sodium hydroxide and 0.123g of sodium aluminate are weighed into a 200mL beaker, and then 19.97g of tetrapropylammonium bromide (TPABr), 1.389g of ammonium fluoride, 20mL of pure water and 0.78g of a Silicalite-1 seed suspension are added and sufficiently dissolved under stirring at room temperature for 1 hour to obtain a solution I. 15g of silica sol (30 wt%) was dissolved in 30g of pure water to obtain solution II, and solution I was added to solution II to obtain a precursor solution. And (3) putting the precursor solution into a glass reactor, stirring for 1h at 35 ℃, then heating to 80 ℃, stirring for 1h, and then performing filter pressing for 1 time by a membrane filter press to obtain a xerogel product. The obtained xerogel is placed in a polytetrafluoroethylene beaker and then is placed in a high-pressure stainless steel hydrothermal reaction kettle filled with 50mL of pure water for sealing. And (3) placing the high-pressure reaction kettle in a homogeneous reactor at 180 ℃ for standing and crystallizing for 12 hours. And (4) taking out the precipitate after crystallization is finished, performing suction filtration to neutrality, and placing the precipitate in a muffle furnace for roasting at the roasting temperature of 600 ℃ for 8 hours. After the calcination, the obtained Na-type ZSM-5 zeolite molecular sieve is placed in 1mol/L ammonium chloride solution, and according to the proportion of 1.0g of ZSM-5 zeolite molecular sieve to 50mL of ammonium chloride solution, the mixture is stirred in water bath at 80 ℃ and ammonium exchange is carried out for 3 hours. The ammonium exchange step was repeated 3 times. After the ammonium exchange is finished, the mixture is filtered, washed and placed in a muffle furnace for roasting, wherein the roasting temperature is 550 ℃, and the roasting time is 4 hours. Calcination gave a pompon-like short b-axis HZSM-5 zeolite molecular sieve, labeled sbx-H-ZSM-5-50 (5 wt% Si-12H).
Putting Zr-Zn metal oxide and the short b-axis HZSM-5 zeolite molecular sieve in a mortar according to the weight ratio of 1; taking 0.5g of composite catalyst to perform 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, the reaction temperature is 410 ℃, and H 2 The volume ratio of the catalyst to CO is 2 -1 g -1 . The results of the performance evaluation are shown in Table 1.
Example 3
Adding 50g of tetraethyl orthosilicate, 30g of pure water and 43.75g of tetrapropylammonium hydroxide (40 wt% aqueous solution) into a 200mL beaker, stirring at 35 ℃ for 2 hours, then heating to 45 ℃ and stirring for 1 hour to obtain a uniform solution; the solution is put into a polytetrafluoroethylene inner container and is put into a high-pressure stainless steel hydrothermal reaction kettle. Placing the high-pressure reaction kettle in a 70 ℃ oven for constant-temperature crystallization for 12 hours; the suspension obtained after the crystallization is finished is directly collected and used as a Silicalite-1 seed suspension.
0.75g of sodium hydroxide and 0.061g of sodium aluminate are weighed into a 200mL beaker, and then 19.97g of tetrapropylammonium bromide (TPABr), 1.389g of ammonium fluoride, 20mL of pure water, and 0.78g of a Silicalite-1 seed suspension are added and sufficiently dissolved under stirring at room temperature for 1 hour to obtain a 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) putting the precursor solution into a glass reactor, stirring for 1h at 35 ℃, heating to 80 ℃, stirring for 1h, and then performing filter pressing for 1 time by a membrane filter press to obtain a xerogel product. The obtained xerogel is placed in a polytetrafluoroethylene beaker and then is placed in a high-pressure stainless steel hydrothermal reaction kettle filled with 50mL of pure water for sealing. And (3) placing the high-pressure reaction kettle in a homogeneous reactor at 180 ℃ for standing and crystallizing for 12 hours. And (4) taking out the precipitate after crystallization is finished, performing suction filtration to neutrality, and placing the precipitate in a muffle furnace for roasting at the roasting temperature of 600 ℃ for 8 hours. After the calcination, the obtained Na-type ZSM-5 zeolite molecular sieve is placed in 1mol/L ammonium chloride solution, and according to the proportion of 1.0g of ZSM-5 zeolite molecular sieve to 50mL of ammonium chloride solution, the mixture is stirred in water bath at 80 ℃ and ammonium exchange is carried out for 3 hours. The ammonium exchange step was repeated 3 times. After the ammonium exchange is finished, the mixture is filtered, washed and placed in a muffle furnace for roasting, wherein the roasting temperature is 550 ℃, and the roasting time is 4 hours. Calcination gave a pompon-like short b-axis HZSM-5 zeolite molecular sieve, labeled sbx-H-ZSM-5-100 (5 wt% Si-12H).
Placing Zr-Zn metal oxide and the short b-axis HZSM-5 zeolite molecular sieve in a mortar according to the weight ratio of 1 to 2 for 5min for grinding and mixing, and then sieving with a 40-60 mesh sieve for granulation and molding to obtain a composite catalyst; taking 0.5g of composite catalyst to perform 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, the reaction temperature is 410 ℃, and H 2 The volume ratio of the catalyst to CO is 2 -1 g -1 . The results of the performance evaluation are shown in Table 1.
Example 4
Adding 50g of tetraethyl orthosilicate, 30g of pure water and 43.75g of tetrapropylammonium hydroxide (40 wt% aqueous solution) into a 200mL beaker, stirring at 35 ℃ for 2h, then heating to 45 ℃ and stirring for 1h to obtain a uniform solution; the solution is placed in a polytetrafluoroethylene liner and is filled into a high-pressure stainless steel hydrothermal reaction kettle. Placing the high-pressure reaction kettle in a 70 ℃ oven for constant-temperature crystallization for 12 hours; the suspension obtained after the crystallization is finished is directly collected and used as a Silicalite-1 seed suspension.
0.75g of sodium hydroxide and 0.041g of sodium aluminate are weighed into a 200mL beaker, and then 19.97g of tetrapropylammonium bromide (TPABr), 1.389g of ammonium fluoride, 20mL of pure water, and 0.78g of a Silicalite-1 seed suspension are added and stirred at room temperature for 1 hour to dissolve sufficiently to obtain 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) putting the precursor solution into a glass reactor, stirring for 1h at 35 ℃, then heating to 80 ℃, stirring for 1h, and then performing filter pressing for 1 time by a membrane filter press to obtain a xerogel product. The obtained xerogel is placed in a polytetrafluoroethylene beaker and then is placed in a high-pressure stainless steel hydrothermal reaction kettle filled with 50mL of pure water for sealing. And (3) placing the high-pressure reaction kettle in a homogeneous reactor at 180 ℃ for standing and crystallizing for 12 hours. And after crystallization is finished, taking out the precipitate, performing suction filtration to neutrality, and placing the precipitate in a muffle furnace for roasting at the roasting temperature of 600 ℃ for 8 hours. After the calcination, the obtained Na-type ZSM-5 zeolite molecular sieve is placed in 1mol/L ammonium chloride solution, and according to the proportion of 1.0g of ZSM-5 zeolite molecular sieve to 50mL of ammonium chloride solution, the mixture is stirred in water bath at 80 ℃ and ammonium exchange is carried out for 3 hours. The ammonium exchange step was repeated 3 times. After the ammonium exchange is finished, the mixture is filtered, washed and placed in a muffle furnace for roasting, wherein the roasting temperature is 550 ℃, and the roasting time is 4 hours. Calcination gave a pompon-like short b-axis HZSM-5 zeolite molecular sieve, labeled sbx-H-ZSM-5-150 (5 wt% Si-12H).
Putting Zr-Zn metal oxide and the short b-axis HZSM-5 zeolite molecular sieve in a mortar according to the weight ratio of 1; taking 0.5g of composite catalyst to perform 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, the reaction temperature is 410 ℃, and H 2 Volume ratio to CO is 2 -1 g -1 . The results of the performance evaluation are shown in Table 1.
Example 5
Adding 50g of tetraethyl orthosilicate, 30g of pure water and 43.75g of tetrapropylammonium hydroxide (40 wt% aqueous solution) into a 200mL beaker, stirring at 35 ℃ for 2h, then heating to 45 ℃ and stirring for 1h to obtain a uniform solution; the solution is placed in a polytetrafluoroethylene liner and is filled into a high-pressure stainless steel hydrothermal reaction kettle. Placing the high-pressure reaction kettle in a 70 ℃ oven for constant-temperature crystallization for 12 hours; the suspension obtained after the crystallization is finished is directly collected and used as a Silicalite-1 seed suspension.
0.75g of sodium hydroxide and 0.021g of sodium aluminate are weighed into a 200mL beaker, and then 19.97g of tetrapropylammonium bromide (TPABr), 1.389g of ammonium fluoride, 20mL of pure water and 0.78g of a Silicalite-1 seed suspension are added and sufficiently dissolved under stirring at room temperature for 1 hour to obtain a solution I. 15g of silica sol (30 wt%) was dissolved in 30g of pure water to obtain solution II, and solution I was added to solution II to obtain a precursor solution. And (3) putting the precursor solution into a glass reactor, stirring for 1h at 35 ℃, then heating to 80 ℃, stirring for 1h, and then performing filter pressing for 1 time by a membrane filter press to obtain a xerogel product. The obtained xerogel is placed in a polytetrafluoroethylene beaker and then is placed in a high-pressure stainless steel hydrothermal reaction kettle filled with 50mL of pure water for sealing. And (3) placing the high-pressure reaction kettle in a homogeneous reactor at 180 ℃ for standing and crystallizing for 12 hours. And (4) taking out the precipitate after crystallization is finished, performing suction filtration to neutrality, and placing the precipitate in a muffle furnace for roasting at the roasting temperature of 600 ℃ for 8 hours. After the calcination, the obtained Na-type ZSM-5 zeolite molecular sieve is placed in 1mol/L ammonium chloride solution, and according to the proportion of 1.0g of ZSM-5 zeolite molecular sieve to 50mL of ammonium chloride solution, the mixture is stirred in water bath at 80 ℃ and ammonium exchange is carried out for 3 hours. The ammonium exchange step was repeated 3 times. After the ammonium exchange is finished, the mixture is filtered, washed and placed in a muffle furnace for roasting, wherein the roasting temperature is 550 ℃, and the roasting time is 4 hours. Calcination gave a pompon-like short b-axis HZSM-5 zeolite molecular sieve, labeled sbx-H-ZSM-5-300 (5 wt% Si-12H).
Placing Zr-Zn metal oxide and the short b-axis HZSM-5 zeolite molecular sieve in a mortar according to the weight ratio of 1 to 2 for 5min for grinding and mixing, and then sieving with a 40-60 mesh sieve for granulation and molding to obtain a composite catalyst; taking 0.5g of composite catalyst to perform reaction evaluation of preparing aromatic hydrocarbon from synthesis gas in a fixed bed reactor, wherein the reaction conditions are as follows: reaction pressureThe force is 50bar, the reaction temperature is 410 ℃, H 2 The volume ratio of the catalyst to CO is 2 -1 g -1 . The results of the performance evaluation are shown in Table 1.
Example 6
Adding 50g of tetraethyl orthosilicate, 30g of pure water and 43.75g of tetrapropylammonium hydroxide (40 wt% aqueous solution) into a 200mL beaker, stirring at 35 ℃ for 2h, then heating to 45 ℃ and stirring for 1h to obtain a uniform solution; the solution is put into a polytetrafluoroethylene inner container and is put into a high-pressure stainless steel hydrothermal reaction kettle. Placing the high-pressure reaction kettle in a 70 ℃ oven for constant-temperature crystallization for 12 hours; the suspension obtained after the crystallization is finished is directly collected and used as a Silicalite-1 seed suspension.
0.75g of sodium hydroxide and 0.031g of sodium aluminate are weighed into a 200mL beaker, and then 19.97g of tetrapropylammonium bromide (TPABr), 1.389g of ammonium fluoride, 20mL of pure water, and 3.12g of a Silicalite-1 seed suspension are added and stirred at room temperature for 1 hour to be sufficiently dissolved to obtain a solution I. 15g of silica sol (30 wt%) was dissolved in 30g of pure water to obtain solution II, and solution I was added to solution II to obtain a precursor solution. And (3) putting the precursor solution into a glass reactor, stirring for 1h at 35 ℃, then heating to 80 ℃, stirring for 1h, and then performing filter pressing for 1 time by a membrane filter press to obtain a xerogel product. The obtained xerogel is placed in a polytetrafluoroethylene beaker and then is placed in a high-pressure stainless steel hydrothermal reaction kettle filled with 50mL of pure water for sealing. And (3) placing the high-pressure reaction kettle in a homogeneous reactor at 180 ℃ for standing and crystallizing for 12 hours. And (4) taking out the precipitate after crystallization is finished, performing suction filtration to neutrality, and placing the precipitate in a muffle furnace for roasting at the roasting temperature of 600 ℃ for 8 hours. After the calcination is finished, the obtained Na-type ZSM-5 zeolite molecular sieve is placed in 1mol/L ammonium chloride solution, and according to the proportion that 1.0g of ZSM-5 zeolite molecular sieve corresponds to 50mL of ammonium chloride solution, the mixture is stirred in water bath at the temperature of 80 ℃ and ammonium exchange is carried out for 3 hours. The ammonium exchange step was repeated 3 times. After the ammonium exchange is finished, the mixture is filtered, washed and placed in a muffle furnace for roasting, wherein the roasting temperature is 550 ℃, and the roasting time is 4 hours. Calcination gave a pillowed short b-axis HZSM-5 zeolite molecular sieve, labeled sbx-H-ZSM-5-200 (20wt% Si-12H).
Putting Zr-Zn metal oxide and the short b-axis HZSM-5 zeolite molecular sieve in a weight ratio of 1Grinding and mixing the materials in a mortar for 5min, and then sieving the materials by a 40-60-mesh sieve for granulation and molding to obtain a composite catalyst; taking 0.5g of composite catalyst to perform 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, the reaction temperature is 410 ℃, and H 2 The volume ratio of the catalyst to CO is 2 -1 g -1 . The results of the performance evaluation are shown in Table 1.
Example 7
Adding 50g of tetraethyl orthosilicate, 30g of pure water and 43.75g of tetrapropylammonium hydroxide (40 wt% aqueous solution) into a 200mL beaker, stirring at 35 ℃ for 2 hours, then heating to 45 ℃ and stirring for 1 hour to obtain a uniform solution; the solution is placed in a polytetrafluoroethylene liner and is filled into a high-pressure stainless steel hydrothermal reaction kettle. Placing the high-pressure reaction kettle in a 70 ℃ oven for constant-temperature crystallization for 60 hours; the suspension obtained after crystallization is directly collected and used as the Silicalite-1 seed crystal suspension.
0.75g of sodium hydroxide and 0.031g of sodium aluminate are weighed into a 200mL beaker, and then 19.97g of tetrapropylammonium bromide (TPABr), 1.389g of ammonium fluoride, 20mL of pure water, and 0.78g of a Silicalite-1 seed suspension are added and stirred at room temperature for 1 hour to dissolve sufficiently to obtain a 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) putting the precursor solution into a glass reactor, stirring for 1h at 35 ℃, then heating to 80 ℃, stirring for 1h, and then performing filter pressing for 1 time by a membrane filter press to obtain a xerogel product. The obtained xerogel is placed in a polytetrafluoroethylene beaker and then is placed in a high-pressure stainless steel hydrothermal reaction kettle filled with 50mL of pure water for sealing. And (3) placing the high-pressure reaction kettle in a homogeneous reactor at 180 ℃ for standing and crystallizing for 12 hours. And (4) taking out the precipitate after crystallization is finished, performing suction filtration to neutrality, and placing the precipitate in a muffle furnace for roasting at the roasting temperature of 600 ℃ for 8 hours. After the calcination is finished, the obtained Na-type ZSM-5 zeolite molecular sieve is placed in 1mol/L ammonium chloride solution, and according to the proportion that 1.0g of ZSM-5 zeolite molecular sieve corresponds to 50mL of ammonium chloride solution, the mixture is stirred in water bath at the temperature of 80 ℃ and ammonium exchange is carried out for 3 hours. The ammonium exchange step was repeated 3 times. After the ammonium exchange is finished, the mixture is filtered, washed and placed in a muffle furnace for roasting, wherein the roasting temperature is 550 ℃, and the roasting time is 4 hours. Calcination gave a pompon-like short b-axis HZSM-5 zeolite molecular sieve, labeled sbx-H-ZSM-5-200 (5 wt% Si-60H).
Putting Zr-Zn metal oxide and the short b-axis HZSM-5 zeolite molecular sieve in a mortar according to the weight ratio of 1; taking 0.5g of composite catalyst to perform 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, the reaction temperature is 410 ℃, and H 2 The volume ratio of the catalyst to CO is 2 -1 g -1 . The results of the performance evaluation are shown in Table 1.
Example 8
Adding 50g of tetraethyl orthosilicate, 30g of pure water and 43.75g of tetrapropylammonium hydroxide (40 wt% aqueous solution) into a 200mL beaker, stirring at 35 ℃ for 2h, then heating to 45 ℃ and stirring for 1h to obtain a uniform solution; the solution is put into a polytetrafluoroethylene inner container and is put into a high-pressure stainless steel hydrothermal reaction kettle. Placing the high-pressure reaction kettle in a 70 ℃ oven for constant-temperature crystallization for 60 hours; the suspension obtained after the crystallization is finished is directly collected and used as a Silicalite-1 seed suspension.
0.75g of sodium hydroxide and 0.031g of sodium aluminate are weighed into a 200mL beaker, and then 19.97g of tetrapropylammonium bromide (TPABr), 1.389g of ammonium fluoride, 20mL of pure water, and 3.12g of a Silicalite-1 seed suspension are added and stirred at room temperature for 1 hour to be sufficiently dissolved to obtain a solution I. 15g of silica sol (30 wt%) was dissolved in 30g of pure water to obtain solution II, and solution I was added to solution II to obtain a precursor solution. And (3) putting the precursor solution into a glass reactor, stirring for 1h at 35 ℃, heating to 80 ℃, stirring for 1h, and then performing filter pressing for 1 time by a membrane filter press to obtain a xerogel product. The obtained xerogel is placed in a polytetrafluoroethylene beaker and then is placed in a high-pressure stainless steel hydrothermal reaction kettle filled with 50mL of pure water for sealing. And (3) placing the high-pressure reaction kettle in a homogeneous reactor at 180 ℃ for standing and crystallizing for 12 hours. And (4) taking out the precipitate after crystallization is finished, performing suction filtration to neutrality, and placing the precipitate in a muffle furnace for roasting at the roasting temperature of 600 ℃ for 8 hours. After the calcination is finished, the obtained Na-type ZSM-5 zeolite molecular sieve is placed in 1mol/L ammonium chloride solution, and according to the proportion that 1.0g of ZSM-5 zeolite molecular sieve corresponds to 50mL of ammonium chloride solution, the mixture is stirred in water bath at the temperature of 80 ℃ and ammonium exchange is carried out for 3 hours. The ammonium exchange step was repeated 3 times. After the ammonium exchange is finished, the mixture is filtered, washed and placed in a muffle furnace for roasting, wherein the roasting temperature is 550 ℃, and the roasting time is 4 hours. Calcination gave a fluffy short b-axis HZSM-5 zeolite molecular sieve labeled sbx-H-ZSM-5-200 (20wt% Si-60H).
Placing Zr-Zn metal oxide and the short b-axis HZSM-5 zeolite molecular sieve in a mortar according to the weight ratio of 1 to 2 for 5min for grinding and mixing, and then sieving with a 40-60 mesh sieve for granulation and molding to obtain a composite catalyst; taking 0.5g of composite catalyst to perform 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, the reaction temperature is 410 ℃, and H 2 The volume ratio of the catalyst to CO is 2 -1 g -1 . The results of the performance evaluation are shown in Table 1.
Comparative example 1
HZSM-5 molecular sieves from Shanghai Fuxu molecular sieves Co., ltd were purchased as molecular sieves. As shown in FIG. 1, the commercial product exhibited the XRD diffraction peak of ZSM-5 (labeled C-H-ZSM-5-200). As shown in fig. 3, the SEM image of the commercial product clearly shows that the molecular sieve is in a cluster or irregular block shape.
Placing Zr-Zn metal oxide and the commercial HZSM-5 zeolite molecular sieve in a mortar according to the weight ratio of 1; taking 0.5g of composite catalyst to perform 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, the reaction temperature is 410 ℃, and H 2 Volume ratio to CO is 2 -1 g -1 . The results of the performance evaluation are shown in Table 1.
Comparative example 2
Adding 50g of tetraethyl orthosilicate, 30g of pure water and 43.75g of tetrapropylammonium hydroxide (40 wt% aqueous solution) into a 200mL beaker, stirring at 35 ℃ for 2h, then heating to 45 ℃ and stirring for 1h to obtain a uniform solution; the solution is put into a polytetrafluoroethylene inner container and is put into a high-pressure stainless steel hydrothermal reaction kettle. Placing the high-pressure reaction kettle in a 70 ℃ oven for constant-temperature crystallization for 60 hours; the suspension obtained after the crystallization is finished is directly collected and used as a Silicalite-1 seed suspension.
0.75g of sodium hydroxide and 0.031g of sodium aluminate are weighed into a 200mL beaker, and then 19.97g of tetrapropylammonium bromide, 20mL of pure water and 3.12g of a Silicalite-1 seed crystal suspension are added and stirred at room temperature for 1 hour to dissolve them sufficiently to obtain a solution I. 15g of silica sol (30 wt%) was dissolved in 30g of deionized water to obtain a solution II, and the solution I was added to the solution II to obtain a precursor solution. And (3) putting the precursor solution into a glass reactor, stirring for 1h at 35 ℃, then heating to 80 ℃, stirring for 1h, and then performing filter pressing for 1 time by a membrane filter press to obtain a xerogel product. The obtained xerogel is placed in a polytetrafluoroethylene beaker and then is placed in a high-pressure stainless steel hydrothermal reaction kettle filled with 50mL of pure water for sealing. And (3) placing the high-pressure reaction kettle in a homogeneous reactor at 180 ℃ for standing and crystallizing for 12 hours. And after crystallization is finished, taking out the precipitate, performing suction filtration to neutrality, and placing the precipitate in a muffle furnace for roasting at the roasting temperature of 600 ℃ for 8 hours. After the calcination is finished, the obtained Na-type ZSM-5 zeolite molecular sieve is placed in 1mol/L ammonium chloride solution, and according to the proportion that 1.0g of ZSM-5 zeolite molecular sieve corresponds to 50mL of ammonium chloride solution, the mixture is stirred in water bath at the temperature of 80 ℃ and ammonium exchange is carried out for 3 hours. After the ammonium exchange is finished, the mixture is filtered, washed and placed 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. Roasting to obtain the lamellar HZSM-5 zeolite molecular sieve.
As shown in figure 1, the prepared product shows XRD diffraction peak (marked as H-ZSM-5-200) of ZSM-5, which indicates that the ZSM-5 zeolite molecular sieve is successfully synthesized. As shown in FIG. 4, in the SEM image of the obtained product, the synthesized H-ZSM-5 molecular sieve material is clearly observed to be in a flake shape.
Putting Zr-Zn metal oxide and the HZSM-5 zeolite molecular sieve into a mortar according to the weight ratio of 1 to 2 for 5min, grinding and mixing, and then sieving with a 40-60-mesh sieve for granulation and molding to obtain a composite catalyst; taking 0.5g of composite catalyst to perform 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, the reaction temperature is 410 ℃, and H 2 Volume ratio to CO 2, reaction gasThe space velocity 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 from Synthesis gas in examples 1 to 8 and comparative examples 1 to 2
In the preparation process, two templates, namely tetrapropyl ammonium bromide and ammonium fluoride, are adopted, so that the molecular sieve can be inhibited from growing along the direction of the b axis, the molecular sieve is induced to generate a lamellar structure, and then a cross pompon shape is formed; in comparative example 2, only one template, tetrapropylammonium bromide, was used, and the resulting structure did not appear to be cross-tapestry; the short b-axis HZSM-5 molecular sieve and the Zr-Zn metal oxide are ground and mixed to be applied to the preparation of aromatic hydrocarbon by synthesis gas, so that the mass transfer of reactants and products is facilitated, the further aromatization of the light aromatic hydrocarbon is inhibited, the catalytic performance is better, the selectivity of the aromatic hydrocarbon is higher than 80%, and the proportion of the light aromatic hydrocarbon is higher than 70%.
Claims (10)
1. A short b-axis HZSM-5 zeolite molecular sieve, characterized in that: the short b-axis HZSM-5 zeolite molecular sieve is in a pompon shape, the thickness of the b-axis is 80-400nm, and the relative thickness ratio of the b-axis to the c-axis is 0.03-0.1.
2. The process of claim 1 for preparing a short b-axis HZSM-5 zeolite molecular sieve, characterized in that it comprises the following steps:
1) Preparation of Silicalite-1 seed suspension: tetraethyl orthosilicate, tetrapropylammonium hydroxide and pure water are mixed and stirred, and then are placed in a high-pressure reaction kettle for constant-temperature aging;
2) Preparing a precursor solution: weighing alkali and aluminum sources in a certain amount in a container, adding a template agent, pure water and a Silicalite-1 seed crystal suspension, finally adding a silicon source aqueous solution, and stirring and mixing to obtain a precursor solution;
3) Preparation of xerogel: heating and stirring the precursor liquid obtained in the step 2), and then performing filter pressing by a membrane filter press to obtain a xerogel product;
4) Hydrothermal crystallization: placing the dried gel obtained in the step 3) into a high-pressure reaction kettle filled with a small amount of pure water for standing and crystallization;
5) Preparation of Na-type ZSM-5: filtering the crystallized product obtained in the step 4) to be neutral, drying and roasting to obtain Na-type ZSM-5;
6) Preparation of H-type ZSM-5: and (3) placing the Na-type ZSM-5 in an ammonium chloride solution, stirring in a water bath to perform ammonium exchange, and then performing suction filtration, washing and roasting to obtain the H-type ZSM-5.
3. The method of claim 2, wherein: in the step 1), the mol ratio of tetraethyl orthosilicate, tetrapropyl ammonium hydroxide and pure water is 1 (0.3-0.5) to 8-50; the constant temperature aging condition is 50-100 ℃ and 6-96 h.
4. The method of claim 2, wherein: in the step 2), the mol ratio of the alkali, the template agent, the aluminum source and the pure water is (0.13-0.65), (0.5-1), (0.0033-0.02) and (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 to 50 percent by weight.
5. The method of claim 2, wherein: 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; the template agent is a double template agent, wherein one of the double template agents is ammonium fluoride, hydrofluoric acid or sodium fluoride, and the other one of the double template agents is tetrapropylammonium bromide, and the ratio of the ammonium fluoride to the tetrapropylammonium bromide is (0.5-1): 1.
6. The method according to claim 2, wherein in step 3), the heating and stirring conditions are as follows: firstly stirring for 1-2 h at 20-45 ℃, then heating to 70-90 ℃ and continuing stirring for 1-2 h; in the step 4), the standing crystallization conditions are as follows: standing and crystallizing for 6-60 h in a homogeneous reactor at 100-180 ℃.
7. The method of claim 2, wherein: in the step 5) and the step 6), the roasting temperature is 400-600 ℃, and the time is 4-8 h; in the step 6), the water bath temperature is 80-90 ℃.
8. The use of a short b-axis HZSM-5 zeolite molecular sieve as claimed in claim 1 and a short b-axis HZSM-5 zeolite molecular sieve prepared by the method of any one of claims 2 to 7, wherein: the method is used for preparing aromatic hydrocarbon by the synthesis gas one-step method.
9. The use of claim 8, wherein: the Zr-Zn metal oxide and the short b-axis HZSM-5 zeolite molecular sieve are ground, mixed, granulated and formed, and then placed in a fixed bed reactor for the reaction of preparing aromatic hydrocarbon from synthesis gas.
10. The use of claim 9, wherein: the weight ratio of the Zr-Zn metal oxide to the short b-axis HZSM-5 zeolite molecular sieve is 1; the reaction conditions for preparing the aromatic hydrocarbon by the synthesis gas are as follows: pressure of 20-60 bar, temperature of 350-450 ℃, 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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