CN111484034A - Preparation method of hierarchical pore ZSM-5 molecular sieve - Google Patents
Preparation method of hierarchical pore ZSM-5 molecular sieve Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 65
- 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 64
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims description 33
- 230000008025 crystallization Effects 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000010902 straw Substances 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000003292 glue Substances 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 235000019353 potassium silicate Nutrition 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-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
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 239000012808 vapor phase Substances 0.000 claims description 2
- 239000011363 dried mixture Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 9
- 241000196324 Embryophyta Species 0.000 description 7
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 240000008042 Zea mays Species 0.000 description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 4
- 235000005822 corn Nutrition 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 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
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- 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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/12—Surface area
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Abstract
The invention belongs to the technical field of preparation of inorganic nonmetallic materials and catalysts, and provides a preparation method of a hierarchical pore ZSM-5 molecular sieve for solving the problem that the diffusion of the ZSM-5 molecular sieve is limited in the using process. The prepared hierarchical pore ZSM-5 molecular sieve has relatively high crystallinity, increases intercrystalline mesopores compared with the conventional micron-sized molecular sieve, improves the problem of molecular diffusion in reactions of hydrocarbons and the like, and prolongs the service life of the catalyst.
Description
Technical Field
The invention belongs to the technical field of preparation of inorganic nonmetallic materials and catalysts, and particularly relates to a hierarchical pore ZSM-5 molecular sieve and a preparation method thereof.
Background
In recent years, researches show that the multi-stage pore ZSM-5 molecular sieve can obviously improve the catalytic performance, improve the diffusion resistance and is more beneficial to prolonging the service life, and the prepared multi-stage pore ZSM-5 molecular sieve has the advantages of good catalytic activity, high target product yield and long catalyst service life, and the like, and Teng Xue and the like (Micropor. Mesopor. Mat.2012,156, 97-105) adopt TPAOH as a single template agent and add a certain amount of seed crystals for induction to prepare the mesoporous ZSM-5 microspheres with the particle size of 3 micrometers, L i Chen and the like (physical chemistry report, 2015,31, 181-188) report that a linear polyamine template agent is used as a single template agent to synthesize the multi-stage pore ZSM-5 molecular sieve with the uniform particle size of 5-15 micrometers in a hydrothermal system.
The hard template agent mainly refers to materials with relatively rigid structures, such as porous silicon, porous carbon, carbon nanotubes, molecular sieves and the like, and the synthesis of the hierarchical pore molecular sieve by the hard template agent is often reported (nanmu, petrochemical, 2005,34 (4), 405-. Schmidt et al (Inorg. chem,2000,39, 2279-.
The freeze drying method is a new method for directly removing water from gel and preparing ultrafine powder with small particle size and less agglomeration (shinr. mukai. chem. mater.,2004,16(24), 4987-. The freeze-dried material has the characteristics of porosity, instant solubility, rehydration property and the like due to the existence of space after water sublimation, and has large specific surface area and high pore volume (V.K.Ivanov. Inorg.Mater.2010,46(1), 43-46). Therefore, the molecular sieve crystal particles prepared by the dry glue obtained by the freeze drying method through a steam transmission method have the characteristics of uniform crystal granularity, large specific surface area and the like (patent CN 102530986B).
According to the invention, ground plant straws and a large amount of conventional micron-sized ZSM-5 molecular sieves are added into a synthesis system, the ground mixture is used as a hard template agent, and a vapor phase transmission method is adopted in combination with a freeze drying technology to synthesize the hierarchical pore ZSM-5 molecular sieve with the particle size of 0.2-1.0 micron.
Disclosure of Invention
(1) Problems to be solved
The invention aims to provide a preparation method of a hierarchical pore ZSM-5 molecular sieve, which solves the problem that the diffusion of hydrocarbon reaction molecules in a conventional micron-sized ZSM-5 molecular sieve is limited, and the method adopts ground plant straws and the conventional micron-sized ZSM-5 molecular sieve to prepare the hierarchical pore ZSM-5 molecular sieve under the synergistic action of a freeze drying technology, so that abundant intercrystalline mesopores are formed. Due to the existence of intercrystalline mesopores, the problem of limited diffusion of low-chain hydrocarbon in the conventional micron-sized ZSM-5 molecular sieve is effectively solved, and the service life of the ZSM-5 molecular sieve is remarkably prolonged.
(2) Technical scheme
A hierarchical pore ZSM-5 molecular sieve is prepared from the following raw materials: silicon source, aluminum source, template agent, plant straw and conventional micron-sized ZSM-5 molecular sieve. Furthermore, the molar ratio of the silicon source, the alkali source, the aluminum source and the template agent is 1:0.05-0.2:0.0001-0.04:0.1-2.0, and the silicon source and the aluminum source in the molar ratio are respectively calculated by silicon oxide and aluminum oxide. The weight ratio of the conventional micron-sized ZSM-5 molecular sieve to the plant straws is 10:0.5-1, and the particle size of the mixed and ball-milled particles is not more than 0.2 micron. The plant straw needs to be dried and pulverized
Further, the silicon source is one or more of silica sol, water glass and white carbon black;
further, the alkali source is sodium hydroxide and water glass, and excessive alkali in the water glass is neutralized by sulfuric acid;
further, the aluminum source is one of aluminum sulfate, sodium aluminate and pseudo-boehmite;
further, the template agent is one or more of n-butylamine, triethylamine, ethylenediamine, ethylamine and ammonia water;
further, the freeze drying refers to that the mixed silicon source, aluminum source and alkali source are dried by freezing, and the drying temperature is 200 ℃ below zero to 60 ℃ below zero.
The invention relates to a hierarchical pore ZSM-5 molecular sieve, which comprises the following specific operation preparation methods:
adding an aluminum source into 5-20 times of water for dissolving, adding the dissolved solution into a silicon source, and fully stirring to obtain a component A; premixing plant straws with a conventional micron-sized ZSM-5 molecular sieve, grinding for 5-10 hours to ensure that the particles of the mixture are not more than 0.2 micron, and calling the ground mixture as a component B; adding the component B into the component A to obtain a mixture C, ultrasonically mixing the mixture C uniformly for 1-5 hours, then carrying out ultralow temperature freeze drying at the temperature of-200 ℃ to-60 ℃ for 5-30 hours, transferring the components to the upper layer of a crystallization kettle after drying, adding a template agent and water into the lower layer, putting the crystallization kettle into an oven, and crystallizing at the temperature of 120-180 ℃ for 10-48 hours; after crystallization is finished, cooling the crystallization kettle, and drying the upper layer product in an oven at the temperature of 100-; and roasting the dried product at the temperature of 450-550 ℃ for 3-6 hours to obtain the hierarchical pore ZSM-5 molecular sieve.
(3) Has the beneficial effects of
The invention provides a preparation method of a hierarchical pore ZSM-5 molecular sieve, and the hierarchical pore ZSM-5 molecular sieve prepared by the method has the advantages of more pore distribution, stable structure at high temperature, adjustable crystal morphology and adjustable silica-alumina ratio.
(4) Description of the drawings
FIG. 1 XRD spectrum of hierarchical pore ZSM-5 molecular sieve 1 prepared in example 1;
FIG. 2 SEM picture of multi-stage pore ZSM-5 molecular sieve 1 prepared in example 1;
figure 3 adsorption desorption isotherms for multi-stage pore ZSM-5 molecular sieve 1 prepared in example 1.
(5) The specific implementation mode is as follows:
the present invention will be described in further detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
Dissolving 0.8g of aluminum sulfate octadecahydrate and 1.2g of sodium hydroxide in 50.0g of deionized water, adding a dissolved solution into white carbon black, fully stirring to obtain a sol A, mixing 40g of a conventional micron-sized ZSM-5 molecular sieve with a silica-alumina ratio of 1000 with corn straws, grinding in a ball mill, adding a proper amount of water during grinding, ball milling for 8 hours to obtain ball-milled slurry B, adding the slurry B into the sol A, uniformly stirring to obtain a mixture C, ultrasonically mixing the mixture C for 3 hours, placing the mixture C into a freeze dryer at 120 ℃ below zero, drying for 24 hours to obtain dry glue, transferring the dry glue into an upper layer screen of a crystallization reaction kettle, adding 5g of n-butylamine and 5g of deionized water into a lower layer, sealing the crystallization reaction kettle, reacting in an oven at 170 ℃ for 20 hours, taking out the crystallization kettle, drying the obtained product at 120 ℃ for 12 hours, roasting at 550 ℃ for 5 hours, exchanging the product once with 0.3 mol/L hydrochloric acid solution at 40 ℃, washing to be close to neutral pH, drying, roasting at a multi-stage molecular sieve ZSM at 1-5, and roasting at 1-stage molecular sieveThe figure is shown in figure 2, the adsorption and desorption isotherms are shown in figure 3, and the related characterization data are shown in table 1
| Characterizing items | Characterization data |
| Silicon to aluminum ratio | 392 |
| Specific surface area | 417cm3/g |
| Degree of crystallinity | 94% |
| Particle size analysis after ball milling D50 | 80-150nm |
Table 1 characterization data for the multi-stage pore ZSM-5 molecular sieve 1 prepared in example 1.
Example 2
Dissolving 0.8g of aluminum sulfate octadecahydrate and 1.2g of sodium hydroxide in 50.0g of deionized water, adding a dissolved solution into silica gel white carbon black, fully stirring to obtain sol A, mixing 40.0g of a conventional micron-sized ZSM-5 molecular sieve with a silica-alumina ratio of 1000 with wheat straws, grinding in a ball mill, ball milling for 8 hours to obtain a ball grinding material B, adding the material B into the sol A, uniformly stirring to obtain a mixture C, ultrasonically mixing the mixture C uniformly for 3 hours, putting the mixture C into a freeze dryer at minus 100 ℃, drying for 24 hours to obtain dry glue, transferring the dry glue into an upper layer screen of a crystallization reaction kettle, adding 5g of 70% ethylamine and 5g of deionized water into a lower layer, sealing the crystallization reaction kettle, carrying out crystallization reaction in an oven at 160 ℃ for 20 hours, taking out the reaction kettle, drying the obtained product at 120 ℃ for 12 hours, roasting at 550 ℃ for 5 hours, exchanging the product once with L hydrochloric acid aqueous solution at 40 ℃, washing until the pH is nearly neutral, drying and roasting again to obtain a multi-stage molecular sieve ZSM-5 molecular sieve with 892 pores.
Example 3
Dissolving 1.8g of aluminum sulfate octadecahydrate and 3.0g of sodium hydroxide in 38.0g of deionized water, adding a dissolved solution into 95.0g of silica sol with the silica content of 29.6%, fully stirring to obtain sol A, mixing 30g of a conventional micron-sized ZSM-5 molecular sieve with the silica-alumina ratio of 200 with soybean straws, grinding in a ball mill, adding a proper amount of water during grinding, carrying out ball milling for 8 hours to obtain ball-milled slurry B, adding the slurry B into the sol A, ultrasonically mixing for 5 hours, putting into a freeze dryer at minus 80 ℃, drying for 24 hours to obtain freeze-dried glue, transferring the dried glue into an upper screen of a crystallization reaction kettle, adding 5g of n-butylamine and 5g of deionized water into a lower layer, sealing the crystallization reaction kettle, carrying out crystallization reaction for 25 hours in an oven at 180 ℃, taking out the crystallization reaction kettle, drying the obtained product at 120 ℃ for 12 hours, roasting at 550 ℃ for 5 hours by using 0.5 mol/L of hydrochloric acid solution at 40 ℃, washing twice to obtain a product, drying the product, and roasting the ZSM-molecular sieve at a pH close to 3-neutral pH value, and roasting at 3-5 to obtain a multi-stage molecular sieve.
Example 4
Dissolving 2.2g of aluminum sulfate octadecahydrate and 2.8g of sodium hydroxide in 38.0g of deionized water, adding a dissolved solution into 95g of silica sol with the silica content of 29.6%, fully stirring to obtain sol A, mixing a conventional micron-sized ZSM-5 molecular sieve with the silica-alumina ratio of 100g with corn straws, grinding in a ball mill, adding a proper amount of water during grinding, carrying out ball milling for 12 hours to obtain ground slurry B, adding the slurry B into the sol A, ultrasonically mixing for 2 hours, putting into a freeze dryer at minus 60 ℃, drying for 24 hours to obtain freeze-dried glue, transferring the dried glue into an upper layer screen of a crystallization reaction kettle, adding 5g of ammonia water and 5g of deionized water into a lower layer, sealing the crystallization reaction kettle, reacting in an oven at 120 ℃ for 48 hours, taking out the crystallization reaction kettle, drying the obtained product at 120 ℃ for 12 hours, roasting at 550 ℃ for 5 hours, exchanging the obtained product with 0.5 mol/L of hydrochloric acid water at 40 ℃ twice, washing until the pH approaches neutral, drying again, and roasting at a multi-stage molecular sieve of ZSM-4 to obtain a product.
Example 5
Diluting 3.5g of concentrated sulfuric acid into 32.0g of deionized water, adding 3.4g of aluminum sulfate octadecahydrate into the diluted sulfuric acid solution, adding the mixed solution into 50.0g of water glass (the content of silicon oxide is 28.9 percent and the content of sodium oxide is 8.7 percent), fully stirring to obtain sol A, mixing 70g of a conventional micron-sized ZSM-5 molecular sieve with the ratio of silicon to aluminum being 100 with corn straws, grinding in a ball mill, adding a proper amount of water during grinding, ball-milling for 6 hours to obtain ball-milled slurry B, adding the slurry B into the sol A, ultrasonically mixing for 5 hours, placing into a freeze dryer at minus 80 ℃, drying for 24 hours to obtain freeze-dried gel, transferring the dried gel into an upper-layer screen of a crystallization reaction kettle, adding 5g of ethylamine and 5g of deionized water into a lower layer, sealing the crystallization reaction kettle, performing crystallization reaction in a drying oven at 150 ℃, taking out the crystallization reaction kettle, drying the obtained product at 120 ℃ for 12 hours, roasting at 550 ℃ for 5 hours, exchanging the product with 0.5 mol/L of hydrochloric acid at a temperature close to 40 ℃, performing crystallization reaction for 10 hours, washing twice, and roasting to obtain a neutral molecular sieve, and drying the product again to obtain a multi-stage molecular sieve.
Comparative example 1
Dissolving 0.8g of aluminum sulfate octadecahydrate and 1.2g of sodium hydroxide in 50.0g of deionized water, adding a dissolved solution into white carbon black, fully stirring to obtain a sol A, adding a proper amount of water into 40g of a conventional micron-sized ZSM-5 molecular sieve with the silica-alumina ratio of 1000, carrying out ball milling to obtain a slurry B, adding the slurry B into the sol A, ultrasonically mixing for 3 hours, putting the sol A into a freeze dryer at minus 120 ℃, drying for 24 hours to obtain dry glue, transferring the dry glue into an upper layer screen of a crystallization reaction kettle, adding 5g of 70% ethylamine and 5g of deionized water into a lower layer, sealing the crystallization reaction kettle, carrying out crystallization reaction for 20 hours in an oven at 140 ℃, taking out the crystallization reaction kettle, drying the product at 120 ℃ for 12 hours, roasting at 550 ℃ for 5 hours, exchanging the product once at 40 ℃ with 0.3 mol/L hydrochloric acid aqueous solution, washing until the pH is nearly neutral, drying and roasting again to obtain the multistage-pore ZSM-5 molecular sieve 6.
Comparative example 2:
dissolving 0.8g of aluminum sulfate octadecahydrate and 1.2g of sodium hydroxide in 50.0g of deionized water, adding a dissolved solution into white carbon black, fully stirring to obtain a sol A, mixing 40g of a conventional micron-sized ZSM-5 molecular sieve with a silica-alumina ratio of 1000 with corn straws, grinding in a ball mill, adding a proper amount of water during grinding, ball milling for 8 hours to obtain ball-milled slurry B, adding the slurry B into the sol A, ultrasonically mixing for 3 hours, placing in a 110 ℃ oven, drying for 24 hours to obtain dry glue, transferring the dry glue into an upper layer screen of a crystallization reaction kettle, adding 5g of 70% ethylamine and 5g of deionized water into a lower layer, sealing the crystallization reaction kettle, performing crystallization reaction in a 140 ℃ oven for 20 hours, taking out the crystallization reaction kettle, drying the product at 120 ℃ for 12 hours, roasting the product at 550 ℃ for 5 hours, exchanging the product once at 40 ℃ with 0.3 mol/L hydrochloric acid aqueous solution, washing until the pH is close to neutral, drying and roasting again to obtain the ZSM-5 molecular sieve with 7 pores.
Comparative analysis of comparative example and example
By operating the conditions in example 1 and comparative example 1, we found that the conventional micron-sized ZSM-5 molecular sieve can also obtain the multi-level pore ZSM-5 molecular sieve with less distribution of mesopores by low-temperature freeze drying in a system without ball milling and plant straw addition. By comparing example 1 with comparative example 2, we have found that the mixed gel is not freeze-dried and gives a lower distribution of mesopores, which plays a very important role in the synthesis of hierarchical pores.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (7)
1. A preparation method of a multi-stage pore ZSM-5 molecular sieve is characterized by comprising the following steps of preparing the following raw materials of a conventional micron-sized ZSM-5 molecular sieve, plant straws, a silicon source, an alkali source, an aluminum source, a template agent and water, wherein the preparation technology of the molecular sieve is combined by a dry glue freezing method and a vapor phase transmission method; the preparation steps are as follows:
step 1, mixing a silicon source, an aluminum source and water to obtain a mixed sol which is marked as a component A;
step 2: mixing and grinding a conventional micron-sized ZSM-5 molecular sieve, plant straws and water, and marking the ground material as a component B;
and step 3: adding the component B into the component A, and uniformly stirring to obtain a mixture C;
and 4, step 4: ultrasonically mixing the mixture C for 1-5 hours, and then freeze-drying for 5-30 hours at the ultralow temperature of 200-60 ℃;
and 5: and (3) placing the dried mixture C in the upper layer of a crystallization reaction kettle, adding a template agent and water into the lower part of the crystallization reaction kettle, crystallizing for 10-48 hours at the temperature of 120-180 ℃, and drying and roasting the obtained product after the crystallization reaction is finished to obtain the hierarchical pore ZSM-5 molecular sieve.
2. The hierarchical pore ZSM-5 molecular sieve according to claim 1, comprising component A having a molar ratio of silicon source, alkali source, aluminum source, templating agent in the range of 1:0.05 to 0.2:0.0001 to 0.04:0.1 to 2.0, the molar ratio of silicon source and aluminum source being calculated as silica and alumina, respectively; mixing the conventional micron-sized ZSM-5 molecular sieve with plant straws according to the weight ratio of 10:0.5-1, grinding, wherein the solid content after grinding is marked as a component B, and the weight ratio of the component B added into the component A is not less than 40%.
3. The hierarchical pore ZSM-5 molecular sieve of claim 1, wherein the silicon source is one or more of silica sol, water glass, silica white and silica gel.
4. The multi-stage pore ZSM-5 molecular sieve of claim 1, wherein the alkali source is sodium hydroxide and water glass, and excess alkali in the water glass is neutralized with sulfuric acid.
5. The multistage pore ZSM-5 molecular sieve of claim 1, wherein the aluminum source is one of aluminum sulfate, sodium aluminate and pseudoboehmite.
6. The hierarchical pore ZSM-5 molecular sieve of claim 1, wherein the template agent is one or more of n-butylamine, triethylamine, ethylenediamine, ethylamine, or ammonia water.
7. The hierarchical pore ZSM-5 molecular sieve of claim 1, wherein the plant straw is dried and pulverized, mixed and ground with a conventional micron ZSM-5 molecular sieve, and the particle size of the ground particles is not greater than 0.2 micron.
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