CN112934260A - Supported silicon-based catalyst, preparation method and application - Google Patents
Supported silicon-based catalyst, preparation method and application Download PDFInfo
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- CN112934260A CN112934260A CN202011478669.3A CN202011478669A CN112934260A CN 112934260 A CN112934260 A CN 112934260A CN 202011478669 A CN202011478669 A CN 202011478669A CN 112934260 A CN112934260 A CN 112934260A
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
Abstract
The invention discloses a supported silicon-based catalyst, a preparation method and application thereof. The invention obtains the silicon-based material after calcining the core-shell structure powder with fly ash floating beads, spherical biochar or polyurethane microspheres as cores and silicon dioxide as shells at the temperature of 500 ℃ for 3-6 h. Mixing the silicon-based material with polyvinylidene fluoride or polytetrafluoroethylene, and pyrolyzing at the temperature of 600-850 ℃ to obtain the modified silicon-based material. Adding a silicon-based material into the mixed solution containing neodymium and bismuth, placing the mixed solution in a reaction kettle at the temperature of 100 ℃ and 130 ℃ for reaction for 5-10h, and then centrifugally separating a product to obtain a mixed solution with a surface alkaline constant Kb and an acid constant Ka of which the ratio is 0.6-1.1: 1. a supported silicon-based catalyst with the pore diameter of 8-80 nm. The porous-channel supported catalyst is obtained by taking the core-shell structure silicon-based material as a precursor through hole expansion and load modification, can be used for catalytic cracking of organic solid wastes, and has the advantages of simple preparation process, high catalytic efficiency, easiness in large-scale production and the like.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a supported silicon-based catalyst, and a preparation method and application thereof.
Background
The technology for preparing high-quality pyrolysis oil by fast catalytic pyrolysis of organic solid wastes can realize the preparation of chemicals and liquid fuels, and is considered to be one of effective ways for realizing fossil energy substitution. However, pyrolysis oil has the defects of complex components, high oxygen content, difficulty in separation and the like, and can be used as alternative fuel after catalytic upgrading. In order to improve the yield of pyrolysis oil and the selectivity of target products, hydrogen supply pyrolysis technology is produced. The technology provides enough hydrogen donor for an organic solid waste pyrolysis reaction system by introducing hydrogen or a hydrogen donor, and stabilizes free radical fragments, thereby obtaining a stable pyrolysis product. The hydrogen donor mainly used at present comprises tetrahydronaphthalene, small molecular alcohols, formate and organic high molecular polymers. Hydrogen and alcohol compounds are expensive and provide a source of hydrogen economically. In addition, hydrogen gas is dangerous to operate at high temperature and high pressure, and has high requirements on equipment. In addition to the addition of a high hydrogen feed, the catalyst support is also an important factor. Microporous molecular sieves (such as HZSM-5) are ideal catalysts for preparing aromatic hydrocarbons by catalytic rapid thermal cracking due to the advantages of regular pore structure, good hydrothermal stability, proper acidity, ideal shape-selective catalytic selectivity and the like. But the single micropore structure of the microporous molecular sieve leads to overlarge mass transfer resistance in the reaction process, thereby not only limiting the reaction rate and the effective utilization of active sites, but also increasing carbon deposition in the reaction process. Therefore, how to strengthen the mass transfer in the catalytic thermal cracking reaction process of the organic solid wastes, reduce carbon deposition in the catalytic process and improve the activity of the catalyst becomes the key of the catalytic pyrolysis of the biomass.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a supported silicon-based catalyst.
The method mainly comprises the following steps:
and (1) mixing the gamma-aminopropyl triethoxysilane (KH-550) with deionized water and butanol to obtain a mixed solution of the gamma-aminopropyl triethoxysilane (KH-550). Wherein the volume ratio of KH-550 to butanol to deionized water is 5-10: 40-60: 30-50.
And (2) adding the fly ash floating bead, the spherical biochar or the polyurethane microsphere into the KH-550 mixed solution, dropwise adding ethyl orthosilicate under ultrasonic oscillation, and after the reaction is finished, performing suction filtration, washing and drying to obtain the core-shell structure powder with the fly ash floating bead, the spherical biochar or the polyurethane microsphere as a core and silicon dioxide as a shell.
Preferably, the mass-volume ratio of the KH-550 mixed solution to the fly ash floating beads, the spherical biochar or the polyurethane microspheres is 100 mL: 30-50 g.
Preferably, the volume ratio of the KH-550 mixed solution to the tetraethoxysilane is 100: 5-15.
Preferably, the particle size of the fly ash floating bead, the spherical biochar or the polyurethane microsphere is less than 200-400 meshes.
And (3) calcining the core-shell structure powder at the temperature of 500-700 ℃ for 3-6h to obtain the silicon-based material.
Step (4), mixing the silicon-based material and the fluorine-containing compound, and then putting the mixture at the temperature of 600-850 ℃ for pyrolysis to obtain a modified silicon-based material; wherein the fluorine-containing compound is polyvinylidene fluoride or polytetrafluoroethylene;
preferably, the mass ratio of the silicon-based material to the fluorine-containing compound is 1: 0.1-0.4.
Step (5), uniformly mixing the neodymium-containing compound, the bismuth-containing compound and the modified silicon-based material, then placing the mixture in a reaction kettle at the temperature of 100 ℃ and 130 ℃ for reaction for 5 to 10 hours, and centrifugally separating the product to obtain a mixture with the surface alkaline constant Kb and the acid constant Ka being 0.6 to 1.1: 1. a supported silicon-based catalyst with the pore diameter of 8-80 nm.
Preferably, the neodymium-containing compound is neodymium chloride, and the bismuth-containing compound is bismuth chloride; the molar ratio of neodymium element in the neodymium-containing compound to bismuth element in the bismuth-containing compound is 1: 1.
preferably, the mass volume ratio of the modified silicon-based material to the total of the neodymium-containing compound and the bismuth-containing compound is 10-30 g: 100 mL.
Another object of the invention is to provide a supported silicon-based catalyst prepared by the above method.
It is a further object of the present invention to provide the use of the above-described supported silicon-based catalyst for the catalytic cracking of organic solid wastes.
According to the invention, the silicon-based material with the core-shell structure is taken as a precursor, and the fluorine-containing compound with the etching effect in the heat treatment process is used for carrying out reaming modification on the mesoporous silicon-based material, so that the pore channel structure is improved, the selectivity of a catalytic cracking product is improved, and the carbon deposition of a catalyst is avoided. In addition, the catalyst activity is improved by loading neodymium and bismuth. The prepared catalyst has a porous channel structure with the aperture of 8-80nm, and the ratio of the surface basic constant Kb to the acid constant Ka is 0.6-1.1: 1. the catalyst has the advantages of proper acidity and alkalinity, small mass transfer resistance in the catalytic reaction process, and directional cutting of large molecules of pyrolysis products after entering catalyst pore channels, so that the catalyst has good selectivity on small molecule products, overcomes the defects of complex preparation process, low catalytic performance and the like of the traditional zeolite molecular sieve, and has the advantages of simple preparation process, high catalytic efficiency, easiness in large-scale production and the like.
Detailed Description
The present invention is further illustrated by the following examples, but the content of the present invention is not limited to the contents of the examples.
Example 1:
1) 30mL of deionized water, 60mL of butanol and 10mL of LKH-550 are mixed to obtain 100mL of KH-550 mixed solution.
2) 30g of fly ash floating beads which are sieved by a 200-mesh sieve are added.
3) Under ultrasonic oscillation, 15mL of ethyl orthosilicate is added dropwise, and after the reaction is finished, the core-shell structure powder is obtained through suction filtration, washing and drying.
4) Calcining the core-shell structure powder at 700 ℃ for 3h to obtain the silicon-based material.
5) Mixing a silicon-based material and polyvinylidene fluoride according to a mass ratio of 1: 0.1, and pyrolyzing at 600 ℃ to obtain the modified silicon-based material.
6) Preparing a mixture of neodymium and bismuth with a molar ratio of 1: 1, 100mL of a mixed solution of neodymium chloride and bismuth chloride. The solid-liquid ratio of the raw materials is 10: adding 10g of silicon-based material into 100 g of the mixture, placing the mixture in a reaction kettle at 130 ℃ for reaction for 5h, and then centrifugally separating the product to obtain a mixture with the surface alkaline constant Kb and the acid constant Ka being 1.1: 1. a supported silicon-based catalyst with a pore diameter of 8 nm.
7) 5g of rice straw and 1.5g of the above catalyst were weighed, and then the mixture was pyrolyzed at 450 ℃ under a nitrogen atmosphere. The content of monocyclic aromatic hydrocarbon reaches 68 percent through gas chromatography mass spectrometry.
Example 2:
1) 50mL of deionized water, 40mL of butanol and 10mL of KH-550 are mixed to obtain 100mL of KH-550 mixed solution.
2) 50g of spherical biochar sieved by a 400-mesh sieve is added.
3) Under ultrasonic oscillation, 5mL of ethyl orthosilicate is added dropwise, and after the reaction is finished, the core-shell structure powder is obtained through suction filtration, washing and drying.
4) Calcining the core-shell structure powder at 500 ℃ for 6h to obtain the silicon-based material.
5) Mixing a silicon-based material and polytetrafluoroethylene according to a mass ratio of 1: 0.4, and pyrolyzing at 850 ℃ to obtain the modified silicon-based material.
6) Preparing a mixture of neodymium and bismuth with a molar ratio of 1: 1, 100mL of a mixed solution of neodymium chloride and bismuth chloride. According to the solid-liquid ratio of 30: adding 30g of silicon-based material into 100 g of the mixture, placing the mixture in a reaction kettle for reaction at 100 ℃ for 10 hours, and then centrifugally separating the product to obtain a mixture with the surface alkaline constant Kb and the acid constant Ka being 0.6: 1. a supported silicon-based catalyst with a pore diameter of 80 nm.
7) 5g of distiller's grains and 2g of the above catalyst were weighed, and then the mixed material was pyrolyzed at 550 ℃ under a nitrogen atmosphere. The content of monocyclic aromatic hydrocarbon reaches 71 percent through gas chromatography mass spectrometry.
Example 3:
1) 40mL of deionized water, 55mL of butanol and 5mL of KH-550 are mixed to obtain 100mL of KH-550 mixed solution.
2) 40g of polyurethane microspheres sieved by a 300-mesh sieve are added.
3) Under ultrasonic oscillation, 8mL of ethyl orthosilicate is added dropwise, and after the reaction is finished, the core-shell structure powder is obtained through suction filtration, washing and drying.
4) Calcining the core-shell structure powder at 600 ℃ for 4h to obtain the silicon-based material.
5) Mixing a silicon-based material and polyvinylidene fluoride according to a mass ratio of 1: 0.2, and pyrolyzing at 650 ℃ to obtain the modified silicon-based material.
6) Preparing a mixture of neodymium and bismuth with a molar ratio of 1: 1, 100mL of a mixed solution of neodymium chloride and bismuth chloride. According to the solid-liquid ratio of 15: adding 15g of silicon-based material into 100 g of the mixture, placing the mixture in a reaction kettle at 110 ℃ for reaction for 7h, and then centrifugally separating the product to obtain a mixture with a surface alkaline constant Kb and an acid constant Ka of which the ratio is 0.7: 1. a supported silicon-based catalyst with a pore diameter of 20 nm.
7) 5g of sludge and 2.5g of the above catalyst were weighed, and then the mixed material was pyrolyzed at 550 ℃ under a nitrogen atmosphere. The monocyclic aromatic content was 65% by gas chromatography mass spectrometry.
Example 4:
1) 35mL of deionized water, 55mL of butanol and 10mL of KH-550 were mixed to obtain 100mL of KH-550 mixed solution.
2) 45g of fly ash floating beads sieved by a 350-mesh sieve are added.
3) Under ultrasonic oscillation, 12mL of tetraethoxysilane is added dropwise, and after the reaction is finished, the core-shell structure powder is obtained through suction filtration, washing and drying.
4) Calcining the core-shell structure powder at 550 ℃ for 5.5h to obtain the silicon-based material.
5) Mixing a silicon-based material and polytetrafluoroethylene according to a mass ratio of 1: 0.25, and pyrolyzing at 800 ℃ to obtain the modified silicon-based material.
6) Preparing a mixture of neodymium and bismuth with a molar ratio of 1: 1, 100mL of a mixed solution of neodymium chloride and bismuth chloride. According to the solid-liquid ratio of 25: adding 25g of silicon-based material into 100 g of the mixture, placing the mixture in a reaction kettle at 100 ℃ for reacting for 8 hours, and then centrifugally separating the product to obtain a mixture with the surface alkaline constant Kb and the acid constant Ka being 0.75: 1. a supported silicon-based catalyst with a pore diameter of 60 nm.
7) 6g of the mixed plastic and 3g of the above catalyst were weighed, and then the mixed material was pyrolyzed at 650 ℃ under a nitrogen atmosphere. The monocyclic aromatic content was 67% by gas chromatography mass spectrometry.
Example 5:
1) 50mL of deionized water, 42mL of butanol and 8mL of LKH-550 are mixed to obtain 100mL of KH-550 mixed solution.
2) 47g of spherical biochar sieved by a 350-mesh sieve is added.
3) Under ultrasonic oscillation, 12mL of tetraethoxysilane is added dropwise, and after the reaction is finished, the core-shell structure powder is obtained through suction filtration, washing and drying.
4) Calcining the core-shell structure powder for 4 hours at 630 ℃ to obtain the silicon-based material.
5) Mixing a silicon-based material and polyvinylidene fluoride according to a mass ratio of 1: 0.35 is mixed and then pyrolyzed at the temperature of 600-850 ℃ to obtain the modified silicon-based material.
6) Preparing a mixture of neodymium and bismuth with a molar ratio of 1: 1, 100mL of a mixed solution of neodymium chloride and bismuth chloride. According to the solid-liquid ratio of 18: adding 18g of silicon-based material into 100 g of the mixture, placing the mixture in a reaction kettle at 115 ℃ for reaction for 7h, and then centrifugally separating the product to obtain a mixture with a surface alkaline constant Kb and an acid constant Ka of which the ratio is 0.75: 1. a supported silicon-based catalyst with a pore diameter of 62 nm.
7) 8g of wheat straw and agricultural mulching film were weighed and 4g of the above catalyst, and then the mixture was pyrolyzed at 500 ℃ under a nitrogen atmosphere. The monocyclic aromatic content was 64% by gas chromatography mass spectrometry.
The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above embodiments, and all embodiments are within the scope of the present invention as long as the requirements of the present invention are met.
Claims (10)
1. A preparation method of a supported silicon-based catalyst is characterized by comprising the following steps:
mixing gamma-aminopropyl triethoxysilane (KH-550) with deionized water and butanol to obtain a mixed solution of the gamma-aminopropyl triethoxysilane (KH-550);
adding fly ash floating beads, spherical biochar or polyurethane microspheres into the KH-550 mixed solution, dropwise adding ethyl orthosilicate under ultrasonic oscillation, and performing suction filtration, washing and drying after the reaction is finished to obtain core-shell structure powder with the fly ash floating beads, the spherical biochar or the polyurethane microspheres as cores and silicon dioxide as shells;
step (3), calcining the core-shell structure powder at the temperature of 500-700 ℃ for 3-6h to obtain a silicon-based material;
step (4), mixing the silicon-based material and the fluorine-containing compound, and then putting the mixture at the temperature of 600-850 ℃ for pyrolysis to obtain a modified silicon-based material; wherein the fluorine-containing compound is polyvinylidene fluoride or polytetrafluoroethylene;
step (5), uniformly mixing the neodymium-containing compound, the bismuth-containing compound and the modified silicon-based material, then placing the mixture in a reaction kettle at the temperature of 100 ℃ and 130 ℃ for reaction for 5 to 10 hours, and centrifugally separating the product to obtain a mixture with the surface alkaline constant Kb and the acid constant Ka being 0.6 to 1.1: 1. a supported silicon-based catalyst with the pore diameter of 8-80 nm.
2. The method for preparing a supported silicon-based catalyst according to claim 1, wherein the volume ratio of the KH-550, butanol and deionized water in the step (1) is 5-10: 40-60: 30-50.
3. The method for preparing the supported silicon-based catalyst according to claim 2, wherein the mass-to-volume ratio of the mixed solution of the KH-550 and the fly ash floating beads, the spherical biochar or the polyurethane microspheres in the step (2) is 100 mL: 30-50 g; the volume ratio of the KH-550 mixed solution to the tetraethoxysilane is 100: 5-15.
4. The method for preparing a supported silicon-based catalyst as claimed in claim 1, wherein the particle size of the fly ash floating bead, the spherical biochar or the polyurethane microsphere in the step (2) is less than 200-400 mesh.
5. The method for preparing a supported silicon-based catalyst according to claim 1, wherein the mass ratio of the silicon-based material to the fluorine-containing compound in the step (4) is 1: 0.1-0.4.
6. The method according to claim 1, wherein the neodymium-containing compound in the step (5) is neodymium chloride, and the bismuth-containing compound is bismuth chloride.
7. The method according to claim 1, wherein the molar ratio of the neodymium element in the neodymium-containing compound to the bismuth element in the bismuth-containing compound in the step (5) is 1: 1.
8. the method for preparing a supported silicon-based catalyst according to claim 1, wherein the mass-to-volume ratio of the modified silicon-based material of the step (5) to the total amount of the neodymium-containing compound and the bismuth-containing compound is 10 to 30 g: 100 mL.
9. A supported silicon-based catalyst prepared by the method of any one of claims 1 to 8.
10. Use of a supported silicon based catalyst for the catalytic cracking of organic solid waste, characterized in that the supported silicon based catalyst is prepared by the method according to any of claims 1-8.
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| CN113926482A (en) * | 2021-10-26 | 2022-01-14 | 宜宾学院 | Preparation method and application of biochar composite photocatalytic material |
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| US20120203042A1 (en) * | 2009-09-09 | 2012-08-09 | Anellotech, Inc. | Systems and processes for catalytic pyrolysis of biomass and hydrocarbonaceous materials for production of aromatics with optional olefin recycle, and catalysts having selected particle size for catalytic pyrolysis |
| CN111974450A (en) * | 2020-08-17 | 2020-11-24 | 杭州电子科技大学 | Fly ash-based catalytic cracking catalyst and preparation method thereof |
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| US20120203042A1 (en) * | 2009-09-09 | 2012-08-09 | Anellotech, Inc. | Systems and processes for catalytic pyrolysis of biomass and hydrocarbonaceous materials for production of aromatics with optional olefin recycle, and catalysts having selected particle size for catalytic pyrolysis |
| CN111974450A (en) * | 2020-08-17 | 2020-11-24 | 杭州电子科技大学 | Fly ash-based catalytic cracking catalyst and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113926482A (en) * | 2021-10-26 | 2022-01-14 | 宜宾学院 | Preparation method and application of biochar composite photocatalytic material |
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