CN113332973A - Preparation method of hydrogenation catalyst - Google Patents
Preparation method of hydrogenation catalyst Download PDFInfo
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- CN113332973A CN113332973A CN202110550332.7A CN202110550332A CN113332973A CN 113332973 A CN113332973 A CN 113332973A CN 202110550332 A CN202110550332 A CN 202110550332A CN 113332973 A CN113332973 A CN 113332973A
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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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
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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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
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
Abstract
The invention provides a preparation method of a hydrogenation catalyst. The catalyst is prepared by using biochar obtained by cracking pig manure as a raw material, carrying out acid washing and metal cation impregnation, providing an acid site by utilizing niobic acid and molybdate and then roasting. The prepared catalyst can be used for the reaction of preparing ethyl levulinate by acid catalytic conversion with fructose as a raw material due to the existence of an acid site, the ethyl levulinate with extremely high yield is generated by the reaction, and the service life of the catalyst is stable.
Description
Technical Field
The invention relates to a preparation method of a hydrogenation catalyst. In order to solve the problems in the prior art, the invention aims to prepare a hydrogenation catalyst of biochar cracked by pig manure, and apply the hydrogenation catalyst to the preparation of levulinic acid by fructose conversion and the production of ester.
In order to achieve the purpose, the invention adopts the following technical scheme: the biochar obtained by cracking solid waste pig manure is used as a raw material, nitric acid and nickel nitrate are used as impregnation liquid, the biochar is synthesized by an impregnation method, acid sites are provided by niobic acid and molybdate, and the biochar is obtained in subsequent treatment.
Background
Levulinic acid is a bio-based platform compound, has a wide application range, and can be upgraded into various high-value organic chemicals. Levulinic acid esters, as important derivatives thereof, have extremely wide applications in medicine and other fields as well.
Current levulinic acid and esters can be prepared from biomass-derived carbon-retaining sugars. Meanwhile, the five-carbon sugar can also be converted to prepare levulinic acid and ester. However, this route is complicated and the polymerization is severe. Processes such as fructose conversion require the co-action of a hydrogenation catalyst and an acid catalyst. If a bifunctional catalyst can be designed and prepared, and the catalyst can be used for hydrogenation and has a hydrogen transfer function, the fructose can be converted into the levulinic acid and the ester in one pot, so that the yield of the biomass to the levulinic acid and the ester is improved.
Disclosure of Invention
Stirring the nickel salt solution with the same concentration for 12 to 36 hours under certain conditions.
The preparation method of the catalyst comprises the following steps:
(1) 6.0 g of dried pig manure raw material is taken and pyrolyzed for 30 minutes at 500 ℃ and the nitrogen flow rate is 100 mL/min, so as to obtain a biochar product.
(2) And (2) completely dissolving the biochar obtained in the step (1) by using a nitric acid solution, then impregnating, and then drying.
(3) Adding nickel salt solutions (1%, 2.5%, 5%, 10%, 20% and 30%) with different concentrations into the sample obtained in the step (2) according to a solid-to-liquid ratio of 1:2-5, completely dissolving the sample by using a nitric acid solution, soaking the sample for 12-36h at room temperature, providing an acidic site by using niobic acid and molybdate, and then drying the sample for 24h at 50-150 ℃.
(4) And (4) roasting the sample obtained in the step (3) for 1-4h at the temperature of 500-.
Preferably, the raw material for cracking in the step (1) is pig manure powder which is dried and uniformly ground.
Preferably, the niobic acid and molybdate in step (3) can provide an acidic site.
Preferably, the nickel salt solution used for impregnation in the step (3) is a nickel nitrate solution.
Preferably, the roasting parameter in the step (4) is 500-700 ℃ roasting for 1-4 h.
A preparation method of a hydrogenation catalyst and an application of the hydrogenation catalyst in fructose conversion are used in a reaction of preparing ethyl levulinate by taking fructose and furfuryl alcohol in a mass ratio of 10-50:1 as raw materials.
Preferably, the reaction temperature is 120-220 ℃, and the reaction pressure is 1-5 MPa.
The invention has the beneficial effects that: the catalyst developed by the invention can realize the direct conversion of fructose into levulinic acid and ester, has remarkable catalytic performance, can greatly slow down the polymerization reaction in the reaction process, and can obtain the levulinic acid and the ester with extremely high yield.
Drawings
FIG. 1 is a flow chart used in example 1;
FIG. 2 is a graph of the yield profile of levulinic acid and ester.
Detailed Description
The embodiments of the present invention will be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) 6.0 g of dried pig manure raw material is taken and pyrolyzed for 30 minutes at 500 ℃ and the nitrogen flow rate is 100 mL/min, so as to obtain a biochar product.
(2) And (2) completely dissolving the biochar obtained in the step (1) by using a nitric acid solution, then impregnating, and then drying.
(3) Adding a nickel salt solution with the concentration of 10% into the sample obtained in the step (2) according to the solid-to-liquid ratio of 1:2-5, completely dissolving the sample by using a nitric acid solution, soaking the sample at room temperature for 12-36h, adding niobic acid and molybdate to provide an acid site, and drying the sample at 50-150 ℃ for 24 h.
(4) And (4) roasting the sample obtained in the step (3) for 4 hours at the temperature of 600 ℃.
Example 2
(1) 6.0 g of dried pig manure raw material is taken and pyrolyzed for 30 minutes at 500 ℃ and the nitrogen flow rate is 100 mL/min, so as to obtain a biochar product.
(2) And (2) completely dissolving the biochar obtained in the step (1) by using a nitric acid solution, then impregnating, and then drying.
(3) Adding a nickel salt solution with the concentration of 5% into the sample obtained in the step (2) according to the solid-to-liquid ratio of 1:2-5, completely dissolving the sample by using a nitric acid solution, soaking the sample at room temperature for 12-36h, adding niobic acid and molybdate to provide an acid site, and drying the sample at 50-150 ℃ for 24 h.
(4) And (4) roasting the sample obtained in the step (3) for 4 hours at the temperature of 600 ℃.
Example 3
(1) 6.0 g of dried pig manure raw material is taken and pyrolyzed for 30 minutes at 500 ℃ and the nitrogen flow rate is 100 mL/min, so as to obtain a biochar product.
(2) And (2) completely dissolving the biochar obtained in the step (1) by using a nitric acid solution, then impregnating, and then drying.
(3) Adding a nickel salt solution with the concentration of 20% into the sample obtained in the step (2) according to the solid-to-liquid ratio of 1:2-5, completely dissolving the sample by using a nitric acid solution, soaking the sample at room temperature for 12-36h, adding niobic acid and molybdate to provide an acid site, and drying the sample at 50-150 ℃ for 24 h.
(4) And (4) roasting the sample obtained in the step (3) for 4 hours at the temperature of 600 ℃.
Example 4
(1) 6.0 g of dried pig manure raw material is taken and pyrolyzed for 30 minutes at 500 ℃ and the nitrogen flow rate is 100 mL/min, so as to obtain a biochar product.
(2) And (2) completely dissolving the biochar obtained in the step (1) by using a nitric acid solution, then impregnating, and then drying.
(3) Adding a nickel salt solution with the concentration of 10% into the sample obtained in the step (2) according to the solid-to-liquid ratio of 1:2-5, completely dissolving the sample by using a nitric acid solution, soaking the sample at room temperature for 12-36h, adding niobic acid and molybdate to provide an acid site, and drying the sample at 50-150 ℃ for 24 h.
(4) And (4) roasting the sample obtained in the step (3) for 4 hours at 500 ℃.
Example 5
(1) 6.0 g of dried pig manure raw material is taken and pyrolyzed for 30 minutes at 500 ℃ and the nitrogen flow rate is 100 mL/min, so as to obtain a biochar product.
(2) And (2) completely dissolving the biochar obtained in the step (1) by using a nitric acid solution, then impregnating, and then drying.
(3) Adding a nickel salt solution with the concentration of 10% into the sample obtained in the step (2) according to the solid-to-liquid ratio of 1:2-5, completely dissolving the sample by using a nitric acid solution, soaking the sample for 12-36h at room temperature, and then drying the sample for 24h at the temperature of 50-150 ℃.
(4) And (4) roasting the sample obtained in the step (3) for 4 hours at 700 ℃.
Example 6
(1) 6.0 g of dried pig manure raw material is taken and pyrolyzed for 30 minutes at 500 ℃ and the nitrogen flow rate is 100 mL/min, so as to obtain a biochar product.
(2) And (2) completely dissolving the biochar obtained in the step (1) by using a nitric acid solution, then impregnating, and then drying.
(3) Adding a nickel salt solution with the concentration of 10% into the sample obtained in the step (2) according to the solid-to-liquid ratio of 1:2-5, completely dissolving the sample by using a nitric acid solution, soaking the sample at room temperature for 12-36h, adding molybdate to provide an acid site, and drying the sample at 50-150 ℃ for 24 h.
(4) And (4) roasting the sample obtained in the step (3) for 1-4h at the temperature of 500-.
Example 7
(1) 6.0 g of dried pig manure raw material is taken and pyrolyzed for 30 minutes at 500 ℃ and the nitrogen flow rate is 100 mL/min, so as to obtain a biochar product.
(2) And (2) completely dissolving the biochar obtained in the step (1) by using a nitric acid solution, then impregnating, and then drying.
(3) Adding a nickel salt solution with the concentration of 10% into the sample obtained in the step (2) according to the solid-to-liquid ratio of 1:2-5, completely dissolving the sample by using a nitric acid solution, soaking the sample at room temperature for 12-36h, adding niobic acid to provide an acid site, and drying the sample at 50-150 ℃ for 24 h.
(4) And (4) roasting the sample obtained in the step (3) for 2 hours at the temperature of 600 ℃.
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, but rather as the subject of any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention.
Claims (11)
1. A preparation method of a hydrogenation catalyst is characterized in that biochar obtained by cracking solid waste pig manure is used as a raw material, nitric acid and nickel nitrate are used as impregnation liquid, the biochar is synthesized by an impregnation method, and niobate and molybdate are used for providing an acid site, and the biochar is obtained in subsequent treatment.
2. The catalyst according to claim 1, wherein the impregnation method is carried out by mixing the catalyst in a solid-to-liquid ratio of 1:2-5, loading the nickel salt solution with different concentrations, and stirring for 12-36h under certain conditions.
3. A method for preparing a catalyst according to any one of claims 1-2, comprising the steps of:
(1) 6.0 g of dried pig manure raw material is taken and pyrolyzed for 30 minutes at 500 ℃ and the nitrogen flow rate is 100 mL/min, so as to obtain a biochar product.
And 4, (2) completely dissolving the biochar obtained in the step (1) by using a nitric acid solution, then impregnating, and then drying.
5, (3) adding nickel salt solutions (1%, 2.5%, 5%, 10%, 20%, 30%) with different concentrations into the sample obtained in the step (2) according to a solid-to-liquid ratio of 1:2-5, completely dissolving the sample with a nitric acid solution, immersing the sample at room temperature for 12-36h, providing an acidic site by utilizing niobic acid and molybdate, and then drying the sample at 50-150 ℃ for 24 h.
And 6, (4) roasting the sample obtained in the step (3) for 1-4h at the temperature of 500-.
7. The method for preparing the catalyst according to claim 3, wherein the raw material for cracking in the step (1) is sun-dried and uniformly ground pig manure powder.
8. The method for preparing a catalyst according to claim 3, wherein the nickel salt solution used for impregnation in the step (3) is a nickel nitrate solution.
9. The method for preparing the catalyst according to claim 3, wherein the calcination parameter in the step (4) is 500-700 ℃ calcination for 1-4 h.
10. The preparation method of the hydrogenation catalyst and the application thereof in fructose conversion according to claims 1-6 are characterized in that the hydrogenation catalyst is used in the reaction of preparing ethyl levulinate by taking fructose and furfuryl alcohol as raw materials in a mass ratio of 10-50: 1.
11. The use as claimed in claim 7, wherein the reaction temperature is 120-220 ℃ and the reaction pressure is 1-5 MPa.
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| CN202110550332.7A CN113332973A (en) | 2021-05-20 | 2021-05-20 | Preparation method of hydrogenation catalyst |
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Citations (6)
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| CN101591222A (en) * | 2009-04-23 | 2009-12-02 | 上海华谊丙烯酸有限公司 | A kind of method of hydrogenating glucose to prepare sorbierite |
| CN105056988A (en) * | 2015-08-09 | 2015-11-18 | 大连理工大学 | Binary niobate-based hydrodeoxygenation catalyst, preparation therefor and application thereof |
| CN105728042A (en) * | 2016-03-07 | 2016-07-06 | 中国科学院山西煤炭化学研究所 | Catalyst for producing levulinate through furfural and preparation method and application of catalyst |
| CN107382716A (en) * | 2017-07-18 | 2017-11-24 | 济南大学 | A kind of method that ethyl levulinate is prepared based on acidic catalyst catalysis furfuryl alcohol |
| CN111330632A (en) * | 2020-05-06 | 2020-06-26 | 济南大学 | Preparation method of zirconium modified beta molecular sieve and application of zirconium modified beta molecular sieve in xylose conversion |
| CN112263989A (en) * | 2020-09-15 | 2021-01-26 | 南京林业大学 | Method for preparing magnetic biochar by one-step method |
-
2021
- 2021-05-20 CN CN202110550332.7A patent/CN113332973A/en active Pending
Patent Citations (6)
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| CN101591222A (en) * | 2009-04-23 | 2009-12-02 | 上海华谊丙烯酸有限公司 | A kind of method of hydrogenating glucose to prepare sorbierite |
| CN105056988A (en) * | 2015-08-09 | 2015-11-18 | 大连理工大学 | Binary niobate-based hydrodeoxygenation catalyst, preparation therefor and application thereof |
| CN105728042A (en) * | 2016-03-07 | 2016-07-06 | 中国科学院山西煤炭化学研究所 | Catalyst for producing levulinate through furfural and preparation method and application of catalyst |
| CN107382716A (en) * | 2017-07-18 | 2017-11-24 | 济南大学 | A kind of method that ethyl levulinate is prepared based on acidic catalyst catalysis furfuryl alcohol |
| CN111330632A (en) * | 2020-05-06 | 2020-06-26 | 济南大学 | Preparation method of zirconium modified beta molecular sieve and application of zirconium modified beta molecular sieve in xylose conversion |
| CN112263989A (en) * | 2020-09-15 | 2021-01-26 | 南京林业大学 | Method for preparing magnetic biochar by one-step method |
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Application publication date: 20210903 |