CN-116889872-B - Non-noble metal catalyst for biomass hydrogenation reaction, method and application

Abstract

The invention belongs to the technical field of materials, and discloses a non-noble metal catalyst for biomass hydrogenation reaction, which is prepared by adding fuel A and metal salt B into distilled water, heating, stirring and dissolving, and evaporating water to obtain gel; the gel is placed in high temperature equipment, and is subjected to combustion reaction to obtain metal oxide powder with spinel structure, and the metal oxide powder is reduced to obtain the catalyst. According to the preparation method of the catalyst, nitrate or acetate of non-noble metal B is used as a raw material, the fuel A is used as a ligand to be chelated with metal ions in the mixing and stirring process to uniformly disperse the metal ions, and the fuel A is used as fuel to be oxidized by metal salt in the solution combustion synthesis process to release heat and decompose to generate gas, so that the obtained spinel oxide is rich in mesopores, the cost of the raw material is low, the environment is protected, the preparation process is simple, the period is short, and the catalyst has great industrial application potential.

Inventors

• ZHANG XUBIN
• LI YONGWANG
• WANG FUMIN

Assignees

• 天津大学

Dates

Publication Date

20260508

Application Date

20230627

Claims (1)

1. 1. The method for preparing the hydrogenation product by using the non-noble metal catalyst is characterized by comprising the following steps: 0.1g of the catalyst is put into a reaction kettle, 1g of furfural and 19g of ethanol are added, H 2 is introduced, the reaction temperature is 150 ℃, the reaction pressure is 1MPa, the reaction time is 5 hours, when the molar ratio of glycine to aluminum nitrate to cobalt acetate is 1.5:0.5:0.5, the conversion rate of the furfural reaches 100%, the yield of the 2-methylfuran reaches 97%, and very high catalytic performance is shown; The preparation method of the non-noble metal catalyst comprises the following steps: 2.813g of aluminum nitrate, 1.328g of cobalt acetate and 1.689g of glycine are dissolved in distilled water, stirring is carried out for 2 hours at 60 ℃ to obtain purple gel, the gel is placed in a muffle furnace at 200 ℃ for 2 hours to obtain gray black spinel powder, the spinel powder is placed in a tubular furnace, H 2 is introduced, reduction is carried out for 1 hour at 400 ℃, the temperature rising and falling speed is 5 ℃ per minute, and the non-noble metal catalyst with a simple substance loaded on the surface is obtained, namely 1.5Gly-Co/CoAl 2 O 4 .

Description

Non-noble metal catalyst for biomass hydrogenation reaction, method and application Technical Field The invention belongs to the technical field of materials, and relates to biomass hydrodeoxygenation, in particular to a non-noble metal catalyst for biomass hydrogenation reaction, a method and application. Background In order to cope with exhaustion of fossil fuels, renewable energy sources such as solar energy, biomass energy, wind energy and water energy are widely paid attention to, wherein the biomass energy is taken as the only renewable carbon source, and has wide application prospect due to the abundant reserves and the concept of conforming to a double-carbon target. The high-added value chemicals and organic synthesis intermediates can be prepared by carrying out operations such as hydrogenation, deoxidation, hydrolysis and the like on biomass raw materials, and the most representative is hydrodeoxygenation reaction of biomass platform compounds furfural and 5-hydroxymethylfurfural. Wherein, the improvement of hydrodeoxygenation activity of furfural and 5-hydroxymethyl furfural and selectivity of target products are important points and difficulties. In the reported researches, metal oxides or active carbon supported metal simple substances are mainly used as catalysts, and although high-efficiency noble metal catalysts such as Pd, pt, ir and the like are developed, the industrial application of the high-efficiency noble metal catalysts is limited by the high price and the scarce resources. Therefore, the development of a non-noble metal catalyst with high catalytic activity and selectivity for biomass hydrogenation reaction is significant. Spinel oxides have excellent versatility, flexible ion arrangement, and multivalent structure compared to single metal oxides, thereby exhibiting more excellent catalytic performance. Spinel oxide is often prepared by high-temperature calcination with Layered Double Hydroxides (LDHs) as precursors, and the harsh synthesis conditions, complicated synthesis steps and long synthesis time of LDHs bring a lot of inconveniences to the preparation of spinel oxide, so that spinel oxide can be obtained in a short time and at a lower temperature by using a solution combustion synthesis method, and the preparation of a catalyst for biomass hydrogenation reaction has not been reported yet. Disclosure of Invention The invention aims to overcome the defects in the prior art and provides a non-noble metal catalyst for biomass hydrogenation reaction, a method and application thereof. The technical scheme adopted for solving the technical problems is as follows: A non-noble metal catalyst for biomass hydrogenation reactions, the preparation method of the non-noble metal catalyst comprising the steps of: (1) Adding fuel A and metal salt B into distilled water, heating, stirring and dissolving, and evaporating water to obtain gel; (2) Placing the gel in high-temperature equipment, and performing combustion reaction to obtain metal oxide powder with a spinel structure; (3) And reducing the metal oxide powder to obtain the non-noble metal catalyst for biomass hydrogenation reaction. Further, the fuel a in step (1) comprises one or more of glycine, urea, citric acid and hexamethylenetetramine; Or the B metal salt in the step (1) comprises Al, K, mn, fe, co, ni, cu and one or more of Zn nitrate or acetate; or in the step (1), the molar ratio of the fuel A to the metal salt B is 0.5-2.5:1; or the mass percentage of the water in the gel in the step (1) is 10-50%. Further, in the step (1), the temperature of stirring and dissolving is 60-80 ℃ and the time is 0.5-2 h. Further, the high-temperature equipment in the step (2) is one of a muffle furnace, an electric heating plate and an oven; or the temperature of the high-temperature equipment in the step (2) is 150-900 ℃ and the placing time is 1-2 hours; Or in the step (3), the metal oxide powder is subjected to reduction reaction in reduction equipment, wherein the reduction equipment is one of a tube furnace and a high-pressure reaction kettle; Or the temperature of the reduction in the step (3) is 300-1000 ℃, and the reduction time is 1-6 h. Further, in the step (3), the reduction heating and cooling rates are 5-10 ℃ per minute; Or the reduction is performed under an atmosphere of H 2. The use of a non-noble metal catalyst as described above in a biomass hydrogenation reaction. The method for preparing the hydrogenation product by using the non-noble metal catalyst comprises the steps of loading the catalyst into a reaction kettle, adding a biomass platform compound and a solvent, introducing gas, reacting at 80-200 ℃ and under the reaction pressure of 0.1-3 MPa, and reacting to obtain the hydrogenation product. Further, the mass ratio of the catalyst to the biomass platform compound to the solvent is 0.1-1:1:14-29. Further, the biomass platform compound comprises one of furfural and 5-hydroxymethylfurfural; or the solvent comprises one