CN-118204086-B - Preparation method and application of boride metal salt catalyst

Abstract

The invention discloses a preparation method of a metal boride salt catalyst and application thereof, wherein a metal salt solution and a sodium borohydride solution are used for mixing preparation, and the preparation method is specifically applied to the preparation of tetrahydrofurfuryl alcohol by using the metal boride salt catalyst, wherein furfural and the obtained metal boride salt catalyst are added into a closed high-pressure reactor with a hydrogen environment of 0.1-5 MPa according to the mass ratio of 96-192:50-100, uniformly mixed, and then heated in a closed manner for 0.5-15 h at the temperature of 30-150 ℃, and then cooled to room temperature, so that tetrahydrofurfuryl alcohol can be obtained. The method has the characteristics of high reduction efficiency, low price and easy acquisition of the catalyst, mild reaction conditions and the like, and the yield of the product is more than 99 percent, thus having good industrialized prospect.

Inventors

• JIA WENLONG
• ZHAO SHUAILONG
• LIU HUAI
• ZHANG RUI
• ZHANG JUNHUA
• PENG LINCAI

Assignees

• 昆明理工大学

Dates

Publication Date

20260505

Application Date

20240318

Claims (3)

1. 1. Use of a metal boride salt catalyst in the preparation of tetrahydrofurfuryl alcohol, comprising the steps of: s1, weighing 1-3 parts of metal salt and 20-100 mL of ultrapure water according to mole numbers, and placing the weighed metal salt into the weighed ultrapure water at room temperature for stirring and dissolving to obtain an initial mixed solution; S2, weighing 1-5 parts of sodium borohydride and 10-50 mL of ultrapure water according to the mole number, and stirring and mixing for 4-6 minutes at room temperature to obtain a sodium borohydride solution; s3, dropwise adding the obtained sodium borohydride solution into the initial mixed solution to obtain mixed liquid containing black precipitate; s4, filtering the obtained mixed liquid by using filter paper to obtain black solid powder; s5, drying the obtained black solid powder at 50-200 ℃ under nitrogen to obtain a tetrahydrofurfuryl alcohol efficient catalyst, wherein the application comprises the steps of adding furfural and the obtained tetrahydrofurfuryl alcohol efficient catalyst into a closed high-pressure reactor according to a mass ratio of 96-192:50-100, uniformly mixing, performing closed heating reaction for 0.5-15 h under the condition of 30-150 ℃ in the presence of hydrogen at a pressure of 0.1-5 MPa, and cooling to room temperature to obtain tetrahydrofurfuryl alcohol; the metal salt contains one or more of metal elements including Cu, ni, mn, fe, co, zn.
2. 2. The method according to claim 1, wherein in S1, the metal salt comprises one or more of sulfate, nitrate, carbonate, chloride, formate, acetate, citrate, acetylacetonate of metal elements.
3. 3. The method of claim 1, wherein in S2, the concentration of the sodium borohydride solution is 2-10 mol/L.

Description

Preparation method and application of boride metal salt catalyst Technical Field The invention relates to the technical field of catalyst preparation, in particular to a preparation method and application of a metal boride catalyst. Background Due to the great social concerns about energy supply and environmental pollution, biomass is considered a promising raw material to meet the demands of the completely sustainable bio-commodity industry. In recent years, the development of new renewable chemicals from sugar platforms, such as biomass-derived chemicals based on 5-hydroxymethylfurfural and levulinic acid, has gained wide acceptance, and the conversion of biomass to fine chemicals to replace fossil resources will be an important layout for energy strategies in the global future green development. Tetrahydrofurfuryl alcohol (THFA) is an important basic organic chemical raw material commonly used as a solvent for grease, wax, resin, dye, cellulose acetate, nitrocellulose, ethylcellulose and the like, a stabilizer for gelatin solution, a wetting agent for the printing industry, a dispersing agent, a decoloring agent for certain medicines, a deodorizing agent and the like. In addition, tetrahydrofurfuryl alcohol is also used for preparing dihydrofuran, lysine, polyamide plastics, plasticizers and the like. Current research on hydrogenation of furfural (FF) to THFA has focused mainly on noble metals such as Ru, pt and Pd, because noble metal catalysts give excellent THFA yields (95-100%) under relatively mild reaction conditions. For example, Y.Cao et al reacted over a synthetic noble metal catalyst RuMoO x/CN at 100℃under 2MPa H 2 for 1 hour with a furfural conversion of 92% and a tetrahydrofurfuryl alcohol selectivity of 99%. While noble metals exhibit excellent catalytic effects, the expensive price of noble metals limits the economic production of THFA. Thus, the development of non-noble metal catalysts (e.g., ni, cu, co, etc.) for the production of THFA is currently receiving increasing attention. However, these catalysts have the disadvantages of low catalytic efficiency and require severe reaction temperatures or hydrogen pressures to obtain high THFA yields. For example, L.Liu et al synthesized bimetallic copper, nickel non-noble metal catalyst Cu-Ni/C nano material reacted for 10 hours at 130 ℃ and 4MPa H 2 to obtain 90.3% tetrahydrofurfuryl alcohol yield, and it is noted that efficient catalysis of FF by non-noble metal catalyst for preparing THFA is still challenging and highly desirable. In summary, the conventional method for preparing tetrahydrofurfuryl alcohol by catalytic hydrogenation of furfural uses noble metal as a catalyst, which is expensive and is not beneficial to practical application, and the non-noble metal catalyst has the defects of low conversion rate, poor selectivity, long reaction time and the like. Compared with the prior art, the metal boride catalyst has the advantages of mild reaction condition, low required hydrogen pressure, simple preparation and great practical application value. Therefore, in order to solve the problems, a tetrahydrofurfuryl alcohol high-efficiency catalyst and a preparation method of tetrahydrofurfuryl alcohol are provided. Disclosure of Invention The invention aims to provide a preparation method of a metal boride salt catalyst prepared from a metal boride material, which is low in cost, easy to prepare, easy to separate and low in production cost, and the yield of the product is high. In order to achieve the technical effects, the preparation method of the tetrahydrofurfuryl alcohol efficient catalyst is characterized by comprising the following steps of: s1, weighing 1-3 parts of metal salt and 20-100 mL of ultrapure water according to mole numbers, and placing the weighed metal salt into the weighed ultrapure water at room temperature for stirring and dissolving to obtain an initial mixed solution; S2, weighing 1-5 parts of sodium borohydride and 10-50 mL of ultrapure water according to the mole number, and stirring and mixing for 4-6 minutes at room temperature to obtain a sodium borohydride solution; s3, dropwise adding the obtained sodium borohydride solution into the initial mixed solution to obtain mixed liquid containing black precipitate; s4, filtering the obtained mixed liquid by using filter paper to obtain black solid powder; S5, drying the obtained black solid powder at 50-200 ℃ under nitrogen to obtain the tetrahydrofurfuryl alcohol efficient catalyst. Further, in S1, the metal salt includes one or more of sulfate, nitrate, carbonate, chloride, formate, acetate, citrate, and acetylacetonate of metal elements. Further, the metal salt contains one or more of metal elements including Cu, ni, mn, fe, co, zn. Further, in S2, the concentration of the sodium borohydride solution is 2-10 mol/L. The invention further aims to provide an application of the metal boride catalyst in preparation of tetrahydrofurfuryl alcohol, which is characterized