A method for preparing a boronized metal salt catalyst and its application

Abstract

This invention discloses a method for preparing a boronized metal salt catalyst and its application. The catalyst is prepared by mixing a metal salt solution and a sodium borohydride solution. Specifically, it is used to prepare tetrahydrofurfuryl alcohol using a boronized metal salt catalyst. Furfural and the aforementioned boronized metal salt catalyst are added to a closed high-pressure reactor with a hydrogen atmosphere of 0.1–5 MPa at a mass ratio of 96–192:50–100 and mixed thoroughly. The mixture is then heated in a closed environment at 30–150°C for 0.5–15 h, and then cooled to room temperature to obtain tetrahydrofurfuryl alcohol. This method features high reduction efficiency, readily available and inexpensive catalyst, and mild reaction conditions; the product yield is over 99%, showing great promise for industrialization.

Description

Technical Field

[0001] This invention relates to the field of catalyst preparation technology, specifically to a method for preparing a boronized metal salt catalyst and its application. Background Technology

[0002] Due to significant societal concerns about energy supply and environmental pollution, biomass is considered a promising raw material for meeting the needs of a fully sustainable bio-products 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 widespread acceptance. Converting biomass into fine chemicals to replace fossil resources will become a crucial part of the global energy strategy for future green development. Tetrahydrofurfural (THFA) is a commonly used and important basic organic chemical raw material, used as a solvent for oils, waxes, resins, dyes, cellulose acetate, cellulose nitrate, ethyl cellulose, etc.; a stabilizer for gelatin solutions; a wetting agent and dispersant in the printing and dyeing industry; and a decolorizing and deodorizing agent for certain pharmaceuticals. Furthermore, THFA is also used in the preparation of dihydrofuran, lysine, polyamide plastics, and plasticizers.

[0003] Current research on the hydrogenation of furfural (FF) to total hydrogen sulfide (THFA) mainly focuses on noble metals (such as Ru, Pt, and Pd) because noble metal catalysts achieve excellent THFA yields (95-100%) under relatively mild reaction conditions. For example, Y. Cao et al. synthesized the noble metal catalyst RuMoO x The reaction of / CN at 100℃ and 2MPa H2 for 1 hour resulted in a furfural conversion of 92% and a tetrahydrofurfuryl alcohol selectivity of 99%. Although noble metals exhibit excellent catalytic effects, their high price limits the economical production of THFA. Therefore, the development of non-noble metal catalysts (such as Ni, Cu, Co, etc.) for THFA production is currently receiving increasing attention. However, these catalysts suffer from low catalytic efficiency and require harsh reaction temperatures or hydrogen pressures to achieve high THFA yields. For example, L. Liu et al. synthesized a bimetallic copper-nickel non-noble metal catalyst, Cu-Ni / C nanomaterials, and achieved a tetrahydrofurfuryl alcohol yield of 90.3% after 10 hours of reaction at 130℃ and 4MPa H2. Notably, the efficient catalytic production of THFA from FF using non-noble metal catalysts remains challenging and highly desirable.

[0004] In summary, previous methods for the catalytic hydrogenation of furfural to tetrahydrofurfuryl alcohol used precious metal catalysts, which were expensive and impractical. Non-precious metal catalysts suffered from low conversion rates, poor selectivity, and long reaction times. In contrast, boron metal salt catalysts offer milder reaction conditions, require lower hydrogen pressures, are simpler to prepare, and have significant practical application value.

[0005] Therefore, in order to solve the above problems, this paper proposes a highly efficient catalyst for tetrahydrofurfuryl alcohol and a method for preparing tetrahydrofurfuryl alcohol. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing a boron metal salt catalyst using inexpensive, easy-to-prepare, easily separable, high-yield, and low-cost boron metal materials.

[0007] To achieve the above-mentioned technical effects, the present invention is implemented through the following technical solution: a method for preparing a tetrahydrofurfuryl alcohol high-efficiency catalyst, characterized by comprising the following steps:

[0008] S1. Weigh 1-3 parts of metal salt and 20-100 mL of ultrapure water according to the molar number, and put the weighed metal salt into the weighed ultrapure water at room temperature and stir to dissolve to obtain the initial mixture.

[0009] S2. Weigh 1-5 parts of sodium borohydride and 10-50 mL of ultrapure water by molar number, and stir and mix at room temperature for 4-6 minutes to obtain a sodium borohydride solution.

[0010] S3. The sodium borohydride solution obtained above is added dropwise to the initial mixture to obtain a mixed liquid containing a black precipitate;

[0011] S4. Filter the obtained mixed liquid using filter paper to obtain a black solid powder;

[0012] S5. The black solid powder obtained by drying under nitrogen at 50-200℃ can be used to obtain the tetrahydrofurfuryl alcohol high-efficiency catalyst.

[0013] Furthermore, in S1, the metal salt comprises one or more of the following: sulfate, nitrate, carbonate, chloride, formate, acetate, citrate, and acetylacetone salt of a metal element.

[0014] Furthermore, the metal salt contains one or more metallic elements, including Cu, Ni, Mn, Fe, Co, and Zn.

[0015] Furthermore, in S2, the concentration of the sodium borohydride solution is 2–10 mol / L.

[0016] Another object of the present invention is to provide an application of using boron metal salt catalyst, characterized in that the application in the preparation of tetrahydrofurfuryl alcohol includes the following steps: furfural and the above-obtained tetrahydrofurfuryl alcohol high-efficiency catalyst are added to a closed high-pressure reactor at a mass ratio of 96-192:50-100 and mixed evenly; the mixture is heated under closed conditions at 30-150°C for 0.5-15 hours; and then cooled to room temperature to obtain tetrahydrofurfuryl alcohol.

[0017] Furthermore, the closed high-pressure reactor contains hydrogen gas at a pressure of 0.1–5 MPa.

[0018] The beneficial effects of this invention are:

[0019] This invention utilizes a boronized metal salt catalyst to catalyze the reduction of furfural to tetrahydrofurfuryl alcohol. The boronized metal salt catalyst is prepared by reducing a metal solution with sodium borohydride. Compared with other metal catalysts, this catalyst exhibits excellent catalytic activity and selectivity, low cost, milder conditions, ease of preparation, and superior performance. The reaction conditions are mild, the reaction time is short, it is easy to operate, the yield is high, and the catalyst can be recycled. Attached Figure Description

[0020] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 This is a flowchart illustrating the preparation process of a boronized metal salt catalyst according to the present invention.

[0022] Figure 2 This is a gas phase diagram of THFA, the product of Example 1 of the present invention;

[0023] Figure 3 This is the mass spectrum of THFA, the product of Example 1 of the present invention. Detailed Implementation

[0024] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] Example 1

[0026] See Figure 1 As shown, a method for preparing a boron metal salt catalyst is characterized by comprising the following steps:

[0027] S1. Weigh 0.018 mol of the required metal salt (one or more of sulfate, nitrate, carbonate, chloride, formate, acetate, citrate, and acetylacetone) and 25 ml of ultrapure water by molar ratio. Place the weighed metal salt into the weighed ultrapure water at room temperature and stir to dissolve to obtain the initial mixture.

[0028] S2. Weigh 0.06 mol of the required sodium borohydride by molar ratio, dissolve the sodium borohydride in 10 mL of ultrapure water, and stir and mix at room temperature for 5 minutes to obtain a 6 mol / L sodium borohydride solution.

[0029] S3. The sodium borohydride solution obtained above is added dropwise to the initial mixture to obtain a mixed liquid containing a black precipitate;

[0030] S4. Filter the obtained mixed liquid using filter paper to obtain a black solid powder;

[0031] S5. The black solid powder obtained by drying under nitrogen at 150°C yields 1 part of boronized metal salt catalyst (Cu). 0.8 Ni1-B).

[0032] Then, 0.096 g of furfural and 0.05 g of the boronized metal salt catalyst prepared above were weighed and added to a closed high-pressure reactor and mixed evenly. The reactor was purged with hydrogen 4 to 5 times to remove air and the hydrogen pressure was maintained at 1 MPa. The reactor was heated and stirred at 120°C for 3 hours to carry out the reduction reaction. The yield of tetrahydrofurfuryl alcohol was 99%.

[0033] Example 2:

[0034] The boronized metal salt catalyst (Cu1Ni1-B) was prepared according to the preparation method of the boronized metal salt catalyst described in Example 1.

[0035] Weigh 0.096 g of furfural and 0.05 g of the boronized metal salt catalyst prepared above and add them to a closed high-pressure reactor. Mix them evenly, purge with hydrogen 4 to 5 times to remove air and maintain a hydrogen pressure of 1 MPa. Heat and stir at 120°C for 3 hours to carry out the reduction reaction. The yield of tetrahydrofurfuryl alcohol is 99%.

[0036] Example 3

[0037] The boronized metal salt catalyst (Cu) was prepared according to the preparation method of the boronized metal salt catalyst described in Example 1. 1.3 Ni1-B);

[0038] Weigh 0.096 g of furfural and 0.05 g of the boronized metal salt catalyst prepared above and add them to a closed high-pressure reactor. Mix them evenly, purge with hydrogen 4 to 5 times to remove air and maintain a hydrogen pressure of 1 MPa. Heat and stir at 120°C for 3 hours to carry out the reduction reaction. The yield of THFA is 98%.

[0039] Example 4

[0040] The boronized metal salt catalyst (Cu) was prepared according to the preparation method of the boronized metal salt catalyst described in Example 1. 1.5 Ni1-B);

[0041] Weigh 0.096 g of furfural and 0.05 g of the boronized metal salt catalyst prepared above and add them to a closed high-pressure reactor. Mix them evenly, purge with hydrogen 4 to 5 times to remove air and maintain a hydrogen pressure of 1 MPa. Heat and stir at 120°C for 3 hours to carry out the reduction reaction. The yield of THFA is 93%.

[0042] Example 5

[0043] The boronized metal salt catalyst (CuCo-B) was prepared according to the preparation method of the boronized metal salt catalyst described in Example 1.

[0044] Weigh 0.096g of furfural and 0.05g of the boronized metal salt catalyst prepared above and add them to a closed high-pressure reactor. Mix them evenly, purge with hydrogen 4-5 times to remove air and maintain a hydrogen pressure of 1MPa. Heat and stir at 120℃ for 3 hours to carry out the reduction reaction. The yield of THFA is 83%.

[0045] Example 6

[0046] The boronized metal salt catalyst (CuZn-B) was prepared according to the preparation method of the boronized metal salt catalyst described in Example 1.

[0047] Weigh 0.096 g of furfural and 0.05 g of the boronized metal salt catalyst prepared above and add them to a closed high-pressure reactor. Mix them evenly, purge with hydrogen 4 to 5 times to remove air and maintain a hydrogen pressure of 1 MPa. Heat and stir at 120°C for 3 hours to carry out the reduction reaction. The yield of THFA is 96%.

[0048] Example 7

[0049] The boronized metal salt catalyst (NiMn-B) was prepared according to the preparation method of the boronized metal salt catalyst described in Example 1.

[0050] Weigh 0.096 g of furfural and 0.05 g of the boronized metal salt catalyst prepared above and add them to a closed high-pressure reactor. Mix them evenly, purge with hydrogen 4 to 5 times to remove air and maintain a hydrogen pressure of 1 MPa. Heat and stir at 80°C for 3 hours to carry out the reduction reaction. The yield of THFA is 86%.

[0051] Example 8

[0052] The boronized metal salt catalyst (NiFe-B) was prepared according to the preparation method of the boronized metal salt catalyst described in Example 1.

[0053] Weigh 0.096 g of furfural and 0.05 g of the boronized metal salt catalyst prepared above and add them to a closed high-pressure reactor. Mix them evenly, purge with hydrogen 4 to 5 times to remove air and maintain a hydrogen pressure of 1 MPa. Heat and stir at 90°C for 3 hours to carry out the reduction reaction. The yield of THFA is 84%.

[0054] Example 9

[0055] The boronized metal salt catalyst (NiZn-B) was prepared according to the preparation method of the boronized metal salt catalyst described in Example 1.

[0056] Weigh 0.096 g of furfural and 0.05 g of the boronized metal salt catalyst prepared above and add them to a closed high-pressure reactor. Mix them evenly, purge with hydrogen 4 to 5 times to remove air and maintain a hydrogen pressure of 1 MPa. Heat and stir at 100°C for 3 hours to carry out the reduction reaction. The yield of THFA is 81%.

[0057] Example 10

[0058] The boronized metal salt catalyst (CuNiZn-B) was prepared according to the preparation method of the boronized metal salt catalyst described in Example 1.

[0059] Weigh 0.096 g of furfural and 0.05 g of the boronized metal salt catalyst prepared above and add them to a closed high-pressure reactor. Mix them evenly, purge with hydrogen 4 to 5 times to remove air and maintain a hydrogen pressure of 1 MPa. Heat and stir at 80°C for 2.5 h to carry out the reduction reaction. The yield of THFA is 91%.

[0060] Example 11

[0061] The boronized metal salt catalyst (NiMnZn-B) was prepared according to the preparation method of the boronized metal salt catalyst described in Example 1.

[0062] Weigh 0.096 g of furfural and 0.05 g of the boronized metal salt catalyst prepared above and add them to a closed high-pressure reactor. Mix them evenly, purge with hydrogen 4 to 5 times to remove air and maintain a hydrogen pressure of 1 MPa. Heat and stir at 120°C for 1 hour to carry out the reduction reaction. The yield of THFA is 88%.

[0063] Example 12

[0064] The boronized metal salt catalyst (CuFeCo-B) was prepared according to the preparation method of the boronized metal salt catalyst described in Example 1.

[0065] Weigh 0.096 g of furfural and 0.05 g of the boronized metal salt catalyst prepared above and add them to a closed high-pressure reactor. Mix them evenly, purge with hydrogen 4 to 5 times to remove air and maintain a hydrogen pressure of 1 MPa. Heat and stir at 120 °C for 1.5 h to carry out the reduction reaction. The yield of THFA is 91%.

[0066] Example 13

[0067] The boronized metal salt catalyst (NiCo-B) was prepared according to the preparation method of the boronized metal salt catalyst described in Example 1.

[0068] Weigh 0.096 g of furfural and 0.05 g of the boronized metal salt catalyst prepared above and add them to a closed high-pressure reactor. Mix them evenly, purge with hydrogen 4 to 5 times to remove air and maintain a hydrogen pressure of 1 MPa. Heat and stir at 120°C for 2 hours to carry out the reduction reaction. The yield of THFA is 93%.

[0069] Example 14

[0070] The boronized metal salt catalyst (NiCoFe-B) was prepared according to the preparation method of the boronized metal salt catalyst described in Example 1.

[0071] Weigh 0.096 g of furfural and 0.05 g of the boronized metal salt catalyst prepared above and add them to a closed high-pressure reactor. Mix them evenly, purge with hydrogen 4 to 5 times to remove air and maintain a hydrogen pressure of 1 MPa. Heat and stir at 120°C for 2.5 h to carry out the reduction reaction. The yield of THFA is 96%.

[0072] Combining the results described in Examples 1 to 14 above, the results are shown in Table 1:

[0073]

[0074] Table 1

[0075] As shown in Table 1, this invention uses a boronized metal salt catalyst to catalyze the reduction of furfural to tetrahydrofurfuryl alcohol. The boronized metal salt catalyst is prepared by reducing a metal solution with sodium borohydride. Compared with other metal catalysts, this catalyst has good catalytic activity and selectivity, low cost, milder conditions, is easy to prepare, and has better performance. The reaction conditions are mild, the reaction time is short, it is easy to operate, the yield is high, and the catalyst can be recycled.

Claims

1. The application of a boronized metal salt catalyst in the preparation of tetrahydrofurfuryl alcohol, characterized in that, Includes the following steps: S1. Weigh 1-3 parts of metal salt and 20-100 mL of ultrapure water according to the molar number, and put the weighed metal salt into the weighed ultrapure water at room temperature and stir to dissolve to obtain the initial mixture. S2. Weigh 1-5 parts of sodium borohydride and 10-50 mL of ultrapure water by molar number, and stir and mix at room temperature for 4-6 minutes to obtain a sodium borohydride solution. S3. The sodium borohydride solution obtained above is added dropwise to the initial mixture to obtain a mixed liquid containing a black precipitate; S4. Filter the obtained mixed liquid using filter paper to obtain a black solid powder; S5. The black solid powder obtained by drying under nitrogen at 50~200°C can be used to obtain the tetrahydrofurfuryl alcohol high-efficiency catalyst. The application includes the following steps: furfural and the tetrahydrofurfuryl alcohol high-efficiency catalyst obtained above are added to a closed high-pressure reactor at a mass ratio of 96~192:50~100 and mixed evenly. The mixture is heated and reacted in the presence of hydrogen at a pressure of 0.1~5MPa at 30~150°C for 0.5~15h. Then it is cooled to room temperature to obtain tetrahydrofurfuryl alcohol. The metal salt contains one or more metallic elements, including Cu, Ni, Mn, Fe, Co, and Zn.

2. The application according to claim 1, characterized in that: In S1, the metal salt comprises one or more of the following: sulfate, nitrate, carbonate, chloride, formate, acetate, citrate, and acetylacetone salt of a metal element.

3. The application according to claim 1, characterized in that: In S2, the concentration of the sodium borohydride solution is 2~10 mol / L.

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