A non-noble metal catalyst for biomass hydrogenation reaction, method and application thereof

Abstract

The application belongs to the technical field of materials, and discloses a non-noble metal catalyst for biomass hydrogenation reaction, and a preparation method thereof, which comprises the following steps: adding A fuel and B metal salt into distilled water, heating, stirring and dissolving, and obtaining a gel along with water evaporation; placing the gel into a high-temperature device, and obtaining metal oxide powder with a spinel structure through a combustion reaction; and reducing the metal oxide powder, thereby obtaining the catalyst. The preparation method of the catalyst uses nitrate or acetate of the non-noble metal B as raw material, and A fuel is chelated with metal ions as a ligand during mixing and stirring, and uniformly disperses the metal ions, and is oxidized by the metal salt as fuel during the solution combustion synthesis, releases heat, decomposes to generate gas, and brings abundant mesopores to the obtained spinel oxide. The raw material is low in cost, green and environment-friendly, the preparation process is simple, the period is short, and the catalyst has great industrial application potential.

Description

Technical Field

[0001] This invention belongs to the field of materials technology and relates to biomass hydrogenation and deoxygenation, particularly a non-precious metal catalyst, method and application for biomass hydrogenation reaction. Background Technology

[0002] To address the depletion of fossil fuels, renewable energy sources such as solar, biomass, wind, and hydropower have gained widespread attention. Among these, biomass energy, as the only renewable carbon source, has broad application prospects due to its abundant reserves and alignment with the "dual carbon" goal. High-value-added chemicals and organic synthesis intermediates can be prepared by hydrogenating, deoxygenating, and hydrolyzing biomass raw materials. The most representative example is the hydrogenation and deoxygenation reaction of the biomass platform compounds furfural and 5-hydroxymethylfurfural.

[0003] Improving the hydrodeoxygenation activity and selectivity of furfural and 5-hydroxymethylfurfural for the target products is both a key focus and a challenge. Reported studies have primarily used metal oxides or activated carbon-supported elemental metals as catalysts. Although highly efficient noble metal catalysts such as Pd, Pt, and Ir have been developed, their high cost and scarcity of resources limit their industrial application. Therefore, developing a non-noble metal catalyst with high catalytic activity and selectivity for biomass hydrogenation reactions is of great significance.

[0004] Compared to monometallic oxides, spinel oxides possess superior versatility, flexible ionic arrangement, and multivalent structure, resulting in more excellent catalytic performance. Spinel oxides are often prepared by high-temperature calcination of layered bimetallic hydroxides (LDHs) as precursors. However, the demanding synthesis conditions, cumbersome steps, and lengthy synthesis time of LDHs pose significant challenges to the preparation of spinel oxides. Solution combustion synthesis can yield spinel oxides in a shorter time and at a lower temperature, and this method has not yet been reported for catalyst preparation in biomass hydrogenation reactions. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a non-precious metal catalyst, method and application for biomass hydrogenation reaction.

[0006] The technical solution adopted by this invention to solve its technical problem is:

[0007] A non-precious metal catalyst for biomass hydrogenation reaction, the preparation method of the non-precious metal catalyst includes the following steps:

[0008] (1) Add fuel A and metal salt B to distilled water, heat and stir to dissolve, and obtain a gel as the water evaporates;

[0009] (2) The above gel is placed in a high-temperature device and subjected to a combustion reaction to obtain a metal oxide powder with a spinel structure;

[0010] (3) Reduce the above metal oxide powder to obtain a non-precious metal catalyst for biomass hydrogenation reaction.

[0011] Further, the fuel A mentioned in step (1) includes one or more of glycine, urea, citric acid and hexamethylenetetramine;

[0012] Alternatively, the metal salt B mentioned in step (1) may include one or more of Al, K, Mn, Fe, Co, Ni, Cu and Zn nitrates or acetates;

[0013] Alternatively, the molar ratio of fuel A to metal salt B in step (1) is 0.5 to 2.5:1;

[0014] Alternatively, the water content in the gel in step (1) is 10-50% by mass.

[0015] Furthermore, the temperature for stirring and dissolving in step (1) is 60–80°C, and the time is 0.5–2 h.

[0016] Furthermore, the high-temperature equipment mentioned in step (2) is one of a muffle furnace, an electric heating plate, or an oven;

[0017] Alternatively, the temperature of the high-temperature equipment mentioned in step (2) is 150 to 900°C, and the placement time is 1 to 2 hours;

[0018] Alternatively, the metal oxide powder described in step (3) undergoes a reduction reaction in a reduction device, which is either a tubular furnace or a high-pressure reactor.

[0019] Alternatively, the reduction temperature in step (3) is 300–1000°C, and the reduction time is 1–6 h.

[0020] Furthermore, the reduction heating and cooling rates in step (3) are 5–10 °C / min;

[0021] Alternatively, the reduction can be carried out in an H2 atmosphere.

[0022] The application of non-precious metal catalysts in biomass hydrogenation reactions as described above.

[0023] A method for preparing hydrogenation products using the non-precious metal catalyst described above, wherein the catalyst is loaded into a reaction vessel, a biomass platform compound and a solvent are added, a gas is introduced, the reaction temperature is 80-200°C, the reaction pressure is 0.1-3 MPa, and the hydrogenation product is obtained by the reaction.

[0024] Furthermore, the mass ratio of the catalyst:biomass platform compound:solvent is 0.1-1:1:14-29.

[0025] Furthermore, the biomass platform compound includes one of furfural and 5-hydroxymethylfurfural;

[0026] Alternatively, the solvent may include one of water, ethanol, propanol, butanol, and pentanol;

[0027] Alternatively, the gas may include one of H2, N2, and Ar.

[0028] Further, the hydrogenation product includes one or more of furfuryl alcohol, tetrahydrofurfuryl alcohol, 2-methylfuran, 2-methyltetrahydrofuran, 1,2-pentanediol, 1,5-pentanediol, 2,5-furandiethanol, 5-methyl-2-furanethanol, 5-methylfurfural, and 2,5-dimethylfuran.

[0029] The advantages and positive effects of this invention are as follows:

[0030] 1. The catalyst preparation method of the present invention uses nitrates or acetates of non-precious metal B as raw materials. During the mixing and stirring process, fuel A acts as a ligand to chelate with metal ions and uniformly disperse the metal ions. During the solution combustion synthesis process, it is oxidized by the metal salt as fuel, releasing heat and decomposing to produce gas, which brings abundant mesopores to the obtained spinel oxide. The raw materials used are inexpensive, green and environmentally friendly, the preparation process is simple and the cycle is short, and it has great potential for industrial application.

[0031] 2. In the solution combustion synthesis stage, the non-precious metal catalyst of this invention induces the Kirkendall effect due to the unbalanced diffusion of materials, resulting in oxygen vacancies on the surface of spinel oxide. More oxygen vacancies are generated during the reduction stage, and the ratio of fuel A to metal salt B affects the content of oxygen vacancies. The oxygen vacancies on the surface of the non-precious metal catalyst promote the adsorption of reactants, adjust the d-band center of the active metal, accelerate the hydrogen overflow process, and significantly improve the catalytic activity.

[0032] 3. The non-precious metal catalyst of this invention has a production efficiency comparable to that of precious metals, can convert more biomass platform compounds at a lower reaction temperature, has good catalytic activity and stability, and has broad prospects for industrial application.

[0033] 4. This invention adjusts the oxygen vacancy content in spinel by changing the ratio of fuel and metal salt, thereby preparing a non-precious metal catalyst with high biomass hydrogenation catalytic activity. Attached Figure Description

[0034] Figure 1 The activity evaluation diagrams are for the catalysts prepared in Examples 1-5 and Comparative Examples 1-2 of this invention.

[0035] Figure 2 This is a comparison chart showing the activity evaluation of the catalysts prepared in Example 3 and Comparative Examples 3-4 of this invention;

[0036] Figure 3 The XRD patterns of the catalysts prepared in Examples 3-5 and Comparative Examples 3-4 of this invention are shown. The peaks of CoAl2O4 spinel and cobalt can be seen from the XRD patterns of each catalyst, indicating that the synthesized non-noble metal catalyst is a spinel oxide with metal elements supported on its surface.

[0037] Figure 4 The EPR diagrams of the catalysts prepared in Examples 2 to 4 of this invention are shown. It can be seen from the EPR diagrams of each catalyst that as the molar ratio of glycine to metal salt in the raw materials increases, the oxygen vacancy content first increases and then decreases. When the molar ratio of glycine to metal salt is 1.5:1, the oxygen vacancy content reaches its maximum value. Detailed Implementation

[0038] The present invention will be further described below with reference to the embodiments. The following embodiments are descriptive and not limiting, and should not be used to limit the scope of protection of the present invention.

[0039] The various experimental operations involved in the specific embodiments are all conventional techniques in the field. For parts not specifically annotated in this document, those skilled in the art can refer to various commonly used reference books, scientific and technological documents or related instructions and manuals prior to the filing date of this invention to carry out the operations.

[0040] A non-precious metal catalyst for biomass hydrogenation reaction, the preparation method of the non-precious metal catalyst includes the following steps:

[0041] (1) Add fuel A and metal salt B to distilled water, heat and stir to dissolve, and obtain a gel as the water evaporates;

[0042] (2) The above gel is placed in a high-temperature device and subjected to a combustion reaction to obtain a metal oxide powder with a spinel structure;

[0043] (3) Reduce the above metal oxide powder to obtain a non-precious metal catalyst for biomass hydrogenation reaction.

[0044] Preferably, the fuel A in step (1) comprises one or more of glycine, urea, citric acid and hexamethylenetetramine;

[0045] Alternatively, the metal salt B mentioned in step (1) may include one or more of Al, K, Mn, Fe, Co, Ni, Cu and Zn nitrates or acetates;

[0046] Alternatively, the molar ratio of fuel A to metal salt B in step (1) is 0.5 to 2.5:1;

[0047] Alternatively, the water content in the gel in step (1) is 10-50% by mass.

[0048] Preferably, the temperature for stirring and dissolving in step (1) is 60-80°C and the time is 0.5-2h.

[0049] Preferably, the high-temperature equipment mentioned in step (2) is one of a muffle furnace, an electric heating plate, or an oven;

[0050] Alternatively, the temperature of the high-temperature equipment mentioned in step (2) is 150 to 900°C, and the placement time is 1 to 2 hours;

[0051] Alternatively, the metal oxide powder described in step (3) undergoes a reduction reaction in a reduction device, which is either a tubular furnace or a high-pressure reactor.

[0052] Alternatively, the reduction temperature in step (3) is 300–1000°C, and the reduction time is 1–6 h.

[0053] Preferably, the reduction heating and cooling rates in step (3) are 5–10 °C / min;

[0054] Alternatively, the reduction can be carried out in an H2 atmosphere.

[0055] The application of non-precious metal catalysts in biomass hydrogenation reactions as described above.

[0056] A method for preparing hydrogenation products using the non-precious metal catalyst described above, wherein the catalyst is loaded into a reaction vessel, a biomass platform compound and a solvent are added, a gas is introduced, the reaction temperature is 80-200°C, the reaction pressure is 0.1-3 MPa, and the hydrogenation product is obtained by the reaction.

[0057] Preferably, the mass ratio of the catalyst:biomass platform compound:solvent is 0.1-1:1:14-29.

[0058] Preferably, the biomass platform compound includes one of furfural and 5-hydroxymethylfurfural;

[0059] Alternatively, the solvent may include one of water, ethanol, propanol, butanol, and pentanol;

[0060] Alternatively, the gas may include one of H2, N2, and Ar.

[0061] Preferably, the hydrogenation product includes one or more of furfuryl alcohol, tetrahydrofurfuryl alcohol, 2-methylfuran, 2-methyltetrahydrofuran, 1,2-pentanediol, 1,5-pentanediol, 2,5-furandiethanol, 5-methyl-2-furanethanol, 5-methylfurfural, and 2,5-dimethylfuran.

[0062] Specifically, the relevant preparation and testing methods are as follows:

[0063] Example 1

[0064] A non-precious metal catalyst for biomass hydrogenation reaction, the preparation method of the non-precious metal catalyst includes the following steps:

[0065] 2.813 g aluminum nitrate, 1.328 g cobalt acetate and 0.563 g glycine were dissolved in distilled water and stirred at 60 °C for 2 h to obtain a purple gel. The gel was placed in a muffle furnace at 200 °C for 2 h to obtain gray-black spinel powder. The spinel powder was then placed in a tube furnace, H2 was introduced, and it was reduced at 400 °C for 1 h with a heating and cooling rate of 5 °C / min to obtain a non-noble metal catalyst 0.5 Gly-Co / CoAl2O4 with surface-supported elemental substances.

[0066] The method for preparing hydrogenation products using the above-mentioned non-precious metal catalyst includes the following steps:

[0067] 0.1g of the catalyst was loaded into a reactor, along with 1g of furfural and 19g of ethanol. H2 was introduced, and the reaction was carried out at 150℃ and 1MPa for 5 hours. The furfural conversion and 2-methylfuran selectivity were as follows: Figure 1 As shown, from Figure 1 As can be seen, when the molar ratio of glycine:aluminum nitrate:cobalt acetate is 0.5:0.5:0.5, the furfural conversion rate reaches 98% and the 2-methylfuran yield reaches 49%.

[0068] Example 2

[0069] A non-precious metal catalyst for biomass hydrogenation reaction, the preparation method of the non-precious metal catalyst includes the following steps:

[0070] 2.813 g aluminum nitrate, 1.328 g cobalt acetate and 1.126 g glycine were dissolved in distilled water and stirred at 60 °C for 2 h to obtain a purple gel. The gel was placed in a muffle furnace at 200 °C for 2 h to obtain gray-black spinel powder. The spinel powder was then placed in a tube furnace, H2 was introduced, and it was reduced at 400 °C for 1 h with a heating and cooling rate of 5 °C / min to obtain a non-noble metal catalyst Gly-Co / CoAl2O4 with surface-supported elemental substances.

[0071] The method for preparing hydrogenation products using the above-mentioned non-precious metal catalyst includes the following steps:

[0072] 0.1g of the catalyst was loaded into a reactor, along with 1g of furfural and 19g of ethanol. H2 was introduced, and the reaction was carried out at 150℃ and 1MPa for 5 hours. The furfural conversion and 2-methylfuran selectivity were as follows: Figure 1 As shown, from Figure 1 As can be seen, when the molar ratio of glycine:aluminum nitrate:cobalt acetate is 1:0.5:0.5, the furfural conversion rate reaches 100% and the 2-methylfuran yield reaches 65%. Compared with Example 1, increasing the glycine content improves the catalytic performance of the catalyst.

[0073] Example 3

[0074] A non-precious metal catalyst for biomass hydrogenation reaction, the preparation method of the non-precious metal catalyst includes the following steps:

[0075] 2.813 g aluminum nitrate, 1.328 g cobalt acetate and 1.689 g glycine were dissolved in distilled water and stirred at 60 °C for 2 h to obtain a purple gel. The gel was placed in a muffle furnace at 200 °C for 2 h to obtain gray-black spinel powder. The spinel powder was then placed in a tube furnace, H2 was introduced, and it was reduced at 400 °C for 1 h with a heating and cooling rate of 5 °C / min to obtain a non-noble metal catalyst 1.5 Gly-Co / CoAl2O4 with surface-supported elemental substances.

[0076] The method for preparing hydrogenation products using the above-mentioned non-precious metal catalyst includes the following steps:

[0077] 0.1g of the catalyst was loaded into a reactor, along with 1g of furfural and 19g of ethanol. H2 was introduced, and the reaction was carried out at 150℃ and 1MPa for 5 hours. The furfural conversion and 2-methylfuran selectivity were as follows: Figure 1 and Figure 2 As shown, from Figure 1 , Figure 2 As can be seen, when the molar ratio of glycine:aluminum nitrate:cobalt acetate is 1.5:0.5:0.5, the furfural conversion rate reaches 100% and the 2-methylfuran yield reaches 97%, exhibiting very high catalytic performance. Comparing Examples 1, 2, 4, and 5, the optimal doping molar ratio of glycine to metal salt is 1.5:1. Figure 4As shown, at this doping ratio, the catalyst has more oxygen vacancies, which is more conducive to the catalytic reaction. Compared with Comparative Examples 3 and 4, the molar doping of aluminum nitrate and cobalt acetate is the most effective. Too high or too low molar ratios will lead to a decrease in the yield of 2-methylfuran. Compared with the advanced catalysts reported in Table 1, Example 3 can exhibit higher production efficiency at a lower reaction temperature, demonstrating its superior catalytic performance.

[0078] Example 4

[0079] A non-precious metal catalyst for biomass hydrogenation reaction, the preparation method of the non-precious metal catalyst includes the following steps:

[0080] 2.813 g aluminum nitrate, 1.328 g cobalt acetate and 2.252 g glycine were dissolved in distilled water and stirred at 60 °C for 2 h to obtain a purple gel. The gel was placed in a muffle furnace at 200 °C for 2 h to obtain gray-black spinel powder. The spinel powder was then placed in a tube furnace, H2 was introduced, and it was reduced at 400 °C for 1 h with a heating and cooling rate of 5 °C / min to obtain a non-noble metal catalyst 2Gly-Co / CoAl2O4 with surface-supported elemental substances.

[0081] The method for preparing hydrogenation products using the above-mentioned non-precious metal catalyst includes the following steps:

[0082] 0.1g of the catalyst was loaded into a reactor, along with 1g of furfural and 19g of ethanol. H2 was introduced, and the reaction was carried out at 150℃ and 1MPa for 5 hours. The furfural conversion and 2-methylfuran selectivity were as follows: Figure 1 As shown, from Figure 1 As can be seen, when the molar ratio of glycine:aluminum nitrate:cobalt acetate is 2:0.5:0.5, the furfural conversion rate reaches 100% and the 2-methylfuran yield reaches 82%. Compared with Examples 1-3, further increasing the amount of glycine causes the catalytic performance of the catalyst to begin to decline.

[0083] Example 5

[0084] A non-precious metal catalyst for biomass hydrogenation reaction, the preparation method of the non-precious metal catalyst includes the following steps:

[0085] 2.813 g aluminum nitrate, 1.328 g cobalt acetate and 2.815 g glycine were dissolved in distilled water and stirred at 60 °C for 2 h to obtain a purple gel. The gel was placed in a muffle furnace at 200 °C for 2 h to obtain gray-black spinel powder. The spinel powder was then placed in a tube furnace, H2 was introduced, and it was reduced at 400 °C for 1 h with a heating and cooling rate of 5 °C / min to obtain a non-noble metal catalyst 2.5Gly-Co / CoAl2O4 with surface-supported elemental substances.

[0086] The method for preparing hydrogenation products using the above-mentioned non-precious metal catalyst includes the following steps:

[0087] 0.1g of the catalyst was loaded into a reactor, along with 1g of furfural and 19g of ethanol. H2 was introduced, and the reaction was carried out at 150℃ and 1MPa for 5 hours. The furfural conversion and 2-methylfuran selectivity were as follows: Figure 1 As shown, from Figure 1 As can be seen, when the molar ratio of glycine:aluminum nitrate:cobalt acetate is 2.5:0.5:0.5, the furfural conversion rate reaches 100% and the 2-methylfuran yield reaches 63%. Compared with Examples 1-4, further increasing the amount of glycine leads to a further decrease in the catalytic performance of the catalyst.

[0088] Comparative Example 1

[0089] A non-precious metal catalyst for biomass hydrogenation reaction, the preparation method of the non-precious metal catalyst includes the following steps:

[0090] 2.813 g aluminum nitrate, 1.328 g cobalt acetate and 0.282 g glycine were dissolved in distilled water and stirred at 60 °C for 2 h to obtain a purple gel. The gel was placed in a muffle furnace at 200 °C for 2 h to obtain gray-black spinel powder. The spinel powder was then placed in a tube furnace, H2 was introduced, and it was reduced at 400 °C for 1 h with a heating and cooling rate of 5 °C / min to obtain a non-noble metal catalyst 0.25 Gly-Co / CoAl2O4 with surface-supported elemental substances.

[0091] The method for preparing hydrogenation products using the above-mentioned non-precious metal catalyst includes the following steps:

[0092] 0.1g of the catalyst was loaded into a reactor, along with 1g of furfural and 19g of ethanol. H2 was introduced, and the reaction was carried out at 150℃ and 1MPa for 5 hours. The furfural conversion and 2-methylfuran selectivity were as follows: Figure 1 As shown, from Figure 1 As can be seen, when the molar ratio of glycine:aluminum nitrate:cobalt acetate is 0.25:0.5:0.5, the furfural conversion rate is 91% and the 2-methylfuran yield is only 24%. Compared with Examples 1-5, the excessively low amount of glycine significantly reduces the catalytic performance of the catalyst.

[0093] Comparative Example 2

[0094] A non-precious metal catalyst for biomass hydrogenation reaction, the preparation method of the non-precious metal catalyst includes the following steps:

[0095] 2.813 g aluminum nitrate, 1.328 g cobalt acetate and 3.097 g glycine were dissolved in distilled water and stirred at 60 °C for 2 h to obtain a purple gel. The gel was placed in a muffle furnace at 200 °C for 2 h to obtain gray-black spinel powder. The spinel powder was then placed in a tube furnace, H2 was introduced, and it was reduced at 400 °C for 1 h with a heating and cooling rate of 5 °C / min to obtain a non-noble metal catalyst 2.75 Gly-Co / CoAl2O4 with surface-supported elemental substances.

[0096] The method for preparing hydrogenation products using the above-mentioned non-precious metal catalyst includes the following steps:

[0097] 0.1g of the catalyst was loaded into a reactor, along with 1g of furfural and 19g of ethanol. H2 was introduced, and the reaction was carried out at 150℃ and 1MPa for 5 hours. The furfural conversion and 2-methylfuran selectivity were as follows: Figure 1 As shown, from Figure 1 As can be seen, when the molar ratio of glycine:aluminum nitrate:cobalt acetate is 2.75:0.5:0.5, the furfural conversion rate is 100%, and the yield of 2-methylfuran decreases to 36%. Compared with Examples 1-5, excessively high glycine content will also significantly reduce the catalytic performance of the catalyst.

[0098] Furthermore, through comparative examples 1 and 2 and examples 1 to 5, it can be seen that the technical problem of the present invention can only be solved when the molar ratio of fuel A to metal salt B is 0.5 to 2.5:1, and only then can the prepared hydrogenated product achieve better performance.

[0099] Comparative Example 3

[0100] A non-precious metal catalyst for biomass hydrogenation reaction, the preparation method of the non-precious metal catalyst includes the following steps:

[0101] 3.376 g aluminum nitrate, 1.063 g cobalt acetate, and 1.689 g glycine were dissolved in distilled water and stirred at 60 °C for 2 h to obtain a purple gel. The gel was placed in a muffle furnace at 200 °C for 2 h to obtain a gray-black spinel powder. The spinel powder was then placed in a tube furnace, H2 was introduced, and it was reduced at 400 °C for 1 h with a heating and cooling rate of 5 °C / min to obtain a non-noble metal catalyst 0.4Co / 0.6Al-Co / CoAl2O4 with surface-supported elemental substances.

[0102] The method for preparing hydrogenation products using the above-mentioned non-precious metal catalyst includes the following steps:

[0103] 0.1g of the catalyst was loaded into a reactor, along with 1g of furfural and 19g of ethanol. H2 was introduced, and the reaction was carried out at 150℃ and 1MPa for 5 hours. The furfural conversion and 2-methylfuran selectivity were as follows: Figure 2 As shown, from Figure 2 As can be seen, when the molar ratio of glycine:aluminum nitrate:cobalt acetate is 1.5:0.6:0.4, the furfural conversion rate reaches 100%, and the 2-methylfuran yield is 38%, which is much lower than that in Example 3. That is, increasing the molar ratio of aluminum nitrate:cobalt acetate significantly reduces the catalytic performance of the catalyst.

[0104] Comparative Example 4

[0105] A non-precious metal catalyst for biomass hydrogenation reaction, the preparation method of the non-precious metal catalyst includes the following steps:

[0106] 2.250 g aluminum nitrate, 1.593 g cobalt acetate and 1.689 g glycine were dissolved in distilled water and stirred at 60 °C for 2 h to obtain a purple gel. The gel was placed in a muffle furnace at 200 °C for 2 h to obtain a gray-black spinel powder. The spinel powder was then placed in a tube furnace, H2 was introduced, and it was reduced at 400 °C for 1 h with a heating and cooling rate of 5 °C / min to obtain a non-noble metal catalyst 0.6Co / 0.4Al-Co / CoAl2O4 with surface-supported elemental substances.

[0107] The method for preparing hydrogenation products using the above-mentioned non-precious metal catalyst includes the following steps:

[0108] 0.1g of the catalyst was loaded into a reactor, along with 1g of furfural and 19g of ethanol. H2 was introduced, and the reaction was carried out at 150℃ and 1MPa for 5 hours. The furfural conversion and 2-methylfuran selectivity were as follows: Figure 2 As shown, from Figure 2 As can be seen, when the molar ratio of glycine:aluminum nitrate:cobalt acetate is 1.5:0.4:0.6, the furfural conversion rate reaches 100%, and the 2-methylfuran yield is 81.5%, which is also lower than that in Example 3. That is, reducing the molar ratio of aluminum nitrate:cobalt acetate will also reduce the catalytic performance of the catalyst.

[0109] Meanwhile, through Comparative Examples 3 and 4 and Example 3, it can also be seen that when the molar ratio of glycine:aluminum nitrate:cobalt acetate is 1.5:0.5:0.5 in this invention, glycine, aluminum nitrate, and cobalt acetate have a synergistic effect, which can synergistically improve the catalytic performance of the prepared non-precious metal catalyst and the relevant performance of the prepared hydrogenation product.

[0110] Furthermore, compared to the highly efficient catalysts reported in recent years, the catalyst prepared in this invention has higher production efficiency and can convert more biomass platform compounds at lower reaction temperatures, as shown in Table 1:

[0111] Table 1 summarizes the catalytic performance of catalysts reported for the hydrogenation of furfural to 2-methylfuran.

[0112]

[0113] References:

[0114] [1] M.G. Dohade, P.L. Dhepe, One pot conversion of furfural to 2-methylfuran in the presence of PtCo bimetallic catalyst, Clean Technologies and Environmental Policy, 20(2017) 703-713.

[0115] [2] X. Chang, A.F. Liu, B. Cai, J.Y. Luo, H. Pan, Y.B. Huang, Catalytic Transfer Hydrogenation of Furfural to 2-Methylfuran and 2-Methyltetrahydrofuran over Bimetallic Copper-Palladium Catalysts, ChemSusChem, 9(2016) 3330-3337.

[0116] [3] N.S. Date, A.M. Hengne, K.W. Huang, R.C. Chikate, C.V. Rode, Single pot selective hydrogenation of furfural to 2-methylfuran over carbon supported iridium catalysts, Green Chemistry, 20(2018) 2027-2037.

[0117] [4] B. Wang, C. Li, B. He, J. Qi, C. Liang, Highly stable and selective Ru / NiFe2O4 catalysts for transfer hydrogenation of biomass-derived furfural to 2-methylfuran, Journal of Energy Chemistry, 26(2017) 799-807.

[0118] [5]P.Panagiotopoulou,D.G.Vlachos,Liquid phase catalytic transferhydrogenation of furfural over a Ru / C catalyst,Applied Catalysis a-General,480(2014)17-24.

[0119] [6]K.Zhou,J.Chen,Y.Cheng,Z.Chen,S.Kang,Z.Cai,Y.Xu,J.Wei,EnhancedCatalytic Transfer Hydrogenation ofBiomass-Based Furfural into 2-Methylfuranover Multifunctional Cu-Re Bimetallic Catalysts,ACS Sustainable Chemistry&Engineering,8(2020)16624-16636.

[0120] [7]W.Liu,Y.Yang,L.Chen,E.Xu,J.Xu,S.Hong,X.Zhang,M.Wei,Atomically-ordered active sites in NiMo intermetallic compound toward low-pressurehydrodeoxygenation of furfural,Applied Catalysis B:Environmental,282(2021).

[0121] [8]S.Srivastava,G.C.Jadeja,J.Parikh,Copper-cobalt catalyzed liquidphase hydrogenation of furfural to 2-methylfuran:An optimization,kinetics andreaction mechanism study,Chemical Engineering Research&Design,132(2018)313-324.

[0122] [9]S.Srivastava,GCJadeja,J.Parikh,A versatile bi-metallic copper-cobalt catalyst for liquid phase hydrogenation offurfural to 2-methylfuran,RscAdvances,6(2016)1649-1658.

[0123]

[10] B. Seemala, CMCai, CEWyman, P. Christopher, Support Induced Control of Surface Composition in Cu–Ni / TiO2 Catalysts Enables High Yield Co-Conversion of HMF and Furfural to Methylated Furans, ACS Catalysis, 7 (2017) 4070-4082.

[0124]

[11]

[0125] Although embodiments of the invention have been disclosed for illustrative purposes, those skilled in the art will understand that various substitutions, variations, and modifications are possible without departing from the spirit and scope of the invention and the appended claims. Therefore, the scope of the invention is not limited to the contents disclosed in the embodiments.

Claims

1. A method for preparing hydrogenation products using a non-precious metal catalyst, characterized in that: Includes the following steps: 0.1g of the catalyst was loaded into a reaction vessel, 1g of furfural and 19g of ethanol were added, H2 was introduced, the reaction temperature was 150℃, the reaction pressure was 1MPa, and the reaction time was 5h. When the molar ratio of glycine:aluminum nitrate:cobalt acetate was 1.5:0.5:0.5, the furfural conversion rate reached 100% and the 2-methylfuran yield reached 97%, showing very high catalytic performance. The preparation method of the non-noble metal catalyst includes the following steps: 2.813 g aluminum nitrate, 1.328 g cobalt acetate and 1.689 g glycine were dissolved in distilled water and stirred at 60 °C for 2 h to obtain a purple gel. The gel was placed in a muffle furnace at 200 °C for 2 h to obtain gray-black spinel powder. The spinel powder was then placed in a tube furnace, H2 was introduced, and it was reduced at 400 °C for 1 h with a heating and cooling rate of 5 °C / min to obtain a non-noble metal catalyst 1.5 Gly-Co / CoAl2O4 with surface-supported elemental substances.

Images