Ordered mesoporous bimetallic solid acid catalyst, preparation method thereof and application of ordered mesoporous bimetallic solid acid catalyst in catalyzing GVL to prepare butene

Abstract

The invention relates to an ordered mesoporous bimetallic solid acid catalyst, a preparation method thereof and an application of the ordered mesoporous bimetallic solid acid catalyst in a reaction of efficiently catalyzing gamma-valerolactone decarboxylation to prepare butene. According to the invention, a triblock copolymer is used as a template agent, a hexagonal ordered mesoporous Nb-SBA-15 molecular sieve is prepared by a hydrothermal synthesis method, and on the basis, an aluminum species is introduced by an impregnation method to construct a bimetallic solid acid Al-Nb-SBA-15 catalyst with an ordered form. The surface of the series of catalysts has a large number of weak acid sites, 7wt% of the Al-Nb-SBA-15 catalyst shows the best catalytic activity, and the butene yield is about 93%. The catalyst provided by the invention is simple in preparation process, has excellent water resistance, and has good catalytic activity on a reaction for preparing butene from a gamma-valerolactone aqueous solution used in actual industrial production.

Description

Technical Field

[0001] The invention belongs to the technical field of catalytic conversion of biomass energy, and specifically relates to an ordered mesoporous bimetallic solid acid catalyst and a preparation method thereof, and application thereof in catalyzing the decarboxylation reaction of gamma-valerolactone to prepare butene. Background Art

[0002] Butene, as an important olefin compound, plays a vital role in both the chemical industry and the energy sector. The current fossil-based butene preparation technology faces the dual challenges of resource depletion and environmental pollution. Therefore, the development of efficient, clean and renewable new butene production processes has become a research hotspot. As a biomass platform compound, γ-valerolactone (GVL) has a high application value in the field of sustainable chemistry due to its unique chemical properties and wide sources. Cellulose and hemicellulose extracted from wood or agricultural waste can be easily hydrolyzed to levulinic acid, which is then hydrogenated to obtain γ-valerolactone. More importantly, GVL can be converted into butene by ring opening and decarboxylation using a specific solid acid catalyst.

[0003] In 2010, James A. Dumesic's group at the University of Wisconsin (Science, 2010, 327(5969): 1110-1114) first demonstrated a method for producing renewable fuels using biomass derivative γ-valerolactone (GVL) as a raw material through an efficient and economical catalytic conversion process. The research team used a low-cost SiO2 / Al2O3 catalyst to catalyze the decarboxylation reaction of γ-valerolactone aqueous solution at 375°C and 36 bar. The main products were separated by using the difference in boiling points of different gases in an oligomerization reactor composed of acid catalysts such as HZSM-5 and Amberlyst-70.

[0004] In 2014, Jesse Q. Bond et al. (Catalysis Science & Technology, 2014, 4: 2267-2279) studied the effect of catalyst characteristics on the yield of butene from the decarboxylation reaction of γ-valerolactone (GVL), especially emphasizing The key role of acid sites in the catalytic process. In the γ-Al2O3 and 5% PWA (phosphotungstic acid) catalyst with poor catalytic activity, the yield of butene was significantly improved by introducing additional 5% phosphotungstic acid.

[0005] In 2015, Zhang Suojiang et al. (Green Chemistry, 2015, 17(2): 1065-1070) used the sol-gel method to synthesize mesoporous SiO2 / Al2O3 for the first time to catalyze the decarboxylation of GVL to produce butene. The synthesized SiO2 / Al2O3 has a molecular weight of 398 m2 ·g -1 The specific surface area and pore size of 6.9nm have both Lewis acid sites and acid sites, and has 0.03mmol·g -1 At a reaction temperature of 350°C, a catalyst dosage of 5wt.% and a reaction time of 4h, the conversion rate of γ-valerolactone is above 99%, and the butene yield is as high as 97%.

[0006] In 2019, Lin et al. (Nature Chemistry Research, 2019, 19, 1-8) introduced niobium and aluminum into HZSM-5 molecular sieves to obtain an ideal Lewis acid and The acid-distributed catalyst NbAlS-1 allows 30% GVL aqueous solution to continuously pass through NbAlS-1 at 300°C and normal pressure to obtain 99% yield of butene. The incorporation of pentavalent niobium not only adjusts the acidity of the molecular sieve and increases the selectivity of butene, but also inhibits the occurrence of catalyst water poisoning, allowing the catalyst to maintain long-term catalytic activity.

[0007] In 2020, Ding et al. (Molecular Catalysis, 2020, 497: 111218) designed and synthesized an amorphous SiO2 / Al2O3 aluminum silicate catalyst with adjustable acidity. The catalyst achieved a selectivity of 97.5% for butene at a GVL conversion rate of 99.5% and maintained excellent stability for 50 hours. In addition, it was also studied that GVL can be converted into C5 + hydrocarbons, and the SiO2 / Al2O3 catalyst was combined with the nano-HZSM-5 catalyst to obtain 57.6% C5 + Good yield of hydrocarbons.

[0008] The applicant's research team has also conducted a series of studies on the design and synthesis of efficient catalysts with excellent pore structure, suitable acid amount and acid type, and good regeneration stability to catalyze the decarboxylation of GVL to butene. Based on mesoporous molecular sieve materials, we loaded different amounts of aluminum by grinding and impregnation methods to synthesize catalysts such as xwt% Al-SBA-15 (CN111203267 A), xwt% Al-KIT-6 (CN 114618559 A), and xwt% MCM-41 (CN 114797949 A).

[0009] In the present invention, we prepare a bimetallic solid acid catalyst by impregnation method based on ordered mesoporous molecular sieve Nb-SBA-15. By designing the catalyst structure, the catalyst reaction performance is optimized. This research invention not only helps to solve the technical problem of efficiently converting biomass platform compound GVL into butene, but also provides technical support for promoting the green conversion and utilization of biomass resources. Summary of the invention

[0010] In order to solve the problems of complex synthesis, high price, poor stability, poor structure, high reaction temperature, long reaction time, etc. of the existing catalyst for catalyzing the decarboxylation of biomass derivative γ-valerolactone to butene, the present invention provides a method for preparing an Al-Nb-SBA-15 catalyst with a short synthesis cycle, a simple preparation process, and being conducive to mass production. No inorganic acid is used in the synthesis process of the obtained catalyst, and it has excellent water resistance during the catalytic reaction process, has good catalytic activity for the reaction of γ-valerolactone aqueous solution to butene used in industrial production, and is suitable for being put into practical application.

[0011] To achieve the above objectives, the experimental scheme adopted by the present invention is: an ordered mesoporous bimetallic solid acid catalyst, the preparation method of which includes the following steps: dissolving a certain mass of an aluminum-containing compound in a solvent, adding a Nb-SBA-15 matrix to the solution after stirring at room temperature, continuing to stir for 4 hours, then heating and stirring, evaporating ethanol, and calcining at high temperature to obtain an Al-Nb-SBA-15 catalyst.

[0012] The preparation method of the above-mentioned ordered mesoporous bimetallic solid acid catalyst, Nb-SBA-15 matrix is ​​as follows: dissolving the template triblock copolymer P123 in a mixed solution of niobium pentachloride and deionized water, stirring in a 40°C water bath to obtain a colorless transparent solution; adding tetraethyl orthosilicate dropwise thereto, keeping the mixed solution at 40°C and stirring overnight; transferring the mixture to a stainless steel reactor lined with polytetrafluoroethylene for aging reaction; filtering and washing, and placing the block solid obtained after filtering in a 60°C oven to dry overnight, and finally calcining at high temperature to obtain the Nb-SBA-15 matrix.

[0013] The above-mentioned ordered mesoporous bimetallic solid acid catalyst, the aging reaction is an aging reaction at 100° C. for 24 hours.

[0014] The above-mentioned ordered mesoporous bimetallic solid acid catalyst is calcined at high temperature in a muffle furnace at 550°C for 5 hours at a heating rate of 1.8°C·min -1 .

[0015] The above-mentioned ordered mesoporous bimetallic solid acid catalyst contains aluminum compounds such as AlCl3, AlCl3·6H2O, Al(NO3)3·9H2O, Al2(SO4)3 and C9H 21 One or more of AlO3.

[0016] The solvent of the ordered mesoporous bimetallic solid acid catalyst is a mixture of one or more of methanol, ethanol, ether, acetone, carbon tetrachloride and water.

[0017] The ordered mesoporous bimetallic solid acid catalyst is fed according to the mass ratio of aluminum atom: Nb-SBA-15 matrix = 0.001 to 0.3:1.

[0018] The above-mentioned ordered mesoporous bimetallic solid acid catalyst, the heating and stirring is heating and stirring in a 60° C. water bath.

[0019] The above-mentioned ordered mesoporous bimetallic solid acid catalyst, the high-temperature calcination is high-temperature calcination at 550° C. for 5 hours.

[0020] The above-mentioned ordered mesoporous bimetallic solid acid catalyst, wherein the mass percentage of Al atoms in the ordered mesoporous bimetallic solid acid catalyst in the Nb-SBA-15 matrix is ​​0.1wt% to 30wt%; the pore size distribution of the catalyst is between 7 and 8nm, and the specific surface area is between 374 and 604m 2 ·g -1 The total pore volume is between 0.47 and 0.69 cm 3 ·g -1 between.

[0021] The ordered mesoporous bimetallic solid acid catalyst is used in catalyzing the decarboxylation of the biomass platform compound γ-valerolactone to produce butene.

[0022] The above application method is as follows: add γ-valerolactone and ordered mesoporous bimetallic solid acid catalyst into a high temperature and high pressure reactor, fill the reactor with nitrogen protection, and react at 280-320°C for 0.5-4h under normal pressure and stirring at a speed of 200-1000r / min.

[0023] The ordered mesoporous bimetallic solid acid catalyst prepared by any of the above preparation methods can be mixed with an industrial binder, extruded, dried, and calcined to maintain a powder state or be made into a conventional catalyst shape in the catalyst field to facilitate industrial application. The beneficial effects of the present invention are:

[0024] 1. The ordered mesoporous bimetallic solid acid catalyst provided by the present invention does not use inorganic acid in the synthesis process, which effectively solves the environmental problems and equipment corrosion problems that may be caused by the use of inorganic acid, and the preparation process is simple.

[0025] 2. The Al-Nb-SBA-15 catalyst prepared by the present invention is rich in surface solid acid sites, has excellent water resistance, has good catalytic activity for the reaction of γ-valerolactone aqueous solution to butene used in industrial production, and is suitable for practical application.

[0026] 3. The mass percentage of Al atoms in the ordered mesoporous bimetallic solid acid catalyst finally obtained by the present invention is 0.1wt% to 30wt% of the Nb-SBA-15 matrix; the pore size distribution of the catalyst is between 7 and 8nm, and the specific surface area is between 374 and 604m 2 ·g -1 The total pore volume is between 0.47 and 0.69 cm 3 ·g -1 between. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is a graph showing the change in the reaction activity of the catalyst obtained in Example 1 for catalyzing the production of butene from γ-valerolactone over time.

[0028] Figure 2 This is a graph showing the change in the reaction activity of the catalyst obtained in Example 1 for catalyzing the preparation of butene from γ-valerolactone as a function of temperature.

[0029] Figure 3 This is a graph showing the change in the reaction activity of the catalyst obtained in Example 1 for catalyzing the preparation of butene from γ-valerolactone as a function of the amount of catalyst used.

[0030] Figure 4 These are transmission electron micrographs of the Nb-SBA-15 (a, b) matrix and the 7 wt% Al-Nb-SBA-15 (c, d) catalyst obtained in Example 1.

[0031] Figure 5 1 is a nitrogen adsorption-desorption curve (a) and a pore size distribution diagram (b) of the catalyst obtained in Example 1. DETAILED DESCRIPTION

[0032] Example 1 Preparation of ordered mesoporous bimetallic solid acid catalyst S (1)

[0033] 1) Preparation of Nb-SBA-15 matrix: 4 g of the template triblock copolymer P123 was dissolved in a mixed solution of 0.6556 g of niobium pentachloride and 126 ml of deionized water, and stirred in a water bath at 40°C to obtain a colorless transparent solution; 9.1 ml of tetraethyl orthosilicate was added dropwise thereto, and the mixed solution was kept at 40°C and stirred overnight; the mixture was transferred to a stainless steel reactor lined with polytetrafluoroethylene, and aged at 100°C for 24 h; the product in the reactor was transferred to a Buchner funnel for suction filtration and washing, and the block solid obtained after suction filtration was placed in a 60°C oven for drying overnight, and finally calcined at 550°C in a muffle furnace for 5 h, with a heating rate of 1.8°C·min -1 , and obtain Nb-SBA-15 matrix;

[0034] 2) Preparation of Al-Nb-SBA-15 catalyst: 0.1037 g of anhydrous aluminum chloride was dissolved in 4.2 mL of anhydrous ethanol, and 0.3 g of Nb-SBA-15 matrix was added to the solution after magnetic stirring at room temperature for 2 h. The solution was stirred for 4 h, and then heated and stirred in a 60°C water bath. The ethanol was evaporated and finally calcined at 550°C for 5 h to obtain a 7 wt% Al-Nb-SBA-15 catalyst synthesized by an impregnation method, marked as S(1), in which the mass fraction of Al atoms in the matrix Nb-SBA-15 was 7 wt%.

[0035] Example 2 Preparation of ordered mesoporous bimetallic solid acid catalyst S (2)

[0036] The method is the same as that described in Example 1, but 0.0148 g AlCl3 is used instead of 0.1037 g AlCl3 in Example 1 to obtain a 1 wt% Al-Nb-SBA-15 catalyst, labeled S(2), wherein the mass fraction of Al atoms in the matrix Nb-SBA-15 is 1 wt%.

[0037] Example 3 Preparation of ordered mesoporous bimetallic solid acid catalyst S (3)

[0038] The method is the same as that described in Example 1, but 0.0444 g AlCl3 is used instead of 0.1037 g AlCl3 in Example 1 to obtain a 3 wt% Al-Nb-SBA-15 catalyst, labeled S(3), wherein the mass fraction of Al atoms in the matrix Nb-SBA-15 is 3 wt%.

[0039] Example 4 Preparation of Ordered Mesoporous Bimetallic Solid Acid Catalyst S (4)

[0040] The method is the same as that described in Example 1, but 0.0741 g AlCl3 is used instead of 0.1037 g AlCl3 in Example 1 to obtain a 5 wt% Al-Nb-SBA-15 catalyst, labeled S(4), wherein the mass fraction of Al atoms in the matrix Nb-SBA-15 is 5 wt%.

[0041] Example 5 Preparation of ordered mesoporous bimetallic solid acid catalyst S (5)

[0042] The method is the same as that described in Example 1, but 0.1333 g AlCl3 is used instead of 0.1037 g AlCl3 in Example 1 to obtain a 9 wt% Al-Nb-SBA-15 catalyst, labeled as S (5), wherein the mass fraction of Al atoms in the matrix Nb-SBA-15 is 9 wt%. Comparative Example 1 Preparation of Solid Acid Catalyst B (1) for Catalyzing the Decarboxylation of γ-Valerolactone to Butene

[0043] The method is the same as that described in Example 1, but without adding AlCl3, to obtain catalyst B(1), in which the mass fraction of Al atoms in the matrix Nb-SBA-15 is 0wt%.

[0044] Comparative Example 2 Preparation of Solid Acid Catalyst B (2) for Catalyzing the Decarboxylation of γ-Valerolactone to Butene

[0045] The method is the same as that described in Example 1, but without adding NbCl5, to obtain B(2) catalyst, in which the mass fraction of Al atoms in the matrix is ​​7wt%.

[0046] Example 6 Determination of the activity of the prepared catalyst in catalyzing the decarboxylation of γ-valerolactone to butene

[0047] A mixture of 1g of γ-valerolactone (GVL), 0.6g of GVL and 0.4g of H2O (60wt% GVL) and 0.04g, 0.06g, 0.08g, 0.1g and 0.12g of the prepared catalyst were added to a 100mL high temperature and high pressure reactor. After the reactor was filled with nitrogen for protection, the reaction was carried out at 280°C, 290°C, 300°C, 310°C, 320°C and 700r / min stirring at normal pressure for 1h, 1.5h, 2h, 2.5h, 3h and 4h. After the reaction was completed, the reactor was put into cold water for rapid cooling. After the temperature of the reaction system dropped to room temperature, the gaseous products generated by the reaction were collected with an aluminum foil gas collection bag and reserved for gas chromatography / gas chromatography-mass spectrometry analysis. The yield of butene was calculated.

[0048] The reaction system is a closed system, and the mass is conserved before and after the reaction. According to the law of conservation of mass, the yield of butene can be calculated by the following formula:

[0049]

[0050] This is the calculation formula for butene yield, where butene yield is expressed as Y (C4) Indicated by, m0 is the total mass of γ-valerolactone initially put into the system, and m1 is the total mass of the remaining liquid in the system after the gas is released. The gas released in the system is composed of equal amounts of butene and carbon dioxide.

[0051] Example 7 Comparison of the activity of different catalysts in the decarboxylation of γ-valerolactone to butene

[0052] The performance of the catalysts obtained in Examples 1-5 and Comparative Example 1 was measured respectively. 6 portions of 1g of γ-valerolactone and 0.1g of the catalysts obtained in Examples 1-5 and Comparative Example 1 were added to a 100mL high temperature and high pressure reactor, and the reactor was filled with nitrogen for protection, and then reacted at 300°C and 700r / min at normal pressure for 1.5h. After the reaction was completed, the reactor was put into cold water for rapid cooling, and after the temperature of the reaction system dropped to room temperature, the gaseous products generated by the reaction were collected with an aluminum foil gas collection bag and reserved for gas chromatography / gas chromatography-mass spectrometry analysis; the butene yield was calculated, and the relevant results are listed in Table 1.

[0053] Table 1 The yield of butene obtained by the catalyst prepared in Examples 1-5 and Comparative Example 1 at 300°C and 700 r / min after 1.5 h of reaction

[0054]

[0055]

[0056] As can be seen from Table 1, under the same reaction temperature, initial pressure, rotation speed and reaction time, by comparing catalysts S(1)-S(5), it can be found that when the aluminum source and solvent are the same, with the increase of Al content in the catalyst, the butene yield first increases and then decreases, among which catalyst S(1) has the highest catalytic activity.

[0057] Example 8 Determination of the activity of the catalyst prepared in Example 1 for catalyzing the production of butene from GVL as a function of reaction time

[0058] The catalytic performance of the catalyst obtained in Example 1 at different reaction times was measured. Six portions of a mixture of 0.6 g GVL and 0.4 g H2O (60 wt% GVL) and 0.1 g of the catalyst obtained in Example 1 were added to a 100 mL high temperature and high pressure reactor. After nitrogen was filled into the reactor for protection, the reactor was reacted at 300°C and 700 r / min at normal pressure for 1 h, 1.5 h, 2 h, 2.5 h, 3 h, and 4 h. The measured butene yields were as follows: Figure 1As shown. From the relationship diagram of the change of butene yield over time in the process of catalyzing the γ-valerolactone to butene reaction of 7wt% Al-Nb-SBA-15 catalyst, it can be seen that when the reaction time is 60min, the butene yield can reach 81.36%, and when the reaction time increases to 120min, the butene yield can reach 92.75%. When the reaction time continues to increase, the degree of improvement in butene yield is not large. The results show that the catalyst obtained in Example 1 has outstanding performance and can obtain a high butene yield in a relatively short time, and has great application potential in catalyzing γ-valerolactone to butene.

[0059] Example 9 Determination of the activity of the catalyst prepared in Example 1 for catalyzing the production of butene from GVL as a function of reaction temperature

[0060] The yield of butene when the catalyst prepared in Example 1 catalyzed GVL at different reaction temperatures was measured. Six portions of a mixture of 0.6 g GVL and 0.4 g H2O (60 wt% GVL) were added to a 100 mL high temperature and high pressure reactor with 0.1 g of the catalyst obtained in Example 1. After nitrogen was filled into the reactor for protection, the reactor was reacted at normal pressure, 700 r / min, and the temperatures were 280°C, 290°C, 300°C, 310°C, and 320°C, respectively, for 2 h. The results are as follows: Figure 2 As shown. With the increase of reaction temperature, the butene yield shows a trend of gradual increase. At a lower temperature of 280℃, the butene yield is 88.79%. When the temperature rises to 300℃, the butene yield has reached 92.75%. As the reaction temperature continues to increase, the reactant conversion in the system is almost complete. The results show that temperature has a great influence on the catalytic reaction of γ-valerolactone to butene, and only under suitable temperature conditions can the catalyst activity be maximized.

[0061] Example 10 Determination of the activity of the catalyst prepared in Example 1 for catalyzing the preparation of butene from GVL as a function of the amount of catalyst used

[0062] 0.04g, 0.06g, 0.08g, 0.1g, 0.12g of the catalyst prepared in Example 1 were added to a mixture of 6 parts of 0.6g GVL and 0.4g H2O (60wt% GVL) in a 100mL high temperature and high pressure reactor. After nitrogen was filled into the reactor for protection, the reaction was carried out at normal pressure, 300°C and 700r / min for 2h. The results are as follows: Figure 3As shown. When 6wt.% of the total amount of reactants was added to the reaction system, the butene yield was only 78.09%. As the amount of catalyst added increased to 8wt.%, a butene yield of 92.32% could be obtained, and as the amount of catalyst continued to increase, the butene yield showed a slow growth trend with a small change range. The results show that the catalyst obtained in Example 1 can ensure production efficiency, reduce reaction costs, and reduce economic investment when used in a small amount, and is suitable for actual industrial production.

[0063] Example 11 Transmission electron microscopy images of the catalysts obtained in Example 1 and Comparative Example 1

[0064] The catalysts S(1) and B(1) obtained in Example 1 and Comparative Example 1 were selected for transmission electron microscopy (TEM) characterization. Figure 4 As shown. Figure 4 (a)(b) It can be seen that the Nb-SBA-15 matrix prepared with tetraethyl orthosilicate TEOS as the silicon source has a long-range ordered two-dimensional hexagonal (P6mm) pore structure with uniform pore size distribution. 7wt% Al-Nb-SBA-15 ( Figure 4 (c)(d)) retain the mesoporous channel structure similar to that of the Nb-SBA-15 support, and there are no obvious aggregates in the pores, which indicates that the Al species introduced by impregnation did not cause blockage of the pores.

[0065] Example 12 Nitrogen adsorption and desorption analysis of the catalysts obtained in Example 1 and Comparative Example 1

[0066] The catalysts S(1) and B(1) obtained in Example 1 and Comparative Example 1 were characterized by nitrogen adsorption-desorption to obtain N2 adsorption-desorption isotherms and pore size distributions, as shown in FIG. Figure 5 As shown. Figure 5 It can be found in (a) that the IV type isotherm unique to mesoporous molecular sieves can be observed for all samples, and an H1 type hysteresis loop is shown, which is a typical feature of mesoporous solids. And at P / P0=0.5-0.8, a sharp increase in the adsorption of N2 can be observed, which is caused by the capillary condensation effect of N2 in the pores. At the same time, according to the adsorption branch calculation of the N2 isotherm, the BET specific surface area of ​​Nb-SBA-15 is 603.911m 2 ·g -1 When Al species are impregnated onto the support, the mesoporous structure performance is reduced. The specific surface area of ​​7wt% Al-Nb-SBA-15 is reduced to 379.392 m 2 ·g -1 . Figure 4The pore size distribution diagram shown in (b) shows that the introduction of Al changes the pore size of the catalyst to a small extent, only changing from the original 7.822 nm to 7.848 nm. The results again reflect that the catalyst obtained in Example 1 retains the highly ordered mesoporous structure of the Nb-SBA-15 carrier.

Claims

1. An ordered mesoporous bimetallic solid acid catalyst, characterized in that: The preparation method comprises the following steps: dissolving a certain mass of an aluminum-containing compound in a solvent, adding a Nb-SBA-15 matrix to the solution after stirring at room temperature, continuing stirring for 4 hours, then heating and stirring, evaporating ethanol, and calcining at high temperature to obtain an Al-Nb-SBA-15 catalyst.

2. An ordered mesoporous bimetallic solid acid catalyst according to claim 1, characterized in that: The preparation method of the Nb-SBA-15 matrix is ​​as follows: dissolving the template triblock copolymer P123 in a mixed solution of niobium pentachloride and deionized water, stirring in a water bath at 40°C to obtain a colorless and transparent solution; adding tetraethyl orthosilicate dropwise thereto, and stirring the mixed solution at 40°C overnight; transferring the mixture to a stainless steel reactor lined with polytetrafluoroethylene for aging reaction; filtering and washing, and placing the block solid obtained after filtering in an oven at 60°C for drying overnight, and finally calcining at high temperature to obtain the Nb-SBA-15 matrix.

3. An ordered mesoporous bimetallic solid acid catalyst according to claim 2, characterized in that: The aging reaction is carried out at 100° C. for 24 hours.

4. The ordered mesoporous bimetallic solid acid catalyst according to claim 2, characterized in that: The high temperature calcination is carried out in a muffle furnace at 550°C for 5 hours, with a heating rate of 1.8°C·min -1 .

5. The ordered mesoporous bimetallic solid acid catalyst according to claim 1, characterized in that: Aluminum compounds are AlCl3, AlCl3·6H2O, Al(NO3)3·9H2O, Al2(SO4)3 and C9H 21 One or more of AlO3.

6. The ordered mesoporous bimetallic solid acid catalyst according to claim 1, characterized in that: The solvent is a mixture of one or more of methanol, ethanol, ether, acetone, carbon tetrachloride and water.

7. The ordered mesoporous bimetallic solid acid catalyst according to claim 1, characterized in that: The materials are added according to the mass ratio of aluminum atom: Nb-SBA-15 matrix = 0.001 to 0.3:

1.

8. The ordered mesoporous bimetallic solid acid catalyst according to claim 1, characterized in that: The heating and stirring is carried out in a 60° C. water bath.

9. The ordered mesoporous bimetallic solid acid catalyst according to claim 1, characterized in that: The high temperature calcination is carried out at 550° C. for 5 hours.

10. Use of the ordered mesoporous bimetallic solid acid catalyst according to any one of claims 1 to 9 in catalyzing the decarboxylation of the biomass platform compound γ-valerolactone to produce butene.

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