Catalytic transfer hydrogenation catalyst based on rubber sludge as well as preparation method and application of catalytic transfer hydrogenation catalyst
By using rubber sludge to prepare catalytic metastatic hydrogenation catalysts, the problem of low γ-pentaurone conversion efficiency in biomass resources, and realized low-cost, green environmental protection catalyst preparation and high-efficiency catalytic reactions.
Patent Information
- Application Number
- CN202411542511.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-31
- Publication Date
- 2025-01-24
AI Technical Summary
The prior art is difficult to efficiently use biomass resources to convert γ-valerolactone efficiently, and the preparation process of the catalyst is complex and costly.
Rubber sludge is used as raw material, and a catalytic transfer hydrogenation catalyst is prepared through pretreatment and calcination steps, which is used to catalytically reduce biomass platform molecules such as alkyl levulinate to prepare γ-valerolactone.
Realize the preparation of catalysts with low -cost, solvents, non -solvents, and metal -free salt, improve the catalytic reducing activity, simplify the preparation process, and green and environmentally friendly.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of natural fragrances, and in particular relates to a rubber sludge-based catalytic transfer hydrogenation catalyst and a preparation method and application thereof. Background Art
[0002] With the large-scale exploitation of fossil resources around the world, environmental problems such as climate warming and acid rain are becoming increasingly severe, and the global energy structure has to face an unprecedented change. As the only renewable carbon resource on the earth, biomass resources not only have the advantages of low pollution, wide distribution and abundant total amount, but also have unique advantages in the recycling of waste resources and the production of biofuels and high-value chemicals compared with other renewable resources. Among them, γ-valerolactone, as a multifunctional biomass-derived platform molecule, shows great potential and important application value in the production of liquid fuels and chemicals. Due to its excellent physical and chemical properties, γ-valerolactone is not only known as one of the most promising biomass platform compounds, but also regarded as a high-quality organic solvent due to its green and environmentally friendly characteristics. Therefore, the development of high-performance and economical catalysts to convert different biomass raw materials into γ-valerolactone has become a hot topic in the field of biomass utilization research. Summary of the invention
[0003] The first purpose of the present invention is to provide a catalyst based on rubber sludge catalytic transfer hydrogenation; the second purpose is to provide a method for preparing the catalyst based on rubber sludge catalytic transfer hydrogenation; the third purpose is to provide an application of the catalyst based on rubber sludge catalytic transfer hydrogenation.
[0004] The first object of the present invention is achieved in that the rubber sludge-based catalytic transfer hydrogenation catalyst is prepared by using rubber sludge, a main by-product of the wastewater treatment stage of a rubber plant, as a raw material through pretreatment and calcination.
[0005] The second object of the present invention is achieved by comprising pre-treatment and calcination steps, specifically comprising: A. Pre-treatment: 1) The rubber sludge from the rubber factory sewage stage is air-dried to a moisture content of 10-12% to obtain material a; 2) Grind material a through a 40-mesh sieve to obtain material b; B. Calcination: Calcinate material b to obtain the target rubber sludge-based catalytic transfer hydrogenation catalyst.
[0006] The third object of the present invention is achieved by using the rubber sludge-based catalytic transfer hydrogenation catalyst in the catalytic reduction transfer hydrogenation of methyl levulinate to prepare γ-valerolactone.
[0007] The specific preparation steps are as follows: The alkyl levulinate and the solvent are mixed and placed in a reaction container, the aforementioned catalytic transfer hydrogenation catalyst based on rubber sludge is added, and the reaction is carried out with isopropanol as a hydrogen donor. After the reaction, γ-valerolactone is obtained. The temperature of the above reaction is 160-210° C., the time is 1-10 hours, the concentration of the alkyl levulinate in the solvent is 1.2wt%, and the mass ratio of the catalyst to methyl levulinate is (0.81~4.84):1.
[0008] In a preferred embodiment of the present invention, the reaction temperature is 160-210° C., the reaction time is 1-10 h, the solvent is 10 ml, the concentration of alkyl levulinate in the solvent is 1.2 wt %, and the mass ratio of the catalyst to the alkyl levulinate is 0.81-4.84:1.
[0009] In a preferred embodiment of the present invention, the alkyl levulinate used is one of methyl levulinate, ethyl levulinate, propyl levulinate or butyl levulinate.
[0010] In a preferred embodiment of the present invention, the hydrogen donor includes but is not limited to at least one of ethanol, n-propanol, isopropanol, n-butanol and sec-butanol.
[0011] The application of the rubber sludge catalytic transfer hydrogenation catalyst in the catalytic reduction biomass platform molecular transfer hydrogenation to prepare γ-valerolactone specifically includes pre-treatment and main reaction steps, specifically including: A. Pretreatment: mixing the biomass platform molecule and the solvent to adjust the mass percentage concentration of the biomass platform molecule in the solvent to 0.8-2.0% to obtain material d, wherein the biomass platform molecule is ethyl levulinate, propyl levulinate, butyl levulinate, levulinic acid, furfural or furfuryl alcohol; B. Main reaction: Place material d in a reaction vessel, add the rubber catalytic transfer hydrogenation catalyst, and react at a temperature of 180-220° C. for 8-12 hours to obtain the target product γ-valerolactone; The mass ratio of the rubber-based catalytic transfer hydrogenation catalyst and the biomass platform molecule is (1.74~3.06):1.
[0012] The application of the rubber sludge-based catalytic transfer hydrogenation catalyst in catalytic reduction of 5-hydroxymethylfurfural transfer hydrogenation to prepare 2,5-dihydroxymethylfuran is specifically to mix 5-hydroxymethylfurfural and a solvent and place them in a reaction container, add the rubber sludge-based catalytic transfer hydrogenation catalyst, react at a temperature of 180-220°C for 8-12 hours to obtain 2,5-dihydroxymethylfuran; the solvent is isopropanol, the concentration of the 5-hydroxymethylfurfural in the solvent is 1.0-1.5wt%, and the mass ratio of the rubber sludge-based catalytic transfer hydrogenation catalyst to 5-hydroxymethylfurfural is (2-3):1.
[0013] The application of the rubber sludge-based catalytic transfer hydrogenation catalyst in catalytic reduction of vanillin and transfer hydrogenation to prepare vanillin alcohol is specifically to mix vanillin and a solvent and place them in a reaction container, add the rubber sludge-based catalytic transfer hydrogenation catalyst, and react at a temperature of 150-250°C for 8-12 hours to obtain vanillin alcohol; the solvent is isopropanol, the concentration of vanillin in the solvent is 1.0-2.0wt%, and the mass ratio of the rubber sludge-based catalytic transfer hydrogenation catalyst and vanillin is (1.5-2.5):1.
[0014] Compared with the background technology, this technical solution has the following advantages: 1. The catalyst prepared by the present invention utilizes rubber sludge to prepare a catalytic transfer hydrogenation catalyst, which effectively reduces alkyl levulinate to prepare γ-valerolactone.
[0015] 2. The present invention provides a low-cost, solvent-free, metal salt-free method for preparing a catalytic transfer hydrogenation catalyst. The preparation process is a metal salt-free, solvent-free preparation process, and the preparation process is simple, green and environmentally friendly, and easy to prepare on a large scale. In this method, the desired catalyst can be obtained by simple grinding and calcination, and the selection of different calcination temperatures during the calcination process can effectively regulate the ratio and number of Bronsted acid sites and Lewis acid sites in the catalyst, thereby greatly improving the catalytic reduction activity of the catalyst.
[0016] The present invention uses a low-cost, solvent-free, metal salt-free method to prepare a catalytic transfer hydrogenation catalyst. The preparation process does not require the use of solvents, metal salts, and other expensive and polluting chemical reagents, and is an economical and environmentally friendly catalyst preparation process. The prepared catalytic transfer hydrogenation catalyst has a high catalytic efficiency and can catalytically reduce alkyl levulinate to prepare gamma-valerolactone under certain reaction conditions. DETAILED DESCRIPTION
[0017] The present invention is further described below in conjunction with the embodiments, but the present invention is not limited in any way. Any changes or substitutions made based on the teachings of the present invention belong to the protection scope of the present invention.
[0018] The rubber sludge catalytic transfer hydrogenation catalyst of the present invention is prepared by taking rubber sludge, a main byproduct of the wastewater treatment stage of a rubber plant, as a raw material through pretreatment and calcination.
[0019] The preparation method of the rubber sludge catalytic transfer hydrogenation catalyst according to the invention includes pretreatment and calcination steps, specifically comprising: A. Pre-treatment: 1) The rubber sludge from the rubber factory sewage stage is air-dried to a moisture content of 10-12% to obtain material a; 2) Grind material a through a 40-mesh sieve to obtain material b; B. Calcination: Calcinate material b to obtain the target rubber sludge-based catalytic transfer hydrogenation catalyst.
[0020] The calcination temperature in step B is 100-600° C. and the calcination time is 1-4 hours.
[0021] The calcination is carried out in an air atmosphere.
[0022] The application of the rubber-based catalytic transfer hydrogenation catalyst of the present invention is the application of the rubber sludge-based catalytic transfer hydrogenation catalyst in the catalytic reduction transfer hydrogenation of methyl levulinate to prepare γ-valerolactone.
[0023] The catalytic reduction of methyl levulinate and transfer hydrogenation to prepare γ-valerolactone includes pre-treatment and main reaction steps, specifically including: A. Pretreatment: Mix methyl levulinate and a solvent to adjust the mass percentage concentration of methyl levulinate in the solvent to 1-1.5% to obtain material c, wherein the solvent is ethanol, n-propanol, isopropanol or sec-butanol; B. Main reaction: Place material c in a reaction vessel, add the rubber-based catalytic transfer hydrogenation catalyst, and react at a temperature of 160-210° C. for 1-10 hours to obtain the target γ-valerolactone; The mass ratio of the rubber-based catalytic transfer hydrogenation catalyst and methyl levulinate is (0.81-4.84):1.
[0024] The application of the rubber catalytic transfer hydrogenation catalyst described in the present invention is the application of the rubber sludge catalytic transfer hydrogenation catalyst in the catalytic reduction biomass platform molecular transfer hydrogenation to prepare γ-valerolactone, which specifically includes pretreatment and main reaction steps, specifically including: A. Pretreatment: mixing the biomass platform molecule and the solvent to adjust the mass percentage concentration of the biomass platform molecule in the solvent to 0.8-2.0% to obtain material d, wherein the biomass platform molecule is ethyl levulinate, propyl levulinate, butyl levulinate, levulinic acid, furfural or furfuryl alcohol; B. Main reaction: Place material d in a reaction vessel, add the rubber catalytic transfer hydrogenation catalyst, and react at a temperature of 180-220° C. for 8-12 hours to obtain the target product γ-valerolactone; The mass ratio of the rubber-based catalytic transfer hydrogenation catalyst and the biomass platform molecule is (1.74~3.06):1.
[0025] The application of the rubber-based catalytic transfer hydrogenation catalyst of the present invention is the application of the rubber sludge-based catalytic transfer hydrogenation catalyst in the catalytic reduction of 5-hydroxymethylfurfural transfer hydrogenation to prepare 2,5-dihydroxymethylfuran. Specifically, 5-hydroxymethylfurfural and a solvent are mixed and placed in a reaction container, and the rubber sludge-based catalytic transfer hydrogenation catalyst is added. The reaction is carried out at a temperature of 180-220° C. for 8-12 hours to obtain 2,5-dihydroxymethylfuran; the solvent is isopropanol, the concentration of the 5-hydroxymethylfurfural in the solvent is 1.0-1.5wt%, and the mass ratio of the rubber sludge-based catalytic transfer hydrogenation catalyst to 5-hydroxymethylfurfural is (2-3):1.
[0026] The application of the rubber-based catalytic transfer hydrogenation catalyst of the present invention is the application of the rubber sludge-based catalytic transfer hydrogenation catalyst in catalytic reduction of vanillin and transfer hydrogenation to prepare vanillin alcohol. Specifically, vanillin and a solvent are mixed and placed in a reaction container, and the rubber sludge-based catalytic transfer hydrogenation catalyst is added. The temperature is 150-250°C and the reaction is carried out for 8-12 hours to obtain vanillin alcohol. The solvent is isopropanol, the concentration of vanillin in the solvent is 1.0-2.0wt%, and the mass ratio of the rubber sludge-based catalytic transfer hydrogenation catalyst to vanillin is (1.5-2.5):1.
[0027] The present invention is further described below with specific implementation cases: Example 1 Preparation of catalytic transfer hydrogenation catalyst based on rubber sludge: The rubber sludge with a moisture content of 10-12% after air drying is ground and passed through a 40-mesh steel sieve. The obtained powder is calcined at 100°C for 2 hours in an air atmosphere to obtain a rubber sludge catalyst calcined at 100°C.
[0028] Reduction reaction process of methyl levulinate: 1 mmol methyl levulinate and 10 ml isopropanol were added to a 25 mL autoclave, and then 0.3 g of the rubber sludge calcined at 100 ° C was added as a catalyst; after sealing the reactor, the reaction was heated to 180 ° C under vigorous stirring (600 rpm) and maintained for 10 hours to terminate the reaction. Agilent 7820 gas chromatograph was used for qualitative and quantitative detection, and the test results are listed in Table 1, serial number 1.
[0029] Example 2 Preparation of catalytic transfer hydrogenation catalyst based on rubber sludge: The rubber sludge with a moisture content of 10-12% after air drying is ground and passed through a 40-mesh steel sieve. The obtained powder is calcined at 200°C for 2 hours in an air atmosphere to obtain a rubber sludge catalyst calcined at 200°C.
[0030] The reduction reaction process of methyl levulinate was the same as that of Example 1, except that the catalyst of Example 1 was replaced by the catalyst of this invention. Qualitative and quantitative detection was performed using an Agilent 7820 gas chromatograph, and the detection results are listed in Table 1, with the serial number being 2.
[0031] Example 3 Preparation of catalytic transfer hydrogenation catalyst based on rubber sludge: The rubber sludge with a moisture content of 10-12% after air drying is ground and passed through a 40-mesh steel sieve. The obtained powder is calcined at 300°C for 2 hours in an air atmosphere to obtain a rubber sludge catalyst calcined at 300°C.
[0032] The reduction reaction process of methyl levulinate was the same as that of Example 1, except that the catalyst of Example 1 was replaced by the catalyst of this invention. Qualitative and quantitative detection was performed using an Agilent 7820 gas chromatograph, and the detection results are listed in Table 1, with serial number 3.
[0033] Example 4 Preparation of catalytic transfer hydrogenation catalyst based on rubber sludge: Rubber sludge with a moisture content of 10-12% after air drying is ground and passed through a 40-mesh steel sieve. The obtained powder is calcined at 400°C for 2 hours in an air atmosphere to obtain a rubber sludge catalyst calcined at 400°C.
[0034] The reduction reaction process of methyl levulinate was the same as that of Example 1, except that the catalyst of Example 1 was replaced by the catalyst of this invention. Qualitative and quantitative detection was performed using an Agilent 7820 gas chromatograph, and the detection results are listed in Table 1, with serial number 4.
[0035] Example 5 Preparation of catalytic transfer hydrogenation catalyst based on rubber sludge: The rubber sludge with a moisture content of 10-12% after air drying is ground and passed through a 40-mesh steel sieve. The obtained powder is calcined at 500°C for 2 hours in an air atmosphere to obtain a rubber sludge catalyst calcined at 500°C.
[0036] The reduction reaction process of methyl levulinate was the same as that of Example 1, except that the catalyst of Example 1 was replaced by the catalyst of this invention. Qualitative and quantitative detection was performed using an Agilent 7820 gas chromatograph, and the detection results are listed in Table 1, with serial number 5.
[0037] Example 6 Preparation of catalytic transfer hydrogenation catalyst based on rubber sludge: The rubber sludge with a moisture content of 10-12% after air drying was ground and passed through a 40-mesh steel sieve. The obtained powder was calcined at 600°C for 2 hours in an air atmosphere to obtain a rubber sludge catalyst calcined at 600°C.
[0038] The reduction reaction process of methyl levulinate was the same as that of Example 1, except that the catalyst of Example 1 was replaced by the catalyst of this invention. Qualitative and quantitative detection was performed using an Agilent 7820 gas chromatograph, and the detection results are listed in Table 1, with serial number 6.
[0039] Example 7 Preparation of catalytic transfer hydrogenation catalyst based on rubber sludge: The rubber sludge with a moisture content of 10-12% after air drying was ground and passed through a 40-mesh steel sieve. The obtained powder was calcined at 400°C for 1 hour in an air atmosphere to obtain a rubber sludge catalyst calcined at 400°C for 1 hour.
[0040] The reduction reaction process of methyl levulinate was the same as that of Example 1, except that the catalyst of Example 1 was replaced by the catalyst of this invention. Qualitative and quantitative detection was performed using an Agilent 7820 gas chromatograph, and the detection results are listed in Table 1, with serial number 7.
[0041] Example 8 Preparation of catalytic transfer hydrogenation catalyst based on rubber sludge: The rubber sludge with a moisture content of 10-12% after air drying was ground and passed through a 40-mesh steel sieve. The obtained powder was calcined at 400°C for 3 hours in an air atmosphere to obtain a rubber sludge catalyst calcined at 400°C for 3 hours.
[0042] The reduction reaction process of methyl levulinate was the same as that of Example 1, except that the catalyst of Example 1 was replaced by the catalyst of this invention. Qualitative and quantitative detection was performed using an Agilent 7820 gas chromatograph, and the detection results are listed in Table 1, with serial number 8.
[0043] Example 9 Preparation of catalytic transfer hydrogenation catalyst based on rubber sludge: The rubber sludge with a moisture content of 10-12% after air drying was ground and passed through a 40-mesh steel sieve. The obtained powder was calcined at 400°C for 4 hours in an air atmosphere to obtain a rubber sludge catalyst calcined at 400°C for 4 hours.
[0044] The reduction reaction process of methyl levulinate was the same as that of Example 1, except that the catalyst of Example 1 was replaced by the catalyst of this invention. Qualitative and quantitative detection was performed using an Agilent 7820 gas chromatograph, and the detection results are listed in Table 1, with serial number 9.
[0045] Example 10 To a 25 mL autoclave, 1 mmol of methyl levulinate and 10 ml of isopropanol were added, and then the rubber sludge (0.3 g) calcined at 400 ° C prepared in Example 4 was added as a catalyst. The reactor was sealed, stirred vigorously (600 rpm), heated to 160 ° C and maintained for 10 hours. After the reaction was terminated, it was cooled to room temperature and sampled. Agilent 7820 gas chromatograph was used for qualitative and quantitative detection. The test results are listed in Table 1 with serial number 10.
[0046] Embodiment 11 To a 25 mL autoclave, 1 mmol of methyl levulinate and 10 ml of isopropanol were added, and then the rubber sludge (0.3 g) calcined at 400 ° C prepared in Example 4 was added as a catalyst. The reactor was sealed, stirred vigorously (600 rpm), heated to 170 ° C and maintained for 10 hours. After the reaction was terminated, it was cooled to room temperature and sampled. Agilent 7820 gas chromatograph was used for qualitative and quantitative detection. The test results are listed in Table 1 with serial number 8.
[0047] Example 12 To a 25 mL autoclave, 1 mmol of ethyl levulinate and 10 ml of isopropanol were added, and then the rubber sludge (0.3 g) calcined at 400 ° C prepared in Example 4 was added as a catalyst. The reactor was sealed, stirred vigorously (600 rpm), heated to 190 ° C and maintained for 10 hours. After the reaction was terminated, it was cooled to room temperature and sampled. Agilent 7820 gas chromatograph was used for qualitative and quantitative detection. The test results are listed in Table 1 with serial number 12.
[0048] Embodiment 13 To a 25 mL autoclave, 1 mmol of n-propyl levulinate and 10 ml of isopropanol were added, and then the rubber sludge (0.3 g) calcined at 400 ° C prepared in Example 4 was added as a catalyst. The reactor was sealed, stirred vigorously (600 rpm), heated to 200 ° C and maintained for 10 hours. After the reaction was terminated, it was cooled to room temperature and sampled. Agilent 7820 gas chromatograph was used for qualitative and quantitative detection. The test results are listed in Table 1 with serial number 13.
[0049] Embodiment 14 To a 25 mL autoclave, 1 mmol of butyl levulinate and 10 ml of isopropanol were added, and then the rubber sludge (0.3 g) calcined at 400 ° C prepared in Example 4 was added as a catalyst. The reactor was sealed and stirred vigorously (600 rpm). It was heated to 210 ° C and maintained for 10 hours. After the reaction was terminated, it was cooled to room temperature and sampled. Agilent 7820 gas chromatograph was used for qualitative and quantitative detection. The test results are listed in Table 1 with serial number 14.
[0050] Embodiments 15 to 19 To a 25 mL autoclave, 1 mmol of methyl levulinate and 10 ml of isopropanol were added, and then the rubber sludge catalyst (0.1, 0.2, 0.4, 0.5, 0.6 g) calcined at 400 ° C prepared in Example 4 was added. The reactor was sealed and stirred vigorously (600 rpm). It was heated to 180 ° C and maintained for 10 hours. After the reaction was terminated, it was cooled to room temperature and sampled. Agilent 7820 gas chromatograph was used for qualitative and quantitative detection. The test results are listed in Table 1 with serial numbers 15 to 19.
[0051] Embodiment 20-24 To a 25 mL autoclave, 1 mmol of methyl levulinate and 10 ml of isopropanol were added, and then 0.3 g of the rubber sludge catalyst calcined at 400 ° C prepared in Example 4 was added. The reactor was sealed and stirred vigorously (600 rpm). It was heated to 180 ° C and maintained for 1, 2, 4, 6, and 8 hours. The reaction was terminated, cooled to room temperature, and samples were taken. Agilent 7820 gas chromatograph was used for qualitative and quantitative detection. The test results are listed in Table 1 with serial numbers 20 to 24.
[0052] Embodiment 25 To a 25 mL autoclave, 1 mmol of methyl levulinate and 10 ml of ethanol were added, and then the rubber sludge (0.3 g) calcined at 400 ° C prepared in Example 4 was added as a catalyst. The reactor was sealed, stirred vigorously (600 rpm), heated to 200 ° C and maintained for 10 hours. After the reaction was terminated, it was cooled to room temperature and sampled. Agilent 7820 gas chromatograph was used for qualitative and quantitative detection. The test results are listed in Table 1 with serial number 25.
[0053] Embodiment 26 To a 25 mL autoclave, 1 mmol of methyl levulinate and 10 ml of n-propanol were added, and then the rubber sludge (0.3 g) calcined at 400 ° C prepared in Example 4 was added as a catalyst. The reactor was sealed, stirred vigorously (600 rpm), heated to 200 ° C and maintained for 10 hours. After the reaction was terminated, it was cooled to room temperature and sampled. Agilent 7820 gas chromatograph was used for qualitative and quantitative detection. The test results are listed in Table 1 with serial number 26.
[0054] Embodiment 27 To a 25 mL autoclave, 1 mmol of methyl levulinate and 10 ml of sec-butanol were added, and then the rubber sludge (0.3 g) calcined at 400 ° C prepared in Example 4 was added as a catalyst. The reactor was sealed, stirred vigorously (600 rpm), heated to 200 ° C and maintained for 10 hours. After the reaction was terminated, it was cooled to room temperature and sampled. Agilent 7820 gas chromatograph was used for qualitative and quantitative detection. The test results are listed in Table 1 with serial number 27.
[0055] Embodiment 28 To a 25 mL autoclave, 1 mmol of ethyl levulinate and 10 ml of isopropanol were added, and then the rubber sludge (0.3 g) calcined at 400 ° C prepared in Example 4 was added as a catalyst. The reactor was sealed, stirred vigorously (600 rpm), heated to 200 ° C and maintained for 10 hours. After the reaction was terminated, it was cooled to room temperature and sampled. Agilent 7820 gas chromatograph was used for qualitative and quantitative detection. The test results are listed in Table 2 with serial number 28.
[0056] Embodiment 29 To a 25 mL autoclave, 1 mmol of propyl levulinate and 10 ml of isopropanol were added, and then the rubber sludge (0.3 g) calcined at 400 ° C prepared in Example 4 was added as a catalyst. The reactor was sealed and stirred vigorously (600 rpm). It was heated to 200 ° C and maintained for 10 hours. After the reaction was terminated, it was cooled to room temperature and sampled. Agilent 7820 gas chromatograph was used for qualitative and quantitative detection. The test results are listed in Table 2 with serial number 29.
[0057] Embodiment 30 To a 25 mL autoclave, 1 mmol of butyl levulinate and 10 ml of isopropanol were added, and then the rubber sludge (0.3 g) calcined at 400 ° C prepared in Example 4 was added as a catalyst. The reactor was sealed, stirred vigorously (600 rpm), heated to 200 ° C and maintained for 10 hours. After the reaction was terminated, it was cooled to room temperature and sampled. Agilent 7820 gas chromatograph was used for qualitative and quantitative detection. The test results are listed in Table 2 with serial number 30.
[0058] Embodiment 31 To a 25 mL autoclave, 1 mmol of levulinic acid and 10 ml of isopropanol were added, and then the rubber sludge (0.3 g) calcined at 400 °C prepared in Example 4 was added as a catalyst. The reactor was sealed, stirred vigorously (600 rpm), heated to 200 °C and maintained for 10 hours. After the reaction was terminated, it was cooled to room temperature and sampled. Agilent 7820 gas chromatograph was used for qualitative and quantitative detection. The test results are listed in Table 2 with serial number 31.
[0059] Embodiment 32 1 mmol of furfural and 10 ml of isopropanol were added to a 25 mL autoclave, and then the rubber sludge (0.3 g) calcined at 400 °C prepared in Example 4 was added as a catalyst. The reactor was sealed and stirred vigorously (600 rpm). It was heated to 200 °C and maintained for 10 hours. After the reaction was terminated, it was cooled to room temperature and sampled. Agilent 7820 gas chromatograph was used for qualitative and quantitative detection. The detection results are listed in Table 2 with serial number 32.
[0060] Embodiment 33 1 mmol of furfuryl alcohol and 10 ml of isopropanol were added to a 25 mL autoclave, and then the rubber sludge (0.3 g) calcined at 400 °C prepared in Example 4 was added as a catalyst. The reactor was sealed and stirred vigorously (600 rpm). It was heated to 200 °C and maintained for 10 hours. After the reaction was terminated, it was cooled to room temperature and sampled. Agilent 7820 gas chromatograph was used for qualitative and quantitative detection. The test results are listed in Table 2 with serial number 33.
[0061] Embodiment 34 To a 25 mL autoclave, 1 mmol 5-hydroxymethylfurfural and 10 ml isopropanol were added, and then the rubber sludge (0.3 g) calcined at 400 °C prepared in Example 4 was added as a catalyst. The reactor was sealed, stirred vigorously (600 rpm), heated to 200 °C and maintained for 10 hours. After the reaction was terminated, it was cooled to room temperature and sampled. Agilent 7820 gas chromatograph and HPLC (Water2487) were used for qualitative and quantitative detection. The test results are listed in Table 2 with serial number 34.
[0062] Embodiment 35 To a 25 mL autoclave, 1 mmol of vanillin and 10 ml of isopropanol were added, and then the rubber sludge (0.3 g) calcined at 400 °C prepared in Example 4 was added as a catalyst. The reactor was sealed, stirred vigorously (600 rpm), heated to 200 °C and maintained for 10 hours. After the reaction was terminated, it was cooled to room temperature and sampled. Agilent 7820 gas chromatograph and HPLC (Water2487) were used for qualitative and quantitative detection. The test results are listed in Table 2 with serial number 35.
[0063] Table 1 Test results of each embodiment of preparing γ-valerolactone with methyl levulinate
[0064] Table 2 Detection results in different reaction substrate examples .
Claims
1. A catalyst for catalytic transfer hydrogenation based on rubber sludge, characterized in that: The rubber sludge-based catalytic transfer hydrogenation catalyst is prepared by taking rubber sludge, a main by-product of the wastewater treatment stage of a rubber plant, as a raw material through pre-treatment and calcination.
2. The method for preparing a rubber sludge catalytic transfer hydrogenation catalyst according to claim 1, characterized in that: The method comprises pre-treatment and calcination steps, specifically including: A. Pre-treatment: 1) The rubber sludge from the rubber factory sewage stage is air-dried to a moisture content of 10-12% to obtain material a; 2) Grind material a through a 40-mesh sieve to obtain material b; B. Calcination: Calcinate material b to obtain the target rubber sludge-based catalytic transfer hydrogenation catalyst.
3. The preparation method according to claim 2, characterized in that: The calcination temperature in step B is 100-600° C. and the calcination time is 1-4 hours.
4. The preparation method according to claim 2 or 3, characterized in that: The calcination is carried out in an air atmosphere.
5. An application of the rubber catalytic transfer hydrogenation catalyst according to claim 1, characterized in that: The rubber sludge-based catalytic transfer hydrogenation catalyst is used in catalytic reduction of methyl levulinate and transfer hydrogenation to prepare gamma-valerolactone.
6. The use according to claim 5, characterized in that: The catalytic reduction of methyl levulinate and transfer hydrogenation to prepare γ-valerolactone includes pre-treatment and main reaction steps, specifically including: A. Pretreatment: Mix methyl levulinate and a solvent to adjust the mass percentage concentration of methyl levulinate in the solvent to 1-1.5% to obtain material c, wherein the solvent is ethanol, n-propanol, isopropanol or sec-butanol; B. Main reaction: Place material c in a reaction vessel, add the rubber-based catalytic transfer hydrogenation catalyst, and react at a temperature of 160-210° C. for 1-10 hours to obtain the target γ-valerolactone; The mass ratio of the rubber-based catalytic transfer hydrogenation catalyst and methyl levulinate is (0.81-4.84):
1.
7. An application of the rubber catalytic transfer hydrogenation catalyst according to claim 1, characterized in that: The application of the rubber sludge catalytic transfer hydrogenation catalyst in the catalytic reduction biomass platform molecular transfer hydrogenation to prepare γ-valerolactone specifically includes pre-treatment and main reaction steps, specifically including: A. Pretreatment: mixing the biomass platform molecule and the solvent to adjust the mass percentage concentration of the biomass platform molecule in the solvent to 0.8-2.0% to obtain material d, wherein the biomass platform molecule is ethyl levulinate, propyl levulinate, butyl levulinate, levulinic acid, furfural or furfuryl alcohol; B. Main reaction: Place material d in a reaction vessel, add the rubber catalytic transfer hydrogenation catalyst, and react at a temperature of 180-220° C. for 8-12 hours to obtain the target product γ-valerolactone; The mass ratio of the rubber-based catalytic transfer hydrogenation catalyst and the biomass platform molecule is (1.74~3.06):
1.
8. An application of the rubber catalytic transfer hydrogenation catalyst according to claim 1, characterized in that: The application of the rubber sludge-based catalytic transfer hydrogenation catalyst in catalytic reduction of 5-hydroxymethylfurfural transfer hydrogenation to prepare 2,5-dihydroxymethylfuran is specifically to mix 5-hydroxymethylfurfural and a solvent and place them in a reaction container, add the rubber sludge-based catalytic transfer hydrogenation catalyst, react at a temperature of 180-220°C for 8-12 hours to obtain 2,5-dihydroxymethylfuran; the solvent is isopropanol, the concentration of the 5-hydroxymethylfurfural in the solvent is 1.0-1.5wt%, and the mass ratio of the rubber sludge-based catalytic transfer hydrogenation catalyst to 5-hydroxymethylfurfural is (2-3):
1.
9. An application of the rubber catalytic transfer hydrogenation catalyst according to claim 1, characterized in that: The application of the rubber sludge-based catalytic transfer hydrogenation catalyst in catalytic reduction of vanillin and transfer hydrogenation to prepare vanillin alcohol is specifically to mix vanillin and a solvent and place them in a reaction container, add the rubber sludge-based catalytic transfer hydrogenation catalyst, and react at a temperature of 150-250°C for 8-12 hours to obtain vanillin alcohol; the solvent is isopropanol, the concentration of vanillin in the solvent is 1.0-2.0wt%, and the mass ratio of the rubber sludge-based catalytic transfer hydrogenation catalyst and vanillin is (1.5-2.5):1.