Bimetal oxide supported catalyst as well as preparation method and application thereof
By using bimetallic oxides as support materials, the metal dispersion and interfacial interaction of the catalyst were optimized, solving the problems of metal dispersion and stability of single metal catalysts in the conversion of 5-hydroxymethylfurfural to 2-aminomethylpiperidine. This resulted in a highly efficient and selective catalytic reaction with good sustainability and high product yield.
Patent Information
- Application Number
- CN202411701193.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-26
- Publication Date
- 2026-05-26
AI Technical Summary
Existing single-metal catalysts suffer from problems such as poor metal dispersion and unstable catalytic efficiency in the conversion of 5-hydroxymethylfurfural to 2-aminomethylpiperidine, making it difficult to achieve a highly efficient, selective and stable catalytic reaction.
By using bimetallic oxides as support materials, and by selecting appropriate metal components and optimizing the interface between the support and the metal, a highly efficient multiphase bimetallic oxide supported catalyst was prepared, which improved the selectivity, activity and stability of the catalyst. Biomass feedstock was then converted into 5-hydroxymethylfurfural through chemical reactions such as hydrolysis and dehydration.
The catalyst achieves efficient reductive amination and hydrogenation cracking of 5-hydroxymethylfurfural. It is easy to separate, has good sustainability and stability, high product yield, and can maintain good catalytic activity after recycling.
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Abstract
Description
Technical Field
[0001] This application relates to a bimetallic oxide supported catalyst, its preparation method and application, and belongs to the field of catalysts. Background Technology
[0002] 2-Aminomethylpiperidine is an important organic compound widely used in the synthesis of pharmaceuticals, agrochemicals, and functional materials. Its structure contains an amino group and a piperidine ring, endowing it with unique chemical activity and reactivity, making it an important intermediate. In medicinal chemistry, it possesses potential biological activity as a precursor for the synthesis of antibacterial, antitumor, and central nervous system disease treatment drugs. Furthermore, it can act as a catalyst or ligand, participating in catalytic reactions, particularly showing significant application value in metal-catalyzed organic reactions. In modern chemical research, the synthetic methods and transformation pathways of 2-aminomethylpiperidine have attracted increasing attention. Researchers have explored the selection of catalysts, optimization of reaction conditions, and development of novel catalytic systems in its synthesis to improve synthetic efficiency and product selectivity (Green Chem. 2024, 26, 2067-2077). 5-Hydroxymethylfurfural, as an important biomass-derived compound, has broad application prospects. The reductive amination reaction of 5-hydroxymethylfurfural can convert it into biologically active compounds such as 2-aminomethylpiperidine, possessing significant economic and industrial value.
[0003] In traditional catalyst systems, single-metal catalysts are widely used due to their high activity. However, these catalysts often suffer from problems such as poor metal dispersion and unstable catalytic efficiency in practical applications. To address these issues, the design of support materials and the optimization of catalyst structure have become important research directions. Bimetallic oxides, as a unique catalytic support material, possess good thermal stability and high surface activity, and their potential in various catalytic reactions has attracted widespread attention.
[0004] In practical applications, bimetallic oxide supports typically provide more uniform metal dispersion and enhance the interaction between the metal and the support, thereby improving catalytic performance. Especially in catalysts, designs where the support is a bimetallic oxide and the active metal is a single metal can improve the selectivity, activity, and stability of the catalyst by selecting appropriate metal components and optimizing the interfacial interaction between the support and the metal. Summary of the Invention
[0005] This invention aims to develop a highly efficient multiphase bimetallic oxide supported catalyst that enables the reduction and amination of hydroxyl and amino groups in 5-hydroxymethylfurfural (5-HMF) to yield amino groups, followed by hydrogenation cleavage and ring-opening to prepare 2-aminomethylpiperidine. 5-HMF can be obtained through various pathways, particularly through biomass conversion processes. In biomass conversion, 5-HMF is typically obtained through the catalytic cleavage or conversion of sugars or lignin compounds. In particular, many plant-based raw materials (such as wood and agricultural waste) can be efficiently converted to 5-HMF through chemical reactions such as hydrolysis and dehydration. According to one aspect of this application, a method for preparing 2-aminomethylpiperidine from 5-HMF is provided, which has a high feedstock utilization rate and mild operating conditions, helping to reduce energy consumption and waste generation. The catalyst used in this method exhibits a synergistic effect between the bimetallic oxide support and the supported metal.
[0006] By using bimetallic oxides in the catalyst, the acidity and basicity of the catalyst can be improved, and the metal dispersion can be effectively stabilized, thereby reducing the metal particle size. This enhances the interaction between the metal and the support, improves electron transfer efficiency, and further promotes the catalytic reaction. Simultaneously, it optimizes the reactive sites on the catalyst surface, facilitating the reductive amination reaction of 5-hydroxymethylfurfural with oxygen-containing functional groups, and further promoting the hydrogenation cracking ring-opening reaction to generate 2-aminomethylpiperidine. The catalyst is easier to separate and recover, reducing the risk of environmental pollution and demonstrating good sustainability. The stability and high efficiency of the catalyst make this catalytic system promising for large-scale applications, especially in green chemistry and biomass conversion.
[0007] According to one aspect of this application, a bimetallic oxide supported catalyst is provided, characterized in that...
[0008] The bimetallic oxide supported catalyst includes a bimetallic oxide support and a metal active component supported on the surface of the bimetallic oxide support.
[0009] The bimetallic oxide carrier contains divalent metal oxides and trivalent metal oxides;
[0010] The divalent metal element oxide is selected from at least one of the oxides of Mg, Ca, Sr, Zn, and Mn;
[0011] The trivalent metal oxide is selected from at least one of the oxides of Al, In, Fe, Cr, and Ce;
[0012] The active metal component is selected from at least one of Pd, Pt, Ru, Ni, and Co;
[0013] In the bimetallic oxide supported catalyst, the mass of the metal active component is 0.1 to 20 wt% of the mass of the metal oxide support.
[0014] Optionally, in the bimetallic oxide supported catalyst, the mass of the metal active component is any value among 0.1 wt%, 1.0 wt%, 5.0 wt%, 15 wt%, and 20 wt% of the mass of the metal oxide support, or a range between any two of the above.
[0015] Optionally, in the bimetallic oxide supported catalyst, the mass of the metal active component is 0.1 to 15 wt% of the mass of the metal oxide support.
[0016] According to another aspect of this application, a method for preparing the above-mentioned bimetallic oxide supported catalyst is provided, comprising the following steps:
[0017] (1) Mix divalent metal precursor, trivalent metal precursor, precipitant and water, stir, react, filter, wash with water, dry and grind to obtain catalyst precursor.
[0018] (2) The catalyst precursor is immersed in an aqueous solution containing a metal active component precursor, dried, and reduced with hydrogen to obtain the bimetallic oxide supported catalyst.
[0019] The divalent metal precursor is selected from at least one of magnesium sulfate, calcium nitrate, strontium nitrate, zinc acetate, and manganese nitrate.
[0020] The trivalent metal precursor is selected from at least one of aluminum nitrate, indium nitrate, ferric sulfate, chromium nitrate, and cerium nitrate.
[0021] The precipitant is selected from at least one of sodium hydroxide, sodium carbonate, ammonia, urea, ammonium chloride, and calcium hydroxide;
[0022] The molar ratio of the divalent metal precursor to the trivalent metal precursor is 1 to 5;
[0023] Optionally, the molar ratio of the divalent metal precursor to the trivalent metal precursor is any value among 1, 2, 3, 4, and 5, or a range between any two of the above.
[0024] The molar ratio of the precipitant to the total molar ratio of the divalent metal precursor and the trivalent metal precursor is 1.5 to 8.
[0025] Optionally, the ratio of the molar amount of the precipitant to the total molar amount of the divalent metal precursor and the trivalent metal precursor is any value among 1.5, 2, 4, 6, and 8, or a range between any two of the above.
[0026] The stirring time is 5 to 120 minutes;
[0027] Optionally, the stirring time is any value among 5 min, 20 min, 60 min, 90 min, and 120 min, or a range between any two of the above.
[0028] Optionally, the stirring time is 10 to 90 minutes;
[0029] The reaction temperature is 100–200°C;
[0030] Optionally, the temperature of the reaction is any value among 100°C, 120°C, 150°C, 180°C, and 200°C, or a range between any two of the above.
[0031] The reaction time is 3–24 hours;
[0032] Optionally, the reaction time is any value among 3h, 6h, 12h, 18h, and 24h, or a range between any two of the above.
[0033] The reaction is a hydrothermal reaction;
[0034] The drying temperature is 50–90°C;
[0035] Optionally, the drying temperature is any value among 50°C, 60°C, 70°C, 80°C, and 90°C, or a range between any two of the above.
[0036] The drying time is 12 to 48 hours.
[0037] Optionally, the drying time is any value among 12h, 18h, 24h, 36h, and 48h, or a range between any two of the above.
[0038] The metal active component precursor is selected from at least one of palladium chloride, hexachloroplatinic acid, ruthenium chloride, nickel nitrate, and cobalt acetate;
[0039] The drying temperature is 80–120°C;
[0040] Optionally, the drying temperature is any value among 80°C, 90°C, 100°C, 110°C, and 120°C, or a range between any two of the above.
[0041] The drying time is 7–20 hours;
[0042] Optionally, the drying time is any value among 7h, 12h, 16h, 18h, and 20h, or a range between any two of the above.
[0043] The temperature for hydrogen reduction is 250–600°C;
[0044] Optionally, the temperature for hydrogen reduction is any value among 150°C, 250°C, 300°C, 500°C, and 600°C, or a range between any two of the above.
[0045] The hydrogen reduction time is 1 to 8 hours.
[0046] Optionally, the hydrogen reduction time can be any value among 1h, 3h, 4h, 6h, and 8h, or a range between any two of the above.
[0047] According to another aspect of this application, a method for catalytically preparing 2-aminomethylpiperidine from 5-hydroxymethylfurfural is provided, comprising the following steps:
[0048] A reducing amination reaction was carried out by introducing hydrogen and ammonia into a solvent containing 5-hydroxymethylfurfural, a catalyst, and a solvent to obtain 2-aminomethylpiperidine.
[0049] The catalyst is selected from the above-mentioned bimetallic oxide supported catalyst.
[0050] The solvent is selected from at least one of methanol, ethanol, tetrahydrofuran, 1,4-dioxane, and toluene;
[0051] The molar amount of the catalyst is 0.1% to 10.0% of the molar amount of 5-hydroxymethylfurfural;
[0052] The molar amount of the catalyst is expressed as the molar amount of the metal active component.
[0053] Optionally, the molar amount of the catalyst is any value among 0.1%, 0.7%, 1.0%, 5.0%, and 10.0% of the molar amount of 5-hydroxymethylfurfural, or a range between any two of the above.
[0054] The temperature for the reductive amination reaction is 150–250 °C;
[0055] Optionally, the temperature of the reductive amination reaction is any value among 150°C, 170°C, 210°C, 230°C, and 250°C, or a range between any two of the above.
[0056] Optionally, the temperature of the reductive amination reaction is 170–210°C;
[0057] The reductive amination reaction takes 3–36 hours.
[0058] Optionally, the time for the reductive amination reaction is any value among 3h, 8h, 12h, 16h, and 36h, or a range between any two of the above.
[0059] Optionally, the reductive amination reaction takes 8 to 16 hours.
[0060] The partial pressure of the hydrogen gas is 0.2–5.0 MPa;
[0061] Optionally, the partial pressure of the hydrogen gas is any value among 0.5 MPa, 1.0 MPa, 1.5 MPa, 2.5 MPa, and 3.0 MPa, or a range between any two of the above.
[0062] Optionally, the partial pressure of the hydrogen gas is 0.5–3.0 MPa;
[0063] The partial pressure of the ammonia gas is 0.2–1.0 MPa;
[0064] Optionally, the partial pressure of the ammonia gas is any value among 0.2 MPa, 0.4 MPa, 0.5 MPa, 0.8 MPa, and 1.0 MPa, or a range between any two of the above.
[0065] Optionally, the partial pressure of the ammonia gas is 0.2 to 0.5 MPa.
[0066] In one specific embodiment, the present invention provides a method for preparing a bimetallic oxide supported catalyst and its application in the efficient preparation of 2-aminomethylpiperidine from 5-hydroxymethylfurfural. The method involves mixing a bimetallic precursor, a precipitant, and water as a solvent, stirring at room temperature, and carrying out a hydrothermal reaction at a certain temperature. After cooling to room temperature, the mixture is filtered, washed with deionized water, dried, ground, and then impregnated in a solution containing a supported metal precursor. After drying, the precursor is obtained as a supported catalyst precursor, which is then reduced under a hydrogen atmosphere to obtain the catalyst. The catalyst support used in this method can interact with the supported metal, exhibiting high catalytic activity and selectivity, easy separation from the reaction system, and excellent cycle stability. This method and its catalyst have significant application potential and are expected to show broad prospects in multiple fields in the future.
[0067] This catalyst can reduce and amination the oxygen-containing functional groups of 5-hydroxymethylfurfural to an amino group, and then further hydrogenate and crack the ring to prepare 2-aminomethylpiperidine. This catalyst has the characteristics of simple preparation process, easy separation from the reaction system, and good catalytic activity after multiple cycles.
[0068] The beneficial effects that this application can produce include:
[0069] 1) The method for preparing 2-aminomethylpiperidine by 5-hydroxymethylfurfural reduction amination provided by the present invention can achieve high selectivity for 2-aminomethylpiperidine due to the interaction between the bimetallic oxide and the supported metal in the catalyst.
[0070] 2) The catalyst system used in this method has good stability, can maintain high catalytic activity, and has a high product yield. The preparation process is simple and easy to carry out, and the catalyst is easy to separate from the reaction system, realizing the effective utilization of resources.
[0071] 3) The catalyst in this application can still maintain good stability after being recycled five times, and the yield of the product remains above 62%. Detailed Implementation
[0072] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0073] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.
[0074] In the embodiments of this application, the conversion rate and yield are calculated as follows:
[0075]
[0076] Example 1
[0077] 2 mmol magnesium sulfate, aluminum nitrate, and a precipitant were mixed thoroughly with 70 mL of water, wherein the molar ratio of magnesium sulfate to aluminum nitrate was 3 (based on metal element), the precipitant was sodium hydroxide, and the molar ratio of the precipitant to the divalent and trivalent metals was 4.0. The mixture was stirred at room temperature for 20 min, and the liquid was transferred to a hydrothermal reactor with a PTFE liner. The mixture was hydrothermally heated at 150 °C for 18 h, cooled to room temperature, filtered, washed with deionized water, dried at 80 °C for 18 h, and then ground to obtain a bimetallic oxide precursor. 1.0 g of the bimetallic oxide precursor and 5.0 wt% ruthenium chloride were added to water saturated with the water content of 1.0 g of the bimetallic oxide precursor. The mixture was stirred at 700 rpm for 20 min, allowed to stand at room temperature for 24 h, and dried at 100 °C for 12 h to obtain a catalyst precursor. This precursor was then reduced at 300 °C for 4 h under a hydrogen atmosphere to obtain the catalyst.
[0078] Application Example 1
[0079] Application of bimetallic oxide supported catalysts in the reductive amination of 5-hydroxymethylfurfural to prepare 2-aminomethylpiperidine:
[0080] 5-Hydroxymethylfurfural, the catalyst prepared in Example 1, and 1,4-dioxane were added to a reaction vessel, and the vessel was closed. The amount of 5-hydroxymethylfurfural used was 1.0 mmol, the molar amount of ruthenium in the catalyst was 0.7% of the molar amount of 5-hydroxymethylfurfural, and the solvent volume was 5 mL. The air in the vessel was purged three times with nitrogen, and then 0.2 MPa ammonia and 1.0 MPa hydrogen were introduced. The temperature was raised to 210 °C, and the reaction was carried out at this temperature for 16 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature, and the catalyst was removed by filtration. Trimethylbenzene (MTBF) was added as an internal standard, and samples were taken for gas chromatography analysis. The conversion rate of 5-hydroxymethylfurfural was 99%, and the GC yield of 2-aminomethylpiperidine was 72%.
[0081] Example 2
[0082] 2 mmol of calcium nitrate, indium nitrate, and a precipitant were mixed thoroughly with 70 mL of water, wherein the molar ratio of calcium nitrate to indium nitrate was 5 (based on metal element content), the precipitant was sodium carbonate, and the molar ratio of the precipitant to the divalent and trivalent metals was 8.0. The mixture was stirred at room temperature for 120 min, and the liquid was transferred to a hydrothermal reactor with a PTFE liner. The mixture was hydrothermally heated at 200 °C for 3 h, cooled to room temperature, filtered, washed with deionized water, dried at 90 °C for 12 h, and then ground to obtain a bimetallic oxide precursor. 1.0 g of the bimetallic oxide precursor and 0.1 wt% palladium chloride were added to 1.0 g of water saturated with the water absorption capacity of the bimetallic oxide precursor. The mixture was stirred at 700 rpm for 20 min, allowed to stand at room temperature for 24 h, and dried at 120 °C for 7 h to obtain a catalyst precursor. This precursor was then reduced at 600 °C for 1 h under a hydrogen atmosphere to obtain the catalyst.
[0083] Application Example 2
[0084] Application of bimetallic oxide supported catalysts in the reductive amination of 5-hydroxymethylfurfural to prepare 2-aminomethylpiperidine:
[0085] 5-Hydroxymethylfurfural, the catalyst prepared in Example 1, and tetrahydrofuran were added to a reaction vessel, and the vessel was closed. The amount of 5-hydroxymethylfurfural used was 1.0 mmol, the molar amount of palladium in the catalyst was 0.1% of the molar amount of 5-hydroxymethylfurfural, and the solvent volume was 5 mL. The air in the vessel was purged three times with nitrogen, and then 0.5 MPa ammonia and 1.5 MPa hydrogen were introduced. The temperature was raised to 170 °C, and the reaction was carried out at this temperature for 8 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature, and the catalyst was removed by filtration. Trimethylbenzene (MTBF) was added as an internal standard, and samples were taken for gas chromatography analysis. The conversion rate of 5-hydroxymethylfurfural was 99%, and the GC yield of 2-aminomethylpiperidine was 70%.
[0086] Example 3
[0087] 2 mmol of strontium nitrate, ferric sulfate, and a precipitant were mixed thoroughly with 70 mL of water, wherein the molar ratio of strontium nitrate to ferric sulfate was 1 (based on metal element). The precipitant was ammonia, and the molar ratio of the precipitant to the divalent and trivalent metals was 1.5. The mixture was stirred at room temperature for 5 min, and the liquid was transferred to a hydrothermal reactor with a PTFE liner. The mixture was hydrothermally heated at 100 °C for 24 h, cooled to room temperature, filtered, washed with deionized water, dried at 50 °C for 48 h, and then ground to obtain a bimetallic oxide precursor. 1.0 g of the bimetallic oxide precursor and 20 wt% cobalt acetate (by mass of the bimetallic oxide precursor) were added to water saturated with the water absorption capacity of 1.0 g of the bimetallic oxide precursor. The mixture was stirred at 700 rpm for 20 min, allowed to stand at room temperature for 24 h, and dried at 80 °C for 20 h to obtain a catalyst precursor. This precursor was then reduced at 150 °C for 8 h under a hydrogen atmosphere to obtain the catalyst.
[0088] Application Example 3
[0089] Application of bimetallic oxide supported catalysts in the reductive amination of 5-hydroxymethylfurfural to prepare 2-aminomethylpiperidine:
[0090] 5-Hydroxymethylfurfural, the catalyst prepared in Example 1, and methanol were added to a reaction vessel, and the vessel was closed. The amount of 5-hydroxymethylfurfural used was 1.0 mmol, the molar amount of cobalt in the catalyst was 10.0% of the molar amount of 5-hydroxymethylfurfural, and the solvent volume was 5 mL. The air in the vessel was purged three times with nitrogen, and then purged with 1.0 MPa ammonia and 3.0 MPa hydrogen. The temperature was raised to 250 °C, and the reaction was carried out at this temperature for 3 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature, and the catalyst was removed by filtration. Trimethylbenzene (MTBF) was added as an internal standard, and samples were taken for gas chromatography analysis. The conversion rate of 5-hydroxymethylfurfural was 99%, and the GC yield of 2-aminomethylpiperidine was 68%.
[0091] Example 4
[0092] 2 mmol of zinc acetate, chromium nitrate, and a precipitant were mixed thoroughly with 70 mL of water, wherein the molar ratio of zinc acetate to chromium nitrate was 4 (based on metal element), the precipitant was urea, and the molar ratio of the precipitant to the divalent and trivalent metals was 6. The mixture was stirred at room temperature for 60 min, and the liquid was transferred to a hydrothermal reactor with a PTFE liner. The mixture was hydrothermally heated at 120 °C for 12 h, cooled to room temperature, filtered, washed with deionized water, dried at 70 °C for 24 h, and then ground to obtain a bimetallic oxide precursor. 1.0 g of the bimetallic oxide precursor and 1.0 wt% hexachloroplatinic acid (by mass of the bimetallic oxide precursor) were added to 1.0 g of water saturated with the water absorption capacity of the bimetallic oxide precursor. The mixture was stirred at 700 rpm for 20 min, allowed to stand at room temperature for 24 h, and dried at 110 °C for 18 h to obtain a catalyst precursor. This precursor was then reduced at 250 °C for 3 h under a hydrogen atmosphere to obtain the catalyst.
[0093] Application Example 4
[0094] Application of bimetallic oxide supported catalysts in the reductive amination of 5-hydroxymethylfurfural to prepare 2-aminomethylpiperidine:
[0095] 5-Hydroxymethylfurfural, the catalyst prepared in Example 1, and ethanol were added to a reaction vessel, and the vessel was closed. The amount of 5-hydroxymethylfurfural used was 1.0 mmol, the molar amount of platinum in the catalyst was 1.0% of the molar amount of 5-hydroxymethylfurfural, and the solvent volume was 5 mL. The air in the vessel was purged three times with nitrogen, and then 0.4 MPa ammonia and 0.5 MPa hydrogen were introduced. The temperature was raised to 150 °C, and the reaction was carried out at this temperature for 36 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature, and the catalyst was removed by filtration. Trimethylbenzene (MTBF) was added as an internal standard, and samples were taken for gas chromatography analysis. The conversion rate of 5-hydroxymethylfurfural was 99%, and the GC yield of 2-aminomethylpiperidine was 67%.
[0096] Example 5
[0097] 2 mmol of manganese nitrate, cerium nitrate, and a precipitant were mixed thoroughly with 70 mL of water, wherein the molar ratio of manganese nitrate to cerium nitrate was 2 (based on metal element content), and the precipitant was ammonium chloride, with a molar ratio of precipitant to divalent metal and trivalent metal of 2. The mixture was stirred at room temperature for 90 min, and the liquid was transferred to a hydrothermal reactor with a PTFE liner. The mixture was hydrothermally heated at 180 °C for 6 h, cooled to room temperature, filtered, washed with deionized water, dried at 60 °C for 36 h, and then ground to obtain a bimetallic oxide precursor. 1.0 g of the bimetallic oxide precursor and 15 wt% nickel nitrate (by weight of the bimetallic oxide precursor) were added to 1.0 g of water saturated with the water absorption capacity of the bimetallic oxide precursor. The mixture was stirred at 700 rpm for 20 min, allowed to stand at room temperature for 24 h, and dried at 90 °C for 16 h to obtain a catalyst precursor. This precursor was then reduced at 500 °C for 6 h under a hydrogen atmosphere to obtain the catalyst.
[0098] Application Example 5
[0099] Application of bimetallic oxide supported catalysts in the reductive amination of 5-hydroxymethylfurfural to prepare 2-aminomethylpiperidine:
[0100] 5-Hydroxymethylfurfural, the catalyst prepared in Example 1, and toluene were added to a reaction vessel, and the vessel was closed. The amount of 5-hydroxymethylfurfural used was 1.0 mmol, the molar amount of nickel in the catalyst was 5.0% of the molar amount of 5-hydroxymethylfurfural, and the amount of solvent was 5 mL. The air in the vessel was purged three times with nitrogen, and then 0.8 MPa ammonia and 2.5 MPa hydrogen were introduced. The temperature was raised to 230 °C, and the reaction was carried out at this temperature for 12 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature, and the catalyst was removed by filtration. Trimethylbenzene (MTBF) was added as an internal standard, and samples were taken for gas chromatography analysis. The conversion rate of 5-hydroxymethylfurfural was 99%, and the GC yield of 2-aminomethylpiperidine was 65%.
[0101] Application Example 6
[0102] After the catalyst was prepared and reduced according to the conditions of Example 1, it was used for the 5-hydroxymethylfurfural reduction amination reaction according to the conditions of Application Example 1. The difference from Application Example 1 is that after the reaction, the catalyst was separated by centrifugation and washed with water by centrifugation 5 times. The 5-hydroxymethylfurfural reduction amination reaction was then circulated again. The catalyst was used in this way 5 times. The results are shown in Table 1.
[0103] Table 1. Effect of catalyst on the reductive amination and recycling of 5-hydroxymethylfurfural
[0104]
[0105] As shown in Table 1, the prepared catalyst maintained high catalytic activity for the reductive amination of 5-hydroxymethylfurfural after five cycles, with the yield of 2-aminomethylpiperidine remaining above 68%. The catalysts provided in Examples 2-5 also maintained high catalytic activity under the same conditions, with the yield of glycine remaining above 62% after five cycles.
[0106] Comparative Example 1
[0107] The catalyst was prepared according to the conditions of Example 1. After reduction, the catalyst was used for the reductive amination reaction of 5-hydroxymethylfurfural. The difference from Example 1 was that, in the catalyst preparation process, magnesium oxide replaced the bimetallic oxide precursor and was mixed with ruthenium chloride, followed by subsequent operations to obtain a magnesium oxide-supported ruthenium catalyst. The conversion rate of 5-hydroxymethylfurfural was 99%, and the yield of 2-aminomethylpiperidine was 30%.
[0108] Comparative Example 2
[0109] The catalyst was prepared according to the conditions of Example 1. After reduction, the catalyst was used for the reductive amination reaction of 5-hydroxymethylfurfural. The difference from Example 1 was that, in the catalyst preparation process, alumina replaced the bimetallic oxide precursor and was mixed with ruthenium chloride, followed by subsequent operations to obtain a magnesium oxide-supported ruthenium catalyst. The conversion rate of 5-hydroxymethylfurfural was 99%, and the yield of 2-aminomethylpiperidine was 35%.
[0110] The catalyst support used in the preparation method of this invention can interact with the supported metal, exhibiting high catalytic activity and selectivity, easy separation from the reaction system, and excellent cycle stability. This method and its catalyst have significant application potential and are expected to show broad prospects in multiple fields in the future.
[0111] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A bimetallic oxide supported catalyst, characterized in that, The bimetallic oxide supported catalyst includes a bimetallic oxide support and a metal active component supported on the surface of the bimetallic oxide support. The bimetallic oxide carrier contains divalent metal oxides and trivalent metal oxides; The divalent metal element oxide is selected from at least one of the oxides of Mg, Ca, Sr, Zn, and Mn; The trivalent metal oxide is selected from at least one of the oxides of Al, In, Fe, Cr, and Ce; The active metal component is selected from at least one of Pd, Pt, Ru, Ni, and Co; In the bimetallic oxide supported catalyst, the mass of the metal active component is 0.1 to 20 wt% of the mass of the metal oxide support.
2. The bimetallic oxide supported catalyst according to claim 1, characterized in that, In the bimetallic oxide supported catalyst, the mass of the metal active component is 0.1 to 15 wt% of the mass of the metal oxide support.
3. A method for preparing a bimetallic oxide supported catalyst according to any one of claims 1 or 2, characterized in that, Includes the following steps: (1) Mix divalent metal precursor, trivalent metal precursor, precipitant and water, stir, react, filter, wash and dry to obtain catalyst precursor; (2) The catalyst precursor is immersed in an aqueous solution containing a metal active component precursor, dried, and reduced with hydrogen to obtain the bimetallic oxide supported catalyst.
4. The preparation method according to claim 3, characterized in that, The divalent metal precursor is selected from at least one of magnesium sulfate, calcium nitrate, strontium nitrate, zinc acetate, and manganese nitrate. The trivalent metal precursor is selected from at least one of aluminum nitrate, indium nitrate, ferric sulfate, chromium nitrate, and cerium nitrate. The precipitant is selected from at least one of sodium hydroxide, sodium carbonate, ammonia, urea, ammonium chloride, and calcium hydroxide; The molar ratio of the divalent metal precursor to the trivalent metal precursor is 1 to 5; The molar ratio of the precipitant to the total molar ratio of the divalent metal precursor and the trivalent metal precursor is 1.5 to 8.
5. The preparation method according to claim 3, characterized in that, The stirring time is 5 to 120 minutes; The reaction temperature is 100–200°C; The reaction time is 3–24 hours; The reaction is a hydrothermal reaction; The drying temperature is 50–90°C; The drying time is 12 to 48 hours.
6. The preparation method according to claim 3, characterized in that, The metal active component precursor is selected from at least one of palladium chloride, hexachloroplatinic acid, ruthenium chloride, nickel nitrate, and cobalt acetate; The drying temperature is 80–120°C; The drying time is 7–20 hours; The temperature for hydrogen reduction is 250–600°C; The hydrogen reduction time is 1 to 8 hours.
7. A method for catalytically preparing 2-aminomethylpiperidine from 5-hydroxymethylfurfural, characterized in that, Includes the following steps: A reducing amination reaction was carried out by introducing hydrogen and ammonia into a solvent containing 5-hydroxymethylfurfural, a catalyst, and a solvent to obtain 2-aminomethylpiperidine. The catalyst is selected from the bimetallic oxide supported catalyst according to any one of claims 1 or 2.
8. The method according to claim 7, characterized in that, The solvent is selected from at least one of methanol, ethanol, tetrahydrofuran, 1,4-dioxane, and toluene; The molar amount of the catalyst is 0.1% to 10.0% of the molar amount of 5-hydroxymethylfurfural; The molar amount of the catalyst is expressed as the molar amount of the metal active component.
9. The method according to claim 7, characterized in that, The temperature for the reductive amination reaction is 150–250 °C; Preferably, the temperature of the reductive amination reaction is 170–210°C; The reductive amination reaction takes 3–36 hours. Preferably, the reductive amination reaction takes 8 to 16 hours.
10. The method according to claim 7, characterized in that, The partial pressure of the hydrogen gas is 0.2–5.0 MPa; Preferably, the partial pressure of the hydrogen gas is 0.5–3.0 MPa; The partial pressure of the ammonia gas is 0.2–1.0 MPa; Preferably, the partial pressure of the ammonia gas is 0.2 to 0.5 MPa.