Carbon supported ionic liquid bimetallic catalyst, method of making and use in the production of cbdo

Abstract

The application belongs to the technical field of catalyst preparation, and discloses a carbon-supported ionic liquid bimetallic catalyst, a preparation method and application thereof.The carbon-supported ionic liquid bimetallic catalyst Ru-M-IL / Ac comprises a carrier and a main metal, an auxiliary metal and an ionic liquid supported on the carrier, the carrier is activated carbon Ac, the main metal is Ru, and the auxiliary metal is Ce, Cu or Ag;in the catalyst, the loading amount of the main metal Ru is 3-8 wt%, and the loading amount of the auxiliary metal is 0.1-0.5 wt% based on the total mass of the catalyst.The catalyst is used for preparing CBDO by CBDK hydrogenation reaction, can ensure that the hydrogenation reaction condition is mild, and the product CBDO has ideal selectivity and cis-trans ratio.

Description

Technical Field

[0001] This application relates to the field of catalyst preparation technology, and in particular to carbon-supported ionic liquid bimetallic catalysts, their preparation methods, and their application in the preparation of CBDO. Background Technology

[0002] 2,2,4,4-Tetramethyl-1,3-cyclobutanediol (CBDO) is an important aliphatic glycol polyester monomer. Polyesters prepared from CBDO not only possess characteristics such as high transparency, high glass transition temperature, good impact resistance, and good toughness, but also eliminate the risk of bisphenol A pollution, making them environmentally friendly. Therefore, 2,2,4,4-Tetramethyl-1,3-cyclobutanediol has broad application prospects and has become one of the polymers most likely to replace traditional resins.

[0003] The known production process of 2,2,4,4-tetramethyl-1,3-cyclobutanediol mainly includes the following steps: Step 1, isobutyric acid or isobutyric anhydride is pyrolyzed to generate dimethyl ketene, and 2,2,4,4-tetramethyl-1,3-cyclobutanedione (CBDK) is prepared by dimerization of dimethyl ketene; Step 2, CBDK is hydrogenated to obtain CBDO, wherein the hydrogenation reaction step of CBDK is the key to this process. For the above-mentioned process, the hydrogenation reaction conditions are quite harsh, generally with a reaction temperature between 100 and 200°C and a pressure between 2 and 4 MPa. These reaction conditions are one of the factors hindering the industrialization of this process. Secondly, the hydrogenation reaction step is prone to generating undesirable byproducts, which affects the selectivity of the product CBDO. Furthermore, the product 2,2,4,4-tetramethyl-1,3-cyclobutanediol exists as a cis-trans isomer, as shown in the following formula. In practical applications, CBDO products with a high cis-trans ratio have advantages such as high CBDO utilization and high glass transition temperature in subsequent polymerization processes. Therefore, improving the selectivity and cis-trans ratio of the product CBDO has become one of the two major challenges of this hydrogenation technology.

[0004]

[0005] Patent document 1 US20120149946A1 discloses ruthenium catalysts and ruthenium powders with various supports for the hydrogenation of CBDK, with a conversion rate of up to 100%. However, the selectivity of CBDO is the highest at 91%, the cis-trans ratio is the highest at 1.11, and the reaction conditions are harsh, with a temperature of 130~140℃ and a pressure of about 3MPa.

[0006] Patent document 2 CN114349596A discloses a method for synthesizing 2,2,4,4-tetraalkyl-1,3-cyclobutanediol. The catalyst used is a ruthenium-indium bimetallic catalyst supported on activated carbon, which increases the stability of the catalyst and appropriately improves the cis-trans ratio of the product. However, the cis-trans ratio is as high as 1.2, and the reaction conditions are harsh, requiring a reaction temperature of 100~200℃ and a pressure of 2~4MPa.

[0007] In summary, existing CBDK hydrogenation processes suffer from harsh reaction conditions and low cis-trans ratios in the product CBDO. Therefore, there is an urgent need to develop a catalyst that can make the CBDK hydrogenation reaction conditions mild and simultaneously achieve high selectivity and cis-trans ratios in the reaction products, thereby enabling the continuous industrial production of CBDO. Summary of the Invention

[0008] To address the technical problems of harsh reaction conditions and relatively low cis-trans ratio of CBDO in existing CBDK hydrogenation processes, this application provides a carbon-supported ionic liquid bimetallic catalyst, its preparation method, and its application in the preparation of CBDO.

[0009] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: First, this application provides a carbon-supported ionic liquid bimetallic catalyst, the catalyst comprising a support and a main metal, a cooperating metal and an ionic liquid supported on the support, wherein the support is activated carbon Ac, the main metal is Ru, and the cooperating metal is Ce, Cu or Ag; wherein, based on the total mass of the catalyst, the loading of the main metal Ru is 3 to 8 wt% and the loading of the cooperating metal is 0.1 to 0.5 wt%.

[0010] Furthermore, the loading of the auxiliary metal Ce is 0.1~0.3wt%, the loading of the auxiliary metal Cu is 0.1~0.5wt%, and the loading of the auxiliary metal Ag is 0.1~0.5wt%.

[0011] Furthermore, the loading of the ionic liquid is 25-35 wt% based on the total mass of the catalyst.

[0012] Furthermore, the ionic liquid is 1-butyl-3-methyl-imidazolium p-methylbenzenesulfonate, 1-propyl-3-methyl-imidazolium chloride, or 1-propyl-3-methylbis(trifluoromethanesulfonyl)imide.

[0013] The catalyst prepared in this application has a specific surface area of ​​600~2000 m². 2 / g, pore size 0.5~20nm, pore volume 0.5~10cm³ 3 / g.

[0014] Secondly, this application also provides a method for preparing the carbon-supported ionic liquid bimetallic catalyst, comprising the following steps: A ruthenium compound was dissolved in deionized water to obtain a ruthenium Ru impregnation solution; a fluxing metal compound was dissolved in deionized water to obtain a fluxing metal M impregnation solution. A mixed impregnation solution is prepared by uniformly mixing the main metal Ru (Ru) impregnation solution and the auxiliary metal M (M) impregnation solution. The mixed impregnation solution is used to impregnate the carrier activated carbon Ac. After impregnation, the carbon-supported bimetallic catalyst Ru-M / Ac is obtained by drying. The carbon-supported bimetallic catalyst Ru-M / Ac was impregnated in the prepared ionic liquid IL impregnation solution, and dried after impregnation to obtain the carbon-supported ionic liquid bimetallic catalyst Ru-M-IL / Ac.

[0015] Furthermore, the drying conditions include a temperature of 110°C and a time of 12 hours. After the impregnation is completed, the process further includes a placement and intermittent stirring step; the placement conditions include indoor placement for 10 hours; the intermittent stirring conditions include stirring for 5 minutes at 1-hour intervals.

[0016] Finally, this application also provides the application of the carbon-supported ionic liquid bimetallic catalyst in the preparation of 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

[0017] Furthermore, the preparation method of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol is as follows: The hydrogenation reaction of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was catalyzed using the carbon-supported ionic liquid bimetallic catalyst to form 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

[0018] Furthermore, the mass concentration of the 2,2,4,4-tetramethyl-1,3-cyclobutanedione solution is 10~40wt%, and the mass of the catalyst accounts for 0.1~2% of the mass of CBDK; the conditions for the hydrogenation reaction include: a temperature of 60~100℃ and a pressure of 0.5~1MPa.

[0019] This application provides a carbon-supported ionic liquid bimetallic catalyst, its preparation method, and its application. The catalyst Ru-M-IL / Ac comprises a support and a main metal, a cooperating metal, and an ionic liquid supported on the support. The support is activated carbon Ac, the main metal is Ru, and the cooperating metal is Ce, Cu, or Ag. Compared with known technologies: First, the catalyst Ru-M-IL / Ac provided in this application introduces an ionic liquid. The microenvironment provided by the ionic liquid drives the migration of the promoter metal, which can effectively accept CBDK molecules and transfer them to the host metal Ru, enabling the hydrogenation reaction to proceed rapidly. Furthermore, the interaction between the ionic liquid and the active component Ru alters the charge density of the Ru particles, significantly increasing the activation level of the reactants and making the CBDK hydrogenation reaction conditions more moderate. The hydrogenation reaction temperature of this application can be controlled between 60 and 100°C, and the pressure can be controlled between 0.5 and 1 MPa. These reaction conditions are more suitable for industrial production.

[0020] Secondly, in known prior art, mild hydrogenation reaction conditions typically reduce the reaction rate, leading to a prolonged reaction time. However, the inventors unexpectedly discovered that using the catalyst provided in this application to catalyze the hydrogenation reaction of CBDK can still achieve a high reaction rate while maintaining mild reaction conditions. This achieves the effect of at least not prolonging the reaction time, and even shortening it, under mild conditions. This application increases the proportion of the main metal Ru in the catalyst to accelerate the hydrogenation reaction rate, but a decrease in the content of the co-metal will reduce the cis-trans ratio of the product. Therefore, this application balances the reaction time and the cis-trans ratio of the product CBDO by adjusting the content of the bimetallic compounds in the catalyst to a suitable ratio range. Under the premise of ensuring mild hydrogenation reaction conditions, a relatively ideal CBDO selectivity and cis-trans ratio can be achieved without an excessively long reaction time. The CBDO product obtained by the hydrogenation reaction of this application has a CBDO selectivity greater than 99.5% and a cis-trans ratio greater than 2.2.

[0021] Finally, the catalyst Ru-M-IL / A provided in this application, when used for the CBDK hydrogenation reaction, ensures mild reaction conditions and high CBDO selectivity and cis-trans ratio without sacrificing CBDK conversion. The conversion rate of the CBDK feedstock in this application can still reach over 98%. Furthermore, the hydrogenation process of this application is simple, requiring no additional isomerization reactors, thus reducing process steps and operating costs.

[0022] As can be seen from the above technical solutions, the catalyst Ru-M-IL / A provided in this application is used to prepare CBDO by hydrogenation reaction of CBDK. The hydrogenation reaction conditions are mild and the selectivity and cis-trans ratio of the product CBDO are good. The preparation process is simple and conducive to industrial production, which can meet the needs of subsequent copolyester product preparation in industry. Attached Figure Description

[0023] Figure 1 A process flow diagram for the preparation of 2,2,4,4-tetramethyl-1,3-cyclobutanediol provided in this application; Figure 2The gas chromatogram of CBDO, the product of the hydrogenation reaction provided in Example 1. Detailed Implementation

[0024] This application discloses a carbon-supported ionic liquid bimetallic catalyst, its preparation method, and its application in the preparation of CBDO. Those skilled in the art can refer to the content of this document and appropriately modify the process parameters to achieve the desired results. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in this invention. The methods and applications of this invention have been described through preferred embodiments. Those skilled in the art will clearly be able to modify or appropriately change and combine the methods and applications described herein without departing from the content, spirit, and scope of this invention to realize and apply the technology of this invention.

[0025] This application provides a carbon-supported ionic liquid bimetallic catalyst Ru-M-IL / Ac, the catalyst comprising a support and a main metal, a cooperating metal and an ionic liquid supported on the support, wherein the support is activated carbon Ac, the main metal is Ru, the cooperating metal M is Ce, Cu or Ag, and IL is an ionic liquid; in the catalyst, the loading of the main metal Ru is 3~8 wt% and the loading of the cooperating metal is 0.1~0.5 wt% based on the total mass of the catalyst.

[0026] When the auxiliary metal is Ce, the loading of Ce is preferably 0.1 to 0.3 wt%; when the auxiliary metal is Cu, the loading of Cu is preferably 0.1 to 0.5 wt%; when the auxiliary metal is Ag, the loading of Ag is preferably 0.1 to 0.5 wt%.

[0027] The ionic liquid is preferably 1-butyl-3-methylimidazolium p-methylbenzenesulfonate, 1-propyl-3-methylimidazolium chloride, or 1-propyl-3-methylbis(trifluoromethanesulfonyl)imide. The loading of the ionic liquid in this application is preferably 25-35 wt%. Within this range, a sufficient microenvironment is ensured, while also enhancing the interaction between the ionic liquid and the host metal Ru, thereby increasing the catalyst activity and enabling the hydrogenation reaction to proceed rapidly and gently. Furthermore, it avoids excessive ionic liquid clogging the pores of the activated carbon support, which would reduce catalyst activity.

[0028] The catalyst prepared in this application preferably has a specific surface area of ​​600-2000 m². 2 / g, pore size preferably 0.5~20nm, pore volume preferably 0.5~10cm³ 3 / g.

[0029] This application also provides a method for preparing the carbon-supported ionic liquid bimetallic catalyst, which mainly includes the following steps: A ruthenium compound was dissolved in deionized water to obtain a ruthenium Ru impregnation solution; a fluxing metal compound was dissolved in deionized water to obtain a fluxing metal M impregnation solution. A mixed impregnation solution is prepared by uniformly mixing the main metal ruthenium (Ru) impregnation solution and the auxiliary metal M impregnation solution. The mixed impregnation solution is then used to impregnate the carrier activated carbon Ac. After impregnation is completed, the carbon-supported bimetallic catalyst Ru-M / Ac is obtained by drying. The carbon-supported bimetallic catalyst Ru-M / Ac was impregnated in the prepared ionic liquid IL impregnation solution, and dried after impregnation to obtain the carbon-supported ionic liquid bimetallic catalyst Ru-M-IL / Ac.

[0030] Specifically, the preparation method of carbon-supported ionic liquid bimetallic catalyst can preferably follow the following steps: Step 1: Dissolve ruthenium chloride in deionized water and dilute to a final volume to prepare a solution containing ruthenium with a concentration of 0.001 g / mL as the main metal ruthenium impregnation solution; dissolve the auxiliary metal compound in deionized water and dilute to a final volume to prepare a solution containing auxiliary metal M with a concentration of 0.001 g / mL as the auxiliary metal impregnation solution. Step 2: After the main metal ruthenium impregnation solution and the auxiliary metal M impregnation solution are stirred evenly to obtain a mixed impregnation solution, a certain mass of activated carbon support Ac is weighed and poured evenly into the impregnation solution; the catalyst after impregnation is placed indoors for 8 hours, stirred for 5 minutes every 1 hour, and finally placed in a 110 ℃ forced-air drying oven for 12 hours to obtain the carbon-supported bimetallic catalyst Ru-M / Ac; Step 3: The carbon-supported bimetallic catalyst Ru-M / Ac is uniformly poured into the ionic liquid impregnation solution. After impregnation, the catalyst is placed indoors for 10 h, stirred for 5 min every 1 h, and then placed in a 110 ℃ forced-air drying oven for 12 h to finally obtain the carbon-supported ionic liquid bimetallic catalyst Ru-M-IL / Ac. The ionic liquid IL mentioned in the above preparation method can preferably be 1-butyl-3-methyl-imidazolium p-methylbenzenesulfonate, 1-propyl-3-methyl-imidazolium chloride, or 1-propyl-3-methylbis(trifluoromethanesulfonyl)imide salt.

[0031] The catalyst prepared in this application has the following loadings based on the total mass of the catalyst: the main metal Ru is 3-8 wt%, the auxiliary metal is 0.1-0.5 wt%, and the ionic liquid is 25-35 wt%.

[0032] This application also provides the application of the aforementioned carbon-supported ionic liquid bimetallic catalyst in the preparation of CBDO; the method for preparing CBDO is as follows: A solution of 2,2,4,4-tetramethyl-1,3-cyclobutanedione (CBDK) and a solution of carbon-supported ionic liquid bimetallic catalyst Ru-M-IL / Ac were mixed and hydrogen gas was introduced to carry out a hydrogenation reaction, forming 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO).

[0033] Specifically, the preferred method for preparing CBDO is as follows: Step 1: Add a measured amount of CBDK and organic solvent to the raw material vessel, stir evenly and heat to 40°C until completely dissolved. Add a measured amount of Ru-Ce-IL / Ac catalyst and organic solvent to the catalyst vessel and stir evenly. Preferably, the raw material CBDK and the catalyst Ru-M-IL / Ac described in this application are prepared into a solution using an organic solvent. Specifically, the organic solvent is preferably one or more of butyl acetate, ethanol, or tetrahydrofuran. The mass concentration of the 2,2,4,4-tetramethyl-1,3-cyclobutanedione solution is preferably 10-40 wt%, and the catalyst mass is preferably 0.1-2% of the CBDK mass. Step 2: Turn on the feed pumps of the raw material reactor and the catalyst reactor, and control the flow rate of the CBDK solution and the catalyst solution to 0.5 BV / h respectively using flow meters. At the same time, continuously introduce hydrogen into the reactor, maintain the hydrogen pressure at 0.5~1 MPa, and maintain the reaction temperature in the reactor at 60~100℃ to carry out the hydrogenation reaction. The reaction liquid at the outlet of the secondary reactor is filtered to remove the catalyst and crystallized to obtain CBDO.

[0034] Specifically, the number of stages in the hydrogenation multistage stirred reactor can be adjusted to 2 to 5 as needed; the filter used for filtration of the reaction liquid is one of the following: plate and frame filter, bag filter, or ceramic membrane filter, and the operating temperature during filtration can preferably be 60 to 100°C.

[0035] The catalyst Ru-M-IL / Ac provided in this application is used for the preparation of 2,2,4,4-tetramethyl-1,3-cyclobutanedione (CBDO). The addition of ionic liquid makes the CBDK hydrogenation reaction conditions milder. The content of the main metal Ru in the catalyst is increased to accelerate the hydrogenation reaction rate. Although a certain product cis-trans ratio is lost, the reaction time is shortened under the premise of mild hydrogenation reaction conditions. At the same time, the selectivity and cis-trans ratio of CBDO suitable for industrial applications are achieved without sacrificing the conversion rate of CBDK.

[0036] To enable those skilled in the art to better understand the present invention, the present invention will be further described in detail below with reference to specific embodiments.

[0037] The test materials used in this application are all commercially available products that can be purchased on the market.

[0038] The cis-trans ratio and selectivity of the product CBDO described in the specific embodiments of this application were calculated by gas chromatography peak surface analysis according to the following formula: Formula 1 for calculating cis-inverse ratio:

[0039] Formula 1: Ws, W i These represent the masses corresponding to cis-CBDO and trans-CBDO, respectively, fs and f i The relative quality correction factors for cis and trans products are (using standard samples with known cis / trans ratios, the peak areas of each are determined using the internal standard method, and then the relative quality correction factors are calculated), As, A i The peak areas of cis-CBDO and trans-CBDO are given by gas chromatography. Formula 2 for Calculating the Selectivity of Product CBDO:

[0040] Formula 2: W0 and W1 are the masses of CBDK before and after the reaction, respectively; f0 is the relative mass correction factor of the raw material CBDK; and A0 and A1 are the gas chromatographic peak areas of CBDK before and after the reaction.

[0041] Unless otherwise specified, the gas chromatography conditions used in this application are as follows: a gas chromatograph equipped with an FID monitor and an Rtx-Wax capillary column (60.0m × 0.32mm × 0.50mm) was used to analyze the samples using the internal standard method. The internal standard was trimethylbenzene. The injection port temperature was 240℃, and the split ratio was 100:1. The monitor temperature was 250℃. The carrier gas was high-purity nitrogen. The column temperature was 60℃ for 5 min, then increased to 180℃ at a rate of 5℃ / min and held for 4 min.

[0042] Example 1 (1) Dissolve 2.0544 g of ruthenium chloride in deionized water and dilute to 1000.0 mL to prepare a solution containing 0.001 g / mL of ruthenium as an impregnation solution for the catalyst. (2) Dissolve 1.7607 g of cerium chloride in deionized water and dilute to 1000.0 mL to prepare a solution containing 0.001 g / mL of cerium as an impregnation solution for the catalyst. (3) First, take 500 ml of ruthenium impregnation solution, then add 10 ml of cerium impregnation solution, and gently stir to mix evenly to obtain a mixed impregnation solution; then, weigh 6.5 g of activated carbon and pour it evenly into the mixed impregnation solution; place the impregnated catalyst indoors for 8 h, stir for 5 min every 1 h, and finally put it in a 110 ℃ forced air drying oven for 12 h to obtain the carbon-supported bimetallic catalyst Ru-Ce / Ac; (4) Take 3.0g of 1-butyl-3-methyl-imidazolium p-methylbenzenesulfonate and dissolve it completely in deionized water. Pour the carbon-supported bimetallic catalyst Ru-M / Ac obtained in step 3 into the ionic liquid impregnation solution. Place the impregnated catalyst indoors for 10 h, stir for 5 min every 1 h, and then put it into a 110 ℃ forced air drying oven for 12 h. Finally, the Ru-Ce-IL / Ac catalyst is obtained.

[0043] (5) Add 20g CBDK and 80g butyl acetate to the raw material tank, stir evenly and heat to 40°C until completely dissolved, add 0.1g of catalyst Ru-Ce-IL / Ac and 10g butyl acetate to the catalyst tank, and stir evenly; (6) Turn on the feed pumps of the raw material reactor and the catalyst reactor. Control the flow rate of the CBDK solution to 0.5 BV / h and the flow rate of the catalyst solution to 0.5 BV / h respectively using flow meters. Simultaneously, continuously introduce hydrogen gas into the reactor, maintaining a hydrogen pressure of 0.8 MPa. Maintain the reaction temperature in the reactor at 90°C. The reaction residence time is approximately 1 hour. The reaction liquid at the outlet of the secondary reactor is filtered to remove the catalyst, and then crystallized and purified to obtain the product CBDO. The product CBDO is detected by gas chromatography. For its gas chromatogram, please refer to [link to gas chromatogram]. Figure 2 The conversion rate of raw material CBDK was 98.5%, the selectivity of product CBDO was 99.6%, and the cis-trans ratio was 2.4.

[0044] Example 2 (1) Dissolve 2.0544 g of ruthenium chloride in deionized water and dilute to 1000.0 mL to prepare a solution containing 0.001 g / mL of ruthenium as an impregnation solution for the catalyst. (2) Dissolve 2.4500g of silver nitrate in deionized water and dilute to 1000.0mL to prepare a solution containing 0.001g / mL of silver as an impregnation solution for the catalyst. (3) First, take 500 ml of ruthenium impregnation solution, then add 10 ml of silver impregnation solution, and gently stir to mix evenly to obtain a mixed impregnation solution; then, weigh 6.5 g of activated carbon and pour it evenly into the impregnation solution, place the impregnated catalyst indoors for 8 h, stir for 5 min every 1 h, and finally put it into a 110 ℃ forced air drying oven for 12 h, carbon-supported bimetallic catalyst Ru-Ag / Ac; (4) Take 3.0g of 1-butyl-3-methyl-imidazolium p-methylbenzenesulfonate and dissolve it completely in deionized water. Pour the carbon-supported bimetallic catalyst Ru-Ag / Ac obtained in step 3 into the ionic liquid impregnation solution evenly. Place the impregnated catalyst indoors for 10 h, stir for 5 min every 1 h, and then put it into a 110 ℃ forced air drying oven for 12 h. Finally, the Ru-Ag-IL / Ac catalyst is obtained.

[0045] (5) Add 20g CBDK and 80g butyl acetate to the raw material tank, stir evenly and heat to 40°C until completely dissolved, add 0.02g Ru-Ag-IL / Ac catalyst and 10g butyl acetate to the catalyst tank, and stir evenly; (6) Turn on the feed pumps of the raw material reactor and the catalyst reactor, and control the flow rate of the CBDK solution to 0.5 BV / h and the flow rate of the catalyst solution to 0.5 BV / h respectively using flow meters. At the same time, continuously introduce hydrogen into the reactor, maintain the hydrogen pressure at 0.8 MPa, maintain the reaction temperature in the reactor at 90°C, and the reaction residence time is about 1 hour. The reaction liquid at the outlet of the secondary reactor is filtered to remove the catalyst, and crystallized to obtain the product CBDO. The conversion rate of CBDK is 98.2%, the selectivity of the product CBDO is 99.5%, and the cis-trans ratio is 2.4.

[0046] Example 3 (1) Dissolve 2.0544 g of ruthenium chloride in deionized water and dilute to 1000.0 mL to prepare a solution containing 0.001 g / mL of ruthenium as an impregnation solution for the catalyst. (2) Dissolve 2.0800g of copper dichloride dihydrate in deionized water and dilute to 1000.0mL to prepare a solution containing 0.001g / mL of copper as an impregnation solution for the catalyst. (3) First, take 500 ml of ruthenium impregnation solution, then add 10 ml of copper impregnation solution, and gently stir to mix evenly to obtain a mixed impregnation solution. Then, weigh 6.5 g of activated carbon and pour it evenly into the impregnation solution. Place the impregnated catalyst indoors for 8 h, stir for 5 min every 1 h, and finally put it in a 110 ℃ forced-air drying oven for 12 h to obtain the carbon-supported bimetallic catalyst Ru-Cu / Ac; (4) Take 3.0g of 1-butyl-3-methyl-imidazolium p-methylbenzenesulfonate and dissolve it completely in deionized water. Pour the carbon-supported bimetallic catalyst Ru-M / Ac obtained in step 3 into the ionic liquid impregnation solution. Place the impregnated catalyst indoors for 10 h, stir for 5 min every 1 h, and then put it into a 110 ℃ forced air drying oven for 12 h. Finally, the Ru-Cu-IL / Ac catalyst is obtained.

[0047] (5) Add 20g CBDK and 80g butyl acetate to the raw material tank, stir evenly and heat to 40°C until completely dissolved, add 0.1g catalyst Ru-Cu-IL / Ac and 10g butyl acetate to the catalyst tank, and stir evenly; (6) Turn on the feed pumps of the raw material reactor and the catalyst reactor, and control the flow rate of the CBDK solution to 0.5 BV / h and the flow rate of the catalyst solution to 0.5 BV / h respectively through the flow meter. At the same time, continuously introduce hydrogen into the reactor and maintain the hydrogen pressure at 0.8 MPa. Maintain the reaction temperature in the reactor at 90°C. The residence time of the reaction is about 1 hour. The reaction liquid at the outlet of the secondary reactor is filtered to remove the catalyst and crystallized to obtain the product CBDO. The conversion rate of CBDK is 98.5%, the selectivity of the product CBDO is 99.7%, and the cis-trans ratio is 2.2.

[0048] Example 4 (1) Dissolve 2.0544 g of ruthenium chloride in deionized water and dilute to 1000.0 mL to prepare a solution containing 0.001 g / mL of ruthenium as an impregnation solution for the catalyst.

[0049] (2) Dissolve 1.7607 g of cerium chloride in deionized water and dilute to 1000.0 mL to prepare a solution containing 0.001 g / mL of cerium as an impregnation solution for the catalyst.

[0050] (3) First, take 800 ml of ruthenium impregnation solution, then add 20 ml of cerium impregnation solution, and gently stir to mix evenly to obtain a mixed impregnation solution; then, weigh 6.5 g of activated carbon and pour it evenly into the impregnation solution; place the impregnated catalyst indoors for 8 h, stir for 5 min every 1 h, and finally put it in a 110 ℃ forced air drying oven for 12 h to obtain the carbon-supported bimetallic catalyst Ru-Ce / Ac; (4) Take 3.0g of 1-propyl-3-methyl-imidazolium chloride and dissolve it completely in deionized water. Pour the carbon-supported bimetallic catalyst Ru-Ce / Ac obtained in step 3 into the ionic liquid impregnation solution evenly. Place the impregnated catalyst indoors for 10 h, stir for 5 min every 1 h, and then put it into a 110 ℃ forced air drying oven for 12 h. Finally, the Ru-Ce-IL / Ac catalyst is obtained.

[0051] (5) Add 20g CBDK and 80g butyl acetate to the raw material tank, stir evenly and heat to 40°C until completely dissolved, add 0.1g catalyst Ru-Ce-IL / Ac and 10g butyl acetate to the catalyst tank, and stir evenly; (6) Turn on the feed pumps of the raw material reactor and the catalyst reactor, and control the flow rate of the CBDK solution to 0.5 BV / h and the flow rate of the catalyst solution to 0.5 BV / h respectively through the flow meter. At the same time, continuously introduce hydrogen into the reactor and maintain the hydrogen pressure at 0.8 MPa. Maintain the reaction temperature in the reactor at 90°C. The residence time of the reaction is about 1 hour. The reaction liquid at the outlet of the secondary reactor is filtered to remove the catalyst and crystallized to obtain the product CBDO. The conversion rate of CBDK is 99.5%, the selectivity of the product CBDO is 99.5%, and the cis-trans ratio is 2.2.

[0052] Example 5 (1) Dissolve 2.0544 g of ruthenium chloride in deionized water and dilute to 1000.0 mL to prepare a solution containing 0.001 g / mL of ruthenium as an impregnation solution for the catalyst.

[0053] (2) Dissolve 1.7607 g of cerium chloride in deionized water and dilute to 1000.0 mL to prepare a solution containing 0.001 g / mL of cerium as an impregnation solution for the catalyst.

[0054] (3) First, take 300 ml of ruthenium impregnation solution, then add 20 ml of cerium impregnation solution, and gently stir to mix evenly to obtain a mixed impregnation solution. Then, weigh 6.5 g of activated carbon and pour it evenly into the impregnation solution. Place the impregnated catalyst indoors for 8 h, stir for 5 min every 1 h, and finally put it in a 110 ℃ forced-air drying oven for 12 h to obtain the carbon-supported bimetallic catalyst Ru-Ce / Ac; (4) Take 3.0g of 1-propyl-3-methyl-imidazolium chloride and dissolve it completely in deionized water. Pour the carbon-supported bimetallic catalyst Ru-Ce / Ac obtained in step 3 into the ionic liquid impregnation solution evenly. Place the impregnated catalyst indoors for 10 h, stir for 5 min every 1 h, and then put it into a 110 ℃ forced air drying oven for 12 h. Finally, the Ru-Ce-IL / Ac catalyst is obtained.

[0055] (5) Add 20g CBDK and 80g butyl acetate to the raw material tank, stir evenly and heat to 40°C until completely dissolved, add 0.1g catalyst Ru-Ce-IL / Ac and 10g butyl acetate to the catalyst tank, and stir evenly; (6) Turn on the feed pumps of the raw material reactor and the catalyst reactor, and control the flow rate of the CBDK solution to 0.5 BV / h and the flow rate of the catalyst solution to 0.5 BV / h respectively using flow meters. At the same time, continuously introduce hydrogen into the reactor, maintain the hydrogen pressure at 0.8 MPa, maintain the reaction temperature in the reactor at 90°C, and the reaction residence time is about 1 hour. The reaction liquid at the outlet of the secondary reactor is filtered to remove the catalyst, and crystallized to obtain the product CBDO. The conversion rate of CBDK is 98.2%, the selectivity of the product CBDO is 99.5%, and the cis-trans ratio is 2.9.

[0056] Example 6 (1) Dissolve 2.0544 g of ruthenium chloride in deionized water and dilute to 1000.0 mL to prepare a solution containing 0.001 g / mL of ruthenium as an impregnation solution for the catalyst. (2) Dissolve 1.7607 g of cerium chloride in deionized water and dilute to 1000.0 mL to prepare a solution containing 0.001 g / mL of cerium as an impregnation solution for the catalyst. (3) First, take 500 ml of ruthenium impregnation solution, then add 10 ml of cerium impregnation solution, gently stir and mix evenly to obtain mixed impregnation solution. Then, weigh 6.5 g of activated carbon and pour it evenly into the impregnation solution. Place the impregnated catalyst indoors for 8 h, stir for 5 min every 1 h, and finally put it into a 110 ℃ forced air drying oven for 12 h to obtain carbon-supported bimetallic catalyst Ru-Ce / Ac; (4) Take 3.0g of 1-propyl-3-methyl-imidazolium chloride and dissolve it completely in deionized water. Pour the carbon-supported bimetallic catalyst Ru-Ce / Ac obtained in step 3 into the ionic liquid impregnation solution evenly. Place the impregnated catalyst indoors for 10 h, stir for 5 min every 1 h, and then put it into a 110 ℃ forced air drying oven for 12 h. Finally, the Ru-Ce-IL / Ac catalyst is obtained.

[0057] (5) Add 20g CBDK and 80g butyl acetate to the raw material tank, stir evenly and heat to 40°C until completely dissolved, add 0.2g Ru-Ce-IL / Ac catalyst and 10g butyl acetate to the catalyst tank, and stir evenly; (6) Turn on the feed pumps of the raw material reactor and the catalyst reactor, and control the flow rate of the CBDK solution to 0.5 BV / h and the flow rate of the catalyst solution to 0.5 BV / h respectively through the flow meter. At the same time, continuously introduce hydrogen into the reactor and maintain the hydrogen pressure at 1 MPa. Maintain the reaction temperature in the reactor at 100℃. The residence time of the reaction is about 1 hour. The reaction liquid at the outlet of the secondary reactor is filtered to remove the catalyst and crystallized to obtain the product CBDO. The conversion rate of CBDK is 99.0%, the selectivity of the product CBDO is 99.5%, and the cis-trans ratio is 2.3.

[0058] Example 7 (1) Dissolve 2.0544 g of ruthenium chloride in deionized water and dilute to 1000.0 mL to prepare a solution containing 0.001 g / mL of ruthenium as an impregnation solution for the catalyst. (2) Dissolve 2.4500g of silver nitrate in deionized water and dilute to 1000.0mL to prepare a solution containing 0.001g / mL of silver as an impregnation solution for the catalyst. (3) First, take 800 ml of ruthenium impregnation solution, then add 20 ml of silver impregnation solution, and gently stir to mix evenly to obtain a mixed impregnation solution. Then, weigh 6.5 g of activated carbon and pour it evenly into the impregnation solution. Place the impregnated catalyst indoors for 8 h, stir for 5 min every 1 h, and finally put it in a 110 ℃ forced-air drying oven for 12 h to obtain the carbon-supported bimetallic catalyst Ru-Ag / Ac; (4) Take 3.0g of 1-butyl-3-methyl-imidazolium p-methylbenzenesulfonate and dissolve it completely in deionized water. Pour the carbon-supported bimetallic catalyst Ru-Ag / Ac obtained in step 3 into the ionic liquid impregnation solution evenly. Place the impregnated catalyst indoors for 10 h, stir for 5 min every 1 h, and then put it into a 110 ℃ forced air drying oven for 12 h. Finally, the Ru-Ag-IL / Ac catalyst is obtained.

[0059] (5) Add 20g CBDK and 80g butyl acetate to the raw material tank, stir evenly and heat to 40°C until completely dissolved, add 0.1g catalyst Ru-Ag-IL / Ac and 10g butyl acetate to the catalyst tank, and stir evenly; (6) Turn on the feed pumps of the raw material reactor and the catalyst reactor, and control the flow rate of the CBDK solution to 0.5 BV / h and the flow rate of the catalyst solution to 0.5 BV / h respectively through the flow meter. At the same time, continuously introduce hydrogen into the reactor and maintain the hydrogen pressure at 0.5 MPa. Maintain the reaction temperature in the reactor at 90°C. The residence time of the reaction is about 1 hour. The reaction liquid at the outlet of the secondary reactor is filtered to remove the catalyst and crystallized to obtain the product CBDO. The conversion rate of CBDK is 98.1%, the selectivity of the product CBDO is 99.5%, and the cis-trans ratio is 3.0.

[0060] Example 8 (1) Dissolve 2.0544 g of ruthenium chloride in deionized water and dilute to 1000.0 mL to prepare a solution containing 0.001 g / mL of ruthenium as an impregnation solution for the catalyst.

[0061] (2) Dissolve 2.0800g of copper dichloride dihydrate in deionized water and dilute to 1000.0mL to prepare a solution containing 0.001g / mL of copper as an impregnation solution for the catalyst.

[0062] (3) First, take 800 ml of ruthenium impregnation solution, then add 20 ml of copper impregnation solution, gently stir and mix evenly to obtain mixed impregnation solution. Then, weigh 6.5 g of activated carbon and pour it evenly into the impregnation solution. Place the impregnated catalyst indoors for 8 h, stir for 5 min every 1 h, and finally put it into a 110 ℃ forced air drying oven for 12 h to obtain carbon-supported bimetallic catalyst Ru-Cu / Ac. (4) Take 3.0g of 1-butyl-3-methyl-imidazolium p-methylbenzenesulfonate and dissolve it completely in deionized water. Pour the carbon-supported bimetallic catalyst Ru-Cu / Ac obtained in step 3 into the ionic liquid impregnation solution evenly. Place the impregnated catalyst indoors for 10 h, stir for 5 min every 1 h, and then put it into a 110 ℃ forced air drying oven for 12 h. Finally, the Ru-Cu-IL / Ac catalyst is obtained.

[0063] (5) Add 20g CBDK and 80g butyl acetate to the raw material tank, stir evenly and heat to 40°C until completely dissolved, add 0.1g catalyst Ru-Cu-IL / Ac and 10g butyl acetate to the catalyst tank, and stir evenly; (6) Turn on the feed pumps of the raw material reactor and the catalyst reactor, and control the flow rate of the CBDK solution to 0.5 BV / h and the flow rate of the catalyst solution to 0.5 BV / h respectively through the flow meter. At the same time, continuously introduce hydrogen into the reactor and maintain the hydrogen pressure at 1 MPa. Maintain the reaction temperature in the reactor at 60°C. The residence time of the reaction is about 1 hour. The reaction liquid at the outlet of the secondary reactor is filtered to remove the catalyst and crystallized to obtain the product CBDO. The conversion rate of CBDK is 98.0%, the selectivity of the product CBDO is 99.6%, and the cis-trans ratio is 2.6.

[0064] Example 9 (1) Dissolve 2.0544 g of ruthenium chloride in deionized water and dilute to 1000.0 mL to prepare a solution containing 0.001 g / mL of ruthenium as an impregnation solution for the catalyst. (2) Dissolve 2.0800g of copper dichloride dihydrate in deionized water and dilute to 1000.0mL to prepare a solution containing 0.001g / mL of copper as an impregnation solution for the catalyst. (3) First, take 300 ml of ruthenium impregnation solution, then add 20 ml of copper impregnation solution, gently stir and mix evenly to obtain mixed impregnation solution. Then, weigh 6.5 g of activated carbon and pour it evenly into the impregnation solution. Place the impregnated catalyst indoors for 8 h, stir for 5 min every 1 h, and finally put it into a 110 ℃ forced air drying oven for 12 h to obtain carbon-supported bimetallic catalyst Ru-Cu / Ac. (4) Take 3.0g of 1-propyl-3-methylbis(trifluoromethanesulfonyl)imide salt and dissolve it completely in deionized water. Pour the carbon-supported bimetallic catalyst Ru-Cu / Ac obtained in step 3 into the ionic liquid impregnation solution evenly. Place the impregnated catalyst indoors for 10 h, stir for 5 min every 1 h, and then put it into a 110 ℃ forced air drying oven for 12 h. Finally, the Ru-Cu-IL / Ac catalyst is obtained.

[0065] (5) Add 20g CBDK and 80g butyl acetate to the raw material tank, stir evenly and heat to 40℃ until completely dissolved, add 0.1g catalyst Ru-Cu-IL / Ac and 10g butyl acetate to the catalyst tank, and stir evenly; (6) Turn on the feed pumps of the raw material reactor and the catalyst reactor, and control the flow rate of the CBDK solution to 0.5 BV / h and the flow rate of the catalyst solution to 0.5 BV / h respectively through the flow meter. At the same time, continuously introduce hydrogen into the reactor and maintain the hydrogen pressure at 1 MPa. Maintain the reaction temperature in the reactor at 100℃. The residence time of the reaction is about 1 hour. The reaction liquid at the outlet of the secondary reactor is filtered to remove the catalyst and crystallized to obtain the product CBDO. The conversion rate of CBDK is 98.5%, the selectivity of the product CBDO is 99.5%, and the cis-trans ratio is 2.7.

[0066] The final product CBDO obtained in Examples 1-9 has a specific surface area of ​​600~2000 m². 2 The pore size is between 0.5 and 20 nm, and the pore volume is between 0.5 and 10 cm³. 3 Between / g.

[0067] Comparative Example 1 (1) Dissolve 2.0544 g of ruthenium chloride in deionized water and dilute to 1000.0 mL to prepare a solution containing 0.001 g / mL of ruthenium as an impregnation solution for the catalyst. (2) Dissolve 1.7607 g of cerium chloride in deionized water and dilute to 1000.0 mL to prepare a solution containing 0.001 g / mL of cerium as an impregnation solution for the catalyst. (3) First, take 800 ml of ruthenium impregnation solution, then add 20 ml of cerium impregnation solution, gently stir and mix evenly to obtain mixed impregnation solution. Then, weigh 6.5 g of activated carbon and pour it evenly into the impregnation solution. Place the impregnated catalyst indoors for 8 h, stir for 5 min every 1 h, and finally put it into a 110 ℃ forced air drying oven for 12 h to obtain carbon-supported bimetallic catalyst Ru-Ce / Ac.

[0068] (4) Add 20g CBDK and 80g butyl acetate to the raw material tank, stir evenly and heat to 40℃ until completely dissolved, add 0.1g catalyst Ru-Ce / Ac and 10g butyl acetate to the catalyst tank, and stir evenly; (5) Turn on the feed pumps of the raw material reactor and the catalyst reactor, and control the flow rate of the CBDK solution to 0.5 BV / h and the flow rate of the catalyst solution to 0.5 BV / h respectively through the flow meter. At the same time, continuously introduce hydrogen into the reactor and maintain the hydrogen pressure at 0.8 MPa. Maintain the reaction temperature in the reactor at 90°C. The residence time of the reaction is about 1 hour. The reaction liquid at the outlet of the secondary reactor is filtered to remove the catalyst and crystallized to obtain the product CBDO. The conversion rate of CBDK is 90.7%, the selectivity of the product CBDO is 85.3%, and the cis-trans ratio is 2.2.

[0069] In this comparative example, the conversion rate and selectivity of CBDK should be similar to those of Example 4 (the CBDK conversion rate of Example 4 is 99.5%, the CBDO selectivity is 99.5%, the reaction temperature needs to reach above 140°C, and the reaction pressure needs to reach above 3MPa).

[0070] Comparative Example 2 (1) Dissolve 2.0544 g of ruthenium chloride in deionized water and dilute to 1000.0 mL to prepare a solution containing 0.001 g / mL of ruthenium as an impregnation solution for the catalyst. (2) Dissolve 2.0923g of zinc chloride in deionized water and dilute to 1000.0mL to prepare a solution containing 0.001g / mL of zinc as an impregnation solution for the catalyst. (3) First, take 800 ml of ruthenium impregnation solution, then add 20 ml of zinc impregnation solution, gently stir and mix evenly to obtain mixed impregnation solution. Then, weigh 6.5 g of activated carbon and pour it evenly into the impregnation solution. Place the impregnated catalyst indoors for 8 h, stir for 5 min every 1 h, and finally put it into a 110 ℃ forced air drying oven for 12 h to obtain carbon-supported bimetallic catalyst Ru-Zn / Ac; (4) Take 3.0g of 1-propyl-3-methyl-imidazolium chloride and dissolve it completely in deionized water. Pour the carbon-supported bimetallic catalyst Ru-Zn / Ac obtained in step 3 into the ionic liquid impregnation solution evenly. Place the impregnated catalyst indoors for 10 h, stir for 5 min every 1 h, and then put it into a 110 ℃ forced air drying oven for 12 h. Finally, the Ru-Zn-IL / Ac catalyst is obtained.

[0071] (5) Add 20g CBDK and 80g butyl acetate to the raw material reactor, stir evenly and heat to 40℃ until completely dissolved; add 0.1g Ru-Zn-IL / Ac catalyst and 10g butyl acetate to the catalyst reactor, and stir evenly; (6) Turn on the feed pumps of the raw material reactor and the catalyst reactor, and control the flow rate of the CBDK solution to 0.5 BV / h and the flow rate of the catalyst solution to 0.5 BV / h respectively through the flow meter. At the same time, continuously introduce hydrogen into the reactor and maintain the hydrogen pressure at 0.8 MPa. Maintain the reaction temperature in the reactor at 90°C. The residence time of the reaction is about 1 hour. The reaction liquid at the outlet of the secondary reactor is filtered to remove the catalyst and crystallized to obtain the product CBDO. The conversion rate of CBDK is 98.0%, the selectivity of the product CBDO is 95.4%, and the cis-trans ratio is 1.2.

[0072] Comparative Example 3 (1) Dissolve 2.0544 g of ruthenium chloride in deionized water and dilute to 1000.0 mL to prepare a solution containing 0.001 g / mL of ruthenium as an impregnation solution for the catalyst. (2) Dissolve 1.7607 g of cerium chloride in deionized water and dilute to 1000.0 mL to prepare a solution containing 0.001 g / mL of cerium as an impregnation solution for the catalyst. (3) First, take 50 ml of ruthenium impregnation solution, then add 20 ml of cerium impregnation solution, gently stir and mix evenly to obtain a mixed impregnation solution. Then, weigh 6.5 g of activated carbon and pour it evenly into the impregnation solution. Place the impregnated catalyst indoors for 8 h, stir for 5 min every 1 h, and finally put it into a 110 ℃ forced air drying oven for 12 h to obtain the carbon-supported bimetallic catalyst Ru-Ce / Ac.

[0073] (4) Take 3.0g of 1-propyl-3-methyl-imidazolium chloride and dissolve it completely in deionized water. Pour the carbon-supported bimetallic catalyst Ru-Ce / Ac obtained in step 3 into the ionic liquid impregnation solution evenly. Place the impregnated catalyst indoors for 10 h, stir for 5 min every 1 h, and then put it into a 110 ℃ forced air drying oven for 12 h. Finally, the Ru-Ce-IL / Ac catalyst is obtained.

[0074] (5) Add 20g CBDK and 80g butyl acetate to the raw material tank, stir evenly and heat to 40°C until completely dissolved. Add 0.1g Ru-Ce-IL / Ac catalyst and 10g butyl acetate to the catalyst tank and stir evenly.

[0075] (6) Turn on the feed pumps of the raw material reactor and the catalyst reactor, and control the flow rate of the CBDK solution to 0.5 BV / h and the flow rate of the catalyst solution to 0.5 BV / h respectively using flow meters. At the same time, continuously introduce hydrogen into the reactor, maintain the hydrogen pressure at 0.8 MPa, maintain the reaction temperature in the reactor at 90°C, and the reaction residence time is about 1 hour. The reaction liquid at the outlet of the secondary reactor is filtered to remove the catalyst, and crystallized to obtain the product CBDO. The conversion rate of CBDK is 73.3%, the selectivity of the product CBDO is 99.5%, and the cis-trans ratio is 8.2.

[0076] In this comparative example, the proportion of the main metal ruthenium decreases while the proportion of the auxiliary metal cerium increases relatively. Due to the increase in the amount of auxiliary metal, the cis-trans ratio increases, and the reaction rate decreases. In the same reaction time, this directly results in insufficient CBDK conversion, which is only about 73%.

[0077] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A carbon-supported ionic liquid bimetallic catalyst, characterized in that, The catalyst includes a support and a main metal, a cooperating metal, and an ionic liquid supported on the support. The support is activated carbon Ac, the main metal is Ru, and the cooperating metal is selected from at least one of Ce, Cu, and Ag. In the catalyst, the loading of the main metal Ru is 3-8 wt% and the total loading of the auxiliary metals is 0.1-0.5 wt% based on the total mass of the catalyst. The ionic liquid is selected from at least one of 1-butyl-3-methyl-imidazolium p-methylbenzenesulfonate, 1-propyl-3-methyl-imidazolium chloride, and 1-propyl-3-methylbis(trifluoromethanesulfonyl)imide.

2. The carbon-supported ionic liquid bimetallic catalyst as described in claim 1, characterized in that, When the auxiliary metal is Ce, the loading of the auxiliary metal Ce is 0.1~0.3wt%; When the auxiliary metal is Cu, the loading of Cu is 0.1~0.5 wt%; When the auxiliary metal is Ag, the loading of the auxiliary metal Ag is 0.1~0.5wt%.

3. The carbon-supported ionic liquid bimetallic catalyst as described in claim 1, characterized in that, The loading of the ionic liquid is 25-35 wt% based on the total mass of the catalyst.

4. The carbon-supported ionic liquid bimetallic catalyst as described in claim 1, characterized in that, The catalyst has a specific surface area of ​​600~2000 m². 2 / g, pore size 0.5~20nm, pore volume 0.5~10cm³ 3 / g.

5. The method for preparing the carbon-supported ionic liquid bimetallic catalyst according to any one of claims 1-4, characterized in that, include: Obtain a mixed impregnation solution containing the main metal and the auxiliary metal; The carrier activated carbon Ac was impregnated with the mixed impregnation solution, and then dried to obtain the carbon-supported bimetallic catalyst Ru-M / Ac. The carbon-supported bimetallic catalyst Ru-M / Ac was impregnated in the prepared ionic liquid IL impregnation solution, and after impregnation was completed, it was dried to obtain the carbon-supported ionic liquid bimetallic catalyst Ru-M-IL / Ac.

6. A method for preparing 2,2,4,4-tetramethyl-1,3-cyclobutanediol, characterized in that, include: The hydrogenation reaction of 2,2,4,4-tetramethyl-1,3-cyclobutanedione is catalyzed by the carbon-supported ionic liquid bimetallic catalyst according to any one of claims 1-4 to form 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

7. The preparation method according to claim 6, characterized in that, The mass concentration of the 2,2,4,4-tetramethyl-1,3-cyclobutanedione solution is 10~40wt%, and the mass of the catalyst accounts for 0.1~2% of the mass of 2,2,4,4-tetramethyl-1,3-cyclobutanedione.

8. The preparation method according to claim 6 or 7, characterized in that, The conditions for the hydrogenation reaction include: a temperature of 60~100℃ and a pressure of 0.5~1MPa.

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