Chiral ligand catalyst and application thereof in preparation of high-selectivity trans-1, 4 cyclohexanediol through hydroquinone hydrogenation reaction
By using chiral ligand catalyst composed of RhCl3, chiral bisphosphine ligand, support and metal salt, the problem of difficult to achieve high selectivity in the synthesis of reverse-1,4-cyclohexanediol is solved, and the synthesis of high selectivity reverse-1,4-cyclohexanediol is achieved, which reduces production costs and expands the production possibility.
Patent Information
- Application Number
- CN202411689027.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-25
- Publication Date
- 2025-02-25
AI Technical Summary
The prior art is difficult to achieve high selectivity in the synthesis of reverse-1,4-cyclohexanediol, resulting in unsatisfactory product ratio, high cost, and difficult to expand production.
A chiral ligand catalyst consisting of RhCl3, chiral bisphosphine ligand, support (such as silica gel 60, activated carbon, TiO2, etc.) and metal salts (such as nitrate or phosphate of Na, Fe, Co, Zn, Cu), is prepared by hydroquinone hydrogenation reaction.
The proportion of reverse-1,4-cyclohexanediol products has been significantly increased, the product quality and yield have been improved, while reducing production costs, and providing the possibility of expanding production.
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Abstract
Description
Technical Field
[0001] The present invention relates to a chiral ligand catalyst for use in the chemical industry and an application thereof, and in particular to a chiral ligand catalyst and an application thereof in the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol. Background Art
[0002] In the synthesis of cardiovascular disease drugs, trans-1,4-cyclohexanediol is a key intermediate in the synthesis of certain statins, such as atorvastatin. Atorvastatin is used to lower blood cholesterol levels and prevent and treat cardiovascular diseases.
[0003] In terms of anticancer drugs, it is an important intermediate for the synthesis of certain paclitaxel analogs. In addition, trans-1,4-cyclohexanediol can also be used to synthesize a series of triazole ester compounds, which can be used to manufacture liquid crystal materials. The highly selective synthesis method of trans-1,4-cyclohexanediol has important research significance. Summary of the invention
[0004] The purpose of the present invention is to provide a chiral ligand catalyst and its application in the synthesis of highly selective trans-1,4-cyclohexanediol. In view of the shortcomings and limitations of the prior art, a cheap and readily available approach is designed to reduce the production cost and effectively increase the proportion of trans-1,4-cyclohexanediol products, thereby providing the possibility of expanding production.
[0005] In order to achieve the above-mentioned object, the present invention provides a chiral ligand catalyst for the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol, wherein the catalyst is composed of a precursor and a ligand, a carrier and a metal salt; the precursor and the ligand are RhCl3 and a chiral diphosphorus ligand; the carrier is any one of silica gel 60, activated carbon, TiO2, γ-Al2O3 or NaY type molecular sieve; the metal salt is any one or more of nitrates or phosphates of Na, Fe, Co, Zn, and Cu.
[0006] The chiral ligand catalyst for the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol, wherein the ligand of the catalyst is a JosiPhos chiral diphosphorus ligand.
[0007] The chiral ligand catalyst for the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol, wherein the catalyst, by mass percentage, the precursor is 0.1-5% of the total mass of the catalyst, and the metal salt is 0-10.0% of the total mass of the catalyst.
[0008] The chiral ligand catalyst for the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol, wherein the catalyst, by mass percentage, the precursor accounts for 2% of the total mass of the catalyst, and the metal salt accounts for 0.25% of the total mass of the catalyst.
[0009] The present invention also provides a method for preparing the chiral ligand catalyst for the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol, wherein the method comprises: step 1, dissolving the precursor and the chiral diphosphorus ligand in water, stirring evenly to obtain a mixed solution; step 2, mixing the carrier with water evenly to obtain a carrier mixed solution; step 3, adding the precursor and ligand mixed solution obtained in step 1 to the carrier mixed solution obtained in step 2, heating and reacting; step 4, filtering the product obtained in step 3, washing it to neutrality, drying it, and then extruding it into a mold; step 5, immersing the molded product obtained in step 4 in a metal salt solution, stirring it evenly; step 6, removing water from the mixed solution obtained in step 5 by evaporating it, heating it to dry it, and finally calcining it at high temperature.
[0010] The above-mentioned preparation method of the chiral ligand catalyst for the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol, wherein, in the step 1, RhCl3 and the chiral diphosphorus ligand are dissolved in ultrapure water, stirred at room temperature for 12 hours, and a mixed solution is obtained.
[0011] The above-mentioned method for preparing a chiral ligand catalyst for the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol, wherein, in the step 3, the precursor and ligand mixed solution is slowly added dropwise to a mixed solution of a carrier and ultrapure water, and the temperature is raised to 45°C for reaction for 4 hours.
[0012] The above-mentioned preparation method of the chiral ligand catalyst for the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol, wherein, in the step 4, the obtained product is filtered and washed with anhydrous ethanol until neutral, then dried at 80°C for 6h, and then formed by extrusion.
[0013] The above-mentioned method for preparing the chiral ligand catalyst for the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol, wherein, in the step 6, the obtained mixed solution is rotary evaporated at a temperature of 60°C, then dried at a temperature of 110°C, and finally calcined at a temperature of 550°C for 4h.
[0014] The present invention also provides an application of a chiral ligand catalyst prepared by the above method in the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol, wherein the catalyst is reduced before use and then used in the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol, the hydrogenation reaction is carried out in a fixed bed reactor, and the reaction conditions are: reaction temperature 50°C-120°C, reaction pressure 1-4MPa, mass concentration of hydroquinone 1%-20%, solvent is any one of ethanol, isopropanol, n-butanol or tetrahydrofuran, the molar ratio of hydrogen to hydroquinone is 10-200:1, and the weight hourly space velocity of hydroquinone is 0.01-0.5h -1 .
[0015] The chiral ligand catalyst provided by the present invention and its application in the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol have the following advantages:
[0016] The present invention provides a chiral ligand catalyst with high trans-1,4-cyclohexanediol selectivity, which is used for the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol, realizes a highly selective synthesis path of trans-1,4-cyclohexanediol, can significantly increase the proportion of trans-1,4-cyclohexanediol products, effectively improve product quality and yield, and reduce production costs, which has important practical significance and broad market prospects. DETAILED DESCRIPTION
[0017] The specific embodiments of the present invention are further described below.
[0018] The present invention provides a chiral ligand catalyst for preparing highly selective trans-1,4-cyclohexanediol by hydrogenation reaction of hydroquinone. The catalyst consists of a precursor and a ligand, a carrier and a metal salt. The precursor and the ligand are RhCl3 and a chiral diphosphorus ligand. The carrier is any one of silica gel 60, activated carbon, TiO2, γ-Al2O3 or NaY molecular sieve. The metal salt is any one or more of nitrates or phosphates of Na, Fe, Co, Zn and Cu.
[0019] Preferably, the ligand of the catalyst is a JosiPhos chiral diphosphorus ligand, namely (R)-1-[(SP)-2-(di-tert-butylphosphino)ferrocenyl]ethylbis(2-methylphenyl)phosphine, model number Josiphos SL-J505-1.
[0020] Chiral bisphosphine ligands are a class of organic molecules that play a role in asymmetric catalysis. They are usually composed of two phosphorus atoms linked together to form a chiral skeleton, on which different substituent groups are connected. The chiral structure of these ligands enables them to form selective interactions with substrate molecules, thereby achieving asymmetric catalytic reactions. In hydrogenation reactions, chiral bisphosphine ligands can control the stereochemistry of hydrogenation reactions through interactions with substrate molecules. This makes chiral bisphosphine ligands useful in industries such as pharmaceuticals, pesticides, and fragrances.
[0021] More preferably, the carrier is silica gel 60, and the metal salt is NaZnPO4 and NaCoPO4.
[0022] Calculated by mass percentage, the precursor accounts for 0.1-5% of the total mass of the catalyst, and the metal salt accounts for 0-10.0% of the total mass of the catalyst.
[0023] More preferably, the catalyst comprises, by mass percentage, 2% of the total mass of the catalyst by the precursor and 0.25% of the total mass of the catalyst by the metal salt.
[0024] The present invention also provides a preparation method of the chiral ligand catalyst for preparing highly selective trans-1,4-cyclohexanediol by hydrogenation reaction of hydroquinone, which comprises: step 1, dissolving a precursor and a chiral diphosphorus ligand in water, stirring evenly, and obtaining a mixed solution; step 2, mixing a carrier with water evenly, and obtaining a carrier mixed solution; step 3, adding the precursor and ligand mixed solution obtained in step 1 to the carrier mixed solution obtained in step 2, heating and reacting; step 4, filtering the product obtained in step 3, washing it to neutrality, drying it, and then extruding it into a mold; step 5, immersing the molded product obtained in step 4 in a metal salt solution, stirring it evenly; step 6, removing water from the mixed solution obtained in step 5 by evaporating it, heating it to dry it, and finally calcining it at high temperature.
[0025] Preferably, step 1 is to dissolve RhCl3 and the chiral diphosphorus ligand in ultrapure water, and stir at room temperature for 12 hours to obtain a mixed solution.
[0026] Step 3, slowly drop the precursor and ligand mixed solution into the mixed solution of the carrier and ultrapure water, and heat to 45° C. to react for 4 hours.
[0027] Step 4, the obtained product is filtered, washed with anhydrous ethanol until neutral, then dried at 80° C. for 6 hours, and then formed by extrusion.
[0028] Step 6, rotary evaporate the obtained mixed solution at 60° C., dry it at 110° C., and finally calcine it at 550° C. for 4 hours.
[0029] The present invention also provides the use of the chiral ligand catalyst prepared by the method in the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol, wherein the catalyst is reduced before use. The preferred reduction conditions are a pressure of 0.1-4.0 MPa, a reduction temperature of 100° C.-400° C., a reduction time of 1-6 h, and a reduction gas of a mixed gas composed of H2 and N2, wherein the volume concentration of hydrogen is 10%-100%.
[0030] The reduced catalyst is then used for the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol. Preferably, the hydrogenation reaction is carried out in a fixed bed reactor, the material of the reactor is 316L stainless steel, and the reaction conditions are: reaction temperature 50°C-120°C, reaction pressure 1-4MPa, mass concentration of hydroquinone 1%-20%, solvent is any one of ethanol, isopropanol, n-butanol or tetrahydrofuran, the molar ratio of hydrogen to hydroquinone is 10-200:1, and the weight hourly space velocity of hydroquinone is 0.01-0.5h -1 .
[0031] More preferably, the conditions of the hydrogenation reaction are: reaction temperature 50°C-80°C, reaction pressure 0.5-1MPa, mass concentration of hydroquinone 1%-5%, solvent ethanol or isopropanol, molar ratio of hydrogen to hydroquinone 1-20:1, and hydroquinone weight hourly space velocity 0.05-0.1h -1 .
[0032] The chiral ligand catalyst provided by the present invention and its application in the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol are further described below in conjunction with the examples.
[0033] It should be noted that these embodiments are merely illustrative and should not be construed as limiting the present invention. Where specific techniques or conditions are not specified in the embodiments, conventional experimental conditions or conditions recommended in the manufacturer's instructions are used. Where the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially, and substitutes with the same or similar effects can be used for equivalent replacement.
[0034] Example 1
[0035] Dissolve 0.2 g of RhCl3 and 0.3 g of chiral diphosphorus ligand in 10.25 g of ultrapure water, stir at room temperature for 12 h to obtain a mixed solution, then weigh 10 g of silica gel 60 and mix it with 30 g of ultrapure water, slowly add the Rh ligand solution dropwise to the silica gel mixture, then react at 45 ° C for 4 h, filter, wash the product with anhydrous ethanol until neutral, and then dry it at 80 ° C for 6 h, and then extrude it into shape.
[0036] Weigh 5 g of the formed catalyst, immerse it in a Na2HPO4 solution with a molar concentration of 0.5 mol / L and a Co(NO3)2 solution with a molar concentration of 0.1 mol / L, mix well, stir for 2 h, then rotary evaporate to dryness at 60 °C, then dry at 110 °C, and finally calcine at 550 °C for 4 h.
[0037] Example 2
[0038] Dissolve 0.4 g of RhCl3 and 0.6 g of chiral diphosphorus ligand in 20.5 g of ultrapure water, stir at room temperature for 12 h to obtain a mixed solution, then weigh 10 g of silica gel 60 and mix it with 30 g of ultrapure water, slowly add the Rh ligand solution dropwise to the silica gel mixture, then react at 45 ° C for 4 h, filter, wash the product with anhydrous ethanol until neutral, and then dry it at 80 ° C for 6 h, and then extrude it into shape.
[0039] Weigh 5 g of the formed catalyst, immerse it in a Na2HPO4 solution with a molar concentration of 0.5 mol / L and a Fe(NO3)2 solution with a molar concentration of 0.1 mol / L, mix well, stir for 2 h, then rotary evaporate at 60 °C, then dry at 110 °C, and finally calcine at 550 °C for 4 h.
[0040] Example 3
[0041] Dissolve 0.2 g of RhCl3 and 0.3 g of chiral diphosphorus ligand in 10.25 g of ultrapure water, stir at room temperature for 12 h to obtain a mixed solution, then weigh 10 g of silica gel 60 and mix it with 30 g of ultrapure water, slowly add the Rh ligand solution dropwise to the silica gel mixture, then react at 45 ° C for 4 h, filter, wash the product with anhydrous ethanol until neutral, and then dry it at 80 ° C for 6 h, and then extrude it into shape.
[0042] Weigh 5 g of the formed catalyst, immerse it in a Na2HPO4 solution with a molar concentration of 0.25 mol / L and a Cu(NO3)2 solution with a molar concentration of 0.05 mol / L, mix well, stir for 2 h, then rotary evaporate to dryness at 60 °C, then dry at 110 °C, and finally calcine at 550 °C for 4 h.
[0043] Example 4
[0044] Dissolve 0.2 g of RhCl3 and 0.3 g of chiral diphosphorus ligand in 10.25 g of ultrapure water, stir at room temperature for 12 h to obtain a mixed solution, then weigh 10 g of silica gel 60 and mix it with 30 g of ultrapure water, slowly add the Rh ligand solution dropwise to the silica gel mixture, then react at 45 ° C for 4 h, filter, wash the product with anhydrous ethanol until neutral, and then dry it at 80 ° C for 6 h, and then extrude it into shape.
[0045] Weigh 5 g of the formed catalyst, immerse it in a Na2HPO4 solution with a molar concentration of 0.5 mol / L and a Zn(NO3)2 solution with a molar concentration of 0.1 mol / L, mix well, stir for 2 h, then rotary evaporate to dryness at 60 °C, then dry at 110 °C, and finally calcine at 550 °C for 4 h.
[0046] Example 5
[0047] Dissolve 0.2 g of RhCl3 and 0.3 g of chiral diphosphorus ligand in 10.25 g of ultrapure water, stir at room temperature for 12 h to obtain a mixed solution, then weigh 10 g of activated carbon and mix it with 30 g of ultrapure water, slowly add the Rh ligand solution dropwise to the activated carbon suspension, then react at 45 °C for 4 h, filter, wash the product with anhydrous ethanol until neutral, then dry at 80 °C for 6 h, and then extrude it into shape.
[0048] Weigh 5 g of the formed catalyst, immerse it in a Na2HPO4 solution with a molar concentration of 0.5 mol / L and a Co(NO3)2 solution with a molar concentration of 0.1 mol / L, mix well, stir for 2 h, then rotary evaporate to dryness at 60 °C, then dry at 110 °C, and finally calcine at 550 °C for 4 h.
[0049] Example 6
[0050] Dissolve 0.2g of RhCl3 and 0.3g of chiral diphosphorus ligand in 10.25g of ultrapure water, stir at room temperature for 12h to obtain a mixed solution, then weigh 10g of TiO2 and mix it with 30g of ultrapure water, slowly add the Rh ligand solution dropwise to the TiO2 suspension, then react at 45℃ for 4h, filter, wash the product with anhydrous ethanol until neutral, then dry at 80℃ for 6h, and then extrude it into shape.
[0051] Weigh 5 g of the formed catalyst, immerse it in a Na2HPO4 solution with a molar concentration of 0.5 mol / L and a Co(NO3)2 solution with a molar concentration of 0.1 mol / L, mix well, stir for 2 h, then rotary evaporate to dryness at 60 °C, then dry at 110 °C, and finally calcine at 550 °C for 4 h.
[0052] Example 7
[0053] Dissolve 0.2 g of RhCl3 and 0.3 g of chiral diphosphorus ligand in 10.25 g of ultrapure water, stir at room temperature for 12 h to obtain a mixed solution, then weigh 10 g of γ-Al2O3 and mix it with 30 g of ultrapure water, slowly add the Rh ligand solution dropwise to the γ-Al2O3 suspension, then react at 45 °C for 4 h, filter, wash the product with anhydrous ethanol until neutral, then dry at 80 °C for 6 h, and then extrude it into shape.
[0054] Weigh 5 g of the formed catalyst, immerse it in a Na2HPO4 solution with a molar concentration of 0.5 mol / L and a Co(NO3)2 solution with a molar concentration of 0.1 mol / L, mix well, stir for 2 h, then rotary evaporate to dryness at 60 °C, then dry at 110 °C, and finally calcine at 550 °C for 4 h.
[0055] Example 8
[0056] Dissolve 0.2 g of RhCl3 and 0.3 g of chiral diphosphorus ligand in 10.25 g of ultrapure water, stir at room temperature for 12 h to obtain a mixed solution, then weigh 10 g of NaY molecular sieve and mix it with 30 g of ultrapure water, slowly add the Rh ligand solution dropwise to the molecular sieve suspension, then react at 45 ° C for 4 h, filter, wash the product with anhydrous ethanol until neutral, and then dry it at 80 ° C for 6 h, and then extrude it into shape.
[0057] Weigh 5 g of the formed catalyst, immerse it in a Na2HPO4 solution with a molar concentration of 0.5 mol / L and a Co(NO3)2 solution with a molar concentration of 0.1 mol / L, mix well, stir for 2 h, then rotary evaporate to dryness at 60 °C, then dry at 110 °C, and finally calcine at 550 °C for 4 h.
[0058] Comparative Example 1
[0059] Dissolve 0.2 g of RhCl3 in 10.25 g of ultrapure water, stir at room temperature for 12 h to obtain a RhCl3 solution, then weigh 10 g of silica gel 60, slowly drop the RhCl3 solution into the silica gel mixture, react at 45 °C for 4 h, filter, wash the product with anhydrous ethanol until neutral, then dry at 80 °C for 6 h, and then extrude it into shape.
[0060] Weigh 5 g of the formed catalyst, immerse it in a Na2HPO4 solution with a molar concentration of 0.5 mol / L and a Co(NO3)2 solution with a molar concentration of 0.1 mol / L, mix well, stir for 2 h, then rotary evaporate to dryness at 60 °C, then dry at 110 °C, and finally calcine at 550 °C for 4 h.
[0061] Comparative Example 2
[0062] Dissolve 0.2 g of RhCl3 in 10.25 g of ultrapure water, stir at room temperature for 12 h to obtain a RhCl3 solution, then weigh 10 g of silica gel 60, slowly drop the RhCl3 solution into the silica gel mixture, react at 45 °C for 4 h, filter, wash the product with anhydrous ethanol until neutral, then dry at 80 °C for 6 h, and then extrude it into shape.
[0063] Weigh 5 g of the formed catalyst, immerse it in a Na2HPO4 solution with a molar concentration of 0.5 mol / L and a Zn(NO3)2 solution with a molar concentration of 0.1 mol / L, mix well, stir for 2 h, then rotary evaporate to dryness at 60 °C, then dry at 110 °C, and finally calcine at 550 °C for 4 h.
[0064] The catalysts prepared in Examples 1 to 8 and Comparative Examples 1 to 2 were used in the hydrogenation reaction of hydroquinone.
[0065] The catalyst is reduced before use. The preferred reduction conditions are pressure 0.1-4.0MPa, reduction temperature 100°C-400°C, reduction time 1-6h, and the reduction gas used is a mixture of H2 and N2, with a hydrogen volume concentration of 10%-100%.
[0066] The reduced catalyst is used to produce highly selective trans-1,4-cyclohexanediol by hydrogenation of hydroquinone. The reaction is carried out in a fixed bed reactor made of 316L stainless steel.
[0067] The preferred reaction conditions are: reaction temperature 50°C-120°C, reaction pressure 1-4MPa, mass concentration of hydroquinone 1%-20%, solvent is any one of ethanol, isopropanol, n-butanol or tetrahydrofuran, molar ratio of hydrogen to hydroquinone is 10-200:1, and weight hourly space velocity of hydroquinone is 0.01-0.5h -1 .
[0068] More preferably, the reaction conditions are: reaction temperature 50°C-80°C, reaction pressure 0.5-1MPa, mass concentration of hydroquinone 1%-5%, solvent ethanol or isopropanol, molar ratio of hydrogen to hydroquinone 1-20:1, and hydroquinone weight hourly space velocity 0.05-0.1h -1 .
[0069] More preferably, the catalyst loading is 5 ml, the reaction temperature is 60°C, the reaction pressure is 0.8 MPa, the mass concentration of hydroquinone is 2%, the solvent is ethanol, the molar ratio of H2 to hydroquinone is 15:1, and the weight hourly space velocity of hydroquinone is 0.1 h -1 .
[0070] The liquid products were analyzed by gas chromatography using an Agilent Poroshell 120 chiral column and a FID detector, and the chromatograms were processed by area percentage normalization.
[0071] The results are shown in Table 1 below.
[0072] Table 1. Results of the hydrogenation reaction of hydroquinone using the catalysts of various examples and comparative examples.
[0073]
[0074] The chiral ligand catalyst provided by the present invention and its application in the preparation of highly selective trans-1,4-cyclohexanediol by hydrogenation reaction of hydroquinone, aiming at the problem that under normal circumstances, the hydrogenation reaction of hydroquinone generates two cis-trans isomers, and the ratio of cis-1,4-cyclohexanediol to trans-1,4-cyclohexanediol is between (6:4) and (3:1), a catalyst with high selectivity for trans-1,4-cyclohexanediol and its preparation method and application are provided, which can increase the ratio of trans-1,4-cyclohexanediol product to between 78% and 90%, thereby providing an effective way for the synthesis method of highly selective trans-1,4-cyclohexanediol.
[0075] Although the content of the present invention has been described in detail through the above preferred embodiments, it should be appreciated that the above description should not be considered as a limitation of the present invention. After reading the above content, it will be apparent to those skilled in the art that various modifications and substitutions of the present invention will occur. Therefore, the protection scope of the present invention should be limited by the appended claims.
Claims
1. A chiral ligand catalyst for the hydrogenation of hydroquinone to produce highly selective trans-1,4-cyclohexanediol, characterized in that: The catalyst is composed of a precursor, a ligand, a carrier and a metal salt; The precursor and ligand are RhCl3 and a chiral diphosphorus ligand; The carrier is any one of silica gel 60, activated carbon, TiO2, γ-Al2O3 or NaY molecular sieve; The metal salt is any one or more of nitrates or phosphates of Na, Fe, Co, Zn, and Cu.
2. The chiral ligand catalyst for preparing highly selective trans-1,4-cyclohexanediol by hydrogenation of hydroquinone as claimed in claim 1, characterized in that: The catalyst has a ligand which is a JosiPhos chiral diphosphorus ligand.
3. The chiral ligand catalyst for preparing highly selective trans-1,4-cyclohexanediol by hydrogenation of hydroquinone as claimed in claim 1, characterized in that: The catalyst, calculated by mass percentage, has a precursor accounting for 0.1-5% of the total mass of the catalyst, and a metal salt accounting for 0-10.0% of the total mass of the catalyst.
4. The chiral ligand catalyst for the hydrogenation of hydroquinone to produce highly selective trans-1,4-cyclohexanediol as claimed in claim 3, characterized in that: The catalyst, calculated by mass percentage, has a precursor accounting for 2% of the total mass of the catalyst, and a metal salt accounting for 0.25% of the total mass of the catalyst.
5. A method for preparing a chiral ligand catalyst for the hydrogenation of hydroquinone to produce highly selective trans-1,4-cyclohexanediol as claimed in any one of claims 1 to 4, characterized in that: The method comprises: Step 1, dissolving the precursor and the chiral diphosphorus ligand in water, stirring evenly to obtain a mixed solution; Step 2, mixing the carrier and water evenly to obtain a carrier mixed solution; Step 3, adding the precursor and ligand mixed solution obtained in step 1 to the carrier mixed solution obtained in step 2, and heating to react; Step 4, filtering the product obtained by the reaction in step 3, washing it to neutrality, drying it, and then extruding it; Step 5, immersing the molded product obtained in step 4 in a metal salt solution and stirring evenly; Step 6, removing water from the mixed solution obtained in step 5 by evaporation, then heating and drying, and finally high-temperature roasting.
6. The method for preparing a chiral ligand catalyst for preparing highly selective trans-1,4-cyclohexanediol by hydrogenation of hydroquinone as claimed in claim 5, characterized in that: In the step 1, RhCl3 and the chiral diphosphorus ligand are dissolved in ultrapure water, and stirred at room temperature for 12 hours to obtain a mixed solution.
7. The method for preparing a chiral ligand catalyst for preparing highly selective trans-1,4-cyclohexanediol by hydrogenation of hydroquinone as claimed in claim 5, characterized in that: In the step 3, the precursor and ligand mixed solution is slowly added dropwise to the mixed solution of the carrier and ultrapure water, and the temperature is raised to 45° C. to react for 4 hours.
8. The method for preparing a chiral ligand catalyst for preparing highly selective trans-1,4-cyclohexanediol by hydrogenation of hydroquinone as claimed in claim 5, characterized in that: In the step 4, the obtained product is filtered, washed with anhydrous ethanol until neutral, then dried at 80° C. for 6 hours, and then formed by extrusion.
9. The method for preparing a chiral ligand catalyst for preparing highly selective trans-1,4-cyclohexanediol by hydrogenation of hydroquinone as claimed in claim 5, characterized in that: In step 6, the obtained mixed solution is rotary evaporated to dryness at a temperature of 60° C., then dried at a temperature of 110° C., and finally calcined at a temperature of 550° C. for 4 hours.
10. Use of a chiral ligand catalyst prepared by the method according to claim 5 in the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol, characterized in that: The catalyst is reduced before use and then used for the hydrogenation reaction of hydroquinone to produce highly selective trans-1,4-cyclohexanediol. The hydrogenation reaction is carried out in a fixed bed reactor under the following reaction conditions: reaction temperature 50°C-120°C, reaction pressure 1-4MPa, mass concentration of hydroquinone 1%-20%, solvent ethanol, isopropanol, Any one of n-butanol or tetrahydrofuran, the molar ratio of hydrogen to hydroquinone is 10-200:1, The weight hourly space velocity of hydroquinone is 0.01-0.5h -1 .