Catalyst for producing 1, 4-cyclohexanedimethanol through hydrogenation of dimethyl 1, 4-cyclohexanedicarboxylate as well as preparation method and application of catalyst

Abstract

The invention relates to a catalyst for preparing 1, 4-cyclohexanedimethanol through hydrogenation of dimethyl 1, 4-cyclohexanedicarboxylate as well as a preparation method and application of the catalyst. The surface of the carrier CeO2 is modified by Zn-Zr alloy, so that the carrier has richer oxygen vacancies, the dispersity of active metal on the surface of the carrier can be improved, and the active metal shows higher performance. The prepared catalyst is applied to a 1, 4-dimethyl cyclohexanedicarboxylate hydrogenation reaction, and 1, 4-cyclohexanedimethanol with higher conversion rate, higher selectivity and higher trans-cis ratio can be obtained.

Description

Technical Field

[0001] The present invention relates to the field of catalysts, and in particular to a catalyst for preparing 1,4-cyclohexanedimethanol by hydrogenating 1,4-cyclohexanedicarboxylic acid dimethyl ester, and a preparation method and application thereof. Background Art

[0002] 1,4-cyclohexanedimethanol plays an important role in organic synthesis. It can participate in esterification, reduction and substitution reactions, and is used to synthesize organic compounds such as drugs, fragrances, dyes and surfactants. In addition, it is one of the important raw materials for the production of polyester resins. In particular, in the manufacturing process of poly(ethylene glycol acrylate), 1,4-cyclohexanedimethanol, as a component of copolymers, helps to improve the strength, transparency and temperature resistance of poly(ethylene glycol acrylate), making it an ideal material for a variety of applications such as plastic bottles, fibers and films. And with the promotion of multiple key driving factors such as polyester resin demand, sustainable packaging trends, automotive industry growth, new technology innovations, green chemistry trends and supply chain diversification, the market demand for 1,4-cyclohexanedimethanol will continue to increase.

[0003] 1,4-cyclohexanedimethanol mainly has two structures, cis and trans. The products produced by 1,4-cyclohexanedimethanol with trans structure have good heat resistance, so 1,4-cyclohexanedimethanol with high anti-cis ratio is more in line with market demand. CN112717941A discloses a preparation method of a catalyst for hydrogenating 1,4-cyclohexanedimethanol from dimethyl 1,4-cyclohexanedicarboxylate, which improves the stability of the catalyst, but the anti-cis ratio of 1,4-cyclohexanedimethanol in the product is relatively low. In the catalyst development technology for hydrogenating dimethyl 1,4-cyclohexanedicarboxylate, 1,4-cyclohexanedimethanol that can make the product have a high anti-cis ratio is a problem that needs to be solved urgently.

[0004] The literature (Luo J, Qu E, Zhou Y, et al. Re / AC catalysts for selective hydrogenation of dimethyl 1,4-cyclohexanedicarboxylate to 1,4-cyclohexanedimethanol: Essential roles of metal dispersion and chemical environment [J]. Applied Catalysis A: General, 2020, 602: 117669.) reported an activated carbon-supported rhenium catalyst for the selective hydrogenation of dimethyl 1,4-cyclohexanedicarboxylate to 1,4-cyclohexanedimethanol. The catalyst does not use highly polluting Cr. Under the conditions of 220 ° C and 10 MPa of hydrogen, the yield of 1,4-cyclohexanedimethanol is 66%. The catalyst is green and environmentally friendly, but it is not suitable for large-scale application because of its low economic benefits.

[0005] The literature (Yang, Lan, Feng, et al. Gas phase hydrogenation of dimethyl 1,4-cyclohexane dicarboxylate over highly dispersed and stable supported copper-based catalysts [J]. Journal of molecular catalysis A: Chemical, 2015.) reported a copper-based catalyst with high dispersibility and a 1,4-cyclohexanedimethanol yield of 95.6%, which provided a new idea for the study of the process of hydrogenating dimethyl 1,4-cyclohexanedicarboxylate to 1,4-cyclohexanedimethanol and had guiding significance for its further industrial application, but the cyclohexanedimethanol reverse-to-cis ratio was not reported. Copper-based catalysts perform well in hydrogenation reactions, and bimetallic catalysts will combine at high temperatures, and the calcined bimetallic catalysts can be reduced in a controllable manner to obtain supported metal nanocatalysts with high metal dispersion and adjustable metal particle size, which can play a synergistic role in the reaction and show higher activity.

[0006] Therefore, this patent provides a Zn-Zr alloy modified CeO 2 A supported copper-based catalyst and a preparation method thereof. The catalyst can be used to produce 1,4-cyclohexanedimethanol with a high trans-cis ratio. Summary of the invention

[0007] One of the technical problems to be solved by the present invention is to provide a low-pollution catalyst for hydrogenation of dimethyl 1,4-cyclohexanedicarboxylate, providing a substitute for the highly polluting Cr-containing catalyst currently used on a large scale.

[0008] The second technical problem to be solved by the present invention is to provide a method for preparing a low-pollution 1,4-cyclohexanedicarboxylic acid dimethyl ester hydrogenation catalyst corresponding to the first problem to be solved. The method can be used to produce a catalyst for 1,4-cyclohexanedicarboxylic acid dimethyl ester hydrogenation, overcoming the shortcomings of low yield and low economic benefit of existing low-pollution catalysts.

[0009] The third technical problem to be solved by the present invention is to provide a method for preparing a 1,4-cyclohexanedicarboxylic acid dimethyl ester hydrogenation catalyst with a high trans-cis ratio corresponding to the first problem solved. The product obtained using the catalyst has a higher trans-cis ratio and is more conducive to industrial application.

[0010] In order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows: a Zn-Zr doped cerium oxide carrier loaded with a copper-based catalyst solves the technical problems of too few active sites and too low activity of current green catalysts. The doped metal is calculated by mass percentage, and the doped metal is mainly copper, supplemented by zinc and zirconium, wherein the copper content in the catalyst is 10-35wt%, and the mass fraction of the total amount of zinc and zirconium doping is controlled to be 0.1-42wt%.

[0011] Preferably, the doping amount of zinc in the catalyst is 1.2-26.5wt%, the doping amount of zirconium is 0.9-15.5wt%, and the copper loading is 12.5-29.5wt%.

[0012] In order to solve the second technical problem mentioned above, the technical solution adopted by the present invention is as follows: a Zn-Zr alloy modified CeO support for the hydrogenation of dimethyl 1,4-cyclohexanedicarboxylate to produce 1,4-cyclohexanedimethanol 2 The preparation method of the supported copper-based catalyst comprises the following specific steps:

[0013] (1) Preparation of ZnZr-CeO 2 Carrier: First, a certain amount of zinc salt, zirconium salt and cerium salt are dissolved in deionized water respectively; alkaline solution and water are prepared into a precipitation solvent in a volume ratio of 1:1; the four solutions are respectively transferred dropwise into the same beaker, stirred for 1-5 hours after the addition is completed, filtered after aging for 1-5 hours, washed three times with deionized water, dried at 50-200°C until completely dry, and after drying, heated to 300-900°C at a rate of 0.5-5°C / min in an air atmosphere, and calcined at a constant temperature for 1-6 hours;

[0014] (2) Catalyst preparation: Take a certain amount of ZnZr-CeO 2The carrier is treated with a salt solution of active metal Cu according to an equal volume impregnation method, dried at 80-150° C. until completely dried, and then calcined at 400-900° C. at a rate of 1-5° C. / min for 1-5 hours in an air atmosphere.

[0015] Preferably, in step (1), the zinc salt is one or more of zinc nitrate, zinc sulfate, zinc acetate, and zinc borate, and the doping amount of zinc is 0.1-30wt%, and zinc nitrate is further preferred, and the doping amount of zinc is 1.2-26.5wt%;

[0016] Preferably, in step (1), the zirconium salt is one or more of zirconium nitrate, zirconium acetate, zirconium silicate, zirconium chloride and zirconium fluoride, and the doping amount of zirconium is 0.1-20wt%, and zirconium chloride is more preferably used, and the doping amount of zirconium is 0.9-15.5wt%.

[0017] Preferably, in step (1), the cerium salt is one or more of cerium chloride, cerium sulfate, and cerium acetate, and more preferably cerium sulfate.

[0018] Preferably, in step (1), the prepared Zn-Zr-CeO 2 Zn-Zr and CeO in the carrier 2 The mass ratio is 1:1-50, and more preferably 1:5-15.

[0019] Preferably, in step (1), the alkaline solution is aqueous ammonia, NaOH solution, Na 2 CO 3 One or more of the solution, more preferably Na 2 CO 3 Solution; the concentration of the alkaline solution is 0.5-20M, further optimized to 2-10M.

[0020] Preferably, in step (1), the stirring time is controlled at 1-5 h, more preferably at 2-5 h; the aging time is controlled at 1-5 h, more preferably at 1-4 h; and the drying temperature is controlled at 50-200° C., more preferably at 80-150° C.

[0021] Preferably, in step (1), the heating rate during calcination is 0.5-5°C / min, the temperature is raised to 300-900°C, and the duration is 1-6 hours, more preferably 2-5°C / min, the temperature is raised to 400-800°C, and the duration is 2-5 hours.

[0022] Preferably, in step (2), the active metal Cu salt is one or more of copper nitrate, copper sulfate, and copper acetylacetonate, most preferably copper sulfate, with a loading of 0.1-50wt%, most preferably 12.5-29.5wt%.

[0023] Preferably, in step (2), the drying temperature is controlled at 50-200°C, more preferably at 80-150°C.

[0024] Preferably, in step (2), the heating rate during calcination is 2-5°C / min, the temperature is raised to 400-800°C, and the duration is 1-6 hours, more preferably 3-5°C / min, the temperature is raised to 400-800°C, and the duration is 2-5 hours.

[0025] In order to solve the third technical problem, the technical solution adopted by the present invention is as follows: a method for producing 1,4-cyclohexanedimethanol with a high reverse-to-cis ratio, using the catalyst for solving the first technical problem, using dimethyl 1,4-cyclohexanedicarboxylate and hydrogen as raw materials, the molar ratio of hydrogen to dimethyl 1,4-cyclohexanedicarboxylate is 50-500, the reaction temperature is 200-350°C, the reaction pressure is 2-12MPa, the volume space velocity of dimethyl 1,4-cyclohexanedicarboxylate is 0.1-1.5h -1 , the reaction produces a product containing 1,4-cyclohexanedimethanol.

[0026] The Zn-Zr alloy modified carrier CeO prepared by the present invention 2 The copper-based catalyst replaced the Cr-containing catalyst, which greatly reduced the pollution to the environment. 2 The supported copper-based catalyst has more active sites than the traditional copper-based catalyst in the hydrogenation reaction of dimethyl 1,4-cyclohexanedicarboxylate. Under the above-mentioned reaction conditions, the optimal results are 99.96% conversion rate of dimethyl 1,4-cyclohexanedicarboxylate, 98.56% selectivity of 1,4-cyclohexanedimethanol, and 79.68% ratio of trans-1,4-cyclohexanedimethanol. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The Zn-Zr alloy modified support CeO prepared in Example 1 2 Scanning electron microscope image of the supported copper-based catalyst. DETAILED DESCRIPTION

[0028] The present invention is described below by means of specific embodiments, but the present invention is not limited thereto.

[0029] The preparation methods and conditions used in the following examples are conventional methods unless otherwise specified; the reagents and materials used in the following examples are commercially available unless otherwise specified.

[0030] [Example 1]

[0031] (1) Preparation of ZnZr-CeO by coprecipitation method 2Carrier: First, take 0.55g zinc nitrate, 0.35g zirconium chloride and 6.0g cerium sulfate and dissolve them in 100ml deionized water respectively; take 100ml 4M NaOH solution; transfer the four solutions drop by drop into the same beaker respectively; after the dropwise addition is completed, stir for 2h, after aging for 2h, filter and wash three times with deionized water, dry at 100℃ until completely dry, after drying, increase the temperature to 600℃ at a rate of 3℃ / min in air atmosphere, and calcine at a constant temperature for 3h.

[0032] (2) Catalyst preparation: 0.65 g ZnZr-CeO 2 For the carrier, 0.75 g of copper sulfate was taken and treated according to the equal volume impregnation method, and dried at 100°C until completely dry. After drying, the temperature was increased to 500°C at a rate of 2°C / min in an air atmosphere and calcined for 3 h.

[0033] Catalyst evaluation: The molar ratio of hydrogen to dimethyl 1,4-cyclohexanedicarboxylate was 100:1, the reaction temperature was 200°C, the reaction pressure was 6 MPa, and during the reaction, the volume space velocity was 0.4 h -1 The conversion rate of dimethyl 1,4-cyclohexanedicarboxylate was 99.96%, the selectivity of 1,4-cyclohexanedimethanol was 98.56%, and the proportion of trans-1,4-cyclohexanedimethanol was 79.68%.

[0034] [Example 2]

[0035] (1) Preparation of ZnZr-CeO by coprecipitation method 2 Carrier: First, take 0.55g zinc nitrate, 0.55g zirconium chloride and 6.0g cerium sulfate and dissolve them in 100ml deionized water respectively; take 100ml 3M NaOH solution; transfer the four solutions drop by drop into the same beaker respectively; after the dropwise addition is completed, stir for 3h, after aging for 3h, filter and wash three times with deionized water, dry at 100℃ until completely dry, after drying, increase the temperature to 600℃ at a rate of 3℃ / min in air atmosphere, and calcine at a constant temperature for 3h.

[0036] (2) Catalyst preparation: 0.65 g ZnZr-CeO 2 For the carrier, 0.75 g of copper sulfate was taken and treated according to the equal volume impregnation method, and dried at 100°C until completely dry. After drying, the temperature was increased to 500°C at a rate of 2°C / min in an air atmosphere and calcined for 3 h.

[0037] Catalyst evaluation: The molar ratio of hydrogen to dimethyl 1,4-cyclohexanedicarboxylate was 100:1, the reaction temperature was 200°C, the reaction pressure was 6 MPa, and during the reaction, the volume space velocity was 0.4 h -1The conversion rate of dimethyl 1,4-cyclohexanedicarboxylate was 98.21%, the selectivity of 1,4-cyclohexanedimethanol was 96.61%, and the proportion of trans-1,4-cyclohexanedimethanol was 73.68%.

[0038] [Example 3]

[0039] (1) Preparation of ZnZr-CeO by coprecipitation method 2 Carrier: First, take 0.15g zinc nitrate, 0.65g zirconium chloride and 6.0g cerium sulfate and dissolve them in 100ml deionized water respectively; take 100ml 3M NaOH solution; transfer the four solutions drop by drop into the same beaker respectively; after the dropwise addition is completed, stir for 3h, after aging for 3h, filter and wash three times with deionized water, dry at 100℃ until completely dry, after drying, increase the temperature to 600℃ at a rate of 3℃ / min in air atmosphere, and calcine at a constant temperature for 3h.

[0040] (2) Catalyst preparation: 0.65 g ZnZr-CeO 2 For the carrier, 0.75 g of copper sulfate was taken and treated according to the equal volume impregnation method, and dried at 100°C until completely dry. After drying, the temperature was increased to 500°C at a rate of 2°C / min in an air atmosphere and calcined for 3 h.

[0041] Catalyst evaluation: The molar ratio of hydrogen to dimethyl 1,4-cyclohexanedicarboxylate was 100:1, the reaction temperature was 200°C, the reaction pressure was 6 MPa, and during the reaction, the volume space velocity was 0.4 h -1 The conversion rate of dimethyl 1,4-cyclohexanedicarboxylate was 94.52%, the selectivity of 1,4-cyclohexanedimethanol was 93.49%, and the proportion of trans-1,4-cyclohexanedimethanol was 73.26%.

[0042] [Example 4-28]

[0043] Zn-Zr alloy modified CeO 2 The supported copper-based catalyst was prepared according to the preparation conditions in Table 1 and the steps similar to those in Example 1. The reaction results in Table 2 were obtained by referring to the conditions in the catalyst evaluation step in Table 2.

[0044] [Comparative Example 1]

[0045] Comparative Example 1 is with ZnZr-CeO 2 The supported copper-based catalyst is used for comparison, indicating that the doped modified CeO 2 The carrier-loaded active metal catalyst has better catalytic performance in the hydrogenation of dimethyl 1,4-cyclohexanedicarboxylate to produce 1,4-cyclohexanedimethanol.

[0046] (1) Prepare pure CeO using the method of Example 12 Carrier, take 1g CeO 2 For the carrier, 0.75 g of copper sulfate was taken and treated according to the equal volume impregnation method, and dried at 100°C until completely dry. After drying, the temperature was increased to 500°C at a rate of 2°C / min in an air atmosphere and calcined for 3 h to obtain a catalyst.

[0047] (2) Catalyst evaluation: The molar ratio of hydrogen to dimethyl 1,4-cyclohexanedicarboxylate was 100:1, the reaction temperature was 200°C, the reaction pressure was 6 MPa, and the volume space velocity was 0.4 h -1 The conversion rate of dimethyl 1,4-cyclohexanedicarboxylate was 74.29%, the selectivity of 1,4-cyclohexanedimethanol was 56.23%, and the proportion of trans-1,4-cyclohexanedimethanol was 53.21%.

[0048] [Comparative Example 2]

[0049] Comparative Example 2 is a ZnZr-CeO prepared by hydrothermal method. 2 The carrier is compared with the carrier prepared by the coprecipitation method in Example 2, which shows that the ZnZr-CeO 2 The carrier has better catalytic performance in the hydrogenation of dimethyl 1,4-cyclohexanedicarboxylate to produce 1,4-cyclohexanedimethanol.

[0050] (1) Preparation of ZnZr-CeO by hydrothermal method 2 Carrier: First, take 0.55g zinc nitrate, 0.55g zirconium chloride and 6.0g cerium sulfate and dissolve them in 100ml deionized water respectively; take 100ml 3M NaOH solution; transfer the four solutions dropwise into the same beaker, stir for 0.5h, transfer into a 500ml reactor, and prevent at 100℃ for 10h, filter the reaction product and wash it three times with deionized water, dry it at 100℃ until it is completely dry, and after drying, increase the temperature to 600℃ at a rate of 3℃ / min in air atmosphere, and calcine at a constant temperature for 3h.

[0051] (2) Catalyst preparation: 0.65 g ZnZr-CeO 2 For the carrier, 0.75 g of copper sulfate was taken and treated according to the equal volume impregnation method, and dried at 100°C until completely dry. After drying, the temperature was increased to 500°C at a rate of 2°C / min in an air atmosphere and calcined for 3 h.

[0052] Catalyst evaluation: The molar ratio of hydrogen to dimethyl 1,4-cyclohexanedicarboxylate was 100:1, the reaction temperature was 200°C, the reaction pressure was 6 MPa, and during the reaction, the volume space velocity was 0.4 h -1The conversion rate of dimethyl 1,4-cyclohexanedicarboxylate was 95.78%, the selectivity of 1,4-cyclohexanedimethanol was 92.94%, and the proportion of trans-1,4-cyclohexanedimethanol was 70.11%.

[0053] The above catalyst evaluation experiments were all conducted in an autoclave using a liquid phase hydrogenation reaction equipped with an electronic temperature controller. A certain amount of the reactant, dimethyl 1,4-cyclohexanedicarboxylate, was dissolved in isopropanol, and the catalyst was added in proportion. H 2 / Ar pre-reduction for a certain time. The reactor was purged with hydrogen three times to remove residual air, and the target reaction pressure was set. The reactor was then heated to the desired temperature under constant stirring to react. After the reaction was completed, the reaction product was taken out and analyzed using an Aglient GC7080 gas chromatograph, with a hydrogen flame ionization detector as the detector.

[0054] The conversion rate and product selectivity of 1,4-cyclohexanedicarboxylic acid dimethyl ester were calculated using the correction factor conversion method, and the formula is as follows:

[0055]

[0056] The conversion rate of dimethyl 1,4-cyclohexanedicarboxylate (DMCD) is:

[0057]

[0058] The selectivity of 1,4-cyclohexanedimethanol (CHDM) is:

[0059]

[0060] The product 1,4-cyclohexanedimethanol is divided into trans-1,4-cyclohexanedimethanol (trans-CHDM) and cis-1,4-cyclohexanedimethanol (cis-CHDM). The ratio formula of trans-1,4-cyclohexanedimethanol (trans-CHDM) is:

[0061]

[0062] Among them, f i is the relative molar correction factor of the corresponding component, A i is the chromatographic peak area of ​​the corresponding component, i is a certain component, and st is the standard substance DMCD used to calculate the relative correction factor. CHDM A represents the relative molar correction factor of the product CHDM, CHDM Indicates the chromatographic peak area corresponding to 1,4-cyclohexanedimethanol,

[0063] A trans-CHDM Represents the chromatographic peak area corresponding to trans-1,4-cyclohexanedimethanol.

[0064] Table 1

[0065]

[0066]

[0067] Table 2

[0068]

[0069] The raw materials and equipment used in the present invention, unless otherwise specified, are all commonly used raw materials and equipment in the art; the methods used in the present invention, unless otherwise specified, are all conventional methods in the art.

[0070] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent transformation made to the above embodiment based on the technical essence of the present invention still falls within the protection scope of the technical solution of the present invention.

Claims

1. A catalyst for preparing 1,4-cyclohexanedimethanol by hydrogenating dimethyl 1,4-cyclohexanedicarboxylate, characterized in that: In the catalyst with Zn-Zr doped CeO2 as carrier and loaded with metallic copper, the mass fraction of the total amount of zinc-zirconium doping is controlled to be 0.1-42wt%, and the copper loading is 10-35wt%.

2. The catalyst according to claim 1, characterized in that: The doping amount of zinc in the catalyst is 1.2-26.5wt%, the doping amount of zirconium is 0.9-15.5wt%, and the copper loading amount is 12.5-29.5wt%.

3. A method for preparing the catalyst as claimed in claim 1 or 2, comprising the following steps: (1) Preparation of ZnZr-CeO2 carrier: dissolving a certain amount of zinc salt, zirconium salt and cerium salt in deionized water respectively; preparing a precipitation solvent by mixing an alkaline solution with water in a volume ratio of 1:1; transferring the four solutions dropwise into the same beaker, stirring and aging, filtering and washing with deionized water, drying at 50-200°C, and then heating to 300-900°C at a rate of 0.5-5°C / min in an air atmosphere, and calcining at a constant temperature; (2) Catalyst preparation: Take a certain amount of ZnZr-CeO2 carrier, treat the active metal copper salt solution according to the equal volume impregnation method, dry at 80-150°C, and then raise the temperature to 400-900°C at a rate of 1-5°C / min in an air atmosphere and calcine for 1-5h.

4. The preparation method according to claim 3, characterized in that: In step (1), the zinc salt is one or more of zinc nitrate, zinc sulfate, zinc acetate, and zinc borate; the zirconium salt is one or more of zirconium nitrate, zirconium acetate, zirconium silicate, zirconium chloride, and zirconium fluoride; the cerium salt is one or more of cerium chloride, cerium sulfate, and cerium acetate; the mass ratio of ZnZr to CeO2 in the prepared ZnZr-CeO2 carrier is 1:1-50; the alkaline solution is one or more of ammonia water, NaOH solution, and Na2CO3 solution, and the concentration of the alkaline solution is 0.5-20M.

5. The preparation method according to claim 3, characterized in that: In step (2), the active metal copper salt is one or more of copper nitrate, copper sulfate, and copper acetylacetonate.

6. The preparation method according to claim 3, characterized in that: In step (1), the stirring time is 1-5h, the aging time is 1-5h, the drying temperature is 50-200°C, the heating rate during calcination is 0.5-5°C / min, the temperature is raised to 300-900°C, and the duration is 1-6h.

7. The preparation method according to claim 3, characterized in that: In step (2), the drying temperature is 50-200°C, the heating rate during calcination is 1-5°C / min, the temperature is raised to 400-900°C, and the calcination is continued for 1-5h.

8. The preparation method according to claim 3, characterized in that: In step (1), the doping amount of zinc is 0.1-30wt%, and the doping amount of zirconium is 0.1-20wt%.

9. The preparation method according to claim 8, characterized in that: In step (1), the doping amount of zinc is 1.2-26.5wt%, and the doping amount of zirconium is 0.9-15.5wt%.

10. The preparation method according to claim 4, characterized in that: In step (1), the mass ratio of Zn-Zr to CeO2 in the prepared ZnZr-CeO2 carrier is 1:5-15.

11. The preparation method according to claim 4, characterized in that: In step (1), the alkaline solution is a Na2CO3 solution, and the concentration of the alkaline solution is 2-10M.

12. The preparation method according to claim 3, characterized in that: In step (1), the stirring time is 2-5 hours, the aging time is 1-4 hours, the drying temperature is 80-150°C, the heating rate during calcination is 2-5°C / min, the temperature is raised to 400-800°C, and the calcination is continued for 2-5 hours.

13. The preparation method according to claim 3, characterized in that: In step (2), the loading amount of active metal copper salt is 12.5-29.5 wt %.

14. The preparation method according to claim 3, characterized in that: In step (2), the drying temperature is 80-150° C., and the heating rate during calcination is further preferably 3-5° C. / min, and the temperature is raised to 400-800° C. for 2-5 hours.

15. Use of the catalyst as claimed in claim 1 or 2 in the hydrogenation of dimethyl 1,4-cyclohexanedicarboxylate to produce 1,4-cyclohexanedimethanol.

16. The use according to claim 15, characterized in that: The catalyst is used, dimethyl 1,4-cyclohexanedicarboxylate and hydrogen are used as raw materials, the molar ratio of hydrogen to dimethyl 1,4-cyclohexanedicarboxylate is 50-500, the reaction temperature is 200-350° C., the reaction pressure is 2-12 MPa, and the volume space velocity of dimethyl 1,4-cyclohexanedicarboxylate is 0.1-1.5 h -1 , the reaction produces a product containing 1,4-cyclohexanedimethanol.

17. The use according to claim 16, characterized in that: The conversion rate of dimethyl 1,4-cyclohexanedicarboxylate is 68.56-99.96%, the selectivity of 1,4-cyclohexanedimethanol is 73.21-98.56%, and the proportion of trans-1,4-cyclohexanedimethanol in the product is 59.24-79.68%.

18. The use according to claim 16, characterized in that: The molar ratio of hydrogen to dimethyl 1,4-cyclohexanedicarboxylate is 100-300, the reaction temperature is 220-300°C, the reaction pressure is 4-8MPa, and the volume space velocity of dimethyl 1,4-cyclohexanedicarboxylate is more preferably 0.2-1.0h -1 .

19. The use according to claim 16, characterized in that: The conversion rate of dimethyl 1,4-cyclohexanedicarboxylate is more preferably 90.00-99.96%, the selectivity of 1,4-cyclohexanedimethanol is more preferably 90.00-98.56%, and the proportion of trans-1,4-cyclohexanedimethanol in the product is more preferably 65.00-79.68%.

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