Preparation method of hydrogenation catalyst and application of hydrogenation catalyst in preparation of 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol

Abstract

The invention provides a preparation method of a hydrogenation catalyst and application of the hydrogenation catalyst in preparation of 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol, a carrier of the hydrogenation catalyst is pretreated, the adsorption capacity of the carrier to active components is improved, the adsorption acting force between the active components and the carrier is enhanced, and the hydrogenation catalyst with excellent catalytic performance is obtained; when the hydrogenation catalyst is applied to preparation of 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol, the application frequency of the catalyst can be increased, the service life of the catalyst can be prolonged, and the purposes of reducing the product cost and improving the market competitiveness can be achieved.

Description

Technical Field

[0001] The invention relates to the technical field of catalysts, and in particular to a method for preparing a hydrogenation catalyst and application of the hydrogenation catalyst in the preparation of 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Background Art

[0002] 2,2,4,4-Tetramethyl-1,3-cyclobutanediol (CBDO) is an important aliphatic monomer and a high-performance copolyester Tritan. TM The important raw material for production. The polymer has the advantages of high transparency, high impact strength, high glass transition temperature, and good toughness. In addition, because polycarbonate resin releases bisphenol A during degradation, it causes environmental hazards such as endocrine disorders in humans, and its use is restricted or banned in some areas. Tritan, a copolyester made from 2,2,4,4-tetramethyl-1,3-cyclobutanediol TM It is an important substitute for polycarbonate, is green and environmentally friendly, and has broad market prospects.

[0003] At present, the industrial production technology of 2,2,4,4-tetramethyl-1,3-cyclobutanediol is mainly based on the route of isobutyric anhydride raw materials. In the first stage, isobutyric anhydride is thermally cracked to produce dimethyl ketone, which is then dimerized into 2,2,4,4-tetramethyl-1,3-cyclobutanedione (TMCD). 2,2,4,4-tetramethyl-1,3-cyclobutanedione is catalytically hydrogenated to obtain 2,2,4,4-tetramethyl-1,3-cyclobutanediol. In addition, a synthetic route using methacryloyl chloride as raw material has also been reported in China.

[0004] CN105732329A discloses a method for synthesizing 2,2,4,4-tetramethyl-1,3-cyclobutanediol, wherein 2,2,4,4-tetramethyl-1,3-cyclobutanedione is used as a reaction raw material, and a hydrogenation reaction is performed to generate 2,2,4,4-tetramethyl-1,3-cyclobutanediol. The catalyst used in the reaction includes copper, zinc, aluminum and chromium elements, and the weight proportions of copper, zinc, aluminum and chromium elements in terms of oxides are as follows: copper oxide accounts for 40 to 70 parts of the total weight of the catalyst; zinc oxide accounts for 10 to 35 parts of the total weight of the catalyst; aluminum oxide accounts for 10 to 20 parts of the total weight of the catalyst; and chromium oxide accounts for 5 to 10 parts of the total weight of the catalyst. The conversion rate of 2,2,4,4-tetramethyl-1,3-cyclobutanedione in a fixed bed high-pressure reaction is 87.7%, and the selectivity of 2,2,4,4-tetramethyl-1,3-cyclobutanediol is 85.8%.

[0005] CN105727967A discloses a catalyst for hydrogenation synthesis of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, a preparation method and application thereof, wherein the catalyst involved is a novel quaternary component catalyst, wherein the active components include copper oxide, zinc oxide, aluminum oxide and chromium oxide, and the catalyst includes copper, zinc, aluminum and chromium elements, wherein the weight proportions of copper, zinc, aluminum and chromium elements in terms of oxides are as follows: copper oxide accounts for 50-60 parts of the total weight of the catalyst; zinc oxide accounts for 15-25 parts of the total weight of the catalyst; aluminum oxide accounts for 15-20 parts of the total weight of the catalyst; and chromium oxide accounts for 5-10 parts of the total weight of the catalyst. The catalyst can convert 2,2,4,4-tetramethyl-1,3-cyclobutanedione into 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and is easy to prepare and has high catalytic activity.

[0006] CN103694083A discloses a method for preparing 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Using isobutyryl chloride as a raw material, triethylamine is added while stirring evenly in an ether solvent, and the reaction is refluxed for 13-16 hours. Wash with dilute hydrochloric acid. Remove the solvent under reduced pressure to obtain the intermediate 2,2,4,4-tetramethyl-1,3-cyclobutanedione. The intermediate is dissolved in a mixed solvent of methanol and water. Adjust the pH to alkaline with NaOH solution, add a certain amount of NaBH4 in batches under ice bath conditions, react at room temperature for 3-5 hours, and then quench with dilute hydrochloric acid. Remove the solvent, extract with anhydrous ethanol, spin off the ethanol and extract with water, and finally remove the water to obtain the product 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

[0007] However, the above-mentioned method for preparing 2,2,4,4-tetramethyl-1,3-cyclobutanediol still has problems such as high cost of the catalyst used and short service life of the catalyst. Summary of the invention

[0008] In view of the problems existing in the prior art, the present invention provides a method for preparing a hydrogenation catalyst and application thereof in the preparation of 2,2,4,4-tetramethyl-1,3-cyclobutanediol. After a specific pretreatment step is performed on a catalyst carrier, a solution containing active components is attached to the treated carrier, thereby greatly improving the adsorption capacity of the carrier for the active components, improving the catalytic performance and service life of the catalyst, and reducing the preparation cost of 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a method for preparing a hydrogenation catalyst, the method for preparing the hydrogenation catalyst comprising the following steps:

[0011] (1) sequentially performing hydrothermal pretreatment, vacuum drying and calcination pretreatment on the catalyst carrier to obtain a treated carrier;

[0012] The reaction liquid used in the hydrothermal pretreatment includes any one of nitric acid, sulfuric acid, hydrogen peroxide, phosphoric acid, hydrochloric acid, urea solution, melamine solution, boric acid, sodium borohydride solution, potassium borohydride solution, ammonium phosphate solution, ammonium hydrogen phosphate solution, sodium phosphate solution or potassium phosphate solution, or a combination of at least two thereof; the concentration of the reaction liquid is 0.1 to 30 wt %; the temperature of the calcination pretreatment is 100 to 500° C.;

[0013] (2) attaching a solution containing active components to the treated carrier, and performing drying and reduction treatment to obtain the hydrogenation catalyst;

[0014] The method of attaching the solution containing the active ingredient to the treated carrier includes any one of an impregnation method, an adsorption method or a spray adsorption method.

[0015] The preparation method of the hydrogenation catalyst of the present invention first performs hydrothermal pretreatment, vacuum drying and calcination pretreatment on the catalyst carrier in sequence to improve the adsorption capacity of the carrier for the active substance and enhance the adsorption force between the active substance and the carrier; then, an impregnation method, an adsorption method or a spray adsorption method is used to attach a solution containing the active component to the treated carrier, and after drying and reduction treatment, a hydrogenation catalyst with high catalytic performance and long service life is obtained.

[0016] The present invention uses a specific reaction liquid to perform hydrothermal pretreatment on the catalyst carrier, which has the effects of removing interstitial impurities, expanding pores, increasing specific surface area, and increasing surface functional groups. If the catalyst carrier is not subjected to hydrothermal pretreatment and directly subjected to calcination pretreatment, some pores will be blocked, reducing the effective specific surface area and other adverse effects. In addition, the concentration of the reaction liquid in the present invention is 0.1-30wt%. When the concentration of the reaction liquid is low, the number of surface functional groups formed will be limited, limiting the adsorption capacity of the metal in the next stage; when the concentration of the reaction liquid is high, the carrier will adsorb too much material, which cannot be removed by calcination, and the residue will affect the adsorption effect.

[0017] The temperature of the calcination pretreatment of the present invention is 100 to 500°C, which has the advantage of removing the pretreatment solution without destroying the main structure of the carrier. When the temperature of the calcination pretreatment is low, it will lead to the inability to remove the pretreatment solution by calcination; when the temperature of the calcination pretreatment is high, it will cause the collapse of the carrier structure, reduce the effective specific surface area, and reduce the adsorption capacity for metals. If the calcination pretreatment is not performed, that is, the catalyst carrier is subjected to hydrothermal pretreatment and vacuum drying, and the solution containing the active component is directly attached to the treated carrier, the substances in the pretreatment liquid will be adsorbed on the carrier sites, hindering the adsorption of metals on the carrier and other adverse effects.

[0018] The reaction solution used in the hydrothermal pretreatment of the present invention includes any one of nitric acid, sulfuric acid, hydrogen peroxide, phosphoric acid, hydrochloric acid, urea solution, melamine solution, boric acid, sodium borohydride solution, potassium borohydride solution, ammonium phosphate solution, ammonium hydrogen phosphate solution, sodium phosphate solution or potassium phosphate solution, or a combination of at least two of them, wherein typical but non-limiting combinations include a combination of nitric acid and sulfuric acid, a combination of hydrogen peroxide and phosphoric acid, a combination of urea solution and melamine solution, a combination of boric acid and potassium borohydride solution, or a combination of ammonium phosphate solution and potassium phosphate solution.

[0019] The concentration of the reaction solution of the present invention is 0.1-30wt%, for example, it can be 0.1wt%, 0.5wt%, 1wt%, 5wt%, 10wt%, 20wt% or 30wt%, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0020] The temperature of the calcination pretreatment of the present invention is 100-500°C, for example, it can be 100°C, 120°C, 150°C, 200°C, 300°C or 500°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0021] Preferably, the catalyst carrier in step (1) comprises any one of silica, diatomaceous earth, molecular sieve, activated carbon, carbon nanotubes or γ-alumina, or a combination of at least two thereof, wherein typical but non-limiting combinations include a combination of silica and diatomaceous earth, a combination of molecular sieve and activated carbon, or a combination of carbon nanotubes and γ-alumina, preferably activated carbon or γ-alumina.

[0022] Preferably, the concentration of the reaction solution is 0.5-10wt%, for example, it can be 0.5wt%, 1wt%, 3wt%, 5wt%, 8wt% or 10wt%, etc., but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0023] Preferably, the temperature of the hydrothermal pretreatment is 10-200°C, for example, it can be 10°C, 20°C, 50°C, 100°C, 150°C or 200°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable; preferably 50-150°C.

[0024] Preferably, the pressure of the hydrothermal pretreatment is 0 to 20 MPa, for example, 0 MPa, 3 MPa, 5 MPa, 10 MPa, 15 MPa or 20 MPa, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable; preferably 1 to 5 MPa.

[0025] Preferably, the hydrothermal pretreatment time is 0.5 to 30 h, for example, 0.5 h, 1 h, 4 h, 8 h, 10 h, 20 h or 30 h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable; preferably, it is 2 to 10 h.

[0026] Preferably, the vacuum drying temperature in step (1) is 50-150°C, for example, 50°C, 80°C, 100°C, 120°C, 140°C or 150°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable; preferably 80-120°C.

[0027] Preferably, the calcination pretreatment in step (1) is carried out under a protective atmosphere.

[0028] Preferably, the protective atmosphere comprises any one of nitrogen, argon or helium or a combination of at least two of them, wherein typical but non-limiting combinations include a combination of nitrogen and argon, a combination of helium and nitrogen, or a combination of argon and helium.

[0029] Preferably, the temperature of the calcination pretreatment is 300-450°C, for example, 300°C, 320°C, 350°C, 400°C, 430°C or 450°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0030] Preferably, the calcination pretreatment time is 0.5 to 20 h, for example, 0.5 h, 1 h, 4 h, 8 h, 10 h, 15 h or 20 h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable; preferably, it is 2 to 8 h.

[0031] Preferably, the liquid-to-solid ratio of the solution containing the active ingredient in step (2) to the treated carrier is 0.5 to 5 mL / g, for example, 0.5 mL / g, 1 mL / g, 1.5 mL / g, 2 mL / g, 4 mL / g or 5 mL / g, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable; the preferred liquid-to-solid ratio is 1 to 3 mL / g.

[0032] Preferably, the active component comprises a primary active component.

[0033] Preferably, the main active component includes any one of Ru, Pt, Pd, Ag or Au or a combination of at least two thereof, wherein typical but non-limiting combinations include a combination of Ru and Pt, a combination of Pd and Ag or a combination of Au and Pt.

[0034] Preferably, based on the total weight of the hydrogenation catalyst, the content of the main active component is 0.5-5wt%, for example, it can be 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt% or 5wt%, etc., but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0035] Preferably, the active component in step (2) further includes a co-active component.

[0036] Preferably, the co-active component includes any one or a combination of at least two of Co, Ni, Cu, La, Ce, Ti, Mo, Zr, Zn, V, Sb, Bi or Nb, wherein typical but non-limiting combinations include a combination of Co and Ni, a combination of Cu and La, a combination of Ce and, a combination of Zr and or a combination of Sb and Nb.

[0037] Preferably, based on the total weight of the hydrogenation catalyst, the content of the co-active component is 0.5-5wt%, for example, 0.5wt%, 1wt%, 2wt%, 2.5wt%, 3wt%, 4wt% or 5wt%, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0038] As a preferred technical solution of the present invention, the preparation method comprises the following steps:

[0039] (1) subjecting the catalyst support to a hydrothermal pretreatment at a temperature of 10 to 200° C. and a pressure of 0 to 20 MPa for 0.5 to 30 h, a vacuum drying at a temperature of 50 to 150° C., and a calcination pretreatment at a temperature of 100 to 500° C. for 0.5 to 20 h, to obtain a treated support;

[0040] The catalyst carrier comprises any one of silicon dioxide, diatomaceous earth, molecular sieve, activated carbon, carbon nanotubes or γ-alumina or a combination of at least two thereof; the reaction liquid used in the hydrothermal pretreatment comprises any one of nitric acid, sulfuric acid, hydrogen peroxide, phosphoric acid, hydrochloric acid, urea solution, melamine solution, boric acid, sodium borohydride solution, potassium borohydride solution, ammonium phosphate solution, ammonium hydrogen phosphate solution, sodium phosphate solution or potassium phosphate solution or a combination of at least two thereof; the concentration of the reaction liquid is 0.1-30wt%; the calcination pretreatment is carried out under a protective atmosphere; the protective atmosphere comprises any one of nitrogen, argon or helium or a combination of at least two thereof;

[0041] (2) attaching a solution containing active components to the treated carrier at a liquid-to-solid ratio of 0.5 to 5 mL / g, and performing drying and reduction treatment to obtain the hydrogenation catalyst;

[0042] The method of attaching the solution containing the active component to the treated carrier includes any one of an impregnation method, an adsorption method or a spray adsorption method;

[0043] The active component includes a main active component; the main active component includes any one of Ru, Pt, Pd, Ag or Au or a combination of at least two thereof; the content of the main active component is 0.5 to 5 wt% based on the total weight of the hydrogenation catalyst;

[0044] The active component also includes a co-active component; the co-active component includes any one or a combination of at least two of Co, Ni, Cu, La, Ce, Ti, Mo, Zr, Zn, V, Sb, Bi or Nb; based on the total weight of the hydrogenation catalyst, the content of the co-active component is 0.5-5wt%.

[0045] In a second aspect, the present invention further provides a hydrogenation catalyst prepared by the method for preparing the hydrogenation catalyst as described in the first aspect.

[0046] The hydrogenation catalyst of the present invention has a simple preparation method, low preparation cost, excellent catalytic performance and long service life, and can be applied to the preparation of 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

[0047] In a third aspect, the present invention further provides an application of the hydrogenation catalyst as described in the second aspect in the preparation of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, wherein the application method comprises the following steps:

[0048] a) adding 2,2,4,4-tetramethyl-1,3-cyclobutanedione, a solvent and the hydrogenation catalyst into a tank reactor;

[0049] b) nitrogen is introduced into the sealed autoclave to replace the air; hydrogen is then introduced to replace the nitrogen in the autoclave, and finally the hydrogen pressure is pressed to 4 MPa;

[0050] c) setting the reaction temperature to 130°C, the reaction time to 3h, and the rotation speed to 200r / min;

[0051] d) starting mechanical stirring to carry out hydrogenation reaction, stopping the reaction and cooling the mixture after reaching a set temperature and finishing the reaction time, thereby obtaining 2,2,4,4-tetramethyl-1,3-cyclobutanediol; and separating the hydrogenation catalyst and recycling it.

[0052] The hydrogenation catalyst of the present invention is used in the preparation of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, has excellent catalytic performance, the conversion rate of 2,2,4,4-tetramethyl-1,3-cyclobutanedione can reach more than 99%, and the selectivity of 2,2,4,4-tetramethyl-1,3-cyclobutanediol can reach more than 99%. The hydrogenation catalyst is used 11 times, and the conversion rate of 2,2,4,4-tetramethyl-1,3-cyclobutanedione and the selectivity of 2,2,4,4-tetramethyl-1,3-cyclobutanediol are still high.

[0053] Compared with the prior art, the present invention has at least the following beneficial effects:

[0054] The method for preparing a hydrogenation catalyst provided by the invention is simple to operate. The obtained hydrogenation catalyst is applied to the preparation of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and can achieve a conversion rate of 2,2,4,4-tetramethyl-1,3-cyclobutanedione and a selectivity of 2,2,4,4-tetramethyl-1,3-cyclobutanediol of more than 99%. After multiple applications, no significant decrease in catalyst performance is observed, the life of the catalyst is extended, and the market competitiveness of 2,2,4,4-tetramethyl-1,3-cyclobutanediol products is improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1 This is the chromatographic analysis spectrum of the liquid sample after the hydrogenation reaction of the hydrogenation catalyst prepared in Example 1. DETAILED DESCRIPTION

[0056] The technical solution of the present invention is further described below with reference to the accompanying drawings and through specific implementation methods.

[0057] The present invention is further described in detail below. However, the following examples are only simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0058] Example 1

[0059] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0060] (1) 10 g of activated carbon, 8 g of concentrated nitric acid with a concentration of 30 wt % and 10 g of deionized water were weighed and added to a 100 mL kettle, and the mixture was hydrothermally heated at 85° C. under mechanical stirring and treated at room pressure for 12 h, and then filtered, washed, dried in a vacuum drying oven at 90° C. overnight, and calcined at 400° C. under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon;

[0061] (2) Weigh 0.65gRuCl3·3H2O in a beaker, add 10mL deionized water and dissolve. Weigh 5g pretreated activated carbon and add it to the above solution, stir for about 15min, let it stand for adsorption for 12h, transfer it to a vacuum oven at 110℃ and dry it for 3h. Then transfer it to a tube furnace for reduction, reduce it at 450℃ for 3h under 10% hydrogen / nitrogen; cool it to room temperature and put it into a glass bottle under nitrogen protection to obtain a 5%Ru / C catalyst.

[0062] Example 2

[0063] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0064] (1) 10 g of activated carbon, 8 g of 2 wt% sulfuric acid and 10 g of deionized water were weighed and added to a 100 mL kettle, and the mixture was hydrothermally heated at 85° C. under mechanical stirring and treated at room pressure for 12 h, and then filtered, washed, dried in a vacuum drying oven at 90° C. overnight, and calcined at 400° C. under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon;

[0065] (2) Weigh 0.65gRuCl3·3H2O in a beaker, add 10mL deionized water and dissolve. Weigh 5g pretreated activated carbon and add it to the above solution, stir for about 15min, let it stand for adsorption for 12h, transfer it to a vacuum oven at 110℃ and dry it for 3h. Then transfer it to a tube furnace for reduction, reduce it at 450℃ for 3h under 10% hydrogen / nitrogen; cool it to room temperature and put it into a glass bottle under nitrogen protection to obtain a 5%Ru / C catalyst.

[0066] Example 3

[0067] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0068] (1) Weigh 10 g of activated carbon, 8 g of 30 wt% hydrogen peroxide and 10 g of deionized water into a 100 mL kettle, hydroheat at 85° C. under mechanical stirring, treat at room pressure for 12 h, then filter and wash, dry in a vacuum drying oven at 90° C. overnight, and calcine at 400° C. under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon.

[0069] (2) Weigh 0.65gRuCl3·3H2O in a beaker, add 10mL deionized water and dissolve. Weigh 5g pretreated activated carbon and add it to the above solution, stir for about 15min, let it stand for adsorption for 12h, transfer it to a vacuum oven at 110℃ and dry it for 3h. Then transfer it to a tube furnace for reduction, reduce it at 450℃ for 3h under 10% hydrogen / nitrogen; cool it to room temperature and put it into a glass bottle under nitrogen protection to obtain a 5%Ru / C catalyst.

[0070] Example 4

[0071] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0072] (1) Weigh 10 g of activated carbon, 8 g of urea and 10 g of deionized water into a 100 mL kettle, hydroheat at 85 °C under mechanical stirring, treat at room pressure for 12 h, then filter and wash, dry in a vacuum oven at 90 °C overnight, and calcine at 400 °C under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon.

[0073] (2) Weigh 0.65gRuCl3·3H2O in a beaker, add 10mL deionized water and dissolve. Weigh 5g pretreated activated carbon and add it to the above solution, stir for about 15min, let it stand for adsorption for 12h, transfer it to a vacuum oven at 110℃ and dry it for 3h. Then transfer it to a tube furnace for reduction, reduce it at 450℃ for 3h under 10% hydrogen / nitrogen; cool it to room temperature and put it into a glass bottle under nitrogen protection to obtain a 5%Ru / C catalyst.

[0074] Example 5

[0075] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0076] (1) Weigh 10 g of activated carbon, 8 g of sodium borohydride and 10 g of deionized water into a 100 mL kettle, hydroheat at 85° C. under mechanical stirring, treat at room pressure for 12 h, then filter and wash, dry in a vacuum drying oven at 90° C. overnight, and calcine at 400° C. under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon.

[0077] (2) Weigh 0.65gRuCl3·3H2O in a beaker, add 10mL deionized water and dissolve. Weigh 5g pretreated activated carbon and add it to the above solution, stir for about 15min, let it stand for adsorption for 12h, transfer it to a vacuum oven at 110℃ and dry it for 3h. Then transfer it to a tube furnace for reduction, reduce it at 450℃ for 3h under 10% hydrogen / nitrogen; cool it to room temperature and put it into a glass bottle under nitrogen protection to obtain a 5%Ru / C catalyst.

[0078] Example 6

[0079] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0080] (1) Weigh 10 g of activated carbon, 8 g of ammonium phosphate and 10 g of deionized water into a 100 mL kettle, hydroheat at 85 °C under mechanical stirring, treat at room pressure for 12 h, then filter and wash, dry in a vacuum oven at 90 °C overnight, and calcine at 400 °C under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon.

[0081] (2) Weigh 0.65gRuCl3·3H2O in a beaker, add 10mL deionized water and dissolve. Weigh 5g pretreated activated carbon and add it to the above solution, stir for about 15min, let it stand for adsorption for 12h, transfer it to a vacuum oven at 110℃ and dry it for 3h. Then transfer it to a tube furnace for reduction, reduce it at 450℃ for 3h under 10% hydrogen / nitrogen; cool it to room temperature and put it into a glass bottle under nitrogen protection to obtain a 5%Ru / C catalyst.

[0082] Example 7

[0083] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0084] (1) Weigh 10 g of γ-alumina, 8 g of 30 wt% hydrochloric acid and 10 g of deionized water into a 100 mL kettle, and heat at 85° C. under mechanical stirring and 5 MPa for 12 h. Then filter and wash, dry in a vacuum drying oven at 100° C. overnight, and calcine at 450° C. under a nitrogen atmosphere for 5 h to obtain pretreated γ-alumina.

[0085] (2) Weigh 0.65gRuCl3·3H2O in a beaker, add 10mL deionized water and dissolve. Weigh 5g pretreated γ-alumina and add it to the above solution, stir for about 15min, let stand for adsorption for 12h, transfer to a vacuum oven at 110℃ and dry for 3h. Then transfer to a tube furnace for reduction, reduce at 450℃ for 3h under 10% hydrogen / nitrogen; cool to room temperature, and put into a glass bottle under nitrogen protection to obtain a 5%Ru / γ-alumina catalyst.

[0086] Example 8

[0087] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0088] (1) Weigh 10 g of γ-alumina, 8 g of melamine and 10 g of deionized water into a 100 mL kettle, and heat at 85° C. under mechanical stirring and 5 MPa for 12 h. Then filter and wash, dry in a vacuum drying oven at 100° C. overnight, and calcine at 450° C. under a nitrogen atmosphere for 5 h to obtain pretreated γ-alumina.

[0089] (2) Weigh 0.65gRuCl3·3H2O in a beaker, add 10mL deionized water and dissolve. Weigh 5g pretreated γ-alumina and add it to the above solution, stir for about 15min, let stand for adsorption for 12h, transfer to a vacuum oven at 110℃ and dry for 3h. Then transfer to a tube furnace for reduction, reduce at 450℃ for 3h under 10% hydrogen / nitrogen; cool to room temperature, and put into a glass bottle under nitrogen protection to obtain a 5%Ru / γ-alumina catalyst.

[0090] Example 9

[0091] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0092] (1) Weigh 10 g of γ-alumina, 8 g of ammonium hydrogen phosphate and 10 g of deionized water into a 100 mL kettle, hydroheat at 85° C. under mechanical stirring, treat at 5 MPa for 12 h, then filter and wash, dry in a vacuum drying oven at 100° C. overnight, and calcine at 450° C. under a nitrogen atmosphere for 5 h to obtain pretreated γ-alumina.

[0093] (2) Weigh 0.65gRuCl3·3H2O in a beaker, add 10mL deionized water and dissolve. Weigh 5g pretreated γ-alumina and add it to the above solution, stir for about 15min, let stand for adsorption for 12h, transfer to a vacuum oven at 110℃ and dry for 3h. Then transfer to a tube furnace for reduction, reduce at 450℃ for 3h under 10% hydrogen / nitrogen; cool to room temperature, and put into a glass bottle under nitrogen protection to obtain a 5%Ru / γ-alumina catalyst.

[0094] Example 10

[0095] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0096] (1) Weigh 10 g of activated carbon, 8 g of concentrated nitric acid with a concentration of 20 wt% and 10 g of deionized water into a 100 mL kettle, hydroheat at 85°C under mechanical stirring and treat at a pressure of 3 MPa for 8 h, then filter and wash, dry in a vacuum drying oven at 90°C overnight, and calcine at 400°C under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon.

[0097] (2) Weigh 0.39gRuCl3·3H2O in a beaker, add 10mL deionized water, and dissolve. Weigh 5g pretreated activated carbon, add it to the above solution, stir for about 15min, let it stand for adsorption for 12h, transfer it to a vacuum oven at 110℃ and dry it for 3h. Then transfer it to a tube furnace for reduction, reduce it at 450℃ for 3h under 10% hydrogen / nitrogen; cool it to room temperature, and put it into a glass bottle under nitrogen protection to obtain a 3%Ru / C catalyst.

[0098] Embodiment 11

[0099] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0100] (1) Weigh 10 g of activated carbon, 8 g of concentrated nitric acid with a concentration of 26 wt% and 10 g of deionized water into a 100 mL kettle, hydroheat at 85°C under mechanical stirring and treat at a pressure of 3 MPa for 8 h, then filter and wash, dry in a vacuum drying oven at 90°C overnight, and calcine at 400°C under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon.

[0101] (2) Weigh 0.13gRuCl3·3H2O in a beaker, add 10mL deionized water, and dissolve. Weigh 5g pretreated activated carbon, add it to the above solution, stir for about 15min, let it stand for adsorption for 12h, transfer it to a vacuum oven at 110℃ and dry it for 3h. Then transfer it to a tube furnace for reduction, reduce it at 450℃ for 3h under 10% hydrogen / nitrogen; cool it to room temperature, and put it into a glass bottle under nitrogen protection to obtain a 1%Ru / C catalyst.

[0102] Example 12

[0103] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0104] (1) Weigh 10 g of activated carbon, 8 g of concentrated nitric acid with a concentration of 26 wt% and 10 g of deionized water into a 100 mL kettle, hydroheat at 85°C under mechanical stirring and treat at a pressure of 3 MPa for 8 h, then filter and wash, dry in a vacuum drying oven at 90°C overnight, and calcine at 400°C under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon.

[0105] (2) Weigh 5 g of pretreated activated carbon and 150 g of deionized water, add them to a three-necked flask, and stir mechanically at room temperature. Weigh 0.65 g of RuCl3·3H2O and dissolve it in 50 mL of deionized water, transfer it to a dropping funnel, and add it dropwise to the activated carbon slurry for adsorption for about 5 hours. Adjust the pH value to about 9 with sodium hydroxide solution, and then use about 20 g of 20% sodium borohydride solution to reduce for about 3 hours. Finally, filter and wash to obtain a wet basis 5% Ru / C catalyst.

[0106] Example 13

[0107] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0108] (1) Weigh 10 g of activated carbon, 8 g of concentrated nitric acid with a concentration of 26 wt% and 10 g of deionized water into a 100 mL kettle, hydroheat at 85°C under mechanical stirring and treat at a pressure of 5 MPa for 6 h, then filter and wash, dry in a vacuum drying oven at 90°C overnight, and calcine at 400°C under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon.

[0109] (2) Weigh 0.65gRuCl3·3H2O in a three-necked flask, add about 5mL deionized water and 50mL ethylene glycol, and heat to 150°C under nitrogen protection and mechanical stirring. Perform reduction treatment for about 3h until the colloid is in a colloidal state. Then, reduce the temperature to 60°C. Weigh 5g pretreated activated carbon and add it to the above colloid, adsorbing it until the upper liquid becomes transparent. Finally, reduce the temperature to room temperature, filter and wash, and obtain a wet basis 5% Ru / C catalyst.

[0110] Embodiment 14

[0111] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0112] (1) Weigh 10 g of activated carbon, 8 g of concentrated nitric acid with a concentration of 26 wt% and 10 g of deionized water into a 100 mL kettle, hydroheat at 85°C under mechanical stirring and treat at a pressure of 5 MPa for 6 h, then filter and wash, dry in a vacuum drying oven at 90°C overnight, and calcine at 400°C under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon.

[0113] (2) Weigh 0.65gRuCl3·3H2O in a beaker, add 10mL deionized water, and dissolve completely; transfer to a spray bottle. Weigh 5g pretreated activated carbon and place it in a small coating machine. Turn on the coating machine at a speed of about 30r / min, aim the spray bottle at the pretreated activated carbon, spray in batches until there is no solution, continue to rotate and stir for about 15min, let it stand for adsorption for 12h, and transfer it to a vacuum oven at 110℃ for drying for 3h. Then transfer it to a tubular furnace for reduction, reduce it at 450℃ for 3h under 10% hydrogen / nitrogen; cool it to room temperature, and put it into a glass bottle under nitrogen protection to obtain a 5%Ru / C catalyst.

[0114] Embodiment 15

[0115] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0116] (1) Weigh 10 g of γ-alumina, 8 g of 30 wt% hydrochloric acid and 10 g of deionized water into a 100 mL kettle, and heat at 85° C. and 8 MPa for 5 h under mechanical stirring. Then filter and wash, dry in a vacuum drying oven at 100° C. overnight, and calcine at 450° C. under a nitrogen atmosphere for 5 h to obtain pretreated γ-alumina.

[0117] (2) Weigh 0.65gRuCl3·3H2O in a three-necked flask, add about 5mL deionized water and 50mL ethylene glycol, and heat to 150°C under nitrogen protection and mechanical stirring, and perform reduction treatment for about 3h until the colloid is in a colloidal state. Then, reduce the temperature to 60°C. Weigh 5g pretreated γ-alumina and add it to the above colloid, adsorbing it until the upper liquid becomes transparent. Finally, reduce the temperature to room temperature, filter and wash, and obtain a wet basis 5% Ru / γ-alumina catalyst.

[0118] Example 16

[0119] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0120] (1) Weigh 10 g of γ-alumina, 8 g of 30 wt% hydrochloric acid and 10 g of deionized water into a 100 mL kettle, and heat at 85° C. and 8 MPa for 5 h under mechanical stirring. Then filter and wash, dry in a vacuum drying oven at 100° C. overnight, and calcine at 450° C. under a nitrogen atmosphere for 5 h to obtain pretreated γ-alumina.

[0121] (2) Weigh 0.65gRuCl3·3H2O in a beaker, add 10mL deionized water, dissolve completely; transfer to a spray bottle. Weigh 5g pretreated γ-alumina and place in a small coating machine. Turn on the coating machine at a speed of about 30r / min, aim the spray bottle at the pretreated γ-alumina, spray in batches until there is no solution, continue to rotate and stir for about 15min, let it stand for adsorption for 12h, transfer to a vacuum oven at 110℃ and dry for 3h. Then transfer to a tubular furnace for reduction, reduce at 450℃ for 3h under 10% hydrogen / nitrogen; cool to room temperature, and put into a glass bottle under nitrogen protection to obtain a 5%Ru / C catalyst.

[0122] Embodiment 17

[0123] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0124] (1) Weigh 10 g of activated carbon, 8 g of concentrated nitric acid with a concentration of 30 wt% and 10 g of deionized water into a 100 mL kettle, hydroheat at 85°C under mechanical stirring and treat at a pressure of 2 MPa for 10 h, then filter and wash, dry in a vacuum drying oven at 90°C overnight, and calcine at 400°C under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon.

[0125] (2) Weigh 0.65gRuCl3·3H2O and 0.10g chloroplatinic acid in a beaker, add 10mL deionized water and dissolve. Weigh 5g pretreated activated carbon and add it to the above solution, stir for about 15min, let it stand for adsorption for 12h, transfer it to a vacuum oven at 110℃ and dry it for 3h. Then transfer it to a tube furnace for reduction, reduce it at 450℃ for 3h under 10% hydrogen / nitrogen; cool it to room temperature, and put it into a glass bottle under nitrogen protection to obtain a 5%Ru-0.5%Pt / C catalyst.

[0126] Embodiment 18

[0127] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0128] (1) Weigh 10 g of activated carbon, 8 g of concentrated nitric acid with a concentration of 30 wt% and 10 g of deionized water into a 100 mL kettle, hydroheat at 85°C under mechanical stirring and treat at a pressure of 2 MPa for 10 h, then filter and wash, dry in a vacuum drying oven at 90°C overnight, and calcine at 400°C under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon.

[0129] (2) Weigh 0.65gRuCl3·3H2O and 0.09g chloroauric acid in a beaker, add 10mL deionized water and dissolve. Weigh 5g pretreated activated carbon and add it to the above solution, stir for about 15min, let it stand for adsorption for 12h, transfer it to a vacuum oven at 110℃ and dry it for 3h. Then transfer it to a tube furnace for reduction, reduce it at 450℃ for 3h under 10% hydrogen / nitrogen; cool it to room temperature and put it into a glass bottle under nitrogen protection to obtain a 5%Ru-0.5%Au / C catalyst.

[0130] Embodiment 19

[0131] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0132] (1) Weigh 10 g of activated carbon, 8 g of concentrated nitric acid with a concentration of 30 wt% and 10 g of deionized water into a 100 mL kettle, hydroheat at 85°C under mechanical stirring and treat at a pressure of 4 MPa for 8 h, then filter and wash, dry in a vacuum drying oven at 90°C overnight, and calcine at 400°C under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon.

[0133] (2) Weigh 0.65gRuCl3·3H2O and 0.05g lanthanum nitrate hydrate into a beaker, add 10mL deionized water and dissolve. Weigh 5g pretreated activated carbon and add it to the above solution, stir for about 15min, let it stand for adsorption for 12h, transfer it to a vacuum oven at 110℃ and dry it for 3h. Then transfer it to a tube furnace for reduction, reduce it at 450℃ for 3h under 10% hydrogen / nitrogen; cool it to room temperature and put it into a glass bottle under nitrogen protection to obtain a 5%Ru-0.5%La / C catalyst.

[0134] Embodiment 20

[0135] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0136] (1) Weigh 10 g of activated carbon, 8 g of concentrated nitric acid with a concentration of 30 wt% and 10 g of deionized water into a 100 mL kettle, hydroheat at 85°C under mechanical stirring and treat at a pressure of 4 MPa for 8 h, then filter and wash, dry in a vacuum drying oven at 90°C overnight, and calcine at 400°C under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon.

[0137] (2) Weigh 0.65gRuCl3·3H2O and 0.05gbismuth nitrate·5H2O in a beaker, add 10mL deionized water and dissolve. Weigh 5g pretreated activated carbon and add it to the above solution, stir for about 15min, let it stand for adsorption for 12h, transfer it to a vacuum oven at 110℃ and dry it for 3h. Then transfer it to a tubular furnace for reduction, reduce it at 450℃ for 3h under 10% hydrogen / nitrogen; cool it to room temperature and put it into a glass bottle under nitrogen protection to obtain a 5%Ru-0.5%Bi / C catalyst.

[0138] Embodiment 21

[0139] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0140] (1) Weigh 10 g of activated carbon, 8 g of concentrated nitric acid with a concentration of 30 wt% and 10 g of deionized water into a 100 mL kettle, hydroheat at 85°C under mechanical stirring and treat at a pressure of 4 MPa for 8 h, then filter and wash, dry in a vacuum drying oven at 90°C overnight, and calcine at 400°C under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon.

[0141] (2) Weigh 0.65gRuCl3·3H2O and 0.32g ammonium molybdate·4H2O in a beaker, add 10mL deionized water and dissolve. Weigh 5g pretreated activated carbon and add it to the above solution, stir for about 15min, let it stand for adsorption for 12h, transfer it to a vacuum oven at 110℃ and dry it for 3h. Then transfer it to a tubular furnace for reduction, reduce it at 450℃ for 3h under 10% hydrogen / nitrogen; cool it to room temperature and put it into a glass bottle under nitrogen protection to obtain a 5%Ru-0.5%Mo / C catalyst.

[0142] Embodiment 22

[0143] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0144] (1) Weigh 10 g of activated carbon, 8 g of concentrated nitric acid with a concentration of 20 wt% and 10 g of deionized water into a 100 mL kettle, hydroheat at 85°C under mechanical stirring and treat at a pressure of 4 MPa for 8 h, then filter and wash, dry in a vacuum drying oven at 90°C overnight, and calcine at 400°C under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon.

[0145] (2) Weigh 0.65gRuCl3·3H2O and 0.32g ammonium vanadate in a beaker, add 10mL deionized water and dissolve. Weigh 5g pretreated activated carbon and add it to the above solution, stir for about 15min, let it stand for adsorption for 12h, transfer it to a vacuum oven at 110℃ and dry it for 3h. Then transfer it to a tube furnace for reduction, reduce it at 450℃ for 3h under 10% hydrogen / nitrogen; cool it to room temperature and put it into a glass bottle under nitrogen protection to obtain a 5%Ru-0.5%V / C catalyst.

[0146] Embodiment 23

[0147] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0148] (1) Weigh 10 g of activated carbon, 8 g of concentrated nitric acid with a concentration of 20 wt% and 10 g of deionized water into a 100 mL kettle, hydroheat at 85°C under mechanical stirring and treat at a pressure of 2 MPa for 10 h, then filter and wash, dry in a vacuum drying oven at 90°C overnight, and calcine at 400°C under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon.

[0149] (2) Weigh 5g of pretreated activated carbon and 150g of deionized water, add them to a three-necked flask, and stir mechanically at room temperature. Weigh 0.65g of RuCl3·3H2O and 0.10g of chloroplatinic acid, dissolve them in 50mL of deionized water, transfer them to a dropping funnel, and add them dropwise to the activated carbon slurry for adsorption for about 5h. Adjust the pH value to about 9 with sodium hydroxide solution, and then use about 20g of 20% sodium borohydride solution to reduce for about 3h. Finally, filter and wash to obtain a wet basis 5% Ru-0.5% Pt / C catalyst.

[0150] Embodiment 24

[0151] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0152] (1) Weigh 10 g of activated carbon, 8 g of concentrated nitric acid with a concentration of 30 wt% and 10 g of deionized water into a 100 mL kettle, hydroheat at 85°C under mechanical stirring and treat at a pressure of 4 MPa for 8 h, then filter and wash, dry in a vacuum drying oven at 90°C overnight, and calcine at 400°C under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon.

[0153] (2) Weigh 5g of pretreated activated carbon and 150g of deionized water, add them to a three-necked flask, and stir mechanically at room temperature. Weigh 0.65g of RuCl3·3H2O and 0.13g of nickel nitrate·4H2O, dissolve them in 50mL of deionized water, transfer them to a dropping funnel, and add them dropwise to the activated carbon slurry for adsorption for about 5h. Adjust the pH value to about 9 with sodium hydroxide solution, and then use about 20g of 20% sodium borohydride solution to reduce for about 3h. Finally, filter and wash to obtain a wet basis 5% Ru-0.5% Ni / C catalyst.

[0154] Embodiment 25

[0155] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0156] (1) Weigh 10 g of γ-alumina, 8 g of 30 wt% hydrochloric acid and 10 g of deionized water into a 100 mL kettle, and heat at 85° C. and 8 MPa for 5 h under mechanical stirring. Then filter and wash, dry in a vacuum drying oven at 100° C. overnight, and calcine at 450° C. under a nitrogen atmosphere for 5 h to obtain pretreated γ-alumina.

[0157] (2) Weigh 0.65gRuCl3·3H2O and 0.10g chloroplatinic acid in a three-necked flask, add about 5mL deionized water and 50mL ethylene glycol, and heat to 150°C under nitrogen protection and mechanical stirring. Perform reduction treatment for about 3h until the colloid is in a colloidal state. Then, lower the temperature to 60°C. Weigh 5g pretreated γ-alumina and add it to the above colloid, adsorbing it until the upper liquid becomes transparent. Finally, cool to room temperature, filter and wash, and obtain a wet basis 5%Ru-0.5%Pt / γ-alumina catalyst.

[0158] Embodiment 26

[0159] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0160] (1) Weigh 10 g of γ-alumina, 8 g of 30 wt% hydrochloric acid and 10 g of deionized water into a 100 mL kettle, and heat at 85° C. and 8 MPa for 5 h under mechanical stirring. Then filter and wash, dry in a vacuum drying oven at 100° C. overnight, and calcine at 450° C. under a nitrogen atmosphere for 5 h to obtain pretreated γ-alumina.

[0161] (2) Weigh 0.65gRuCl3·3H2O and 0.13gnickel nitrate·4H2O in a three-necked flask, add about 5mL deionized water and 50mL ethylene glycol, and heat to 150°C under nitrogen protection and mechanical stirring. Perform reduction treatment for about 3h until the colloid is in a colloidal state. Then, lower the temperature to 60°C. Weigh 5g pretreated γ-alumina and add it to the above colloid, adsorbing it until the upper liquid becomes transparent. Finally, cool to room temperature, filter and wash, and obtain a wet-basis 5%Ru-0.5%Ni / γ-alumina catalyst.

[0162] Embodiment 27

[0163] This embodiment provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0164] (1) Weigh 10 g of activated carbon, 8 g of concentrated nitric acid with a concentration of 15 wt% and 10 g of deionized water into a 100 mL kettle, hydroheat at 85°C under mechanical stirring and treat at a pressure of 2 MPa for 10 h, then filter and wash, dry in a vacuum drying oven at 90°C overnight, and calcine at 400°C under a nitrogen atmosphere for 5 h to obtain pretreated activated carbon.

[0165] (2) Weigh 0.65gRuCl3·3H2O and 0.10g chloroplatinic acid in a three-necked flask, add about 5mL deionized water and 50mL ethylene glycol, and heat to 150°C under nitrogen protection and mechanical stirring. Perform reduction treatment for about 3h until the colloid is in a colloidal state. Then, lower the temperature to 60°C. Weigh 5g pretreated activated carbon and add it to the above colloid, adsorbing it until the upper liquid becomes transparent. Finally, cool to room temperature, filter and wash, and obtain a wet-basis 5%Ru-0.5%Pt / C catalyst.

[0166] Comparative Example 1

[0167] This comparative example provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0168] Weigh 0.65gRuCl3·3H2O in a beaker, add 10mL deionized water, and dissolve. Weigh 5g activated carbon, add to the above solution, stir for about 15min, let stand for adsorption for 12h, transfer to a vacuum oven at 110℃ and dry for 3h. Then transfer to a tube furnace for reduction, reduce at 450℃ for 3h under 10% hydrogen / nitrogen; cool to room temperature, and put into a glass bottle under nitrogen protection to obtain a 5%Ru / C catalyst.

[0169] Comparative Example 2

[0170] This comparative example provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0171] Weigh 0.65gRuCl3·3H2O in a beaker, add 10mL deionized water, and dissolve. Weigh 5gγ-alumina, add to the above solution, stir for about 15min, let stand for adsorption for 12h, transfer to a vacuum oven at 110℃ and dry for 3h. Then transfer to a tube furnace for reduction, reduce at 450℃ for 3h under 10% hydrogen / nitrogen; cool to room temperature, and put into a glass bottle under nitrogen protection to obtain a 5%Ru / γ-alumina catalyst.

[0172] Comparative Example 3

[0173] This comparative example provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0174] Weigh 0.65gRuCl3·3H2O in a beaker, add 10mL deionized water, dissolve completely; transfer to a spray pot. Weigh 5g activated carbon and place in a small coating machine. Turn on the coating machine at a speed of about 30r / min, aim the spray pot at the carrier, spray in batches until there is no solution, continue to rotate and stir for about 15min, let it stand for adsorption for 12h, transfer to a vacuum oven at 110℃ for 3h. Then transfer to a tubular furnace for reduction, reduce at 450℃ for 3h under 10% hydrogen / nitrogen; cool to room temperature, and put into a glass bottle under nitrogen protection to obtain a 5%Ru / C catalyst.

[0175] Comparative Example 4

[0176] This comparative example provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0177] Weigh 0.65gRuCl3·3H2O in a three-necked flask, add about 5mL deionized water and 50mL ethylene glycol, and heat to 150℃ under nitrogen protection and mechanical stirring. Reduce for about 3h to form a colloidal state. Then, lower the temperature to 60℃. Weigh 5g activated carbon and add it to the above colloid, adsorb until the upper liquid becomes transparent. Finally, cool to room temperature, filter and wash to obtain a wet basis 5% Ru / C catalyst.

[0178] Comparative Example 5

[0179] This comparative example provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0180] (1) Weigh 10 g of activated carbon and dry it in a vacuum drying oven at 90° C. overnight, and calcine it at 400° C. for 5 h under a nitrogen atmosphere to obtain pretreated activated carbon;

[0181] (2) Weigh 0.65gRuCl3·3H2O in a beaker, add 10mL deionized water and dissolve. Weigh 5g pretreated activated carbon and add it to the above solution, stir for about 15min, let it stand for adsorption for 12h, transfer it to a vacuum oven at 110℃ and dry it for 3h. Then transfer it to a tube furnace for reduction, reduce it at 450℃ for 3h under 10% hydrogen / nitrogen; cool it to room temperature and put it into a glass bottle under nitrogen protection to obtain a 5%Ru / C catalyst.

[0182] Comparative Example 6

[0183] This comparative example provides a method for preparing a hydrogenation catalyst, the preparation method comprising the following steps:

[0184] (1) 10 g of activated carbon, 8 g of concentrated nitric acid with a concentration of 30 wt % and 10 g of deionized water were weighed and added to a 100 mL kettle, and hydrothermaled at 85° C. under mechanical stirring and treated at room pressure for 12 h, and then filtered, washed, and dried in a vacuum drying oven at 90° C. overnight to obtain pretreated activated carbon;

[0185] (2) Weigh 0.65gRuCl3·3H2O in a beaker, add 10mL deionized water and dissolve. Weigh 5g pretreated activated carbon and add it to the above solution, stir for about 15min, let it stand for adsorption for 12h, transfer it to a vacuum oven at 110℃ and dry it for 3h. Then transfer it to a tube furnace for reduction, reduce it at 450℃ for 3h under 10% hydrogen / nitrogen; cool it to room temperature and put it into a glass bottle under nitrogen protection to obtain a 5%Ru / C catalyst.

[0186] The catalysts prepared in the above examples and comparative examples were used to hydrogenate 2,2,4,4-tetramethyl-1,3-cyclobutanedione (TMCD) to prepare 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO), and the specific steps were as follows:

[0187] Weigh 5.3g TMCD crystals and dissolve them in 120mL isobutyl isobutyrate (TMCD mass content 5wt%). Transfer the above solution to a high-pressure reactor, weigh 1.5g of dried catalyst and add it to the reactor, and seal the reactor. Use nitrogen / hydrogen to replace the air in the reactor alternately, replace it 5 times, and finally fill it with hydrogen to a pressure of 4MPa. Turn on the mechanical stirring, set the speed to 200r / min, set the reaction temperature, turn on the temperature controller, raise the room temperature to 130°C, and continue to react at this temperature for 3h. After the reaction is completed, turn off the temperature control, start cooling, and cool to room temperature. The system is emptied, the reactor is opened, and the liquid and catalyst in the reactor are separated by filtration. After the liquid sample is miscible with ethanol in equal volumes, the content of the substance is analyzed by gas chromatography, and finally the conversion rate and selectivity of the reaction are calculated.

[0188] The conversion of TMCD and the selectivity of CBDO are calculated as follows:

[0189]

[0190]

[0191] Where, m is the mass of the collected liquid, m0 is the amount of raw material fed, and W TMCD % is the percentage of TMCD in the sample after the reaction, W CBDO % is the percentage of CBDO in the sample after the reaction.

[0192] The specific hydrogenation reaction results are shown in Table 1 below.

[0193] Table 1

[0194]

[0195]

[0196]

[0197] From Table 1 we can see that:

[0198] (1) It can be seen from Examples 1 to 27 that the hydrogenation catalyst obtained by the method for preparing the hydrogenation catalyst provided by the present invention is applied to the preparation of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and the conversion rate of TMCD can reach more than 99%, and the selectivity of CBDO can reach more than 99%;

[0199] (2) From Comparative Examples 1 to 6, it can be seen that in Comparative Example 5, the catalyst support is not subjected to hydrothermal pretreatment, and in Comparative Example 6, the catalyst support is not subjected to calcination pretreatment, which results in the prepared catalyst being used in the preparation of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and the conversion rate of TMCD and the selectivity of CBDO are both reduced; in Comparative Examples 1 to 4, the catalyst support is not subjected to hydrothermal pretreatment, vacuum drying and calcination pretreatment, and the solution containing the active component is directly attached to the support to prepare the hydrogenation catalyst. When used in the preparation of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, the conversion rate of TMCD and the selectivity of CBDO are greatly reduced.

[0200] The chromatographic analysis spectrum of the liquid sample after the hydrogenation reaction of the hydrogenation catalyst prepared in Example 1 of the present invention is as follows: Figure 1 As shown, from Figure 1 It can be seen that no retention peak of the raw material TMCD was observed, and the hydrogenation reaction of the raw material was complete; except for the solvent isobutyl isobutyrate and the diluent ethanol for chromatographic analysis, only obvious retention peaks of the cis / trans substances of the product CBDO were observed, and the selectivity of the product was high.

[0201] The catalysts after the hydrogenation of 2,2,4,4-tetramethyl-1,3-cyclobutanedione (TMCD) to prepare 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO) in Example 17 and Comparative Example 1 were simply rinsed with isobutyl isobutyrate solvent to remove adsorbed reaction raw materials or product substances, and then put into the high-pressure reactor again for multiple application tests. The reaction evaluation process is as described above. The specific application test results are shown in Table 2 below.

[0202] Table 2

[0203]

[0204]

[0205] From Table 2 we can see that:

[0206] (1) After the hydrogenation catalyst prepared in Example 17 was used to hydrogenate 2,2,4,4-tetramethyl-1,3-cyclobutanedione (TMCD) to prepare 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO), 11 application tests were carried out, and no significant decrease in catalyst performance was observed, which extended the life of the catalyst and improved the market competitiveness of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol product.

[0207] (2) After the hydrogenation catalyst prepared in Comparative Example 1 was used to hydrogenate 2,2,4,4-tetramethyl-1,3-cyclobutanedione (TMCD) to prepare 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO), only four application tests were carried out, and the catalyst performance was significantly reduced. The conversion rate of TMCD was only 79%, and the selectivity of CBDO was only 48%. The catalyst could not be further applied, and the service life of the hydrogenation catalyst was short.

[0208] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing a hydrogenation catalyst, characterized in that: The preparation method of the hydrogenation catalyst comprises the following steps: (1) sequentially performing hydrothermal pretreatment, vacuum drying and calcination pretreatment on the catalyst carrier to obtain a treated carrier; The reaction liquid used in the hydrothermal pretreatment includes any one of nitric acid, sulfuric acid, hydrogen peroxide, phosphoric acid, hydrochloric acid, urea solution, melamine solution, boric acid, sodium borohydride solution, potassium borohydride solution, ammonium phosphate solution, ammonium hydrogen phosphate solution, sodium phosphate solution or potassium phosphate solution, or a combination of at least two thereof; the concentration of the reaction liquid is 0.1 to 30 wt %; the temperature of the calcination pretreatment is 100 to 500° C.; (2) attaching a solution containing active components to the treated carrier, and performing drying and reduction treatment to obtain the hydrogenation catalyst; The method of attaching the solution containing the active ingredient to the treated carrier includes any one of an impregnation method, an adsorption method or a spray adsorption method.

2. The preparation method according to claim 1, characterized in that: The catalyst carrier of step (1) comprises any one of silicon dioxide, diatomaceous earth, molecular sieve, activated carbon, carbon nanotubes or γ-alumina or a combination of at least two thereof, preferably activated carbon or γ-alumina; Preferably, the concentration of the reaction solution is 0.5 to 10 wt %; Preferably, the temperature of the hydrothermal pretreatment is 10 to 200°C, preferably 50 to 150°C; Preferably, the pressure of the hydrothermal pretreatment is 0 to 20 MPa, preferably 1 to 5 MPa; Preferably, the hydrothermal pretreatment time is 0.5 to 30 hours, preferably 2 to 10 hours.

3. The preparation method according to claim 1 or 2, characterized in that: The vacuum drying temperature in step (1) is 50-150°C, preferably 80-120°C.

4. The preparation method according to any one of claims 1 to 3, characterized in that: The calcination pretreatment in step (1) is carried out under a protective atmosphere; Preferably, the protective atmosphere comprises any one of nitrogen, argon or helium, or a combination of at least two thereof; Preferably, the temperature of the calcination pretreatment is 300-450°C; Preferably, the calcination pretreatment time is 0.5 to 20 hours, preferably 2 to 8 hours.

5. The preparation method according to any one of claims 1 to 4, characterized in that: The liquid-to-solid ratio of the solution containing the active ingredient in step (2) to the treated carrier is 0.5 to 5 mL / g, preferably 1 to 3 mL / g; Preferably, the active component comprises a main active component; Preferably, the main active component includes any one of Ru, Pt, Pd, Ag or Au, or a combination of at least two of them.

6. The preparation method according to claim 5, characterized in that: Based on the total weight of the hydrogenation catalyst, the content of the main active component is 0.5-5wt%.

7. The preparation method according to any one of claims 1 to 6, characterized in that: The active component in step (2) further includes a co-active component; Preferably, the auxiliary active component includes any one of Co, Ni, Cu, La, Ce, Ti, Mo, Zr, Zn, V, Sb, Bi or Nb, or a combination of at least two thereof.

8. The preparation method according to claim 7, characterized in that: Based on the total weight of the hydrogenation catalyst, the content of the auxiliary active component is 0.5-5wt%.

9. A hydrogenation catalyst prepared by the method for preparing a hydrogenation catalyst according to any one of claims 1 to 8.

10. Use of the hydrogenation catalyst as claimed in claim 9 in the preparation of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, characterized in that: The application method comprises the following steps: a) adding 2,2,4,4-tetramethyl-1,3-cyclobutanedione, a solvent and the hydrogenation catalyst into a tank reactor; b) introducing nitrogen into the sealed autoclave to replace the air; Then hydrogen is introduced to replace the nitrogen in the kettle, and finally the hydrogen pressure is pressed to 4MPa; c) setting the reaction temperature to 130°C, the reaction time to 3h, and the rotation speed to 200r / min; d) starting mechanical stirring to carry out hydrogenation reaction, stopping the reaction and cooling the mixture after reaching a set temperature and finishing the reaction time, thereby obtaining 2,2,4,4-tetramethyl-1,3-cyclobutanediol; and separating the hydrogenation catalyst and recycling it.

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