CN107115862B

CN107115862B - Hydrogenation catalyst and preparation method thereof

Info

Publication number: CN107115862B
Application number: CN201710482023.4A
Authority: CN
Inventors: 王志文; 王绍伟; 杨克俭
Original assignee: China Tianchen Engineering Corp; Tianjin Tianchen Green Energy Resources Engineering Technology and Development Co Ltd
Current assignee: China Tianchen Engineering Corp; Tianjin Tianchen Green Energy Resources Engineering Technology and Development Co Ltd
Priority date: 2017-06-22
Filing date: 2017-06-22
Publication date: 2020-03-10
Anticipated expiration: 2037-06-22
Also published as: CN107115862A

Abstract

The invention discloses a hydrogenation catalyst and a preparation method thereof. The catalyst is used in the technological process of preparing cyclohexene by selective hydrogenation of benzene. The active component of the catalyst is ruthenium, the preparation method comprises the steps of catalyst precursor preparation, modified precursor preparation, catalyst intermediate passivation, catalyst finished product preparation and the like, and the hydrogenation catalyst obtained by the method is applied to the technical process of preparing cyclohexene through selective hydrogenation of benzene and has the characteristics of high activity, high cyclohexene selectivity and stable catalyst performance.

Description

Hydrogenation catalyst and preparation method thereof

Technical Field

The invention belongs to the technical field of catalyst preparation, and particularly relates to a hydrogenation catalyst and a preparation method thereof.

Background

Cyclohexene is an important organic chemical raw material. As an intermediate, cyclohexene can be widely used in the production of pharmaceuticals, pesticides, fuels, detergents, explosives, feed additives, polyesters and other fine chemicals. The method for industrially obtaining cyclohexene is more. Conventionally, cyclohexanol dehydration, halogenated cyclohexane dehydrohalogenation, Birch reduction and the like have been carried out. In the traditional method, cyclohexanol, halogenated cyclohexane and alkali metal or alkaline earth metal with higher cost are used as raw materials, so that the process is complex, and the production cost of cyclohexene is higher.

Benzene catalytic selective hydrogenation is a new method for preparing cyclohexene by using cheap benzene as raw material through selective hydrogenation. The development and industrial application of the method obviously reduce the production cost of cyclohexene, and the method can be applied to the industrial large-scale production of important products such as cyclohexanol, cyclohexanone, adipic acid and the like. In the production of nylon, compared with the traditional routes of producing cyclohexane by complete hydrogenation of benzene and producing KA oil by free radical oxidation of cyclohexane, the route of preparing cyclohexene by partial hydrogenation of benzene and synthesizing cyclohexanol by hydration of cyclohexene consumes less hydrogen 1/3, does not generate wastes such as acid, ester and the like, and can comprehensively utilize only cyclohexane as a byproduct, so that the carbon yield reaches more than 99%. The process for preparing cyclohexene by partial hydrogenation of benzene occupies an important position in the nylon production industry, and is intensively researched by a plurality of large companies and scientific research institutions.

Patent CN1197651C discloses an amorphous ruthenium-boron-containing catalyst for selective hydrogenation of benzene and a preparation method thereof, which can be used for preparing a supported catalyst and an unsupported catalyst, but according to the data provided in the patent examples, the selectivity of the prepared catalyst is generally about 60%, and certain difficulties exist in industrialization.

The patent CN1304109C discloses a preparation method, a modulation method and a regeneration method of a catalyst for preparing cyclohexene by selective hydrogenation of benzene, wherein the catalyst comprises an active component Ru, a rare earth element La and a dispersant ZrO₂The composition of the catalyst and the method for adjusting the conversion rate and selectivity of the catalyst and regenerating the catalyst are provided.

Patent CN100402145C discloses a preparation method and application of a catalyst for preparing cyclohexene by selective hydrogenation of benzene, which states that ruthenium nanoparticles can be prepared in the presence of a surfactant and a porous inorganic protective layer is provided for the ruthenium nanoparticles by hydrolyzing ethyl orthosilicate.

Patent CN1978053B discloses a preparation method and application of a catalyst for preparing cyclohexene by selective hydrogenation of benzene, in the preparation method disclosed in the patent, a ruthenium-containing solution is mixed with a zirconia carrier containing yttrium oxide, and then reduced by using an aqueous alkali solution added with sodium borohydride.

Patent CN1176886C discloses a catalyst for preparing cyclohexene by selective hydrogenation of benzene and a preparation method thereof, wherein active components and auxiliary agent precursors are firstly adsorbed on a dispersant and then reduced by a chemical method. When the conversion rate of benzene of the prepared catalyst is 40%, the selectivity of cyclohexene reaches about 85%.

Patent CN100518928C discloses a catalyst for producing cycloolefin and a method for producing cycloolefin. The catalyst for preparing cycloolefin consists of ruthenium compound, zinc hydroxide, boron compound and zirconium oxide. The examples given in this patent are all for the preparation of cyclohexene by selective hydrogenation of benzene. From the results of the examples, the cyclohexene selectivity of the catalyst is about 37%, and the catalyst stability is better.

Patent US4678861 discloses a process for the preparation of cyclohexene by the hydrogen reduction of a ruthenium supported solid support, which is a lanthanide metal oxide.

The activity, cyclohexene selectivity and stability of the catalyst for preparing cyclohexene by benzene selective hydrogenation are always the key problems of the industrialization of the benzene selective hydrogenation technology. In the industrial production of cyclohexene by selective hydrogenation of benzene using a catalyst containing ruthenium and zinc as active components, it is desirable to increase the conversion of benzene and the selectivity of cyclohexene as much as possible while increasing the effectiveness of the catalyst and to maintain the normal activity of the catalyst for as long as possible. At present, the industrial benzene partial hydrogenation process is mainly used for producing adipic acid and caprolactam, and the technical level is generally that the conversion rate of benzene is 40% and the selectivity of cyclohexene is about 80%.

The patent discloses a hydrogenation catalyst and a preparation method thereof, and obtains the hydrogenation catalyst with high activity, high cyclohexene selectivity and high stability. The hydrogenation catalyst prepared by the method can achieve the effects of benzene conversion rate of 50% and cyclohexene selectivity of over 80%, greatly improves production efficiency and system capacity, reduces system separation energy consumption, reduces production cost, and has good economic benefit.

Disclosure of Invention

In view of the above, the present invention aims to provide a catalyst for preparing cyclohexene by benzene selective hydrogenation, which has high activity, high cyclohexene selectivity and high stability, and comprises an active component and an auxiliary agent M, wherein the active component mainly comprises Ru and Zn, and the auxiliary agent M is one or more of Fe, Mg, Ca, Cu, Mo and Zn.

Preferably, the weight ratio of the active component to the auxiliary agent is Ru: zn: m is 1: (5-15): (0.0001-0.005).

Another object of the present invention is to provide a method for preparing the above hydrogenation catalyst, comprising the steps of:

A. catalyst precursor preparation

Adding a ruthenium compound and a soluble zinc salt into desalted water, fully dissolving, heating to 70-100 ℃, stirring the solution for 1-3 hours, and titrating the solution to a pH value of 5-8 by using an alkali solution to form a catalyst precursor;

B. preparation of modified precursor

Adding an auxiliary agent M into the catalyst precursor, wherein the auxiliary agent M is one or more of soluble salts of Fe, Mg, Ca, Cu, Mo and Zn, and adsorbing the auxiliary agent M on the surface of the precursor by utilizing the adsorption capacity of the catalyst precursor to form a modified catalyst precursor;

C. preparation of catalyst intermediate

Pre-reducing the catalyst precursor by using hydrogen under the conditions that the temperature is 50-90 ℃ and the pressure is 0.6-5 MPa, separating out a catalyst intermediate in a solid form after pre-reduction, and washing the catalyst intermediate until chloride ions cannot be detected;

D. catalyst intermediate passivation

Soaking the obtained catalyst intermediate in zinc sulfate solution with zinc ion concentration of 0.1-4 wt%, and passivating the catalyst intermediate at 150-210 ℃ and nitrogen pressure of 0.6-5 MPa for 0.5-50 hours;

E. preparation of catalyst finished product

And after the passivation is finished, reducing the system pressure to be below 3MPa, then filling hydrogen into the system until the system pressure is 3-6 MPa, wherein the reaction time is 0.5-50 hours, and after the reaction is finished, reducing the temperature and releasing the pressure to obtain a catalyst finished product.

Preferably, the ruthenium compound in step a is one of ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium nitrate and ruthenium sulfate, and ruthenium chloride is preferred.

Preferably, the soluble zinc salt in step a is one of zinc chloride, zinc bromide, zinc iodide, zinc nitrate and zinc sulfate, and preferably zinc chloride.

Preferably, the soluble salt of Fe, Mg, Ca, Cu, Mo, Zn in step B is one of soluble hydrochloride, sulfate, nitrate of the above metals, preferably hydrochloride.

Compared with the prior art, the hydrogenation catalyst and the preparation method thereof have the following advantages:

(1) compared with the catalyst for preparing cyclohexene by selective hydrogenation of benzene disclosed in the previous patent, the catalyst has the characteristics of high benzene conversion rate, high cyclohexene selectivity and stable catalyst performance. The conversion rate of cyclohexene prepared by selective hydrogenation of benzene used in industry is about 40% generally, and the selectivity is about 80%. The catalyst is evaluated on a laboratory small kettle evaluation device, the conversion rate is generally between 50 and 60 percent within 15 to 20min, and the selectivity is about 80 percent; the catalyst for preparing cyclohexene by selective hydrogenation of benzene disclosed by the invention can obtain a conversion rate of 65-75% and the selectivity is kept above 80% by evaluation on a laboratory small kettle evaluation device. The application result of the device for preparing cyclohexene by selective hydrogenation of industrial benzene shows that the conversion rate of the catalyst exceeds 50 percent and the selectivity exceeds 80 percent.

(2) The performance stability of the hydrogenation catalyst disclosed by the invention is shown in the following aspects. On the one hand, the catalyst has long failure period in industrial use, thereby bringing the advantage of low catalyst consumption. According to actual use data, the annual use amount of the catalyst can be reduced by more than 30% compared with that of the traditional catalyst; on the other hand, because the catalyst comprises a passivation process in the preparation process disclosed by the invention, no impact is brought to a production device system in the catalyst adding process. The traditional catalyst generally has the problems of high conversion rate and low selectivity after being added into a production device system, and the catalyst effectively avoids the problems, so that the selectivity of the catalyst after being added into the production device system does not have a decline trend; in addition, the catalyst can be recovered to the conversion rate and selectivity level of the product more quickly than the traditional catalyst in the initial start-up period after the production device is stopped.

(3) The hydrogenation catalyst disclosed by the invention is applied to the production process of partial benzene hydrogenation, and has low catalyst consumption rate, stable system and high activity, so that the system capacity and the material separation energy consumption are reduced, the produced cyclohexene (serving as an intermediate product for producing caprolactam and adipic acid) is also greatly reduced, and the economic benefit of a production device can be effectively improved.

Detailed Description

Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.

The present invention will be described in detail with reference to examples.

In the following examples, the catalyst evaluation was carried out by the following methods:

2 g of catalyst, 10 g of zirconia, 50 g of zinc sulfate heptahydrate and 280ml of water are added into a 1L high-pressure reaction kettle, and after the high-pressure reaction kettle is sealed, the air in the reaction kettle is replaced by hydrogen. And starting the stirrer, and carrying out cold stirring for 1 hour under the condition that the reaction kettle is not heated so as to ensure that the catalyst and the zirconia are uniformly mixed. And then starting heating and continuously stirring, adding 140ml of benzene into the reaction kettle after the temperature in the reaction kettle is stabilized at 140 ℃, starting timing, sampling 5 minutes, 10 minutes, 15 minutes, 20 minutes and 25 minutes after the reaction is started, analyzing the sample by gas chromatography, obtaining the molar ratio of unreacted benzene, cyclohexene, cyclohexane and other byproducts in the sampled sample, and calculating the conversion rate, selectivity and cyclohexene yield of the reaction at the sampling moment. The catalyst evaluation device who uses is a high pressure batch autoclave, specifically includes feeding jar, feeding buffer tank, sample jar, cooler, gas-liquid separation jar and product receiving bottle, and the feeding jar passes through the pipeline and is connected with feeding buffer tank and high pressure batch autoclave in proper order, and high pressure batch autoclave passes through the pipeline and is connected with cooler, gas-liquid separation jar and product receiving bottle in proper order, and the upper portion of feeding buffer tank is provided with the evacuation pipe, and the upper portion of gas-liquid separation jar is provided with the evacuation pipe, and the upper portion of product receiving bottle is provided with the evacuation pipe, is provided with the sampling tube in the high pressure batch autoclave, and the sampling tube is in with the setting the outside sample jar of high pressure batch autoclave is connected, the hydrogen input tube pass through the tee bend respectively with the upper portion of feeding buffer tank with the. The catalyst evaluation device is specifically disclosed in patent CN 102139194B.

Example 1

A. 30g of RuCl₃·xH₂O and 6g of ZnSO₄·7H₂O was dissolved in pure water, and then sufficiently stirred at 70 ℃ C (dissolution temperature) for 2 hours, followed by titration with an aqueous sodium hydroxide solution (titration end point)) Obtaining a catalyst precursor until the pH is 7;

B. dropwise adding ferric chloride solution into the catalyst precursor, and controlling the total addition of ferric chloride so that the ratio of Fe: ru ═ 0.002: 1, fully stirring and mixing to enable cations to be adsorbed on the surface of a catalyst precursor to obtain a modified catalyst precursor;

C. pre-reducing the catalyst precursor by using hydrogen under the conditions that the temperature is 80 ℃ and the hydrogen partial pressure is 2.0MPa, and then washing and precipitating until chloride ions cannot be detected to obtain a catalyst intermediate;

D. adding the obtained catalyst intermediate and zinc sulfate solution with zinc ion concentration (solution concentration) of 1.0 wt% into a reaction kettle, introducing nitrogen, controlling the temperature at 190 ℃, the pressure at 2.0MPa, and the passivation time at 2.0 hours;

E. the pressure of the reaction kettle is released to 2.0MPa, hydrogen is filled into the reaction kettle until the pressure of the reaction kettle (the pressure in the reaction kettle) is 4.0MPa, and the reaction lasts for 18 hours. And after the reaction is finished, cooling and decompressing to obtain a catalyst finished product.

Example 2

A. 30g of RuCl₃·xH₂After dissolving O and 2.84g of zinc chloride in pure water, the mixture was sufficiently stirred at 80 ℃ (dissolution temperature) for 1 hour, and then titrated with an aqueous sodium hydroxide solution (titration end point) to pH 5 to obtain a catalyst precursor;

B. and (3) dropwise adding a ferric sulfate solution into the catalyst precursor, and controlling the total addition of ferric sulfate to ensure that the ratio of Fe: ru 0.0001: 1, fully stirring and mixing to enable cations to be adsorbed on the surface of a catalyst precursor to obtain a modified catalyst precursor;

C. pre-reducing the catalyst precursor by using hydrogen under the conditions that the temperature is 50 ℃ and the hydrogen partial pressure is 1.0MPa, and then washing and precipitating until chloride ions cannot be detected to obtain a catalyst intermediate;

D. adding the obtained catalyst intermediate and zinc sulfate solution with zinc ion concentration (solution concentration) of 0.1 wt% into a reaction kettle, introducing nitrogen, controlling the temperature at 150 ℃, the pressure at 0.6MPa, and the passivation time at 0.5 h;

E. the pressure of the reaction kettle is released to 2.0MPa, hydrogen is filled into the reaction kettle until the pressure of the reaction kettle (the pressure in the reaction kettle) is 3.0MPa, and the reaction lasts for 0.5 hour. And after the reaction is finished, cooling and decompressing to obtain a catalyst finished product.

Example 3

A. 30g of RuCl₃·xH₂After dissolving O and 2.66g of zinc nitrate in pure water, the mixture was sufficiently stirred at 90 ℃ (dissolution temperature) for 1 hour, and then titrated with an aqueous sodium hydroxide solution (titration end point) to pH 5 to obtain a catalyst precursor;

B. and (3) dropwise adding a copper sulfate solution into the catalyst precursor, and controlling the total addition of copper sulfate to ensure that the ratio of Cu: ru 0.005: 1, fully stirring and mixing to enable cations to be adsorbed on the surface of a catalyst precursor to obtain a modified catalyst precursor;

C. pre-reducing the catalyst precursor by using hydrogen under the conditions that the temperature is 90 ℃ and the hydrogen partial pressure is 0.6MPa, and then washing and precipitating until chloride ions cannot be detected to obtain a catalyst intermediate;

D. adding the obtained catalyst intermediate and zinc sulfate solution with zinc ion concentration (solution concentration) of 0.4 wt% into a reaction kettle, introducing nitrogen, controlling the temperature at 180 ℃, the pressure at 1.0MPa, and the passivation time at 50 hours;

E. the pressure of the reaction kettle is released to 2.0MPa, hydrogen is filled into the reaction kettle until the pressure of the reaction kettle (the pressure in the reaction kettle) is 3.5MPa, and the reaction is carried out for 50 hours. And after the reaction is finished, cooling and decompressing to obtain a catalyst finished product.

Example 4

A. 30g of RuCl₃·xH₂After dissolving O and 2.66g of zinc nitrate in pure water and sufficiently stirring at 100 ℃ (dissolution temperature) for 1 hour, titrating with an aqueous sodium hydroxide solution (titration end point) to pH 5 to obtain a catalyst precursor;

B. and (3) dropwise adding a copper chloride solution into the catalyst precursor, and controlling the total addition of copper sulfate to ensure that the ratio of Cu: ru 0.001: 1, fully stirring and mixing to enable cations to be adsorbed on the surface of a catalyst precursor to obtain a modified catalyst precursor;

D. adding the obtained catalyst intermediate and zinc sulfate solution with zinc ion concentration (solution concentration) of 0.8 wt% into a reaction kettle, introducing nitrogen, controlling the temperature at 200 ℃, the pressure at 2.0MPa, and the passivation time at 30 hours;

E. the pressure of the reaction kettle is released to 2.0MPa, hydrogen is filled into the reaction kettle until the pressure of the reaction kettle (pressure in the reaction kettle) is 6.0MPa, and the reaction is carried out for 20 hours. And after the reaction is finished, cooling and decompressing to obtain a catalyst finished product.

Example 5

A. 30g of RuCl₃·xH₂After dissolving O and 2.66g of zinc nitrate in pure water, the mixture was sufficiently stirred at 80 ℃ (dissolution temperature) for 3 hours, and then titrated with an aqueous sodium hydroxide solution (titration end point) to pH 6 to obtain a catalyst precursor;

B. and dropwise adding a magnesium sulfate solution into the catalyst precursor, wherein the total addition amount of magnesium sulfate is controlled so that the ratio of Mg: ru 0.005: 1, fully stirring and mixing to enable cations to be adsorbed on the surface of a catalyst precursor to obtain a modified catalyst precursor;

D. adding the obtained catalyst intermediate and zinc sulfate solution with zinc ion concentration (solution concentration) of 1.2 wt% into a reaction kettle, introducing nitrogen, controlling the temperature at 210 ℃, the pressure at 5.0MPa, and the passivation time at 0.5 h;

E. the pressure of the reaction kettle is released to 2.0MPa, hydrogen is filled into the reaction kettle until the pressure of the reaction kettle (pressure in the reaction kettle) is 5.0MPa, and the reaction is carried out for 20 hours. And after the reaction is finished, cooling and decompressing to obtain a catalyst finished product.

Example 6

A. 30g of RuCl₃·xH₂O and 2.84g of zinc chloride were dissolved in pure water, and after stirring thoroughly at 80 ℃ (dissolution temperature) for 2 hours, the solution was titrated with an aqueous sodium hydroxide solution (titration end point) to pH 6 to obtain a catalystDriving a body;

B. and dropwise adding a calcium chloride solution into the catalyst precursor, and controlling the total addition of magnesium sulfate so that the ratio of Ca: ru ═ 0.0005: 1, fully stirring and mixing to enable cations to be adsorbed on the surface of a catalyst precursor to obtain a modified catalyst precursor;

D. adding the obtained catalyst intermediate and zinc sulfate solution with zinc ion concentration (solution concentration) of 2.0 wt% into a reaction kettle, introducing nitrogen, controlling the temperature at 195 ℃, the pressure at 2.0MPa, and the passivation time at 2.0 hours;

Example 7

A. 30g of RuCl₃·xH₂After dissolving O and 2.84g of zinc chloride in pure water, the mixture was sufficiently stirred at 90 ℃ (dissolution temperature) for 3 hours, and then titrated with an aqueous sodium hydroxide solution (titration end point) to pH 6 to obtain a catalyst precursor;

B. and dropwise adding a molybdenum nitrate solution into the catalyst precursor, and controlling the total addition of magnesium sulfate so that Mo: ru ═ 0.002: 1, fully stirring and mixing to enable cations to be adsorbed on the surface of a catalyst precursor to obtain a modified catalyst precursor;

D. adding the obtained catalyst intermediate and zinc sulfate solution with zinc ion concentration (solution concentration) of 4.0 wt% into a reaction kettle, introducing nitrogen, controlling the temperature at 195 ℃, the pressure at 2.0MPa, and the passivation time at 3.0 hours;

Example 8

A. 30g of RuCl₃·xH₂O and 6g of ZnSO₄·7H₂Dissolving O in pure water, stirring thoroughly for 3 hours at 85 ℃ (dissolution temperature), and then titrating with an aqueous sodium hydroxide solution (titration end point) to pH 8 to obtain a catalyst precursor;

D. adding the obtained catalyst intermediate and zinc sulfate solution with zinc ion concentration (solution concentration) of 1.5 wt% into a reaction kettle, introducing nitrogen, controlling the temperature at 195 ℃, the pressure at 2.5MPa, and the passivation time at 5.0 hours;

Example 9

A. 30g of RuCl₃·xH₂O and 6g of ZnSO₄·7H₂Dissolving O in pure water, stirring the solution sufficiently at 80 ℃ (dissolution temperature) for 3 hours, and then titrating the solution with an aqueous sodium hydroxide solution (titration end point) to pH 8 to obtain a catalyst precursor;

D. adding the obtained catalyst intermediate and zinc sulfate solution with zinc ion concentration (solution concentration) of 1.5 wt% into a reaction kettle, introducing nitrogen, controlling the temperature at 195 ℃, the pressure at 1.5MPa, and the passivation time at 3.0 hours;

Example 10

D. adding the obtained catalyst intermediate and zinc sulfate solution with zinc ion concentration (solution concentration) of 1.1 wt% into a reaction kettle, introducing nitrogen, controlling the temperature at 195 ℃, the pressure at 2.0MPa, and the passivation time at 2.0 hours;

The evaluation results of the catalysts obtained in examples 1 to 10 are shown in Table 1.

TABLE 1 evaluation results of catalyst samples in examples 1 to 10

Note: the conversion and selectivity are reported in wt%.

The present invention can solve the problems of low activity, low selectivity, poor stability, high consumption, etc. of the prior benzene selective hydrogenation catalyst, and the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A preparation method of a hydrogenation catalyst is characterized by comprising the following steps: the method comprises the following steps:

A. catalyst precursor preparation

B. preparation of modified precursor

Adding an auxiliary agent M into the catalyst precursor, wherein the auxiliary agent M is one or more of soluble salts of Fe, Mg, Ca, Cu and Mo, and the auxiliary agent M is adsorbed on the surface of the precursor to form a modified catalyst precursor;

C. preparation of catalyst intermediate

Pre-reducing the modified catalyst precursor by using hydrogen under the conditions that the temperature is 50-90 ℃ and the pressure is 0.6-5 MPa, separating out a catalyst intermediate in a solid form after pre-reduction, and washing the catalyst intermediate until chloride ions cannot be detected;

D. catalyst intermediate passivation

Soaking the obtained catalyst intermediate in a zinc sulfate solution with zinc ion concentration of 0.1-4 wt%, and passivating the catalyst intermediate at the temperature of 150-210 ℃ and under the nitrogen pressure of 0.6-5 MPa for 0.5-50 hours;

E. preparation of catalyst finished product

2. The method of claim 1, wherein: the ruthenium compound in the step A is one of ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium nitrate and ruthenium sulfate.

3. The method of claim 1, wherein: the soluble zinc salt in the step A is one of zinc chloride, zinc bromide, zinc iodide, zinc nitrate and zinc sulfate.

4. The method of claim 1, wherein: the soluble salt of Fe, Mg, Ca, Cu and Mo in the step B is one of soluble hydrochloride, sulfate or nitrate of the metals.

5. A hydrogenation catalyst obtainable by the process of any one of claims 1 to 4, characterized in that: the composite material comprises an active component and an auxiliary agent M, wherein the active component comprises Ru and Zn as main components, and the auxiliary agent M is one or more of Fe, Mg, Ca, Cu and Mo.

6. The hydrogenation catalyst of claim 5, wherein: the weight ratio of the active component to the auxiliary agent is Ru: zn: m is 1: (5-15): (0.0001-0.005).