CN111375419B

CN111375419B - Hydrogenation catalyst and preparation method thereof

Info

Publication number: CN111375419B
Application number: CN201811643348.7A
Authority: CN
Inventors: 金浩; 杨光; 朱慧红; 刘璐; 孙素华; 杨涛
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2018-12-29
Filing date: 2018-12-29
Publication date: 2022-07-12
Anticipated expiration: 2038-12-29
Also published as: CN111375419A

Abstract

The invention discloses a hydrogenation catalyst and a preparation method thereof, wherein the preparation method comprises the steps of dissolving iron-containing inorganic salt and citric acid ammonium salt in water to obtain a solution A; carrying out balling molding on the small-pore alumina, simultaneously adding the solution A to obtain alumina A, putting the alumina A into a ball rolling machine, and uniformly adding the large-pore alumina and the solution A in the rolling process to obtain alumina B; treating the alumina B and drying to obtain alumina C; the catalyst is obtained after the active metal component is loaded. The catalyst obtained by the method has uneven pore distribution, not only has higher hydrodemetallization activity and impurity capacity such as metal, but also has higher desulfurization activity, is not easy to be blocked by impurities such as metal, and can ensure the stability of the catalyst in the long-term operation process of a device.

Description

Hydrogenation catalyst and preparation method thereof

Technical Field

The invention belongs to the technical field of oil refining chemical industry, relates to a catalytic material and a preparation method thereof, and particularly relates to a hydrogenation catalyst and a preparation method thereof.

Background

In recent years, the quality of crude oil is increasingly poor, and the demand of light oil products is increased year by year, so that the development of deep processing of heavy oil and the increase of the added value of products have important practical significance. The hydrogenation technology as a main processing means faces great challenges, and the development of a better hydrogenation process and a hydrogenation catalyst with higher activity is urgently needed. The reaction performance of the heavy oil hydrogenation catalyst depends on the inherent catalytic characteristics of the active components and is closely related to the properties of the catalyst carrier. The specific surface area, pore structure, surface acidity, etc. of the carrier have important effects on the dispersion degree of the active component, the interaction between the active component and the carrier, the diffusion of reactant molecules and the anti-poisoning capability of the catalyst. At present, alumina is the most widely used carrier in the field of heavy oil hydrogenation, and has good mechanical properties and low price. Along with the continuous improvement of the requirement on the catalytic performance of the hydrogenation catalyst, the index requirement of the alumina carrier is also continuously improved, so that a great deal of alumina modification research work is carried out by the researchers.

In the heavy oil hydrogenation process, Ni and V are deposited on the catalyst in the form of sulfides, and the deposits block the outer pore channels of the catalyst, so that the catalyst is deactivated. Therefore, the property of the carrier, particularly the pore volume and the pore distribution directly determine the length of the stable operation period of the catalyst, and the carrier with high pore volume and high pore size distribution ratio can effectively reduce the inactivation speed of the catalyst and improve the operation period of the device.

CN1206037A discloses a residual oil hydrodemetallization catalyst, the method of the invention is characterized in that a physical pore-expanding agent and a chemical pore-expanding agent are added simultaneously in the preparation process of an alumina carrier, and then an active component is loaded on the carrier in a spray impregnation mode, the pore volume of the catalyst is 0.80-1.20 mL/g, the specific surface area is 110-200 m²A few pores of 15 to 20nm in diameter/g.

US4448896 discloses a hydrodesulfurization and heavy metal catalyst, the preparation method of which is to load the active component onto a catalyst with a specific surface area of 100-350 m²The preparation method of the alumina carrier comprises the steps of mixing active alumina or an active alumina precursor with carbon black, molding and roasting, wherein the pore radius is 3.75-7500 nm, and the pore volume is 0.5-1.5 mL/g.

The catalysts disclosed in the above patents all have high demetallization activity, but their hydrodesulfurization and carbon residue removal activities are relatively low due to their increased pore volume and large pore ratio. CN101492612A discloses a hydrotreating catalyst and a preparation method thereof, wherein an alumina carrier is prepared by mixing and kneading proper small-pore alumina and large-pore alumina, and then a hydrogenation active component and a basic metal component are loaded to prepare the catalyst. Although the catalyst can give consideration to both hydrogenation deacidification activity and hydrogenation demetalization activity and the capability of dissolving impurities such as metals, part of the small-pore alumina is distributed on the outer surface of the carrier in the preparation process of the carrier and is easy to be blocked by impurities such as metals.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides a hydrogenation catalyst and a preparation method thereof, in particular to a heavy oil hydrogenation catalyst and a preparation method thereof. The catalyst has uneven pore distribution, not only has higher hydrodemetallization activity and metal impurity-containing capacity, but also has higher desulfurization activity, and is not easy to be blocked by metal and other impurities, so that the stability of the catalyst in the long-period operation process of the device can be ensured, and the catalyst is particularly suitable for the field of heavy oil hydrogenation.

The first aspect of the present invention provides a preparation method of a hydrogenation catalyst, which comprises the following steps:

(1) dissolving iron-containing inorganic salt and ammonium citrate salt in water to obtain a solution A;

(2) carrying out balling molding on the small-hole alumina, and simultaneously adding the solution A to obtain alumina A;

(3) putting the alumina A into a ball rolling machine, and uniformly adding the macroporous alumina and the solution A in the rolling process to obtain alumina B;

(4) treating the alumina B with vapor-containing gas, and then further drying to obtain alumina C;

(5) mixing a compound containing a hydrogenation metal component with ammonia water to obtain a solution C;

(6) and (4) mixing the solution C obtained in the step (5) with the alumina C obtained in the step (4), uniformly mixing, drying and roasting to obtain the catalyst.

In the preparation method of the hydrogenation catalyst, the iron-containing inorganic salt in the step (1) is one or more of ferric nitrate, ferric chloride and ferric sulfate, and ferric nitrate is preferred.

In the preparation method of the hydrogenation catalyst, the ammonium citrate in the step (1) is one or more of ammonium dihydrogen citrate, ammonium monohydrogen citrate and ammonium citrate.

In the preparation method of the hydrogenation catalyst, the adding amount of the iron-containing inorganic salt (Fe) in the step (1)₂O₃By mass) is 1 to 5wt% of the final carrier content.

In the preparation method of the hydrogenation catalyst, the addition amount (by mass of citric acid) of the ammonium citrate in the step (1) is 1-5 wt% of the final carrier content.

In the preparation method of the hydrogenation catalyst, the concentration of the iron-containing inorganic salt in the solution A in the step (1) is 0.01-0.50 g/mL, and the concentration of the ammonium citrate salt is 0.005-0.20 g/mL.

In the preparation method of the hydrogenation catalyst, the mass ratio of the solution A to the microporous alumina in the step (2) is 0.7-1.5.

In the preparation method of the hydrogenation catalyst, the mass ratio of the solution A to the macroporous alumina in the step (3) is 0.7-1.5.

In the preparation method of the hydrogenation catalyst, the specific properties of the small-pore alumina in the step (2) are as follows: the specific surface area is 260-400 m²The pore volume is 0.7-1.0 mL/g, and the average pore diameter is 8-12 nm.

In the preparation method of the hydrogenation catalyst, the specific properties of the macroporous alumina in the step (3) are as follows: the specific surface area is 120-250 m²A pore volume of 0.7 to 1.0mL/g, and an average pore diameter of 15 to 30 nm.

In the preparation method of the hydrogenation catalyst, the small-pore alumina in the step (2) and the large-pore alumina in the step (3) can adopt commercially available products meeting the requirements, and can also be prepared by the existing method. Specifically, the material is preferably prepared by roasting pseudo-boehmite as a raw material. The pseudo-boehmite powder can be a commercial product or can be prepared according to the existing method. The small-pore alumina can be obtained by roasting pseudo-boehmite powder, wherein the roasting temperature is 550-750 ℃, and the roasting time is 1-5 h. The macroporous alumina can also be obtained by roasting pseudo-boehmite powder, wherein the roasting temperature is 800-1000 ℃, and the roasting time is 1-5 h.

In the preparation method of the hydrogenation catalyst, the balling method in the step (2) can be one or more of extrusion ball-throwing forming, rolling forming and spray drying forming.

In the preparation method of the hydrogenation catalyst, the particle size of the alumina A in the step (2) is 0.1-2.0 mm.

In the preparation method of the hydrogenation catalyst, in the alumina B in the step (3), the grain diameter of the alumina A is 10-90% of the grain diameter of the alumina B.

In the preparation method of the hydrogenation catalyst, in the step (4), the vapor-containing gas is vapor or a mixed gas of the vapor and a carrier gas, and the volume ratio of the vapor to the carrier gas in the mixed gas is 1: 5-2: 1, preferably 1: 4-1: 1; the carrier gas is air, nitrogen or inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.

In the preparation method of the hydrogenation catalyst, in the step (4), the treatment process is to introduce vapor-containing gas to treat the alumina B, the treatment temperature is 140-180 ℃, and the treatment time is 2-6 h.

In the preparation method of the hydrogenation catalyst, the volume space velocity of the vapor-containing gas and the alumina B in the step (4) is 500-2000 h^-1。

In the preparation method of the hydrogenation catalyst, the drying temperature in the step (4) is 90-120 ℃, and the drying time is 3-12 h.

In the preparation method of the hydrogenation catalyst, the alumina C in the step (4) is spherical, and the particle size is 0.1-2.5 mm, preferably 0.2-2.0 mm.

In the preparation method of the hydrogenation catalyst, other metals, such as one or more of Fe, Zr, Ti, B, La and Ce, can be introduced into the alumina C obtained in the step (4).

In the preparation method of the hydrogenation catalyst, the compound containing the hydrogenation metal component in the step (5) is a compound containing a VIB group metal and/or a VIII group metal, the VIB group metal-containing compound can be one or more of a molybdenum-containing compound and a tungsten-containing compound, and the VIII group metal-containing compound is one or more of a nickel-containing compound and a cobalt-containing compound. The molybdenum-containing compound may be ammonium heptamolybdate and/or ammonium tetramolybdate, preferably ammonium heptamolybdate; the tungsten-containing compound is ammonium metatungstate; the nickel-containing compound is basic cobalt carbonate; the cobalt-containing compound is basic cobalt carbonate.

In the preparation method of the hydrogenation catalyst according to the present invention, the compound containing the hydrogenation metal component in step (5) is preferably a molybdenum-containing compound and a nickel-containing compound, and the molybdenum-containing compound may be ammonium heptamolybdate and/or ammonium tetramolybdate, preferably ammonium heptamolybdate; the nickel-containing compound is basic nickel carbonate.

In the preparation method of the hydrogenation catalyst, the concentration of the ammonia water in the step (5) is 15wt% -25 wt%.

In the preparation method of the hydrogenation catalyst, the drying conditions in the step (6) comprise: the drying temperature is 90-120 ℃, and the drying time is 1-12 h; the roasting conditions include: the roasting temperature is 300-600 ℃, and the roasting time is 1-5 h.

The second aspect of the invention provides a hydrogenation catalyst obtained by the preparation method. The hydrogenation catalyst comprises a hydrogenation active metal component, an auxiliary agent and a carrier. The hydrogenation active metal component is one or more of VIB group metals and/or VIII group metals.

In the hydrogenation catalyst, the VIB group metal is Mo and/or W, and the VIII group metal is Ni and/or Co.

In the above hydrogenation catalyst, the hydrogenation metal component is more preferably Mo and Ni.

In the hydrogenation catalyst, the auxiliary agent is Fe₂O₃The content of the auxiliary agent is 1 to 5 weight percent based on the weight of the catalyst.

In the hydrogenation catalyst, other metals, such as one or more of Zr, Ti, B, La and Ce, can be introduced into the catalyst carrier.

The hydrogenation catalyst of the present invention can be prepared by conventional methods such as impregnation, kneading and the like, and preferably by impregnation. The carrier is prepared by a conventional impregnation method by adopting an impregnation method to load the active metal component, and can adopt a spray impregnation method, a saturated impregnation method or a supersaturated impregnation method. If the method for loading the hydrogenation active metal component on the carrier is an impregnation method, the method comprises the steps of preparing a solution of a compound containing hydrogenation active metal, impregnating the carrier by using the solution, and then drying, roasting or not roasting, wherein the hydrogenation active metal component is one or more of VIB group metals and/or VIII group metals, the concentration of the compound containing the hydrogenation active metal in the solution and the dosage of the solution enable the content of the VIB group metal component in the final catalyst to be 1-30 wt% calculated by oxides and based on the catalyst; the content of the VIII group metal component is 1wt% -15 wt%. The drying conditions include: the temperature is 90-120 ℃, and the time is 1-10 h; the roasting conditions include: the temperature is 300-600 ℃, and the time is 1-10 h.

In the above hydrogenation catalyst, the properties of the hydrogenation catalyst are as follows: the specific surface area is 120-380 m²The pore volume is 0.60 to 0.95 mL/g.

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

1. in the preparation method of the hydrogenation catalyst, the small-pore alumina with relatively high specific surface and relatively small pore diameter is used as the inner core of the carrier, then the large-pore alumina with relatively small specific surface and relatively large pore diameter is used as the outer layer of the carrier, the ammonium citrate is introduced in the forming process of the carrier, and then the alumina is further treated by adopting the vapor-containing gas. The catalyst prepared by the carrier solves the problem that the prior heavy oil hydrogenation catalyst has unmatched hydrogenation demetalization activity, hydrogenation desulfurization activity, metal containing capacity and other impurity capacities. The catalyst has the characteristics of uneven pore distribution and difficult blockage by impurities such as metal, can ensure the stability of the catalyst in the long-period operation process of a device, and is particularly suitable for the field of heavy oil hydrogenation.

2. In the preparation method of the hydrogenation catalyst, in the process of treating the alumina B by using the vapor gas, the release of ammonia can improve the number of macropores of the alumina carrier; the generated citric acid makes the carrier acidic, can interact with an alkaline hydrogenation metal ammonia solution in the carrier impregnation process, is beneficial to the dispersion of active metals, and can play a role in reaming the alumina carrier again in the roasting process to improve the number of macropores of the alumina carrier.

3. The preparation method of the heavy oil hydrogenation catalyst has the advantages of novel route, simple method, easy implementation and operation and low energy consumption.

Detailed Description

The embodiments and effects of the present invention are further illustrated by the following specific examples. In the present invention, wt% is a mass fraction.

The spherical carrier abrasion in the invention is tested by a high-speed air jet method. This Method has been established by ASTM in the United states as a Standard for the Attrition performance testing of small particle Catalysts, see ASTM D5757-00 (Standard Test Method for Determination of the Attribution and inhibition of Powdered Catalysts by Air Jets). The basic principle is that under the action of high-speed airflow, catalyst particles are in a fluidized state, fine powder is generated by friction among the particles and between the particles and the wall of the catalyst, and the amount of the fine powder generated by unit mass of the catalyst in unit time, namely, the abrasion index (abrasion) is used as an index for evaluating the abrasion resistance of the catalyst.

The specific surface area and the pore volume are measured by adopting a low-temperature liquid nitrogen physical adsorption method, and are particularly measured by adopting a low-temperature nitrogen adsorption instrument of American Mike company ASAP2420 model; the specific process comprises the following steps: and (3) carrying out vacuum treatment on a small amount of sample at 300 ℃ for 3-4 h, and finally placing the product under the condition of low temperature (-200 ℃) of liquid nitrogen for nitrogen absorption-desorption test. Wherein the surface area is obtained according to a BET equation, and the pore size distribution is obtained according to a BJH model.

The inventionIn the examples and the comparative examples, the small-pore alumina is prepared by roasting pseudo-boehmite powder at 700 ℃, and the specific surface area is 320m²The pore volume is 0.822 mL/g; the macroporous alumina is prepared by roasting pseudo-boehmite powder at 900 ℃, and the specific surface area of the macroporous alumina is 150m²The pore volume is 0.881 mL/g.

Example 1

(1) Preparing mixed solution

171.7g of ferric nitrate and 37.0g of ammonium dihydrogen citrate are dissolved in water to prepare 2200mL of mixed solution A, wherein the concentration of the ferric nitrate is 0.08g/mL, and the concentration of the ammonium dihydrogen citrate is 0.018 g/mL.

(2) Preparation of the support

1000g of small-hole alumina is made into spherical particles through rolling forming in a ball rolling machine, 1200mL of mixed solution A is sprayed in the ball rolling process, the rotating speed of the ball rolling machine is 35 rpm, and after the ball rolling is finished, 0.4-0.5 mm spherical alumina A is prepared; and then weighing 100g of alumina A, putting the alumina A into a ball rolling machine, uniformly scattering 700g of macroporous alumina in the rolling process, simultaneously spraying 840mL of mixed solution A, wherein the rotating speed of the ball rolling machine is 35 rpm, and after the ball rolling is finished, preparing 0.8-1.0 mm spherical alumina B. Carrying out steam treatment on the alumina B at the temperature of 150 ℃ for 4h, wherein the volume space velocity of the steam and the alumina B is 800h^-1To obtain alumina C. And drying the alumina C at 110 ℃ for 8h to obtain the spherical carrier with the particle size of 0.8-1.0 mm.

(3) Catalyst preparation

Dissolving 14.0g of ammonium heptamolybdate and 4.6g of basic nickel carbonate in an ammonia water solution with the concentration of 20wt%, and filtering to obtain 85mL of constant volume, thereby obtaining the Mo-Ni ammonia water solution.

Adding Mo-Ni ammonia water solution into 100g of prepared carrier, uniformly mixing, standing for 3h, drying at 110 ℃ for 4h, and roasting at 500 ℃ for 3h to obtain the catalyst, wherein MoO is₃The content was 10.0wt%, and the NiO content was 2.2 wt%. The physicochemical properties of the catalyst are shown in Table 1, and the abrasion data are shown in Table 2.

(4) Catalyst evaluation

The activity of the catalyst was evaluated by using an autoclave, and the properties of the feedstock oil used are shown in Table 3, and the evaluation conditions were as follows: the reaction pressure was 15.0MPa, the reaction temperature was 420 ℃, the reaction time was 1 hour, the oil ratio was 13:1, and the evaluation results are shown in Table 4.

Example 2

(1) Preparing mixed solution

227.3g of ferric nitrate and 53.0g of diammonium hydrogen citrate are dissolved in water to prepare 1800mL of mixed solution A, wherein the concentration of the ferric nitrate is 0.126g/mL, and the concentration of the diammonium hydrogen citrate is 0.027 g/mL.

(2) Preparation of the support

1000g of small-hole alumina is made into spherical particles through rolling forming in a ball rolling machine, 1200mL of mixed solution A is sprayed in the ball rolling process, the rotating speed of the ball rolling machine is 35 rpm, and after the ball rolling is finished, 0.6-0.7 mm of spherical alumina A is prepared; then weighing 100g of alumina A, putting the alumina A into a ball rolling machine, uniformly scattering 363g of macroporous alumina in the rolling process, simultaneously spraying 435mL of mixed solution A, wherein the rotating speed of the ball rolling machine is 35 rpm, and after the ball forming is finished, preparing 1.0-1.2 mm spherical alumina B. Carrying out water vapor treatment on the alumina B at the temperature of 160 ℃ for 4h, wherein the volume space velocity of the water vapor and the alumina B is 800h^-1To obtain alumina C. And drying the alumina C at 110 ℃ for 8h to obtain the spherical carrier with the particle size of 1.0-1.2 mm.

(3) Catalyst preparation

Dissolving 22.6g of ammonium heptamolybdate and 8.0g of basic nickel carbonate in an ammonia water solution with the concentration of 20wt%, and filtering to obtain 85mL of constant volume to obtain the Mo-Ni ammonia water solution.

Adding Mo-Ni ammonia water solution into 100g of prepared carrier, mixing uniformly, standing for 3h, drying at 110 ℃ for 4h, and roasting at 500 ℃ for 3h to obtain the catalyst, wherein MoO is₃The content was 15.0wt%, and the NiO content was 3.5 wt%. The physicochemical properties of the catalyst are shown in Table 1, and the abrasion data are shown in Table 2.

(4) Catalyst evaluation

The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 4.

Example 3

(1) Preparing mixed solution

235.7g of ferric nitrate and 59.0g of ammonium citrate are dissolved in water to prepare 1800mL of mixed solution A, wherein the concentration of the ferric nitrate is 0.168g/mL, and the concentration of the ammonium citrate is 0.042 g/mL.

(2) Preparation of the support

1000g of small-hole alumina is made into spherical particles through rolling forming in a ball rolling machine, 1200mL of mixed solution A is sprayed in the ball rolling process, the rotating speed of the ball rolling machine is 35 rpm, and after the ball rolling is finished, 0.8-1.0 mm of spherical alumina A is prepared; and then weighing 100g of alumina A, putting the alumina A into a ball rolling machine, uniformly scattering 114g of macroporous alumina in the rolling process, simultaneously spraying 95mL of mixed solution A, wherein the rotating speed of the ball rolling machine is 35 rpm, and after the ball rolling is finished, preparing 1.0-1.2 mm spherical alumina B. Carrying out steam treatment on the alumina B at the temperature of 170 ℃ for 4h, wherein the volume space velocity of the steam and the alumina B is 800h^-1To obtain alumina C. And drying the alumina C at 110 ℃ for 8h to obtain the spherical carrier with the particle size of 1.0-1.2 mm.

(3) Catalyst preparation

32.6g of ammonium heptamolybdate and 11.8g of basic nickel carbonate are dissolved in an ammonia water solution with the concentration of 20wt%, and the volume is 85mL after filtration, thus obtaining the Mo-Ni ammonia water solution.

Adding Mo-Ni ammonia water solution into 100g of prepared carrier, mixing uniformly, standing for 3h, drying at 110 ℃ for 4h, and roasting at 500 ℃ for 3h to obtain the catalyst, wherein MoO is₃The content was 20.0wt%, and the NiO content was 4.8 wt%. The physicochemical properties of the catalyst are shown in Table 1, and the abrasion data are shown in Table 2.

(4) Catalyst evaluation

Example 4

In example 1, the ammonium heptamolybdate was changed to 22.6g and the basic nickel carbonate was changed to 8.0g, and the rest of example 1 was repeated to obtain a catalyst in which MoO was contained₃The content was 15.0wt%, and the NiO content was 3.5 wt%. The physicochemical properties of the catalyst are shown in Table 1, and the abrasion data are shown in Table 2.

Example 5

In example 1, ammonium heptamolybdate was changed to 32.6g and basic nickel carbonate was changed to 118g, as in example 1, to obtain a catalyst in which MoO₃The content was 20.0wt%, and the NiO content was 4.8 wt%. The physicochemical properties of the catalyst are shown in Table 1, and the abrasion data are shown in Table 2.

Example 6

In example 1, the catalyst was prepared as in example 1 except that the basic nickel carbonate was changed to 4.6g of basic cobalt carbonate. MoO in catalyst₃The content was 10.0wt%, and the CoO content was 2.2 wt%. The physicochemical properties of the catalyst are shown in Table 1, and the abrasion data are shown in Table 2.

Comparative example 1

In example 1, the mixed solution A was changed to an aqueous ferric nitrate solution of 1800mL in total, wherein the concentration of ferric nitrate was 0.08 g/mL. The physicochemical properties of the catalyst are shown in Table 1, and the abrasion data are shown in Table 2.

Comparative example 2

Compared with the example 1, the water vapor treatment step is omitted, the carrier precursor is directly dried and roasted to obtain the final carrier, the rest is the same as the example 1, the physicochemical properties of the catalyst are shown in a table 1, and the abrasion data are shown in a table 2.

TABLE 1 physicochemical Properties of the catalyst

TABLE 2 attrition of catalyst

TABLE 3 Properties of the feed oils

TABLE 4 catalyst evaluation results

The results of the evaluation of the activity of comparative example 1 are shown in Table 4, where the activity is 100.

Claims

1. A preparation method of a hydrogenation catalyst comprises the following steps:

(4) treating the alumina B with vapor-containing gas, and further drying to obtain alumina C;

2. The process for producing a hydrogenation catalyst according to claim 1, wherein: in the step (1), the iron-containing inorganic salt is one or more of ferric nitrate, ferric chloride and ferric sulfate; the ammonium citrate salt is one or more of ammonium dihydrogen citrate, ammonium monohydrogen citrate and ammonium citrate.

3. A process for preparing a hydrogenation catalyst according to claim 1 or 2, characterized in that: in the step (1), the iron-containing inorganic salt is ferric nitrate.

4. The process for producing a hydrogenation catalyst according to claim 1, wherein: the adding amount of the iron-containing inorganic salt in the step (1) is 1 to 5 weight percent of the final carrier content.

5. The process for producing a hydrogenation catalyst according to claim 1, wherein: the adding amount of the ammonium citrate in the step (1) is 1 to 5 weight percent of the final carrier content.

6. The process for producing a hydrogenation catalyst according to claim 1, wherein: in the step (1), the concentration of the iron-containing inorganic salt in the solution A is 0.01-0.50 g/mL, and the concentration of the ammonium citrate salt is 0.005-0.20 g/mL.

7. The process for producing a hydrogenation catalyst according to claim 1, wherein: the mass ratio of the solution A to the small-hole alumina in the step (2) is 0.7-1.5.

8. The process for producing a hydrogenation catalyst according to claim 1, wherein: the mass ratio of the solution A to the macroporous alumina in the step (3) is 0.7-1.5.

9. The process for producing a hydrogenation catalyst according to claim 1, wherein: the properties of the small-pore alumina in the step (2) are as follows: the specific surface area is 260-400 m²The pore volume is 0.7-1.0 mL/g, and the average pore diameter is 8-12 nm.

10. The process for producing a hydrogenation catalyst according to claim 1, wherein: the properties of the macroporous alumina described in step (3) are as follows: the specific surface area is 120-250 m²(iv)/g, pore volume of 0.7 to 1.0mL/g, and average pore diameter of 15 to 30 nm.

11. The process for producing a hydrogenation catalyst according to claim 1, wherein: the balling method in the step (2) is one or more of extrusion ball-throwing forming, rolling forming and spray drying forming.

12. The process for producing a hydrogenation catalyst according to claim 1, wherein: in the step (2), the particle size of the alumina A is 0.1-2.0 mm.

13. The process for producing a hydrogenation catalyst according to claim 1, wherein: in the alumina B in the step (3), the grain diameter of the alumina A is 10 to 90 percent of that of the alumina B.

14. The process for producing a hydrogenation catalyst according to claim 1, wherein: the vapor-containing gas in the step (4) is water vapor or a mixed gas of water vapor and a carrier gas, the volume ratio of the water vapor to the carrier gas in the mixed gas is 1: 5-2: 1, the carrier gas is air, nitrogen or an inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.

15. The process for producing a hydrogenation catalyst according to claim 1, wherein: the vapor-containing gas in the step (4) is water vapor or a mixed gas of water vapor and a carrier gas, the volume ratio of the water vapor to the carrier gas in the mixed gas is 1: 4-1: 1, the carrier gas is air, nitrogen or an inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.

16. The process for producing a hydrogenation catalyst according to claim 1, wherein: and (4) introducing vapor-containing gas to treat the alumina B in the treatment process in the step (4), wherein the treatment temperature is 140-180 ℃, and the treatment time is 2-6 h.

17. The process for producing a hydrogenation catalyst according to claim 1, wherein: in the step (4), the drying temperature is 90-120 ℃, and the drying time is 3-12 h.

18. The process for producing a hydrogenation catalyst according to claim 1, wherein: the alumina C in the step (4) is spherical, and the particle size is 0.1-2.5 mm.

19. A process for preparing a hydrogenation catalyst as claimed in claim 1 or 18, characterized in that: the alumina C in the step (4) is spherical, and the particle size is 0.2-2.0 mm.

20. The process for producing a hydrogenation catalyst according to claim 1, wherein: the compound containing the hydrogenation metal component in the step (5) is a compound containing a VIB group metal and/or a VIII group metal.

21. The process for producing a hydrogenation catalyst as claimed in claim 20, wherein: the group VIB metal-containing compound is one or more of a molybdenum-containing compound and a tungsten-containing compound, and the group VIII metal-containing compound is one or more of a nickel-containing compound and a cobalt-containing compound.

22. A process for preparing a hydrogenation catalyst as claimed in claim 1 or 20, characterized in that: in the step (5), the compound containing the hydrogenation metal component is a molybdenum-containing compound and a nickel-containing compound, and the molybdenum-containing compound is ammonium heptamolybdate and/or ammonium tetramolybdate; the nickel-containing compound is basic nickel carbonate.

23. A process for preparing a hydrogenation catalyst as claimed in claim 1 or 20, characterized in that: in the step (5), the compound containing the hydrogenation metal component is a molybdenum-containing compound and a nickel-containing compound, and the molybdenum-containing compound is ammonium heptamolybdate; the nickel-containing compound is basic nickel carbonate.

24. The process for producing a hydrogenation catalyst according to claim 1, wherein: the concentration of ammonia water in the step (5) is 15wt% -25 wt%.

25. The process for producing a hydrogenation catalyst according to claim 1, wherein: the drying conditions in the step (6) comprise: the drying temperature is 90-120 ℃, and the drying time is 1-12 h; the roasting conditions include: the roasting temperature is 300-600 ℃, and the roasting time is 1-5 h.

26. A hydrogenation catalyst characterized by: the hydrogenation catalyst is prepared by the method of any one of claims 1 to 25.

27. A hydrogenation catalyst as claimed in claim 26, wherein: the hydrogenation catalyst comprises a hydrogenation active metal component, an auxiliary agent and a carrier, wherein the hydrogenation active metal component is one or more of VIB group metals and/or VIII group metals, and the auxiliary agent is Fe₂O₃。

28. A hydrogenation catalyst as claimed in claim 27, wherein: the VIB group metal is Mo and/or W, and the VIII group metal is Ni and/or Co.