CN113042041B

CN113042041B - Coal tar hydrogenation catalyst, and preparation method and application thereof

Info

Publication number: CN113042041B
Application number: CN201911371016.2A
Authority: CN
Inventors: 朱慧红; 金浩; 吕振辉; 刘璐; 杨光; 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: 2019-12-27
Filing date: 2019-12-27
Publication date: 2022-03-08
Anticipated expiration: 2039-12-27
Also published as: CN113042041A

Abstract

The invention discloses a coal tar hydrogenation catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, preparing high-silicon pseudo-boehmite, then mixing the obtained high-silicon pseudo-boehmite with an auxiliary agent, forming, drying and roasting to obtain a carrier, finally introducing an active metal component onto the obtained carrier, and further drying and roasting to obtain the catalyst. According to the preparation method of the coal tar hydrogenation catalyst, high-silicon pseudo-boehmite is used as a raw material in the preparation process, and an auxiliary agent is added in the preparation of the carrier and enters an alumina structure to form a component with water resistance, so that the water resistance of the catalyst is improved, and the coal tar hydrogenation catalyst with good wear resistance and hydrogenation performance is prepared.

Description

Coal tar hydrogenation catalyst, and preparation method and application thereof

Technical Field

The invention relates to the field of petrochemical industry, relates to preparation and application of a coal tar hydrogenation catalyst, and particularly relates to preparation and application of a boiling bed coal tar hydrogenation catalyst.

Background

China is a country rich in coal, low in gas and deficient in oil, and the processing and utilization of coal tar are increasingly regarded by the country. Coal tar is a liquid byproduct obtained in the pyrolysis process of coal, has irritant odor, black or black brown and sticky liquid, and has the yield of about 3-4%.

The coal tar raw material contains a large amount of unsaturated hydrocarbons such as olefin and polycyclic aromatic hydrocarbon, sulfur and nitrogen compounds, and has the characteristics of high acidity, high colloid content, poor product stability (light stability, storage stability and oxidation stability) and the like, so that a large amount of sulfide and nitride can be generated by direct combustion, and serious environmental pollution is caused. Clean processing and efficient utilization of coal tar is becoming increasingly important. The coal tar hydrogenation technology is an effective way for solving the problems, can prolong the industrial chain, improve the resource utilization rate, reduce the pollution and extract products with high added value.

The composition distribution and the molecular structure of the coal tar and the petroleum fraction have obvious difference, namely the oxygen content is high; secondly, the heavy component content is high, and the heavy metal content is high; high aromatic hydrocarbon components, especially condensed ring aromatic hydrocarbon and unsaturated olefin are easy to condense under heated condition. Therefore, the catalyst is required to have stronger water resistance, good hydrogenation and impurity removal performance and good anti-coking performance. Compared with the conventional petroleum fraction hydrogenation catalyst, the water resistance requirement is more outstanding. The improvement of the performance of the carrier raw material is the basis for preparing the water-resistant coal tar catalyst, so that the development of the carrier raw material with excellent performance is very important.

The coal tar hydrogenation catalyst usually adopts pseudo-boehmite as a carrier raw material. The industrial production method of pseudo-boehmite mainly comprises an organic aluminum alkoxide method and an inorganic neutralization method according to different raw materials. Among them, the inorganic neutralization method is generally industrially carried out by three production methods: aluminum chloride process, aluminum sulfate process, and carbonization process. In the three methods, aluminum hydroxide is generated by adopting a neutralization method, and then impurity sodium is removed in the washing process, so that the washing water consumption is high, and a large amount of waste water is generated.

CN201610674763.3 discloses a low-impurity pseudo-boehmite, its manufacturing method and manufacturing device. The mass percentage of metal ion impurities in the low-impurity pseudo-boehmite is less than or equal to 0.1 percent. The method comprises preparing pseudoboehmite as raw material into slurry; acidifying the slurry to obtain an acidified raw material pseudo-boehmite; aging at a set temperature for a set time to obtain an aged raw material pseudo-boehmite; enabling the aged pseudo-boehmite to pass through cation exchange resin at a set flow rate, so that metal ion impurities in the aged pseudo-boehmite are removed; drying the raw material pseudo-boehmite from which the metal ion impurities are removed to obtain the pseudo-boehmite with low impurities, wherein the mass percentage of the metal ion impurities is less than or equal to 0.1%. The device comprises a first container, a second container, a third container and a drying device. The method carries out impurity sodium treatment on the prepared pseudo-boehmite, does not reduce the impurity content in the preparation process, and belongs to the post-treatment process.

CN200610027539.1 discloses a coal liquefied oil boiling bed hydrotreating catalyst carrier and a preparation method thereof. The carrier contains alumina fiber besides the components of the conventional hydrogenation catalyst carrier, and the content of the alumina fiber in the carrier is 3-10 wt%. The carrier has good mechanical strength and wear resistance, and improves the stability of the catalyst taking the carrier as the carrier. The alumina cellulose is added to improve the wear resistance of the catalyst, and the method does not start from the direction of source carrier raw materials and has limited improvement range.

Disclosure of Invention

Aiming at the problems in the prior art, the invention aims to provide a coal tar hydrogenation catalyst, and a preparation method and application thereof. According to the preparation method of the coal tar hydrogenation catalyst, high-silicon pseudo-boehmite is used as a raw material in the preparation process, and an auxiliary agent is added in the preparation of the carrier and enters an alumina structure to form a component with water resistance, so that the water resistance of the catalyst is improved, and the coal tar hydrogenation catalyst with good wear resistance and hydrogenation performance is prepared.

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

s1, preparing high-silicon pseudo-boehmite;

s2, mixing the high-silicon pseudo-boehmite obtained in the step S1 with an auxiliary agent, and then forming, drying and roasting to obtain a carrier;

s3, introducing an active metal component to the carrier obtained in the step S2, and further drying and roasting to obtain the catalyst.

In the preparation method of the coal tar hydrogenation catalyst, the auxiliary agent in the step S2 is one or more of nickel salt, lanthanum salt, rhodium salt and silica sol, preferably at least one of nickel salt, lanthanum salt and rhodium salt; wherein, the nickel salt can be one or more of nickel nitrate, nickel sulfate, nickel chloride and nickel acetate; the lanthanum salt can be one or more of lanthanum nitrate and lanthanum chloride; the rhodium salt can be one or more of rhodium nitrate, rhodium chloride and rhodium sulfate; the addition amount of the auxiliary agent is 1-5 wt% (calculated by oxide) of the high-silicon pseudo-boehmite, and preferably 1-3wt% (calculated by oxide).

In the preparation method of the coal tar hydrogenation catalyst, when the high-silicon pseudo-boehmite is mixed with the auxiliary agent in the step S2, an additive may be added according to needs, wherein the additive may be one or more of citric acid, acetic acid, tartaric acid, polyethylene glycol, polyvinyl alcohol, methyl cellulose and polyacrylamide, and is preferably one or more of polyethylene glycol, methyl cellulose and polyacrylamide.

In the preparation method of the coal tar hydrogenation catalyst, in the step S2, the drying is carried out at 100-200 ℃ for 2-20 hours, and the roasting is carried out at 600-900 ℃ for 1-8 hours.

In the preparation method of the coal tar hydrogenation catalyst, the drying in the step S3 is drying at 80-200 ℃ for 2-20 hours, and the roasting is roasting at 400-600 ℃ for 2-6 hours.

In the preparation method of the coal tar hydrogenation catalyst, the forming technology in the step S2 is selected by the person skilled in the art according to the actual needs in the existing forming method, and may be any one or more of clover, tetrafoil, sphere, strip, etc.

In the preparation method of the coal tar hydrogenation catalyst, the method for introducing the active metal component in step S3 may adopt a conventional method in the art, such as an impregnation method, a kneading method, and the like, and preferably adopts an impregnation method. The carrier is prepared by adopting a conventional impregnation method when an active metal component is loaded by adopting an impregnation method, and can adopt a spray impregnation method, a saturated impregnation method or a supersaturated impregnation method. For example, the method of supporting the active metal component on the carrier is an impregnation method which comprises preparing a solution of an active metal-containing compound and impregnating the carrier with the solution.

In the preparation method of the coal tar hydrogenation catalyst, in the step S3, the active metal is selected from at least one of group VIB metals and group VIII metals in the periodic table of elements, and particularly is selected from at least one of Mo, W, Ni and Co. Preferably, the group VIB metal is Mo and/or W and the group VIII metal is Ni and/or Co. The content of the metal component of the VIB group is 1wt% to 30wt%, and the content of the metal component of the VIII group is 1wt% to 15wt%, relative to 100wt% of the total weight of the hydrogenation catalyst.

In the preparation method of the coal tar hydrogenation catalyst, the high-silicon pseudo-boehmite is prepared in the step S1 by the following method:

(1) mixing an aqueous solution containing aluminate, an aqueous solution containing a silicon source, an aqueous solution containing an organic acid source, a cation exchange resin suspension and water, and uniformly mixing to obtain a material A;

(2) carrying out hydrothermal treatment on the material A, and then adding a cation exchange resin suspension to obtain a material B;

(3) and separating the material B to obtain cation exchange resin and slurry, and further filtering and drying the slurry to obtain the high-silicon pseudo-boehmite.

In the preparation method of the high-silicon pseudo-boehmite, the aluminate in the step (1) is a meta-aluminate, specifically sodium meta-aluminate, and the causticity ratio of the sodium meta-aluminate is 1.15-1.35, preferably 1.20-1.30; the concentration of the sodium metaaluminate aqueous solution is 20-100gAl calculated by oxide₂O₃Preferably 30 to 70gAl₂O₃And L. IntoIn one step, the flow rate of adding the sodium metaaluminate solution into the reaction system is preferably 5mL/min-30mL/min, and preferably 10mL/min-30 mL/min. The preparation process of the sodium metaaluminate aqueous solution can be as follows: mixing and boiling aluminum hydroxide and sodium hydroxide to prepare 400gAl with the concentration of 300-₂O₃the/L solution is then diluted to the desired concentration with an aqueous solution containing 1-5 wt% NaOH.

In the preparation method of the high-silicon pseudo-boehmite, the silicon source in the step (1) can be water glass and/or silica sol, preferably water glass is adopted, and further preferably the modulus of the water glass is 2.5-3.2; the concentration of the water glass solution is 20-100gSiO calculated by oxide₂Per L, preferably 40-60gSiO₂And L. The flow rate of adding the water glass solution into the reaction system is 10mL/min-40mL/min, preferably 10mL/min-30 mL/min.

In the above method for producing high-silica pseudo boehmite, the cation exchange resin may be at least one kind selected from a macroporous strongly acidic styrene-based cation exchange resin and a sulfonated styrene-based gel-type strongly acidic cation exchange resin, more preferably at least one kind selected from a D001 macroporous strongly acidic styrene-based cation exchange resin, a D002 macroporous strongly acidic styrene-based cation exchange resin and a D61 macroporous strongly acidic styrene-based cation exchange resin, and still more preferably at least one kind selected from a D001 macroporous strongly acidic styrene-based cation exchange resin and a D61 macroporous strongly acidic styrene-based cation exchange resin.

In the above-mentioned method for producing high-silica pseudoboehmite, the particle size of the cation exchange resin is generally 20 to 150 mesh, preferably 40 to 80 mesh.

In the method for preparing the high-silicon pseudo-boehmite, the organic acid source is an acid or an acid derivative containing an organic group in a molecular structure. The organic group is represented by the formula

The groups represented (also referred to as polyether groups). In the polyether group, Ra is a hydrogen atom or an optionally substituted C1-30 hydrocarbon group, preferably selected from C1-30 straight or branched chainAlkyl and optionally substituted C6-20 aryl, preferably selected from C5-20 straight or branched chain alkyl and phenyl, more preferably C9-15 straight or branched chain alkyl. In addition, the n groups R1, equal to or different from each other, are each independently selected from C1-6 linear or branched alkylene groups, preferably C2-4 linear or branched alkylene groups, more preferably ethylene groups. n represents the average degree of polymerization of the polyether groups and is generally a number from 0 to 200, preferably a number from 0 to 100, more preferably a number from 5 to 50 or from 5 to 20. In addition, in order to facilitate the production process of the present invention, the number of carbon atoms (which means the total number of carbon atoms contained in the entire molecular structure) of the organic acid source is generally at most 30, preferably at most 20, and more preferably at most 15.

In the method for producing the high-silicon pseudo-boehmite, the pKa of the organic acid source is larger than the pKa of the cation exchange resin and smaller than the pKa of the alkaline aluminum source. The acidity coefficient pKa of the organic acid source is generally in the range of 0 to 8, preferably 2 to 8, and more preferably 3 to 6.

In the above-mentioned process for producing high-silicon pseudo-boehmite, the organic acid source may be at least one selected from the group consisting of a carboxylic acid, a salt of the carboxylic acid, an organic ester/salt of the carboxylic acid, a phosphonic acid, a salt of the phosphonic acid, an organic ester/salt of the phosphonic acid, a phosphonous acid, a salt of the phosphonous acid, an organic ester/salt of the phosphonous acid, an organic ester/carbonate, an organic ester/salt of carbonic acid, an organic ester/salt of phosphoric acid, an organic ester/salt of phosphorous acid, an organic ester/salt of sulfuric acid, an organic ester of sulfurous acid, an organic ester/salt of sulfurous acid, and is preferably selected from the group consisting of an organic ester/carbonate, an organic ester/salt of carbonic acid, an organic ester/salt of phosphoric acid, an organic ester/salt of phosphorous acid, an organic ester/salt of phosphorous acid, and a salt of phosphorous acid, At least one of an organic phosphate, an organic phosphite, and an organic phosphite, more preferably at least one selected from the group consisting of organic phosphates and organic phosphites, and particularly an organic phosphate. Preferably, the organic group is of the formula

The groups represented (also referred to as polyether groups). In the polyether group, Ra is a hydrogen atom or an optionally substituted C1-30 hydrocarbon group, preferably selected from C1-30 linear or branched alkyl groups and optionally substituted C6-20 aryl groups, preferably selected from C5-20 linear or branched alkyl groups and phenyl groups, more preferably C9-15 linear or branched alkyl groups. In addition, the n groups R1, equal to or different from each other, are each independently selected from C1-6 linear or branched alkylene groups, preferably C2-4 linear or branched alkylene groups, more preferably ethylene groups. n represents the average degree of polymerization of the polyether groups and is generally a number from 0 to 200, preferably a number from 0 to 100, more preferably a number from 5 to 50 or from 5 to 20.

In the above process for producing a high-silicon pseudo-boehmite, the organic phosphate may be a mono-organic phosphate or a di-organic phosphate, and more preferably is at least one selected from the group consisting of a monoalkyl ether phosphate, a dialkyl ether phosphate, a monoalkyl phosphate and a dialkyl phosphate, particularly at least one selected from the group consisting of a mono-C9-C15 alkyl ether phosphate, a mono-C9-C15 alkyl phosphate, a di-C9-C15 alkyl phosphate and a di-C9-C15 alkyl ether phosphate, further preferably a mono-C9-C15 alkyl ether phosphate, and further preferably a mono-C9 alkyl ether phosphate.

In the preparation method of the high-silicon pseudo-boehmite, the organic phosphate ester is a compound shown in a structural formula (I);

（I）

in the formula (I), each A, which is the same as or different from each other, is independently selected from the group consisting of a hydrogen ion, an ammonium ion (NH 4 +), a metal ion (such as an alkali metal ion or an alkaline earth metal ion, particularly a sodium ion), and a salt of the formula

The groups represented (also referred to as polyether groups). Preferably, at least one a is a hydrogen ion, more preferably both a are hydrogen ions. Here, R0 is selected from the group consisting of a hydrogen atom, an optionally substituted C1-30 linear or branched alkyl group and an optionally substituted C6-20 aryl group,preferably selected from the group consisting of C5-20 linear or branched alkyl and phenyl, more preferably C9-15 linear or branched alkyl, and even more preferably C9 linear or branched alkyl. In addition, the n groups R1, equal to or different from each other, are each independently selected from C1-6 linear or branched alkylene groups, preferably C2-4 linear or branched alkylene groups, more preferably ethylene groups. n represents the average degree of polymerization of the polyether groups and is generally a number from 0 to 200, preferably a number from 0 to 100, more preferably a number from 5 to 50 or from 5 to 20.

In the above-mentioned method for producing high-silicon pseudo-boehmite, the HLB value of the organic acid source is generally 3 to 8, preferably 3 to 6. Here, after determining the specific chemical structure of the organic acid source, the corresponding HLB value thereof may be measured or calculated by a method known in the related art, or may be obtained by referring to known data.

In the above-mentioned process for producing high-silicon pseudo-boehmite, the weight ratio of the aluminate (in terms of alumina) and the silicon source (in terms of silica) to the organic acid source in step (1) is generally 2:1 to 20:1, preferably 2:1 to 16: 1.

In the preparation method of the high-silicon pseudo-boehmite, the weight ratio of the cation exchange resin in the step (1) to the cation exchange resin in the step (2) is generally 8: 1-4: 1.

In the above-mentioned method for producing high-silicon pseudoboehmite, the reaction temperature (referring to the temperature of the reaction mixture in the reactor) in the step (1) is generally 60 ℃ to 90 ℃, preferably 60 ℃ to 80 ℃.

In the above method for preparing high-silicon pseudo-boehmite, the aqueous solution containing aluminate, the aqueous solution containing a silicon source, the aqueous solution containing an organic acid source and the suspension of the cation exchange resin in step (1) may be fed simultaneously in a cocurrent manner, or may be fed separately into the reactor, and preferably fed simultaneously in a cocurrent manner. In addition, when the materials are separately fed into the reactor, the order of feeding the materials is not particularly limited, and it is preferable to feed the aqueous solution containing the aluminate, the aqueous solution containing the silicon source, and the aqueous solution containing the organic acid source, and then to feed the suspension of the cation exchange resin.

In the above method for preparing high-silicon pseudo-boehmite, the amount of the water in the step (1) is 5 to 20vol%, preferably 5 to 15vol% of the total volume of the reaction system (e.g., reactor).

In the preparation method of the high-silicon pseudo-boehmite, the concentration of the aqueous solution of the organic acid source in the step (1) is 0.015-0.35 g/mL. The flow rate of adding the aqueous solution of the organic acid source into the reaction system is 1.25mL/min-10 mL/min.

In the above method for preparing high-silica pseudo-boehmite, the solid content of the cation exchange resin suspension is 30 to 80wt%, preferably 50 to 80 wt%.

In the above method for preparing high-silicon pseudo-boehmite, the cation exchange resin suspension in the step (1) is added to the reaction system at such a flow rate or in such an amount that the pH of the reaction system is maintained at 7.5 to 12.0, preferably 8.0 to 11.0.

In the preparation method of the high-silicon pseudo-boehmite, the hydrothermal treatment in the step (2) is carried out in a closed container, the treatment temperature is 200-260 ℃, preferably 200-250 ℃, and the treatment time is 4-12h, preferably 6-2 h.

In the preparation method of the high-silicon pseudo-boehmite, the cation exchange resin suspension is added into the reaction system in the step (2) in an amount such that the pH value of the first mixed solution is 7.0-8.5, preferably 7.0-8.0.

In the above method for preparing high-silicon pseudo-boehmite, the separation in step (3) may be performed by separating the cation exchange resin from the second mixed solution with a 100-mesh 120-mesh screen. The separated cation exchange resin can be regenerated and recycled.

In the preparation method of the high-silicon pseudo-boehmite, the drying temperature in the step (3) is generally 100-150 ℃, and the drying time is generally 6-10 hours.

In the preparation method of the high-silicon pseudo-boehmite, the slurry is separated into a filter cake and a filtrate in the step (3) by adopting a filtration mode and the like, the filter cake is dried to obtain the high-silicon pseudo-boehmite, and the filtrate can be recycled.

Second aspect of the inventionThe coal tar hydrogenation catalyst prepared by the preparation method has the following properties: the specific surface area is 120-200m²The pore volume is 0.50-0.75mL/g, the infrared acid amount is 0.20-0.35mmol/g, and the abrasion index is less than 1.0%.

In the third aspect of the invention, a coal tar hydrogenation method is provided, wherein the hydrogenation method comprises the steps of mixing coal tar and hydrogen, and then carrying out hydrogenation reaction in the presence of the coal tar hydrogenation catalyst.

In the coal tar hydrogenation method, the coal tar is one or more of medium-low temperature coal tar and high-temperature coal tar.

In the coal tar hydrogenation method, the hydrogenation reaction conditions are as follows: the reaction pressure is 8-20MPa, the reaction temperature is 350-410 ℃, the liquid hourly space velocity is 0.1-2.0h < -1 >, and the volume ratio of hydrogen to oil is 100-.

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

1. according to the preparation method of the coal tar hydrogenation catalyst, high-silicon pseudo-boehmite is used as a raw material in the preparation process, and an auxiliary agent is added in the preparation of the carrier and enters an alumina structure to form a component with water resistance, so that the water resistance of the catalyst is improved, and the coal tar hydrogenation catalyst with good wear resistance and hydrogenation performance is prepared.

2. In the preparation method of the coal tar hydrogenation catalyst, the washing step in the existing method can be saved in the preparation process of the high-silicon pseudo-boehmite, the generation of wastewater is reduced, the preparation process flow is simplified, the pseudo-boehmite with low sodium content can be ensured to be obtained, and the surface acidity of the prepared alumina product can be improved. Therefore, the filtered slurry can be recycled, thereby realizing closed cycle of the production process and no discharge of pollutants. Is particularly suitable to be used as a carrier raw material of a coal tar hydrogenation catalyst.

3. In the preparation method of the coal tar hydrogenation catalyst, the cation exchange resin is added in two steps in the preparation process of the high-silicon pseudo-boehmite, so that the sodium content of the obtained high-silicon pseudo-boehmite can be further reduced, and the pseudo-boehmite product with lower sodium content can be obtained.

Detailed Description

The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments.

All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.

In the context of the present specification, the term "ester" includes monoesters and polyesters, depending on the type of acid.

In the context of the present specification, the expression "ester/salt" refers to a mixture of ester and salt.

In the context of the present specification, the acidity coefficient pKa is measured in the non-salt form of the corresponding substance (in particular the organic acid source). Here, the non-salt form refers to a form obtained by replacing all metal ions or ammonium ions contained in the substance with hydrogen ions.

In the context of the present specification, the pore volume and specific surface area of high-silicon aluminum oxide are analyzed using low-temperature nitrogen adsorption.

In the context of the present specification, the expression "optionally substituted" means optionally substituted by one or more groups (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) selected from halogen, hydroxy, mercapto, amino, aminocarbonyl, nitro, oxo, thio, cyano, C1-6 straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, C2-6 straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, C2-6 straight or branched chain (halo) yne (oxy, thio, amino, carbonyl) yl, C3-20 cycloalkyl, C3-20 cycloalkyl (oxy, thio, amino) yl, C3-20 cycloalkyl C1-6 straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, C3-20 cycloalkyl C2-6 straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, C3-20 cycloalkyl C2-6 straight or branched (halo) alkyne (oxy, thio, amino, carbonyl) group, C3-20 cycloalkenyl, C3-20 cycloalkenyl (oxy, thio, amino) group, C3-20 cycloalkenyl C1-6 straight or branched (halo) alkane (oxy, thio, amino, carbonyl) group, C3-20 cycloalkenyl C2-6 straight or branched (halo) alkene (oxy, thio, amino, carbonyl) group, C3-20 cycloalkenyl C2-6 straight or branched (halo) alkyne (oxy, thio, amino, carbonyl) group, C6-20 aryl group, C6-20 aryl (oxy, thio, amino) group, C6-20 aryl C1-6 straight or branched (halo) alkane (oxy, thio, amino, carbonyl) group, C6-20 aryl C2-6 straight or branched (halo) alkene (oxy, thio, amino, carbonyl) group, C3929-20 aryl C2-6 straight or branched (halo) alkyne (oxy, thio, amino) carbonyl) group, C2 9-20 aryl group, C2-6 straight or branched (halo) alkyne (oxy, thio, carbonyl) group, Sulfur, ammonia, carbonyl) group, C4-20 heteroaryl group, C4-20 heteroaryl (oxygen, sulfur, ammonia) group, C4-20 heteroaryl C1-6 straight or branched (halo) alk (oxygen, sulfur, ammonia, carbonyl) group, C4-20 heteroaryl C2-6 straight or branched (halo) en (oxygen, sulfur, ammonia, carbonyl) group, C4-20 heteroaryl C2-6 straight or branched (halo) yne (oxygen, sulfur, ammonia, carbonyl) group, C2-20 heterocyclyl group, C2-20 heterocyclyl (oxygen, sulfur, ammonia) group, C2-20 heterocyclyl C1-6 straight or branched (halo) alk (oxygen, sulfur, ammonia, carbonyl) group, C2-20 heterocyclyl C2-6 straight or branched (halo) en (oxygen, sulfur, ammonia, carbonyl) group and C2-20 heterocyclyl C2-6 straight or branched (halo) alk (oxygen, sulfur, ammonia, carbonyl) yl group, Carbonyl) group (at a feasible position). When a plurality of these substituents are present, two adjacent substituents (for example, molecular chain ends of two substituents) may be bonded to each other to form a divalent substituent structure. For example, two adjacent C1-6 linear or branched alkyl groups may be bonded to each other to form the corresponding alkylene structure. Alternatively, two adjacent C1-6 linear or branched alkoxy groups may for example form the corresponding alkylenedioxy structure, two adjacent C1-6 linear or branched alkylamino groups may for example form the corresponding alkylenediamino structure, two adjacent C1-5 linear or branched alkylthio groups may for example form the corresponding alkylenedithio structure, etc. Preferable examples of the substituent include a halogen, a C1-6 linear or branched alkyl group and the like. Here, the expression "(halo) alkyl (oxy, thio, amino, carbonyl) group" means: alkyl, haloalkyl, alkoxy, alkylthio, alkylamino, alkylcarbonyl, haloalkoxy, haloalkylthio, haloalkylamino or haloalkylcarbonyl, the expression "(halo) ene (oxy, thio, amino, carbonyl) group" means: alkenyl, haloalkenyl, alkenyloxy, alkenylthio, alkenylamino, alkenylcarbonyl, haloalkenyloxy, haloalkenylthio, haloalkenylamino or haloalkenylcarbonyl, the expression "(halo) alkyne (oxy, thio, amino, carbonyl)" means: alkynyl, haloalkynyl, alkynyloxy, alkynylthio, alkynylamino, alkynylcarbonyl, haloalkynyloxy, haloalkynylthio, haloalkynylamino or haloalkynylcarbonyl, the expression "(oxy, thio, amino) group" means oxy, thio or amino. Here, the halo includes monohalo, dihalogen, trihalo, perhalo, etc.

All percentages, parts, ratios, etc. referred to in this specification are by weight and pressures are gauge pressures unless otherwise specifically indicated.

Example 1

Is prepared by mixing and boiling aluminum hydroxide and sodium hydroxide to 345gAl₂O₃The solution of/L is diluted by aqueous solution containing 3.5wt% of NaOH to prepare a caustic ratio of 1.30 and a concentration of 40 gAl₂O₃L of sodium metaaluminate solution for standby; the preparation concentration is 50gSiO₂A water glass solution with the modulus of 2.8 is used for standby; preparing a C9 monoalkyl ether phosphate (pKa =4.3, HLB = 7) solution with a concentration of 0.2g/mL for later use; d001 macroporous strong acidic styrene cation exchange resin with 60 meshes is prepared into suspension with solid content of 50wt% for standby.

Adding 800mL of deionized water serving as bottom water into a 5000mL reactor, starting stirring and heating, heating the deionized water to 70 ℃, then adding the four materials into the reactor in a parallel flow manner, controlling the flow rate of sodium metaaluminate to be 15mL/min, the flow rate of water glass to be 13mL/min, and the flow rate of C9 monoalkyl ether phosphate solution to be 2.5mL/min, controlling the pH value of slurry in the reactor to be 8.0 by adjusting the flow rate of D001 macroporous strongly acidic styrene cation exchange resin suspension, and keeping the temperature and the pH value of the slurry in the reactor constant. After the reaction is finished, the obtained slurry is heated to 240 ℃ in a closed pressure-resistant container, the temperature is kept constant for 6 hours, D001 macroporous strongly acidic styrene cation exchange resin suspension is added, and the pH value of the slurry is adjusted to 7.0. And separating the cation exchange resin from the slurry by adopting a 100-mesh screen, and regenerating and recycling the separated cation exchange resin. Filtering the slurry to separate out filter cake and filtrate, wherein the filtrate can be recycled, and drying the obtained filter cake for 8 hours at 120 ℃ to obtain the high-silicon pseudo-boehmite a 1.

1000g of manufactured a1 high-silicon pseudo-boehmite is weighed, 7g of sesbania powder, 17.5g of citric acid and 12.96g of basic nickel carbonate are added, then the mixture is pelletized, and the pelletized sample is roasted for 5 hours at 700 ℃ to obtain a carrier Z1 with the granularity of 0.4-0.5 mm.

49.55g of phosphoric acid is weighed, 900mL of distilled water is added, 107.66g of molybdenum oxide and 49.35g of basic nickel carbonate are sequentially added, the mixture is heated and stirred until the molybdenum oxide and the basic nickel carbonate are completely dissolved, and the solution is metered to 1000mL by using distilled water, so that a metal solution L1 is obtained.

The carrier Z1 was saturated and impregnated with L1 solution, dried at 110 deg.C for 2h, and calcined at 480 deg.C for 5h to obtain catalyst C1, with specific properties shown in Table 1.

Example 2

The other conditions were the same as in example 1 except that the concentration of water glass was changed to 30gSiO₂The flow rate is 13.3 mL/min, the D001 macroporous strong-acid styrene cation exchange resin of 60 meshes is changed into the D002 macroporous strong-acid styrene cation exchange resin of 80 meshes, the pH value of slurry in a reactor is changed to 8.5, the obtained slurry is aged for 7 hours at 250 ℃ to obtain the high-silicon pseudo-boehmite a2, the carrier Z-2 and the catalyst C-2, and the specific properties of the catalyst are shown in Table 1.

Example 3

Otherwise, the procedure of example 1 was repeated except that C9 monoalkyl ether phosphate was changed to C9 alkyl phosphate (pKa =4.8, HLB = 5), the pH for gelling was adjusted to 9.0, and the drying conditions were changed to 150 ℃ for 6 hours, to obtain high-silica pseudoboehmite a 3.

1000g of a3 pseudo-boehmite raw material prepared by the method is taken, 7.3g of carbon black and 32.47g of rhodium nitrate are added, then the mixture is pelletized, and the pelletized sample is roasted for 3 hours at 800 ℃ to obtain a carrier Z3 with the granularity of 0.3-0.7mm, and the properties of the carrier are shown in Table 1.

51.61g of phosphoric acid is weighed, 900mL of distilled water is added, 140.18g of molybdenum oxide and 64.25g of basic nickel carbonate are sequentially added, the solution is heated and stirred until the molybdenum oxide and the basic nickel carbonate are completely dissolved, and the solution is metered to 1000mL by using distilled water to obtain a solution L2.

The carrier Z3 was saturated and impregnated with the solution L2, dried at 110 ℃ for 4 hours, and calcined at 550 ℃ for 3 hours to obtain catalyst C3, the specific properties of which are shown in Table 1.

Example 4

The other conditions were the same as in example 1 except that the concentration of sodium metaaluminate was changed to 30 gAl₂O₃The flow rate is changed to 10mL/min, and the water glass concentration is changed to 60gAl₂O₃The flow rate is changed to 10mL/min, the concentration of the C9 monoalkyl ether phosphate solution is changed to 0.08g/mL, and the flow rate is changed to 8mL/min, so that the high-silicon pseudo-boehmite a5 is obtained.

1000g of a4 pseudo-boehmite raw material prepared by the method is taken, 10.5g of sesbania powder, 8.5g of polyethylene glycol (6000) and 38.89g of basic nickel carbonate are added, then the mixture is pelletized, and the pelletized sample is roasted for 3 hours at 600 ℃ to obtain a carrier Z4 with the granularity of 0.3-0.7 mm.

The carrier Z4 was saturated and impregnated with the solution L1, dried at 110 deg.C for 2h, and calcined at 580 deg.C for 4h to obtain catalyst C4, with specific properties shown in Table 3.

Comparative example 1

Is prepared by mixing and boiling aluminum hydroxide and sodium hydroxide to 345gAl₂O₃The solution of/L is diluted by aqueous solution containing 3.5wt% of NaOH to prepare a caustic ratio of 1.30 and a concentration of 40 gAl₂O₃L of sodium metaaluminate solution for standby; the preparation concentration is 50gSiO₂A water glass solution with the modulus of 2.8 is used for standby; a C9 monoalkyl ether phosphate (pKa =4.3, HLB = 7) solution was prepared at a concentration of 0.2g/mL for use.

Adding 800mL of deionized water serving as bottom water into a 5000mL reactor, starting stirring and heating, heating the deionized water to 70 ℃, adding the materials into the reactor in a parallel flow manner, controlling the flow rate of sodium metaaluminate to be 15mL/min, the flow rate of water glass to be 13mL/min and the flow rate of a C9 monoalkyl ether phosphate solution to be 2.5mL/min, and keeping the temperature of slurry in the reactor constant. And after the reaction is finished, heating the obtained slurry to 240 ℃ in a closed pressure-resistant container, keeping the temperature constant for 6 hours, filtering the slurry to separate a filter cake and filtrate, washing the filter cake to a pH value of 7.0 by using distilled water, and drying the obtained filter cake for 8 hours at 120 ℃ to obtain the high-silicon pseudo-boehmite b 1.

1000g of prepared b1 high-silicon pseudo-boehmite is weighed, 7g of sesbania powder, 17.5g of citric acid and 12.96g of basic nickel carbonate are added, then the mixture is pelletized, and the pelletized sample is roasted for 5 hours at 700 ℃ to obtain a carrier F1 with the granularity of 0.4-0.5 mm. The carrier F1 was saturated and impregnated with the solution L1, dried at 110 deg.C for 2h, and calcined at 480 deg.C for 5h to obtain the catalyst CF1, the specific properties of which are shown in Table 2.

Comparative example 2

Is prepared by mixing and boiling aluminum hydroxide and sodium hydroxide to 345gAl₂O₃The solution of/L is diluted by aqueous solution containing 3.5wt% of NaOH to prepare a caustic ratio of 1.30 and a concentration of 40 gAl₂O₃L of sodium metaaluminate solution for standby; the preparation concentration is 50gSiO₂A water glass solution with the modulus of 2.8 is used for standby; d001 macroporous strong acidic styrene cation exchange resin with 60 meshes is prepared into suspension with solid content of 50wt% for standby.

Adding 800mL of deionized water into a 5000mL reactor as bottom water, starting stirring and heating, heating the deionized water to 70 ℃, adding the materials into the reactor in a parallel flow manner, controlling the flow rate of sodium metaaluminate to be 15mL/min and the flow rate of water glass to be 13mL/min, controlling the pH value of slurry in the reactor to be 8.0 by adjusting the flow rate of D001 macroporous strong-acid styrene cation exchange resin suspension, and keeping the temperature and the pH value of the slurry in the reactor constant. After the reaction is finished, the obtained slurry is heated to 240 ℃ in a closed pressure-resistant container, the temperature is kept constant for 6 hours, D001 macroporous strongly acidic styrene cation exchange resin suspension is added, and the pH value of the slurry is adjusted to 7.0. And separating the cation exchange resin from the slurry by adopting a 100-mesh screen, and regenerating and recycling the separated cation exchange resin. The slurry was filtered to separate a filter cake and a filtrate, the filter cake was washed with distilled water to a pH of 7.0, and the obtained filter cake was dried at 120 ℃ for 8 hours to obtain high-silicon pseudo-boehmite b2 of comparative example.

1000g of prepared b2 high-silicon pseudo-boehmite is weighed, 7g of sesbania powder, 17.5g of citric acid and 12.96g of basic nickel carbonate are added, then the mixture is pelletized, and the pelletized sample is roasted for 5 hours at 700 ℃ to obtain a carrier F2 with the granularity of 0.4-0.5 mm. The carrier F2 was saturated and impregnated with the solution L1, dried at 110 deg.C for 2h, and calcined at 480 deg.C for 5h to obtain the catalyst CF2, the specific properties of which are shown in Table 2.

Comparative example 3

Is prepared by mixing and boiling aluminum hydroxide and sodium hydroxide to 345gAl₂O₃The solution of/L is diluted by aqueous solution containing 3.5wt% of NaOH to prepare a caustic ratio of 1.30 and a concentration of 40 gAl₂O₃L of sodium metaaluminate solution for standby; the preparation concentration is 50gSiO₂A water glass solution with a modulus of 2.8 is used. Adding the sodium metaaluminate solution and the water glass solution into a 5000mL reactor, and introducing CO into the reactor₂And air, controlling the temperature of slurry in the reactor to be constant at 22 ℃, finishing the reaction when the pH value of the slurry in the reactor is 10.5, filtering, washing a filter cake to be neutral by deionized water which is 60 times of the generated pseudoboehmite, and drying for 8 hours at 120 ℃ to obtain the high-silicon pseudoboehmite b3 of the comparative example.

1000g of prepared b3 high-silicon pseudo-boehmite is weighed, 7g of sesbania powder, 17.5g of citric acid and 12.96g of basic nickel carbonate are added, then the mixture is pelletized, and the pelletized sample is roasted for 5 hours at 700 ℃ to obtain a carrier F3 with the granularity of 0.4-0.5 mm. The carrier F3 was saturated and impregnated with the solution L1, dried at 110 deg.C for 2h, and calcined at 480 deg.C for 5h to obtain the catalyst CF3, the specific properties of which are shown in Table 2.

Comparative example 4

1000g of manufactured a1 high-silicon pseudo-boehmite is weighed, 7g of sesbania powder and 17.5g of citric acid are added, then the mixture is pelletized, and the pelletized sample is roasted for 5 hours at 700 ℃ to obtain a carrier F4 with the granularity of 0.4-0.5 mm.

The carrier F4 was saturated with L1 solution, dried at 110 deg.C for 2h, and calcined at 480 deg.C for 5h to obtain the catalyst CF4, with specific properties shown in Table 1.

Table 1 examples 1-4 properties of the catalysts

Table 2 comparison of the properties of the catalysts 1-4

Evaluation test:

the catalyst is subjected to activity evaluation on a Continuous Stirred autoclave (CSTR), the catalyst is filled to 100mL, and the fluidized bed Reactor and the Continuous Stirred Tank Reactor (CSTR) are similar to each other, have good full back-mixing performance and have equivalent reaction kinetic characteristics. Therefore, the CSTR can be used instead of the ebullated bed reactor for catalyst performance evaluation. The properties of the raw oil and the evaluation conditions are shown in Table 3. The results of other evaluations, which were compared with the activity of comparative example 3, are shown in Table 4, taking the activity of comparative example 3 as 100.

TABLE 3 coal tar Properties and evaluation conditions

TABLE 4 catalyst CSTR hydrogenation unit evaluation results

As can be seen from table 4: compared with the catalyst prepared by a comparative example, the fluidized bed hydrogenation catalyst prepared by the research increases the impurity removal rate and provides a high-quality raw material for subsequent coal tar processing.

Medium and low temperature coal tar is adopted, the properties are shown in table 3, 100mL of the catalyst of the embodiment 1 and the catalyst of the comparative example 4 are respectively used for reaction on a CSTR, the continuous operation is carried out for 3000 hours, and the particle size analysis is carried out on the catalyst after the operation, which is shown in table 5. As can be seen from the data in the table: the increase rate of the proportion of less than 0.4mm in the particle size distribution of the coal tar catalyst prepared by the method is less, which shows that the catalyst has better wear resistance and water resistance.

TABLE 5 catalyst particle size distribution

Claims

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

s1 preparing high-silicon pseudo-boehmite, which is prepared by the following method:

(3) separating the material B to obtain cation exchange resin and slurry, and further filtering and drying the slurry to obtain high-silicon pseudo-boehmite;

s2, mixing the high-silicon pseudo-boehmite obtained in the step S1 with an auxiliary agent, and then forming, drying and roasting to obtain a carrier, wherein the auxiliary agent is one or more of nickel salt, lanthanum salt, rhodium salt and silica sol;

s3, introducing an active metal component onto the carrier obtained in the step S2, and further drying and roasting to obtain a catalyst;

wherein the organic acid source has a pKa greater than the pKa of the cation exchange resin and less than the pKa of the aluminate; the acidity coefficient pKa of the organic acid source is 0-8; the organic acid source is organic phosphate ester which is a compound shown in a structural formula (I);

（I）

in the formula (I), each A is the same as or different from each other, and is independently selected from the group consisting of a hydrogen ion, an ammonium ion (NH 4 +), a metal ion, and a metal ion represented by the formula

The metal ion is alkali metal ion or alkaline earth metal ion;

R₀selected from the group consisting of a hydrogen atom, an optionally substituted C1-30 straight or branched chain alkyl group, and an optionally substituted C6-20 aryl group; n radicals R1, equal to or different from each other, are each independently selected from C1-6 linear or branched alkylene radicals, n representing the average degree of polymerization of the polyether radical and being a number from 0 to 200.

2. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: at least one of A is hydrogen ion, the metal ion is sodium ion, R₀Selected from C5-20 linear or branched alkyl and phenyl, n radicals R1, equal to or different from each other, are each independently selected from C2-4 linear or branched alkylene radicals, n represents the average degree of polymerization of the polyether radical and is a number from 0 to 50.

3. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: both A are hydrogen ions, R₀Selected from C9-15 linear or branched alkyl groups, n groups R1, equal to or different from each other, each independently selected from ethylene groups, n representing the average degree of polymerization of the polyether group, is a number from 5 to 50.

4. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: r₀Selected from C9 linear or branched alkyl groups, n representing the average degree of polymerization of the polyether group, is a number from 5 to 50.

5. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the assistant in the step S2 is at least one of nickel salt, lanthanum salt and rhodium salt; wherein the nickel salt is one or more of nickel nitrate, nickel sulfate, nickel chloride and nickel acetate; the lanthanum salt is one or more of lanthanum nitrate and lanthanum chloride; the rhodium salt is one or more of rhodium nitrate, rhodium chloride and rhodium sulfate.

6. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: and step S2, adding an additive when the high-silicon pseudo-boehmite is mixed with the auxiliary agent, wherein the additive is one or more of citric acid, acetic acid, tartaric acid, polyethylene glycol, polyvinyl alcohol, methyl cellulose and polyacrylamide.

7. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: and step S2, adding an additive when the high-silicon pseudo-boehmite is mixed with the auxiliary agent, wherein the additive is one or more of polyethylene glycol, methylcellulose and polyacrylamide.

8. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: in the step S2, the drying is carried out at 200 ℃ for 2-20 hours and the roasting is carried out at 900 ℃ for 1-8 hours at 100-.

9. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: in the step S3, the drying is carried out at 80-200 ℃ for 2-20 hours, and the roasting is carried out at 400-600 ℃ for 2-6 hours.

10. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: in step S3, the active metal is selected from at least one of metals of group VIB and group VIII of the periodic table of elements.

11. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the active metal in step S3 is at least one selected from Mo, W, Ni, and Co.

12. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: in the step (1), the aluminate is meta-aluminate.

13. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: in the step (1), the aluminate is sodium metaaluminate, the causticity ratio of the sodium metaaluminate is 1.15-1.35, and the concentration of the sodium metaaluminate aqueous solution is 20-100gAl calculated by oxide₂O₃/L。

14. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: in the step (1), the aluminate is meta-aluminumSodium, wherein the causticity ratio of the sodium metaaluminate is 1.20-1.30; the concentration of sodium metaaluminate aqueous solution is 30-70gAl calculated by oxide₂O₃/L。

15. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: in the step (1), the silicon source is water glass and/or silica sol.

16. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: in the step (1), the silicon source is water glass, and the modulus of the water glass is 2.5-3.2; the concentration of the water glass solution is 20-100gSiO calculated by oxide₂/L。

17. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: in the step (1), the silicon source is water glass, and the modulus of the water glass is 2.5-3.2; the concentration of the water glass solution is 40-60gSiO calculated by oxide₂/L。

18. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the cation exchange resin is strong-acid cation exchange resin, and is selected from at least one of macroporous strong-acid styrene cation exchange resin and sulfonated styrene gel type strong-acid cation exchange resin.

19. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the cation exchange resin is at least one of D001 macroporous strong-acid styrene cation exchange resin, D002 macroporous strong-acid styrene cation exchange resin and D61 macroporous strong-acid styrene cation exchange resin.

20. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the organic acid source has an acidity coefficient pKa of 2 to 8.

21. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the organic acid source has an acidity coefficient pKa of 3 to 6.

22. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the organic phosphate ester is a mono-organic phosphate ester or a di-organic phosphate ester.

23. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the organic phosphate ester is at least one selected from monoalkyl ether phosphate ester, dialkyl ether phosphate ester, monoalkyl phosphate ester and dialkyl phosphate ester.

24. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the organic phosphate ester is at least one selected from mono-C9-C15 alkyl ether phosphate, mono-C9-C15 alkyl phosphate, di-C9-C15 alkyl phosphate and di-C9-C15 alkyl ether phosphate.

25. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the organic phosphate ester is mono-C9-C15 alkyl ether phosphate.

26. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the organic phosphate ester is mono-C9 alkyl ether phosphate.

27. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the weight ratio of the cation exchange resin in the step (1) to the cation exchange resin in the step (2) is 8: 1-4: 1.

28. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the reaction temperature in the step (1) is 60-90 ℃.

29. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the reaction temperature in the step (1) is 60-80 ℃.

30. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the amount of the water in the step (1) is 5 to 20vol% of the total volume of the reaction system.

31. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the amount of the water in the step (1) is 5 to 15vol% of the total volume of the reaction system.

32. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the concentration of the aqueous solution of the organic acid source in the step (1) is 0.015 to 0.35 g/mL.

33. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the solid content of the cation exchange resin suspension is 30-80 wt%.

34. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the solid content of the cation exchange resin suspension is 50-80 wt%.

35. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: in the step (1), the flow rate or the dosage of the cation exchange resin suspension added into the reaction system enables the pH value of the reaction system to be maintained at 7.5-12.0.

36. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: in the step (1), the flow rate or the dosage of the cation exchange resin suspension added into the reaction system enables the pH value of the reaction system to be maintained at 8.0-11.0.

37. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: the hydrothermal treatment in the step (2) is carried out in a closed container, the treatment temperature is 200-260 ℃, and the treatment time is 4-12 h.

38. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: and (3) adding the cation exchange resin suspension into the reaction system in the step (2) in an amount so that the pH value of the material A reaches 7.0-8.5.

39. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: and (3) adding the cation exchange resin suspension into the reaction system in the step (2) in an amount so that the pH value of the material A reaches 7.0-8.0.

40. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: in the step (3), the separation adopts a 100-120-mesh screen to separate the cation exchange resin from the material B.

41. A coal tar hydrogenation catalyst obtained by the preparation method of any one of claims 1 to 40, wherein the properties of the catalyst are as follows: the specific surface area is 120-200m²The pore volume is 0.50-0.75mL/g, the infrared acid amount is 0.20-0.35mmol/g, and the abrasion index is less than 1.0%.

42. A coal tar hydrogenation method, wherein the hydrogenation method comprises the steps of mixing coal tar and hydrogen, and then carrying out hydrogenation reaction in the presence of the coal tar hydrogenation catalyst according to claim 41.

43. The coal tar hydrogenation process of claim 42, wherein: the coal tar is one or more of medium-low temperature coal tar and high-temperature coal tar.

44. The coal tar hydrogenation process of claim 42, wherein: the hydrogenation reaction conditions were as follows: the reaction pressure is 8-20MPa, the reaction temperature is 350-410 ℃, the liquid hourly space velocity is 0.1-2.0h < -1 >, and the volume ratio of hydrogen to oil is 100-.