Coal tar hydrogenation catalyst, its preparation and coal tar hydrogenation process

Abstract

This invention discloses a coal tar hydrogenation catalyst, its preparation method, and a coal tar hydrogenation process. The preparation method comprises: (1) treating an organic polymer to obtain material A; (2) mixing material A, boehmite powder, and an aqueous solution of the polymer and molding it to obtain a carrier precursor; (3) heat-treating the carrier precursor, then mixing it with a soluble nickel salt solution and drying and calcining it to obtain a modified carrier; and (4) introducing an active metal component onto the modified carrier and drying and calcining it to obtain the coal tar hydrogenation catalyst. This invention also provides a coal tar hydrogenation catalyst prepared by the above method, and a coal tar hydrogenation process. The catalyst has high tolerance to metal impurities, high water resistance, hydrogenation demetallization activity, and stability, and can meet the requirements for catalyst indicators during long-term stable operation of the hydrogenation unit.

Description

Technical Field

[0001] This invention belongs to the field of petrochemical technology and relates to a catalytic material and its preparation method, particularly to a coal tar hydrogenation catalyst, its preparation method, and a coal tar hydrogenation process. Background Technology

[0002] The comprehensive utilization of coal is an important component of the national energy strategy. The national coal industry plan has already proposed "deep processing and clean utilization" of coal, "vigorously developing coal chemical industry, developing coal-based liquid fuels, promoting the construction of coal gasification and liquefaction demonstration projects, making up for insufficient oil and gas supply, and improving the level of national energy security." Conducting research on the comprehensive utilization of coal tar resources will help alleviate the increasingly tight oil supply situation and guide the healthy and orderly development of the coal industry. The research and industrial application of coal tar comprehensive utilization technologies will inevitably drive the development of related industries and play a vital role in the value-added transformation of China's abundant coal resources and regional economic development.

[0003] Coal tar is a liquid product obtained during the dry distillation and gasification of coal. It is characterized by high aromatic content, olefin content, oxygen content, and a high C-H ratio. Due to imperfections in the cooling and collection processes, impurities such as coal dust and inorganic salts from the cooling water are mixed into the coal tar. If direct fixed-bed hydrotreating is used, fine coal particles will deposit on the catalyst surface or between catalyst bed layers, causing a pressure drop in the fixed bed and affecting the operating cycle and product quality. Therefore, pretreatment of the raw materials is necessary to reduce the content of coal dust and impurities, providing qualified feedstock for the fixed bed.

[0004] CN202110144831.6 discloses a coal tar hydrogenation catalyst and its preparation method. The catalyst includes a first active material and a second active material. The first active material includes at least one group VIB oxide, and the second active material includes at least one group IB, VIIB, or VIII oxide. The molar ratio M1 / M2 of the first active material and the second active material M2 is 10–1. The catalyst support is a molecular sieve that has undergone pore-expanding treatment, and the active component is also doped with carbon. The preparation method of the catalyst is as follows: the support, active material precursor, and urea are subjected to low-temperature hydrothermal treatment to obtain catalyst precursor A; catalyst precursor A is impregnated in a carbon source-containing solution to obtain catalyst precursor B; catalyst precursor B is heat-treated in an inert atmosphere to obtain the catalyst. The coal tar hydrogenation catalyst provided by this patent has excellent hydrodenitrification and hydrodesulfurization capabilities, but its water resistance is not strong, making it not very suitable for coal tar with high oxygen content.

[0005] CN1206037A discloses a residue oil hydrodemetallization catalyst and its preparation method. The catalyst uses Group VIII and / or Group VIB metals as active components, supported on a macroporous alumina support. The pore volume of this support is 0.80~1.20 mL / g (mercury intrusion porosimetry), and the specific surface area is 110~200 m². 2 The catalyst has a pore diameter of 15-20 nm and a bulk density of 0.50-0.60 g / mm². The preparation method of this residue oil hydrodemetallization catalyst involves adding carbon black powder as a physical pore expander and phosphorus, silicon, or boron-containing compounds that can chemically react with boehmite or alumina during the mixing process. The mixture is kneaded into a plastic body, extruded into strips, dried, and calcined to obtain a support. The active component is then loaded onto the support by spray impregnation, followed by drying and calcination to obtain the catalyst. However, due to the large and non-concentrated particles of the carbon black powder used in the support preparation process, the pore distribution of the support is diffuse and unconcentrated, resulting in poor mechanical strength. More importantly, the pores of the obtained catalyst support are not unobstructed, and some catalyst pores cannot be fully utilized. During use, metal is easily deposited in the narrow pores, which accelerates the catalyst deactivation rate. Furthermore, if directly applied to coal tar hydrotreating reactions, its water resistance needs further improvement. Summary of the Invention

[0006] This invention provides a coal tar hydrogenation catalyst, its preparation method, and a coal tar hydrogenation process. The catalyst is particularly suitable for hydrogenating hydrocarbon-containing materials such as coal tar with high water and oxygen content using a fluidized bed reactor. The coal tar hydrogenation catalyst provided by this invention exhibits high tolerance to metal impurities, as well as high water resistance, hydrogenation demetallization activity, and stability, meeting the catalyst performance requirements for long-term stable operation of hydrogenation units.

[0007] To address the technical problems in the prior art, the present invention includes the following technical solutions:

[0008] The first aspect of this invention aims to provide a method for preparing a coal tar hydrogenation catalyst, comprising the following steps:

[0009] (1) Under mixing conditions, an aqueous solution of a nitrogen-containing weakly alkaline compound is mixed with an organic polymer, and after uniform mixing, material A is obtained;

[0010] (2) Under contact conditions, the material A obtained in step (1), the pseudoboehmite powder and the aqueous solution of the organic polymer after heat treatment are mixed, mixed evenly and then molded to obtain the carrier precursor;

[0011] (3) The carrier precursor obtained in step (2) is heat-treated at 100-300℃, then mixed with a soluble nickel salt solution, mixed evenly, and then dried and calcined to obtain the modified carrier.

[0012] (4) An active metal component is introduced onto the modified support obtained in step (3) and then dried and calcined to obtain a coal tar hydrogenation catalyst.

[0013] Furthermore, in the above-mentioned method for preparing the coal tar hydrogenation catalyst, the organic polymer is selected from at least one of starch and cellulose ether, preferably starch. More preferably, the starch is one or more of mung bean starch, cassava starch, sweet potato starch, potato starch, wheat starch, water chestnut starch, lotus root starch, and corn starch, preferably one or more of corn starch and potato starch; the cellulose ether is at least one of methylcellulose, carboxymethylcellulose, ethylcellulose, hydroxyethylmethylcellulose, hydroxyethylcellulose, benzylcellulose, hydroxypropylmethylcellulose, benzyl cyanoethylcellulose, cyanoethylcellulose, carboxymethyl hydroxyethylcellulose, and phenylcellulose.

[0014] Furthermore, in the above-mentioned method for preparing the coal tar hydrogenation catalyst, the nitrogen-containing weakly basic compound in step (1) can be selected from one or more of ammonia, ammonium carbonate, and ammonium bicarbonate, preferably ammonia. Even further, the concentration of the aqueous solution of the nitrogen-containing weakly basic compound is 2wt% to 40wt%, preferably 5wt% to 35wt%.

[0015] Furthermore, in the above-mentioned method for preparing coal tar hydrogenation catalyst, the mass ratio of the organic polymer and the nitrogen-containing weakly basic compound in step (1) is 1:0.05 to 1:0.5.

[0016] Furthermore, in the above-mentioned method for preparing coal tar hydrogenation catalyst, the properties of the pseudoboehmite powder after calcination at 600℃ in step (2) are as follows: specific surface area is 270~320m². 2 / g, with a pore volume of 0.9–1.1 mL / g. The above-mentioned pseudoboehmite can be a commercially available product or a pseudoboehmite prepared according to existing methods.

[0017] Furthermore, in the above-mentioned method for preparing coal tar hydrogenation catalyst, the amount of material A added in step (2) is 5wt% to 35wt% of the dry weight of boehmite powder, preferably 10wt% to 30wt%.

[0018] Furthermore, in the above-mentioned method for preparing the coal tar hydrogenation catalyst, the concentration of the aqueous solution of the organic polymer in step (2) is 0.5wt% to 8wt%, preferably 1wt% to 5wt%. The specific preparation process of the aqueous solution of the organic polymer after heat treatment is as follows: the organic polymer is added to water and heated and mixed at 60 to 100°C. After the organic polymer B is completely dissolved, the aqueous solution of the organic polymer is obtained. Under normal circumstances, the mixing time is controlled at 10 to 40 minutes.

[0019] Furthermore, in the above-mentioned method for preparing the coal tar hydrogenation catalyst, the ratio of the amount of the aqueous solution of the heated organic polymer added in step (2) to the total mass of material A and pseudoboehmite powder is 0.5 to 1.2.

[0020] Furthermore, in the above-mentioned method for preparing coal tar hydrogenation catalyst, the molding described in step (2) can be any of the molding methods existing in the art, and can be any shape such as spherical, strip, clover, or four-leaf clover, preferably spherical or strip. Specifically, it can be one or more of the following molding methods: extrusion balling molding, roll forming, and spray drying molding.

[0021] Furthermore, in the above-mentioned method for preparing coal tar hydrogenation catalyst, the carrier precursor obtained in step (2) is heated at 150-250°C in step (3) for 3-12 hours.

[0022] Furthermore, in the above-mentioned method for preparing coal tar hydrogenation catalyst, the soluble nickel salt in step (3) can be selected from one or more of nickel nitrate, nickel acetate, nickel chloride, and nickel sulfate.

[0023] Furthermore, in the above-mentioned method for preparing coal tar hydrogenation catalyst, the drying in step (3) is generally carried out at 60-120°C. The specific drying method can be selected from any of the existing drying methods, and those skilled in the art can make the selection according to actual needs.

[0024] Furthermore, in the above-mentioned method for preparing coal tar hydrogenation catalyst, the calcination in step (3) is a two-stage calcination. The first stage is calcination under an inert atmosphere, which is one or more of nitrogen, helium, neon, argon, krypton, and xenon, preferably nitrogen. The calcination temperature is 600-800℃ and the calcination time is 1-5h. The second stage is calcination under an air atmosphere, with a temperature of 600-800℃ and a calcination time of 1-5h.

[0025] Furthermore, in the above-mentioned method for preparing coal tar hydrogenation catalyst, the introduction of active metal components in step (4) can be any one or more of the methods existing in the art, specifically at least one of the methods such as mixing and impregnation, with impregnation being preferred.

[0026] Furthermore, in the above-mentioned method for preparing coal tar hydrogenation catalyst, the active metal component in step (4) is one or more of Group VIB metals and / or Group VIII metals, wherein the Group VIB metal is generally Mo and / or W, and the Group VIII metal is generally Ni and / or Co.

[0027] Furthermore, in the above-mentioned method for preparing coal tar hydrogenation catalyst, the active metal components in step (4) are Mo and Ni.

[0028] Furthermore, in the above-mentioned method for preparing coal tar hydrogenation catalyst, when introducing the active metal component in step (4), an auxiliary agent P can also be introduced.

[0029] Furthermore, in the above-mentioned method for preparing coal tar hydrogenation catalyst, the drying temperature in step (4) is 80-120℃ and the drying time is 4-12h.

[0030] Furthermore, in the above-mentioned method for preparing coal tar hydrogenation catalyst, the calcination temperature in step (4) is 400-600℃ and the calcination time is 1-5h; the calcination is carried out under an oxygen-containing atmosphere, specifically in the presence of air and oxygen.

[0031] Furthermore, in the above-mentioned method for preparing the coal tar hydrogenation catalyst, when the active metal component in step (4) is prepared by impregnation, an aqueous solution containing the active metal component and P is first prepared, and then a support is added for impregnation treatment. After further drying and calcination, the catalyst is obtained. The aqueous solution containing the active metal component and P is obtained by uniformly mixing the precursor containing the active metal component, water, and a phosphorus-containing compound. Preferably, the precursor containing the active metal component is a compound containing a Group VIB metal and / or a Group VIII metal. The compound containing the Group VIB metal can be one or more of a molybdenum-containing compound and a tungsten-containing compound, and the compound containing the Group VIII metal can be one or more of a nickel-containing compound and a cobalt-containing compound. The molybdenum-containing compound can be molybdenum oxide and / or ammonium heptamolybdate; the nickel-containing compound is basic nickel carbonate and / or nickel nitrate; and the cobalt-containing compound is basic cobalt carbonate and / or cobalt nitrate. The phosphorus-containing compound can be one or more of phosphoric acid, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; the concentration of the hydrogenated metal component in the aqueous solution containing the hydrogenated metal component and P is 0.03–0.5 g / mL (calculated as hydrogenated metal oxide), and the concentration of P is 0–0.05 g / mL, preferably 0.002–0.05 g / mL. The standing time is generally 1–3 hours.

[0032] A second aspect of this invention aims to provide a coal tar hydrogenation catalyst, which is obtained using the preparation method described above.

[0033] Furthermore, in the above-mentioned coal tar hydrogenation catalyst, the coal tar hydrogenation catalyst includes an active metal component, a modified support, and optional additives. The active metal component is one or more of Group VIB metals and / or Group VIII metals, the additives are nickel oxide and phosphorus pentoxide, and the support is nickel-containing alumina.

[0034] Furthermore, in the aforementioned coal tar hydrogenation catalyst, based on catalyst weight and calculated as oxides, the content of Group VIB metal components is 4 wt% to 8 wt%; Group VIB metals are generally Mo and / or W; the content of Group VIII metal components is 1 wt% to 3 wt%; and Group VIII metals are generally Ni and / or Co. The content of the auxiliary agent nickel oxide is 1.0 wt% to 5.0 wt%; and the content of phosphorus pentoxide is 0.3 wt% to 1.0 wt%.

[0035] Furthermore, in the above-mentioned coal tar hydrogenation catalyst, the active metal components are preferably Mo and Ni.

[0036] Furthermore, in the above-mentioned coal tar hydrogenation catalyst, the specific surface area of ​​the coal tar hydrogenation catalyst is 150–220 m². 2 / g, with a pore volume of 0.60–0.80 mL / g; the pore volume of pores with a diameter greater than 50 nm accounts for 2%–15% of the total pore volume.

[0037] The third aspect of this invention aims to provide a coal tar hydrogenation process, in which coal tar feedstock enters a reaction unit and reacts under the combined action of hydrogen and the aforementioned coal tar hydrogenation catalyst.

[0038] Furthermore, in the above-mentioned coal tar hydrogenation process, the coal tar feedstock can be any one of low-temperature coal tar, medium-temperature coal tar, or high-temperature coal tar.

[0039] Furthermore, in the above-mentioned coal tar hydrogenation process, the reaction unit is equipped with at least one hydrogenation reactor. The hydrogenation reactor can be one or more of the following: fixed bed hydrogenation reactor, suspended bed hydrogenation reactor, and fluidized bed hydrogenation reactor. It is preferred to be a fluidized bed hydrogenation reactor, and even more preferably a fluidized bed reactor with a three-phase separator inside the reactor, such as the fluidized bed reactor with a three-phase separator developed by Sinopec (Dalian) Petrochemical Research Institute Co., Ltd.

[0040] Furthermore, in the above-mentioned coal tar hydrogenation process, the process conditions are as follows: reaction pressure is 10–20 MPa, reaction temperature is 300–420 °C, and liquid hourly space velocity is 0.2–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300–1000.

[0041] Compared with the prior art, the coal tar hydrogenation catalyst and its preparation method provided by the present invention have the following advantages:

[0042] 1. In the preparation method of the coal tar hydrogenation catalyst provided by the present invention, the organic polymer is first reacted with a nitrogen-containing weakly basic compound and then mixed with boehmite powder. This ensures that the organic polymer treated with the nitrogen-containing weakly basic compound mainly plays a pore-expanding role in the subsequent carrier preparation process. However, the adhesiveness of this organic polymer cannot meet the requirements for use. It is further mixed with an aqueous solution of the organic polymer obtained by heat treatment. Because the organic polymer decomposes into small molecules in hot water, the aqueous solution has high adhesiveness, which can ensure strong interaction between materials in the reaction system, especially between boehmite powder. This can enhance the interaction force between the alumina carriers obtained in the subsequent preparation and improve the strength and wear resistance of the carrier.

[0043] 2. In the preparation method of the coal char hydrogenation catalyst provided by the present invention, during the low-temperature heating treatment of the support precursor obtained in step (2), the ammonia in the nitrogen-containing weakly basic compound that interacts with the organic polymer will volatilize and be adsorbed by interacting with the strong acid sites on the alumina. Then, the introduced soluble nickel salt will interact with the ammonia on the alumina and be adsorbed on the strong acid sites of the alumina. After calcination, it will occupy the strong acid sites of the alumina. When an active metal is subsequently introduced on this basis, the interaction between the active metal and the support alumina can be weakened, and the utilization rate of the active metal can be improved. At the same time, under the high-temperature calcination conditions, nickel will further interact with the alumina, which can improve the hydrothermal stability of the catalyst.

[0044] 3. In the preparation method of the coal tar hydrogenation catalyst provided by the present invention, the organic polymer is calcined in an inert atmosphere to generate macroporous carbon material on alumina. This carbon material is completely burned off during the subsequent calcination in an air atmosphere. This process can expand the pores of the alumina support, increase the number of macropores in the alumina support, and make the catalyst pores less prone to blockage by impurities such as metals. This improves the catalyst's metal-carrying capacity and ensures the stability of the catalyst during long-term operation of the device. It is especially suitable for the hydrogenation treatment process of feedstock oils with high water and oxygen content, such as coal tar. Detailed Implementation

[0045] The technical solution and effects of the present invention are further illustrated below through specific embodiments. In the present invention, wt% is the mass fraction.

[0046] In this invention, the wear of the spherical carrier is tested using the high-speed air jet method. This method has been established by ASTM (American Society for Testing and Research) as a standard for testing the wear performance of small-particle catalysts, see ASTM D5757-00 (Standard Test Method for Determination of Attrition and Abrasion of Powdered Catalysts by Air Jets). Its basic principle is that under the action of a high-speed airflow, the catalyst particles are fluidized, and friction between particles and between particles and the container wall generates fine powder. The amount of fine powder generated per unit mass of catalyst per unit time, i.e., the wear index (wear loss), serves as an indicator for evaluating the catalyst's wear resistance.

[0047] In this invention, the specific surface area and pore volume were measured using a cryogenic liquid nitrogen physical adsorption method, specifically using a Micron ASAP2420 cryogenic nitrogen adsorption instrument. The procedure involved: a small sample was vacuum-treated at 300°C for 3-4 hours, and finally, the product was placed under liquid nitrogen cryogenic (-200°C) conditions for nitrogen adsorption-desorption testing. The surface area was obtained using the BET equation, and the pore size distribution was obtained using the BJH model.

[0048] Example 1

[0049] (1) Carrier preparation

[0050] Mix 52.5g of corn starch with 50g of 10wt% ammonia water to obtain mixture A; weigh 15.0g of corn starch and add it to 285g of water, heat at 70℃ for 20min to obtain a heat-treated organic polymer aqueous solution; add 300g of pseudoboehmite powder (specific surface area 300m²) 2 Mixture A (with a pore volume of 0.98 mL / g) and a heat-treated aqueous solution of an organic polymer were mixed and then extruded and spherically shaped to obtain a spherical carrier precursor. The carrier precursor was then subjected to low-temperature heat treatment at 200℃ for 4 hours to obtain carrier precursor A. 200 mL of an aqueous solution containing 24.53 g of nickel nitrate was added to carrier precursor A, and the mixture was dried at 90℃ for 8 hours, then calcined at 700℃ for 2 hours under a nitrogen atmosphere, and then calcined at 700℃ for 3 hours under an air atmosphere to obtain spherical carriers with a particle size of 0.5–0.8 mm. The carrier yield and wear data are shown in Table 1.

[0051] (2) Catalyst preparation

[0052] Dissolve 1.57g of phosphoric acid H3PO4 (concentration 85wt%) in 50mL of water, then add 4.27g of molybdenum trioxide and 1.88g of basic nickel carbonate, heat to 100℃ and stir under reflux for 2.0h, filter and make up to 85mL to obtain Mo-Ni-P aqueous solution.

[0053] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 2h. Then, it was dried at 110℃ for 8h and calcined at 450℃ for 3h to obtain the catalyst, in which the content of MoO3 was 4.0wt%, the content of NiO was 1.0wt%, and the content of P was 0.4wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0054] (3) Catalyst evaluation

[0055] The catalyst was evaluated over a long period using a CSTR hydrogenation evaluation system, with an operating time of 1500 hours. The evaluation conditions were: reaction temperature 380℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.4 h⁻¹. -1 The hydrogen-to-oil volume ratio was 500:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0056] Example 2

[0057] (1) Carrier preparation

[0058] 42.0 g of corn starch was mixed with 40 g of a 15 wt% ammonium carbonate aqueous solution to obtain mixture A; 15.0 g of corn starch was weighed and added to 285 g of water, and heated at 70 °C for 20 min to obtain a heat-treated organic polymer aqueous solution; 300 g of pseudoboehmite powder (specific surface area 300 μm) was added... 2 Mixture A (with a pore volume of 0.98 mL / g) and a heat-treated aqueous solution of an organic polymer were mixed and then extruded and spherically shaped to obtain a spherical carrier precursor. The carrier precursor was then subjected to low-temperature heat treatment at 200℃ for 4 hours to obtain carrier precursor A. 200 mL of an aqueous solution containing 20.99 g of nickel acetate was added to carrier precursor A, and the mixture was dried at 90℃ for 8 hours, then calcined at 750℃ for 2 hours under a nitrogen atmosphere, and then calcined at 750℃ for 3 hours under an air atmosphere to obtain spherical carriers with a particle size of 0.5–0.8 mm. The carrier yield and wear data are shown in Table 1.

[0059] (2) Catalyst preparation

[0060] Dissolve 1.99 g of phosphoric acid H3PO4 (concentration 85 wt%) in 50 mL of water, then add 5.42 g of molybdenum trioxide and 2.40 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and bring the volume to 85 mL to obtain the Mo-Ni-P aqueous solution.

[0061] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 3h. Then, it was dried at 110℃ for 4h and calcined at 550℃ for 3h to obtain the catalyst, which contained 5.0wt% MoO3, 1.25wt% NiO, and 0.5wt% P. The physicochemical properties of the catalyst are shown in Table 2.

[0062] (3) Catalyst evaluation

[0063] The catalyst evaluation conditions were the same as in Example 1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0064] Example 3

[0065] (1) Carrier preparation

[0066] Mix 31.5g of corn starch with 40g of a 25wt% ammonium bicarbonate aqueous solution to obtain mixture A; weigh 15.0g of corn starch and add it to 285g of water, heat at 70℃ for 20min to obtain a heat-treated organic polymer aqueous solution; add 300g of pseudoboehmite powder (specific surface area 300m²) 2Mixture A (with a pore volume of 0.98 mL / g) and a heat-treated aqueous solution of an organic polymer were mixed and then extruded and spherically shaped to obtain a spherical carrier precursor. The carrier precursor was then subjected to low-temperature heat treatment at 200℃ for 4 hours to obtain carrier precursor A. 200 mL of an aqueous solution containing 22.18 g of nickel sulfate was added to carrier precursor A, and the mixture was dried at 90℃ for 8 hours, then calcined at 800℃ for 2 hours under a nitrogen atmosphere, and then calcined at 800℃ for 3 hours under an air atmosphere to obtain spherical carriers with a particle size of 0.5–0.8 mm. The carrier yield and wear data are shown in Table 1.

[0067] (2) Catalyst preparation

[0068] Dissolve 2.43 g of phosphoric acid H3PO4 (concentration 85 wt%) in 50 mL of water, then add 6.59 g of molybdenum trioxide and 2.91 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and bring the volume to 85 mL to obtain the Mo-Ni-P aqueous solution.

[0069] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 2h. Then, it was dried at 110℃ for 8h and calcined at 450℃ for 3h to obtain the catalyst, in which the content of MoO3 was 6.0wt%, the content of NiO was 1.5wt%, and the content of P was 0.6wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0070] (3) Catalyst evaluation

[0071] The catalyst evaluation conditions were the same as in Example 1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0072] Example 4

[0073] The preparation was essentially the same as in Example 3, except that 31.5g of corn starch was replaced with 31.5g of potato starch, and 15.0g of corn starch was replaced with 15.0g of potato starch. Spherical supports with a particle size of 0.5~0.8mm were obtained. The support yield and wear data are shown in Table 1. A catalyst was prepared, containing 6.0wt% MoO3, 1.5wt% NiO, and 0.6wt% P. The physicochemical properties of the catalyst are shown in Table 2.

[0074] The catalyst was evaluated in the same way as in Example 3. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0075] Example 5

[0076] The preparation was essentially the same as in Example 3, except that 31.5g of corn starch was replaced with 26.51g of methylcellulose, and 15.0g of corn starch was replaced with 12.64g of methylcellulose. Spherical supports with a particle size of 0.5~0.8mm were obtained. The support yield and wear data are shown in Table 1. A catalyst was prepared, containing 6.0wt% MoO3, 1.5wt% NiO, and 0.6wt% P. The physicochemical properties of the catalyst are shown in Table 2.

[0077] The catalyst was evaluated in the same way as in Example 3. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0078] Comparative Example 1

[0079] (1) Carrier preparation

[0080] Mix 52.5g of corn starch with 50g of 10wt% ammonia water to obtain mixture A; add 300g of pseudoboehmite powder (specific surface area 300m²) 2 Mixture A (0.98 mL / g pore volume), 15.0 g corn starch, and water were mixed and then extruded and spherically shaped to obtain a spherical carrier precursor. The carrier precursor was subjected to low-temperature heat treatment at 200℃ for 4 h to obtain carrier precursor A. 200 mL of an aqueous solution containing 24.53 g nickel nitrate was added to carrier precursor A, and the mixture was dried at 90℃ for 8 h, then calcined at 700℃ for 2 h under a nitrogen atmosphere, and then calcined at 700℃ for 3 h under an air atmosphere to obtain spherical carriers with a particle size of 0.5~0.8 mm. The carrier yield and wear data are shown in Table 1.

[0081] (2) Catalyst preparation

[0082] Dissolve 1.57g of phosphoric acid H3PO4 (concentration 85wt%) in 50mL of water, then add 4.27g of molybdenum trioxide and 1.88g of basic nickel carbonate, heat to 100℃ and stir under reflux for 2.0h, filter and make up to 85mL to obtain Mo-Ni-P aqueous solution.

[0083] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 2h. Then, it was dried at 110℃ for 8h and calcined at 450℃ for 3h to obtain the catalyst, in which the content of MoO3 was 4.0wt%, the content of NiO was 1.0wt%, and the content of P was 0.4wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0084] (3) Catalyst evaluation

[0085] The catalyst was evaluated over a long period using a CSTR hydrogenation evaluation system, with an operating time of 1500 hours. The evaluation conditions were: reaction temperature 380℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.4 h⁻¹.-1 The hydrogen-to-oil volume ratio was 500:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0086] Comparative Example 2

[0087] (1) Carrier preparation

[0088] Weigh 15.0g of corn starch and add it to 285g of water. Heat at 70℃ for 20min to obtain a heat-treated organic polymer aqueous solution. Add 300g of pseudoboehmite powder (specific surface area 300m²) to the solution. 2 52.5 g of corn starch (with a pore volume of 0.98 mL / g) and a heat-treated aqueous solution of an organic polymer were mixed and then extruded and spherically shaped to obtain a spherical carrier precursor. The carrier precursor was then subjected to low-temperature heat treatment at 200 °C for 4 h to obtain carrier precursor A. 200 mL of an aqueous solution containing 24.53 g of nickel nitrate was added to carrier precursor A, and the mixture was dried at 90 °C for 8 h, then calcined at 700 °C for 2 h under a nitrogen atmosphere, and then calcined at 700 °C for 3 h under an air atmosphere to obtain spherical carriers with a particle size of 0.5–0.8 mm. The carrier yield and wear data are shown in Table 1.

[0089] (2) Catalyst preparation

[0090] Dissolve 1.57g of phosphoric acid H3PO4 (concentration 85wt%) in 50mL of water, then add 4.27g of molybdenum trioxide and 1.88g of basic nickel carbonate, heat to 100℃ and stir under reflux for 2.0h, filter and make up to 85mL to obtain Mo-Ni-P aqueous solution.

[0091] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 2h. Then, it was dried at 110℃ for 8h and calcined at 450℃ for 3h to obtain the catalyst, in which the content of MoO3 was 4.0wt%, the content of NiO was 1.0wt%, and the content of P was 0.4wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0092] (3) Catalyst evaluation

[0093] The catalyst was evaluated over a long period using a CSTR hydrogenation evaluation system, with an operating time of 1500 hours. The evaluation conditions were: reaction temperature 380℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.4 h⁻¹. -1 The hydrogen-to-oil volume ratio was 500:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0094] Comparative Example 3

[0095] (1) Carrier preparation

[0096] Mix 52.5g of corn starch with 50g of 10wt% ammonia water to obtain mixture A; weigh 15.0g of corn starch and add it to 285g of water, heat at 70℃ for 20min to obtain a heat-treated organic polymer aqueous solution; add 300g of pseudoboehmite powder (specific surface area 300m²) 2 Mixture A (with a pore volume of 0.98 mL / g) and a heat-treated aqueous solution of an organic polymer were mixed and then extruded and spherical to obtain a spherical carrier precursor. The carrier precursor was then subjected to low-temperature heat treatment at 200℃ for 4 hours to obtain carrier precursor A. It was then calcined at 700℃ for 2 hours under a nitrogen atmosphere, followed by calcination at 700℃ for 3 hours under an air atmosphere to obtain spherical carriers with a particle size of 0.5–0.8 mm. The carrier yield and wear data are shown in Table 1.

[0097] (2) Catalyst preparation

[0098] Dissolve 1.57g of phosphoric acid H3PO4 (concentration 85wt%) in 50mL of water, then add 4.27g of molybdenum trioxide and 1.88g of basic nickel carbonate, heat to 100℃ and stir under reflux for 2.0h, filter and make up to 85mL to obtain Mo-Ni-P aqueous solution.

[0099] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 2h. Then, it was dried at 110℃ for 8h and calcined at 450℃ for 3h to obtain the catalyst, in which the content of MoO3 was 4.0wt%, the content of NiO was 1.0wt%, and the content of P was 0.4wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0100] (3) Catalyst evaluation

[0101] The catalyst was evaluated over a long period using a CSTR hydrogenation evaluation system, with an operating time of 1500 hours. The evaluation conditions were: reaction temperature 380℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.4 h⁻¹. -1 The hydrogen-to-oil volume ratio was 500:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0102] Table 1 Carrier yield and wear

[0103]

[0104] Table 2 Physicochemical properties of catalysts

[0105]

[0106] Table 3 Properties of Crude Oil

[0107]

[0108] Table 4 Catalyst Evaluation Results

[0109]

[0110] With the activity of Comparative Example 1 as 100, the evaluation results of the other activities compared with the Comparative Example are shown in Table 4.

Claims

1. A method for preparing a coal tar hydrogenation catalyst, the method comprising the following steps: (1) Under mixing conditions, an aqueous solution of a nitrogen-containing weak alkaline compound is mixed with an organic polymer and the mixture is homogeneous to obtain material A; the nitrogen-containing weak alkaline compound is selected from one or more of ammonia, ammonium carbonate, and ammonium bicarbonate. (2) Under contact conditions, the material A obtained in step (1), the pseudoboehmite powder and the aqueous solution of the heat-treated organic polymer are mixed, mixed evenly and then molded to obtain the carrier precursor; the preparation process of the aqueous solution of the heat-treated organic polymer is as follows: the organic polymer is added to water and heated and mixed at 60-100°C. After the organic polymer is completely dissolved, the aqueous solution of the heat-treated organic polymer is obtained. (3) The carrier precursor obtained in step (2) is heat-treated at 100-300℃, then mixed with a soluble nickel salt solution, mixed evenly, and then dried and calcined to obtain the modified carrier. (4) An active metal component is introduced onto the modified support obtained in step (3) and then dried and calcined to obtain a coal tar hydrogenation catalyst; the active metal component is one or more of Group VIB metals and / or Group VIII metals; an auxiliary agent P is introduced when the active metal component is introduced. The organic polymer is starch and / or cellulose ether.

2. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: The organic polymer is starch.

3. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: The starch is one or more of the following: mung bean starch, tapioca starch, sweet potato starch, potato starch, wheat starch, water chestnut starch, lotus root starch, and corn starch; the cellulose ether is at least one of the following: methylcellulose, carboxymethylcellulose, ethylcellulose, hydroxyethylmethylcellulose, hydroxyethylcellulose, benzylcellulose, hydroxypropylmethylcellulose, benzyl cyanoethylcellulose, cyanoethylcellulose, carboxymethyl hydroxyethylcellulose, and phenylcellulose.

4. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: The starch is corn starch and / or potato starch.

5. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: The nitrogen-containing weakly basic compound in step (1) is ammonia.

6. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: The concentration of the nitrogen-containing weakly alkaline compound aqueous solution in step (1) is 2wt% to 40wt%.

7. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: The concentration of the aqueous solution of the nitrogen-containing weakly alkaline compound in step (1) is 5 wt% to 35 wt%.

8. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: The mass ratio of the organic polymer and the nitrogen-containing weakly basic compound in step (1) is 1:0.05 to 1:0.

5.

9. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: The properties of the pseudoboehmite powder after calcination at 600℃ in step (2) are as follows: specific surface area is 270~320m². 2 / g, with a pore volume of 0.9~1.1mL / g.

10. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: In step (2), the amount of material A added by mass is 5 wt% to 35 wt% of the dry basis weight of the pseudo-boehmite powder.

11. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: In step (2), the amount of material A added by mass is 10wt% to 30wt% of the dry basis weight of the pseudoboehmite powder.

12. 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 polymer in step (2) is 0.5wt% to 8wt%.

13. 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 polymer in step (2) is 1 wt% to 5 wt%.

14. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: The ratio of the amount of the aqueous solution of the heated organic polymer added in step (2) to the total mass of material A and pseudoboehmite powder is 0.5 to 1.

2.

15. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: In step (3), the carrier precursor obtained in step (2) is heated at 150-250℃ for 3-12 hours.

16. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: The soluble nickel salt in step (3) is selected from one or more of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate.

17. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: The roasting in step (3) is a two-stage roasting. The first stage is roasting in an inert atmosphere, which is one or more of nitrogen, helium, neon, argon, krypton and xenon. The roasting temperature is 600-800℃ and the roasting time is 1-5h. The second stage is roasting in an air atmosphere, with a roasting temperature of 600-800℃ and a roasting time of 1-5h.

18. The method for preparing the coal tar hydrogenation catalyst according to claim 17, characterized in that: The inert atmosphere is nitrogen.

19. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: Group VIB metals are Mo and / or W, and Group VIII metals are Ni and / or Co.

20. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: The active metal components in step (4) are Mo and Ni.

21. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: In step (4), the drying temperature is 80-120℃ and the drying time is 4-12h; in step (4), the calcination temperature is 400-600℃ and the calcination time is 1-5h; the calcination is carried out under an oxygen-containing atmosphere.

22. The method for preparing the coal tar hydrogenation catalyst according to claim 1, characterized in that: In step (4), the roasting is carried out in the presence of air or oxygen.

23. A coal tar hydrogenation catalyst, wherein the coal tar hydrogenation catalyst is obtained by the preparation method described in any one of claims 1-22.

24. The coal tar hydrogenation catalyst according to claim 23, characterized in that: Based on the weight of the catalyst, the content of Group VIB metal components, calculated as oxides, is 4 wt% to 8 wt%; the content of Group VIII metal components is 1 wt% to 3 wt%; the content of nickel as oxides is 1.0 wt% to 5.0 wt%; and the content of phosphorus pentoxide is 0.3 wt% to 1.0 wt%.

25. The coal tar hydrogenation catalyst according to claim 23 or 24, characterized in that: The specific surface area of ​​the coal tar hydrogenation catalyst is 150–220 m². 2 / g, with a pore volume of 0.60–0.80 mL / g; the pore volume of pores with a diameter greater than 50 nm accounts for 2%–15% of the total pore volume.

26. A coal tar hydrogenation process, wherein the coal tar feedstock enters a reaction unit and reacts under the combined action of hydrogen and the coal tar hydrogenation catalyst described in any one of claims 23-25.

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