A coal tar hydrogenation catalyst and its preparation method

Abstract

The present invention discloses a coal tar hydrogenation catalyst and a preparation method thereof. In the mixing condition, the preparation method uniformly mixes a silicon source, an organic polymer, an organic acid and water to obtain material A; uniformly mixes material A with pseudo-boehmite powder to obtain material B; fully mixes pseudo-boehmite powder and an aqueous solution of the heat-treated organic polymer and then performs a shaping treatment to obtain a carrier precursor; under the condition of rolling forming, adds material B and an aqueous solution of the heat-treated organic polymer to the carrier precursor, and after treatment, performs drying and roasting in an inert atmosphere to obtain a carrier, and after introducing active metal components, performs drying and roasting to obtain the coal tar hydrogenation catalyst. The prepared coal tar hydrogenation catalyst is beneficial to the gradual hydrogenation reaction of coal tar, and improves the activity, stability and utilization rate of the catalyst.

Description

Technical Field

[0001] The present invention belongs to the technical field of coal chemical industry, and particularly relates to a coal tar hydrogenation catalyst and a preparation method thereof. Background Art

[0002] Coal tar is a by-product of the processes of coal coking, dry distillation and gasification, and its domestic output exceeds 10 million tons. The traditional processing methods of coal tar aim at physical separation and extraction of single-component or narrow-fraction products, and extract wash oil, light oil, anthracene oil, industrial naphthalene, crude phenol and low-quality asphalt from coal tar. The components of coal tar are complex, the content of high-value-added components is low, and the low-value-added components with high content are difficult to utilize. The conventional refining process flow is complex, with many equipment, high energy consumption, serious secondary pollution and poor economic benefits. If coal tar is simply treated and burned as low-quality fuel oil, a large amount of sewage or atmospheric pollutants such as NOx and SOx will be generated. Therefore, using coal tar as raw material to produce fuel oil through hydrogenation process can produce obvious economic and social benefits, and effectively alleviate the current situation of energy shortage in China.

[0003] The coal tar hydrogenation technology is the main direction for exploring new clean utilization technologies of coal tar. By using the hydrogenation process, deep removal of heteroatoms such as sulfur, nitrogen and oxygen in coal tar raw materials, saturation of unsaturated olefins and aromatics can be completed, so as to increase the H / C ratio of coal tar, improve its stability and obtain high-quality fuel oil. It can extend the industrial chain, improve resource utilization rate, reduce pollution and extract high-value-added products. There is a large gap in the future market of vehicle fuels in China. Producing fuel oil by hydrogenating coal tar will be a new way for the processing and utilization of coal tar, and also has important strategic significance for the sustainable development of energy.

[0004] Coal tar is rich in oxygen elements. During the hydrogenation process, oxygen adds hydrogen to form water, and these waters have an adverse impact on the pore structure and mechanical properties of the catalyst under high temperature and high pressure conditions. Therefore, how to improve the water resistance of the catalyst on the premise of ensuring the hydrogenation performance is the research direction.

[0005] CN201210308181.5 discloses a coal tar hydrodemetallization catalyst and a preparation method thereof. It includes: (1) taking or preparing an alumina support; (2) treating the alumina support in step (1) with an organic acid solution with a pH value lower than 3, and then impregnating the acid-treated alumina support with an aluminum nitrate solution, and obtaining a modified alumina support through drying and calcination; (3) loading hydrogenation active components by an impregnation method to obtain a coal tar hydrodemetallization catalyst. Compared with the prior art, the coal tar hydrodemetallization catalyst of the present invention has more prominent activity and activity stability, and the operation cycle of the catalyst is longer.

[0006] CN202110144831.6 discloses a coal tar hydrogenation catalyst and its preparation method. The catalyst includes a first active substance and a second active substance, the first active substance includes at least one of the VIB group oxides, the second active substance includes at least one of the IB, VIIB or VIII group oxides, the molar ratio M1 / M2 of the metal M1 in the first active substance and the metal M2 in the second active substance is 10-1, the carrier of the catalyst is a molecular sieve that has been pore-enlarged, and the active component is also doped with C. The preparation method of the catalyst is: the carrier, the active substance precursor and urea are subjected to low-temperature hydrothermal treatment to obtain a catalyst precursor A, the catalyst precursor A is impregnated in a solution containing a carbon source to obtain a catalyst precursor B, and the 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 hydrodenitrogenation and hydrodesulfurization capabilities. Summary of the Invention

[0007] The present invention provides a coal tar hydrogenation catalyst and a preparation method thereof. The prepared coal tar hydrogenation catalyst has a spherical core-shell structure and an uneven pore distribution structure. The shell layer has larger pores and weak acidity, which is conducive to de-impurity reactions such as hydrogenation deoxygenation and demetallization of the coal tar raw material. Then, further deep hydrogenation and conversion reactions of the coal tar occur in the core layer, which is more conducive to the gradual hydrogenation reaction of the coal tar and improves the activity, stability and utilization rate of the catalyst.

[0008] A first aspect of the present invention provides a method for preparing a coal tar hydrogenation catalyst, comprising the following steps:

[0009] (1) Under mixing conditions, a silicon source, an organic high molecular polymer, an organic acid and water are mixed and heated to obtain material A;

[0010] (2) mixing the material A obtained in step (1) with pseudo-boehmite powder, and mixing them evenly to obtain material B;

[0011] (3) The pseudo-boehmite powder and the heated organic polymer aqueous solution are fully mixed and sphericalized to obtain a carrier precursor;

[0012] (4) placing the carrier precursor obtained in step (3) into a rolling ball device, adding the material B obtained in step (2) and the heated organic high molecular polymer aqueous solution under rolling forming conditions, and further drying and calcining under an inert atmosphere to obtain a carrier after treatment;

[0013] (5) An active metal component is introduced into the carrier obtained in step (4), followed by drying and calcination to obtain a coal tar hydrogenation catalyst.

[0014] Furthermore, in the above-mentioned method for preparing the coal tar hydrogenation catalyst, the silicon source in step (1) is one or more of ethyl orthosilicate and silica sol.

[0015] Further, in the preparation method of the above coal tar hydrogenation catalyst, the mass ratio of the amount of silicon source added in step (1) calculated as silica to the dry basis mass of pseudoboehmite powder in step (2) is 1:19 - 4:6.

[0016] Further, in the preparation method of the above coal tar hydrogenation catalyst, the organic polymer in step (1), step (3) and step (4) is one or more of starch, cellulose ether, and flour, preferably starch. Further, the starch is one or several of mung bean starch, cassava starch, sweet potato starch, potato starch, wheat starch, water chestnut starch, lotus root starch, corn starch, preferably corn starch and / or potato starch; the cellulose ether can be at least one of methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, and phenyl cellulose, preferably methyl cellulose.

[0017] Further, in the preparation method of the above coal tar hydrogenation catalyst, the organic acid in step (1) is one or a mixture of two or more of citric acid, acetic acid, lactic acid, malic acid, tartaric acid, preferably citric acid.

[0018] Further, in the preparation method of the above coal tar hydrogenation catalyst, the mass ratio of the organic polymer in step (1) to water is 0.1 - 0.5.

[0019] Further, in the preparation method of the above coal tar hydrogenation catalyst, the mass ratio of the organic polymer and the organic acid in step (1) is 1:0.1 - 1:5.

[0020] Further, in the preparation method of the above coal tar hydrogenation catalyst, the heating treatment temperature in step (1) is 30 - 50 °C, and the treatment time is 2 - 6 h.

[0021] Further, in the preparation method of the above coal tar hydrogenation catalyst, the amount of the organic polymer added in step (1) is 5 wt% - 35 wt%, preferably 10 wt% - 30 wt% of the dry basis mass of pseudoboehmite powder in step (2).

[0022] Further, in the preparation method of the above coal tar hydrogenation catalyst, the pseudoboehmite powder described in step (2) can be a commercially available product or the pseudoboehmite powder prepared according to the existing method.

[0023] Further, in the preparation method of the above-mentioned coal tar hydrogenation catalyst, the pseudo-boehmite powder described in steps (2) and (3) may be the same or different.

[0024] Further, in the preparation method of the above-mentioned coal tar hydrogenation catalyst, the properties of the pseudo-boehmite powder described in steps (2) and (3) after calcination at 600 °C are as follows: the specific surface area is 280 - 330 m 2 / g, and the pore volume is 0.9 - 1.1 mL / g. The above-mentioned pseudo-boehmite can be a commercially available product or a pseudo-boehmite prepared according to existing methods.

[0025] Further, in the preparation method of the above-mentioned coal tar hydrogenation catalyst, the mass concentration of the heat-treated aqueous solution of the organic polymer in steps (3) and (4) is 0.5 wt% - 8 wt%, preferably 1 wt% - 5 wt%. The preparation method is: adding the organic polymer into water, heating and stirring at 60 - 100 °C for 10 - 40 min, and obtaining the heat-treated aqueous solution of the organic polymer after the organic polymer is completely dissolved.

[0026] Further, in the preparation method of the above-mentioned coal tar hydrogenation catalyst, the ratio of the addition amount of the heat-treated aqueous solution of the organic polymer described in step (3) to the dry weight of the pseudo-boehmite powder is 0.5 - 2.0.

[0027] Further, in the preparation method of the above-mentioned coal tar hydrogenation catalyst, the ball forming and shaping in step (3) are not particularly limited, and those skilled in the art can select any one of the existing ball forming and shaping methods in the art according to actual needs, such as extrusion and ball throwing forming, rolling forming, spray drying forming, etc.

[0028] Further, in the preparation method of the above-mentioned coal tar hydrogenation catalyst, the ratio of the addition amount of the heat-treated aqueous solution of the organic polymer described in step (4) to the mass of the mixed material B is 0.1 - 1.0.

[0029] Further, in the preparation method of the above-mentioned coal tar hydrogenation catalyst, the drying temperature in step (4) is 70 - 120 °C, and the drying time is 3 - 12 h.

[0030] Further, in the preparation method of the above-mentioned coal tar hydrogenation catalyst, the inert atmosphere in step (4) is one or more of nitrogen, helium, neon, argon, krypton, xenon, etc., preferably nitrogen; the calcination temperature is 600 - 800 °C, and the calcination time is 1 - 5 h.

[0031] Further, in the preparation method of the above-mentioned coal tar hydrogenation catalyst, the particle size of the carrier in step (4) is 0.3 - 2.0 mm, preferably 0.5 - 1.8 mm.

[0032] Further, in the preparation method of the above-mentioned coal tar hydrogenation catalyst, any one or more of the existing methods in the art can be used to introduce the active metal components in step (5). Specifically, at least one of the methods such as kneading and impregnation can be used, and the impregnation method is preferably used.

[0033] Further, in the preparation method of the above-mentioned coal tar hydrogenation catalyst, the active metal components in step (5) are one or more of Group VIB metals and / or Group VIII metals. Among them, the Group VIB metals are generally Mo and / or W, and the Group VIII metals are generally Ni and / or Co; preferably, the active metal components are Mo and Ni.

[0034] Further, in the preparation method of the above-mentioned coal tar hydrogenation catalyst, an auxiliary agent P can also be introduced when introducing the active metal components in step (5). [[ID=II]]

[0035] Further, in the preparation method of the above-mentioned coal tar hydrogenation catalyst, the drying in step (5) is carried out at 80 - 120 °C for 4 - 12 h; the calcination temperature is 400 - 600 °C, and the calcination time is 1 - 5 h.

[0036] Further, in the preparation method of the above-mentioned coal tar hydrogenation catalyst, when the active metal components are introduced by the impregnation method in step (5), first, a precursor containing the active metal components, water, and optionally a phosphorus-containing compound are mixed evenly to obtain an aqueous solution containing hydrogenation metal components and P. Then, it is mixed evenly with the carrier and obtained the catalyst after standing, drying, and calcination. Specifically, the precursor containing the active metal components is a compound containing Group VIB metals and / or Group VIII metals. The compound containing Group VIB metals can be one or more of molybdenum-containing compounds and tungsten-containing compounds. The compound containing Group VIII metals is one or more of nickel-containing compounds and cobalt-containing compounds. The molybdenum-containing compound can be molybdenum oxide and / or ammonium heptamolybdate; the nickel-containing compound is nickel basic carbonate and / or nickel nitrate; the cobalt-containing compound is cobalt basic carbonate and / or cobalt nitrate. The phosphorus-containing compound can be one or more of phosphoric acid, ammonium dihydrogen phosphate, and ammonium hydrogen phosphate; the concentration of the hydrogenation metal components in the aqueous solution containing hydrogenation metal components and P is 0.05 - 1.0 g / mL (calculated as hydrogenation metal oxides), and the concentration of P is 0 - 0.1 g / mL, preferably 0.002 - 0.1 g / mL. The standing time is 1 - 3 h.

[0037] In the second aspect of the present invention, a coal tar hydrogenation catalyst is provided, and the coal tar hydrogenation catalyst is obtained by the above preparation method.

[0038] Further, in the above coal tar hydrogenation catalyst, the coal tar hydrogenation catalyst comprises an active metal component, an optional promoter, and a support. The active metal component is one or more of Group VIB metals and / or Group VIII metals. The promoter is phosphorus pentoxide. The support comprises an inner layer of alumina and an outer layer of an alumina-silica composite material. The active metal and the promoter exist on the support in the form of oxides.

[0039] Further, in the above coal tar hydrogenation catalyst, the support has a core-shell structure, wherein the outer layer is an alumina-silica composite material with a mesoporous pore distribution. Based on the weight of the support, the content of alumina in the core layer is 20% - 70%, and the content of the alumina-silica in the outer layer is 30% - 80%.

[0040] Further, in the above coal tar hydrogenation catalyst, the silica content in the outer layer alumina-silica is 3% - 12%, preferably 5% - 10%.

[0041] Further, in the above coal tar hydrogenation catalyst support, the diameter of the support particles is 0.3 - 2.0 mm, preferably 0.5 - 1.8 mm.

[0042] Further, in the above coal tar hydrogenation catalyst, based on the weight of the catalyst and in terms of oxides, the content of the metal component of Group VIB is 4 wt% - 10 wt%; the content of the metal component of Group VIII is 1 wt% - 4 wt%; and the content of the promoter phosphorus pentoxide is 0.8 wt% - 2.5 wt%.

[0043] Further, in the above coal tar hydrogenation catalyst, the properties of the coal tar hydrogenation catalyst are as follows: the specific surface area is 160 - 250 m 2 / g, the pore volume is 0.50 - 0.80 mL / g; the proportion of the mesopore volume with a pore diameter of 10 - 50 nm in the total pore volume is 70% - 98%.

[0044] In the third aspect of the present invention, an application of the above coal tar hydrogenation catalyst in the process of coal tar hydrogenation treatment is provided.

[0045] Further, in the application of the above coal tar hydrogenation catalyst in the process of coal tar hydrogenation treatment, the coal tar can be at least one of low-temperature coal tar, medium-temperature coal tar, and high-temperature coal tar.

[0046] Furthermore, in the application of the above coal tar hydrogenation catalyst in the coal tar hydrogenation process, the process conditions of the hydrogenation process are as follows: the reaction pressure is 10 - 20 MPa, the temperature is 300 - 450 °C, and the liquid hourly space velocity is 0.2 - 1.5 h -1 , and the hydrogen-oil volume ratio is 500 - 1000.

[0047] The coal tar hydrogenation catalyst and its preparation method provided by the present invention have the following technical effects:

[0048] 1. In the preparation method of the coal tar hydrogenation catalyst provided by the present invention, after the organic polymer is heat-treated, it decomposes into small molecules in water, making the aqueous solution have high adhesiveness, which can enhance the interaction force between pseudo-boehmite powders, improve the strength and wear resistance of the carrier; the organic polymer is modified by organic acid, the molecules become smaller and the adhesiveness weakens, and when mixed with pseudo-boehmite powders, it can increase the mesopore ratio of the alumina carrier; in the presence of organic acid, the silicon source hydrolyzes to form a silica-alumina network skeleton structure, improving the water resistance of the catalyst, and at the same time, the presence of silica also weakens the interaction between the active metal and alumina.

[0049] 2. In the preparation method of the coal tar hydrogenation catalyst provided by the present invention, the organic acid used to modify the organic polymer will interact with the basic sites on alumina and adsorb. After calcination in an inert atmosphere, carbon is in-situ generated on the basic sites of the alumina carrier. On the one hand, it can play a role in blocking the active metal, avoiding the migration and aggregation of the active metal during low-temperature calcination, which is beneficial to improving the dispersion of the active metal on the carrier. On the other hand, it can avoid the strong interaction between the active metal and the basic sites of the carrier during calcination, making the active metal on the catalyst more easily sulfided. Finally, the carbon is burned off by calcination in an oxygen-containing atmosphere to restore the basic sites of alumina. At the same time, during the impregnation process of the active metal solution, it is also more conducive to the active metal entering the internal pores of the carrier, improving the utilization rate of the active metal.

[0050] 3. In the preparation method of the coal tar hydrogenation catalyst of the present invention, the acid-modified organic polymer becomes mesoporous carbon material after calcination in an inert atmosphere. Since the water absorption rate of the carbon material is lower than that of alumina, the presence of the carbon material reduces the water absorption rate of the shell-layer alumina carrier. During the impregnation of the active metal, relatively less active metal is adsorbed on the shell-layer alumina of the carrier, while relatively more active metal is adsorbed on the inner-layer alumina of the carrier. The prepared catalyst has an uneven distribution of active metal, with relatively more active metal distributed inside the catalyst and relatively less active metal distributed outside the catalyst, making the hydrogenation activity of the catalyst show a gradient distribution.

[0051] 4. The coal tar hydrogenation catalyst provided by the present invention has a core-shell structure with different pore size distributions and activity distributions. The outer layer of the catalyst can effectively remove and preliminarily convert impurities such as metals, oxygen, sulfur, and nitrogen in coal tar, and the core layer of the catalyst can achieve further conversion of coal tar. Successive hydrogenation reactions of coal tar are realized on one catalyst, improving the properties of coal tar hydrogenation products and providing higher-quality raw materials for subsequent processes. At the same time, the alumina-silica on the outer layer improves the water resistance of the catalyst, which is more conducive to successive hydrogenation reactions of coal tar and improves the activity, stability, and utilization rate of the catalyst. Detailed Embodiments

[0052] The technical solutions and effects of the present invention are further illustrated below through specific examples. In the present invention, wt% is the mass fraction.

[0053] In the present invention, the specific surface area and pore volume are measured by the low-temperature liquid nitrogen physical adsorption method, specifically measured by the low-temperature nitrogen adsorption instrument of the ASAP2420 model of the American Micromeritics company; the specific process: take a small amount of sample and vacuum-treat it at 300°C for 3 - 4 h, and finally place the product under the condition of low-temperature liquid nitrogen (-200°C) for nitrogen adsorption-desorption test. The surface area is obtained according to the BET equation, and the pore size distribution is obtained according to the BJH model.

[0054] In the present invention, the abrasion index of microsphere carriers with a size less than 0.8 mm is tested by the high-speed air injection method (see ASTM D5757-00), and the abrasion index of microsphere carriers with a size greater than 0.8 mm is measured by the drum method using a KM-ZV abrasion tester.

[0055] Example 1

[0056] Mix 117.8 g of tetraethyl orthosilicate, 63 g of corn starch, 63 g of citric acid, and 210 g of water, heat the mixture to 40°C after mixing evenly, and process for 3 h to obtain Material A; then mix it with 600 g of pseudo-boehmite powder (specific surface area 292 m 2 / g, pore volume 1.05 mL / g), and obtain Material B after mixing evenly; weigh 80 g of corn starch and add it to 2000 g of water, heat at 70°C for 20 min to obtain the heated organic polymer aqueous solution; mix 400 g of pseudo-boehmite powder (specific surface area 292 m 2 / g, pore volume 1.05 mL / g) and 380 g of the heated organic polymer aqueous solution, and prepare a spherical carrier precursor after forming and shaping; put the prepared spherical carrier precursor into a ball rolling machine, and then evenly add Material B and 350 g of the heated organic polymer aqueous solution during the rolling and forming process. Dry the formed material at 110°C for 8 h. Then calcine it at 650°C for 3 h under a nitrogen atmosphere to obtain 0.5 - 0.8 mm spherical carriers. The carrier yield and abrasion data are shown in Table 1.

[0057] Dissolve 1.57 g of phosphoric acid H3PO4 (concentration 85 wt%) in 50 mL of water, then add 4.27 g of molybdenum trioxide and 1.88 g of nickel basic carbonate, heat up to 100 °C and stir and reflux for 2.0 h. After filtration, make up the volume to 85 mL to obtain the Mo-Ni-P aqueous solution.

[0058] Add all of the Mo-Ni-P aqueous solution to 100 g of the prepared support. After mixing evenly, let it stand for 2 h, then dry at 110 °C for 8 h and calcine at 550 °C for 3 h to obtain the catalyst, where the MoO3 content is 4.0 wt%, the NiO content is 1.0 wt%, and the P content is 0.4 wt%. The physical and chemical properties of the catalyst are shown in Table 2.

[0059] Catalyst evaluation

[0060] Use a CSTR hydrogenation evaluation device to conduct a long-term activity evaluation of the catalyst for 1500 h. The catalyst evaluation conditions are: reaction temperature 380 °C, reaction pressure 15.0 MPa, volume space velocity 0.4 h -1 , hydrogen-oil volume ratio 600:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0061] Example 2

[0062] Mix 117.8 g of tetraethyl orthosilicate, 84 g of corn starch, 84 g of citric acid and 280 g of water. After mixing evenly, heat to 40 °C and treat for 3 h to obtain material A; then mix it with 600 g of pseudo-boehmite powder (specific surface area 292 m 2 / g, pore volume 1.05 mL / g) to obtain material B after mixing evenly; weigh 80 g of corn starch and add it to 2000 g of water, heat at 70 °C for 20 min to obtain the heated organic polymer aqueous solution; mix 600 g of pseudo-boehmite powder (specific surface area 292 m 2 / g, pore volume 1.05 mL / g) and 580 g of the heated organic polymer aqueous solution, and after forming into spheres, obtain the spherical support precursor; put the obtained spherical support precursor into a rolling ball machine, and then evenly add material B and 260 g of the heated organic polymer aqueous solution during the rolling forming process. Dry the formed material at 110 °C for 8 h. Then calcine at 700 °C for 3 h under a nitrogen atmosphere to obtain a 0.5 - 0.8 mm spherical support. The support yield and abrasion data are shown in Table 1.

[0063] 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 nickel basic carbonate, heat up to 100 °C and stir and reflux for 2.0 h. After filtration, make up the volume to 85 mL to obtain the Mo-Ni-P aqueous solution.

[0064] Add all of the Mo-Ni-P aqueous solution to 100 g of the prepared support, mix evenly and let stand for 2 h, then dry at 110 °C for 8 h and calcine at 450 °C for 3 h to obtain the catalyst, where the MoO3 content is 6.0 wt%, the NiO content is 1.5 wt%, and the P content is 0.6 wt%. The physical and chemical properties of the catalyst are shown in Table 2.

[0065] Catalyst evaluation

[0066] Use a CSTR hydrogenation evaluation device to conduct a long-term activity evaluation of the catalyst for 1500 h. The catalyst evaluation conditions are: reaction temperature 380 °C, reaction pressure 15.0 MPa, volume space velocity 0.4 h -1 , hydrogen-oil volume ratio 600:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0067] Example 3

[0068] Mix 78.5 g of tetraethyl orthosilicate, 70 g of corn starch, 70 g of citric acid and 230 g of water, heat to 40 °C after mixing evenly and treat for 3 h to obtain material A; then mix it with 400 g of pseudo-boehmite powder (specific surface area 292 m 2 / g, pore volume 1.05 mL / g), and obtain material B after mixing evenly; weigh 80 g of corn starch and add it to 2000 g of water, heat at 70 °C for 20 min to obtain the heated organic polymer aqueous solution; add 600 g of pseudo-boehmite powder (specific surface area 292 m 2 / g, pore volume 1.05 mL / g) and 570 g of the heated organic polymer aqueous solution, and after forming into spheres, obtain the spherical support precursor; put the prepared spherical support precursor into a rolling ball machine, and then evenly add material B and 150 g of the heated organic polymer aqueous solution during the rolling forming process. Dry the formed material at 110 °C for 8 h. Then calcine at 750 °C for 3 h under a nitrogen atmosphere to obtain a 0.5 - 0.8 mm spherical support. The support yield and abrasion data are shown in Table 1.

[0069] Dissolve 3.34 g of phosphoric acid H3PO4 (concentration 85 wt%) in 50 mL of water, then add 9.06 g of molybdenum trioxide and 4.01 g of nickel basic carbonate, heat up to 100 °C and stir and reflux for 2.0 h. After filtration, make up the volume to 85 mL to obtain the Mo-Ni-P aqueous solution.

[0070] All of the Mo-Ni-P aqueous solution was added to 100 g of the prepared support. After mixing evenly, it was allowed to stand for 2 h, then dried at 110 °C for 8 h and calcined at 550 °C for 3 h to obtain a catalyst, in which the MoO3 content was 8.0 wt%, the NiO content was 2.0 wt%, and the P content was 0.8 wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0071] Catalyst evaluation

[0072] A CSTR hydrogenation evaluation device was used to conduct a long-term activity evaluation of the catalyst for 1500 h. The catalyst evaluation conditions were: reaction temperature 380 °C, reaction pressure 15.0 MPa, volumetric space velocity 0.4 h -1 , and hydrogen-oil volume ratio 600:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0073] Example 4

[0074] It was basically the same as Example 3, except that 70 g of corn starch was changed to 70 g of potato starch, and 80 g of corn starch was changed to 80 g of potato starch, to prepare a spherical support with a particle size of 0.5 - 0.8 mm. The support yield and abrasion data are shown in Table 1. A catalyst was prepared, in which the MoO3 content was 8.0 wt%, the NiO content was 2.0 wt%, and the P content was 0.8 wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0075] The catalyst evaluation was the same 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.

[0076] Example 5

[0077] It was basically the same as Example 3, except that 70 g of corn starch was changed to 58.91 g of methyl cellulose, and 80 g of corn starch was changed to 67.41 g of methyl cellulose, to prepare a spherical support with a particle size of 0.5 - 0.8 mm. The support yield and abrasion data are shown in Table 1. A catalyst was prepared, in which the MoO3 content was 8.0 wt%, the NiO content was 2.0 wt%, and the P content was 0.8 wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0078] The catalyst evaluation was the same 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.

[0079] Example 6

[0080] It was basically the same as Example 3, except that the 0.5 - 0.8 mm spherical support was changed to a 1.2 - 1.5 mm spherical support. The support yield and abrasion data are shown in Table 1. A catalyst was prepared, in which the MoO3 content was 8.0 wt%, the NiO content was 2.0 wt%, and the P content was 0.8 wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0081] The catalyst evaluation was the same 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.

[0082] Comparative Example 1

[0083] (1) Support preparation

[0084] 117.8 g of tetraethyl orthosilicate, 63 g of corn starch, 63 g of citric acid, and 210 g of water were mixed. After mixing evenly, it was heated to 40 °C and treated for 3 h to obtain Material A; then it was mixed with 600 g of pseudo-boehmite powder (specific surface area 292 m 2 / g, pore volume 1.05 mL / g), and after mixing evenly, Material B was obtained; 400 g of pseudo-boehmite powder (specific surface area 292 m 2 / g, pore volume 1.05 mL / g), 15.2 g of corn starch, and 380 g of water were mixed. After forming into spheres, a spherical support precursor was prepared; the prepared spherical support precursor was placed in a rolling ball machine, and then during the rolling forming process, Material B, 14 g of corn starch, and 350 g of water were evenly added. The formed material was dried at 110 °C for 8 h. Then, it was calcined in a nitrogen atmosphere at 650 °C for 3 h to obtain a 0.5 - 0.8 mm spherical support. The support yield and abrasion data are shown in Table 1.

[0085] (2) Catalyst preparation

[0086] 1.57 g of phosphoric acid H3PO4 (concentration 85 wt%) was dissolved in 50 mL of water, then 4.27 g of molybdenum trioxide and 1.88 g of basic nickel carbonate were added. The temperature was raised to 100 °C and stirred under reflux for 2.0 h. After filtration, it was made up to 85 mL in volume, and the Mo-Ni-P aqueous solution was obtained.

[0087] All of the Mo-Ni-P aqueous solution was added to 100 g of the prepared support. After mixing evenly, it was left standing for 2 h, then dried at 110 °C for 8 h and calcined at 550 °C for 3 h to obtain a catalyst, in which the MoO3 content was 4.0 wt%, the NiO content was 1.0 wt%, and the P content was 0.4 wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0088] (3) Catalyst evaluation

[0089] A CSTR hydrogenation evaluation device was used to conduct a long-term activity evaluation of the catalyst for 1500 h. The catalyst evaluation conditions were: reaction temperature 380 °C, reaction pressure 15.0 MPa, volume space velocity 0.4 h -1 , hydrogen-oil volume ratio 600:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0090] Comparative Example 2

[0091] (1)Support preparation

[0092] Mix 117.8 g of tetraethyl orthosilicate, 63 g of corn starch and 210 g of water. After mixing evenly, heat to 40 °C and treat for 3 h to obtain Material A; then mix it with 600 g of pseudo-boehmite powder (specific surface area 292 m 2 / g, pore volume 1.05 mL / g) to obtain Material B after mixing evenly; weigh 80 g of corn starch and add it to 2000 g of water, heat at 70 °C for 20 min to obtain the heated organic polymer aqueous solution; mix 400 g of pseudo-boehmite powder (specific surface area 292 m 2 / g, pore volume 1.05 mL / g) and 380 g of the heated organic polymer aqueous solution, and after forming into spheres, obtain the spherical carrier precursor; put the obtained spherical carrier precursor into a rolling ball machine, and then evenly add Material B and 350 g of the heated organic polymer aqueous solution during the rolling forming process. Dry the formed material at 110 °C for 8 h. Then, calcine it at 650 °C for 3 h under a nitrogen atmosphere to obtain a 0.5 - 0.8 mm spherical carrier. The carrier yield and abrasion data are shown in Table 1.

[0093] (2) Catalyst preparation

[0094] Dissolve 1.57 g of phosphoric acid H3PO4 (concentration 85 wt%) in 50 mL of water, then add 4.27 g of molybdenum trioxide and 1.88 g of nickel basic carbonate, heat to 100 °C and stir and reflux for 2.0 h. After filtration, make up the volume to 85 mL to obtain the Mo-Ni-P aqueous solution.

[0095] Add all the Mo-Ni-P aqueous solution to 100 g of the prepared carrier, mix evenly and let it stand for 2 h, then dry at 110 °C for 8 h and calcine at 550 °C for 3 h to obtain the catalyst, where the MoO3 content is 4.0 wt%, the NiO content is 1.0 wt%, and the P content is 0.4 wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0096] (3) Catalyst evaluation

[0097] Use a CSTR hydrogenation evaluation device to conduct a long-term activity evaluation of the catalyst for 1500 h. The catalyst evaluation conditions are: reaction temperature 380 °C, reaction pressure 15.0 MPa, volume space velocity 0.4 h -1 , hydrogen-oil volume ratio 600:1. The properties of the raw material oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0098] Comparative Example 3

[0099] (1) Carrier preparation

[0100] Mix 63 g of corn starch, 63 g of citric acid and 210 g of water. After mixing evenly, heat the mixture to 40 °C and process it for 3 h to obtain Material A. Then mix it with 600 g of pseudo-boehmite powder (specific surface area 292 m 2 / g, pore volume 1.05 mL / g) to obtain Material B after mixing evenly. Weigh 80 g of corn starch and add it to 2000 g of water, and heat it at 70 °C for 20 min to obtain an aqueous solution of heat-treated organic polymer. Mix 400 g of pseudo-boehmite powder (specific surface area 292 m 2 / g, pore volume 1.05 mL / g) and 380 g of the heat-treated aqueous solution of organic polymer. After forming and shaping, a spherical carrier precursor is prepared. Put the prepared spherical carrier precursor into a rolling ball machine, and then evenly add Material B and 350 g of the heat-treated aqueous solution of organic polymer during the rolling forming process. Dry the formed material at 110 °C for 8 h. Then calcine it at 650 °C for 3 h in a nitrogen atmosphere to obtain a 0.5 - 0.8 mm spherical carrier. The carrier yield and abrasion data are shown in Table 1.

[0101] (2) Catalyst preparation

[0102] Dissolve 1.57 g of phosphoric acid H3PO4 (concentration 85 wt%) in 50 mL of water, then add 4.27 g of molybdenum trioxide and 1.88 g of nickel basic carbonate, heat up to 100 °C and stir and reflux for 2.0 h. After filtration, make up the volume to 85 mL to obtain an Mo-Ni-P aqueous solution.

[0103] Add all the Mo-Ni-P aqueous solution to 100 g of the prepared carrier, mix evenly and let it stand for 2 h, then dry it at 110 °C for 8 h and calcine it at 550 °C for 3 h to obtain a catalyst, where the MoO3 content is 4.0 wt%, the NiO content is 1.0 wt%, and the P content is 0.4 wt%. The physical and chemical properties of the catalyst are shown in Table 2.

[0104] (3) Catalyst evaluation

[0105] Use a CSTR hydrogenation evaluation device to conduct a long-term activity evaluation of the catalyst for 1500 h. The catalyst evaluation conditions are: reaction temperature 380 °C, reaction pressure 15.0 MPa, volume space velocity 0.4 h -1 , hydrogen-oil volume ratio 600:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0106] Table 1 Carrier yield and abrasion

[0107] <\

[0108] Table 2 Physical and chemical properties of the catalyst

[0109]

[0110] Table 3 Properties of feedstock oil

[0111]

[0112] Table 4 Catalyst evaluation results

[0113]

[0114] Taking the activity of Comparative Example 1 as 100, the evaluation results after comparing the activities of other examples with that of the Comparative Example are shown in Table 4.

Claims

1. A preparation method of a coal tar hydrogenation catalyst, comprising the following steps: (1) Under mixing conditions, mix a silicon source, an organic polymer, an organic acid, and water, and obtain material A after heat treatment; (2) Mix material A obtained in step (1) with pseudo-boehmite powder, and obtain material B after mixing evenly; (3) Thoroughly mix pseudo-boehmite powder and an aqueous solution of the heat-treated organic polymer, and obtain a carrier precursor after pelletizing and forming; (4) Put the carrier precursor obtained in step (3) into a rolling ball device, add material B obtained in step (2) and an aqueous solution of the heat-treated organic polymer under rolling forming conditions, and further obtain a carrier after drying and calcining in an inert atmosphere; (5) Introduce active metal components onto the carrier obtained in step (4), and obtain a coal tar hydrogenation catalyst after drying and calcining. The active metal components are one or more of Group VIB metals and / or Group VIII metals; an auxiliary agent P is introduced when introducing the active metal components; Among them, The organic polymer in step (1), step (3), and step (4) is one or more of starch, cellulose ether, and flour; the preparation method of the aqueous solution of the heat-treated organic polymer in step (3) and step (4) is to add the organic polymer to water, heat and stir at 60-100 °C for 10-40 min, and obtain the aqueous solution of the heat-treated organic polymer after the organic polymer is completely dissolved.

2. The preparation method of the coal tar hydrogenation catalyst according to claim 1, wherein, The silicon source in step (1) is one or more of tetraethyl orthosilicate and silica sol.

3. The preparation method of the coal tar hydrogenation catalyst according to claim 1, wherein, The mass ratio of the silicon source added in step (1) based on the mass of silicon oxide to the dry basis mass of the pseudo-boehmite powder in step (2) is 1:19-4:

6.

4. The preparation method of the coal tar hydrogenation catalyst according to claim 1, wherein, The organic polymer is starch.

5. The preparation method of the coal tar hydrogenation catalyst according to claim 1, wherein, The starch is one or more of 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 methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, and phenyl cellulose.

6. The preparation method of the coal tar hydrogenation catalyst according to claim 1 or 5, wherein, The starch is corn starch and / or potato starch; the cellulose ether is methyl cellulose.

7. The preparation method of the coal tar hydrogenation catalyst according to claim 1, wherein, The organic acid in step (1) is one or a mixture of two or more of citric acid, acetic acid, lactic acid, malic acid, and tartaric acid.

8. The preparation method of the coal tar hydrogenation catalyst according to claim 1 or 7, wherein, The organic acid in step (1) is citric acid.

9. The preparation method of the coal tar hydrogenation catalyst according to claim 1, wherein, The mass ratio of the organic polymer to water in step (1) is 0.1-0.5; the mass ratio of the organic polymer to the organic acid is 1:0.1-1:

5.

10. The preparation method of the coal tar hydrogenation catalyst according to claim 1, wherein, The heat treatment temperature in step (1) is 30-50 °C.

11. The preparation method of the coal tar hydrogenation catalyst according to claim 1, wherein, The addition amount of the organic polymer in step (1) by mass is 5 wt%-35 wt% of the dry basis mass of the pseudo-boehmite powder in step (2).

12. The preparation method of the coal tar hydrogenation catalyst according to claim 1, wherein, The addition amount of the organic polymer in step (1) by mass is 10 wt%-30 wt% of the dry basis mass of the pseudo-boehmite powder in step (2).

13. The preparation method of the coal tar hydrogenation catalyst according to claim 1, wherein, The mass concentration of the heat-treated aqueous solution of the organic polymer in steps (3) and (4) is 0.5 wt% to 8 wt%.

14. The preparation method of the coal tar hydrogenation catalyst according to claim 1, wherein, The mass concentration of the heat-treated aqueous solution of the organic polymer in steps (3) and (4) is 1 wt% to 5 wt%.

15. The preparation method of the coal tar hydrogenation catalyst according to claim 1, wherein, The ratio of the addition amount of the heat-treated aqueous solution of the organic polymer in step (3) to the dry weight of the pseudo-boehmite powder is 0.5 to 2.

0.

16. The preparation method of the coal tar hydrogenation catalyst according to claim 1, wherein, The mass ratio of the addition amount of the heat-treated aqueous solution of the organic polymer in step (4) to material B is 0.1 to 1.

0.

17. The preparation method of the coal tar hydrogenation catalyst according to claim 1, wherein, The drying temperature in step (4) is 70 to 120 °C, and the drying time is 3 to 12 h.

18. The preparation method of the coal tar hydrogenation catalyst according to claim 1, wherein, The inert atmosphere in step (4) is one or more of nitrogen, helium, neon, argon, krypton, and xenon; the calcination temperature is 600 to 800 °C, and the calcination time is 1 to 5 h.

19. The preparation method of the coal tar hydrogenation catalyst according to claim 1, wherein, The Group VIB metal is Mo and / or W, and the Group VIII metal is Ni and / or Co.

20. The preparation method of the coal tar hydrogenation catalyst according to claim 1, wherein, The drying in step (5) is carried out at 80 to 120 °C for 4 to 12 h; the calcination temperature is 400 to 600 °C, and the calcination time is 1 to 5 h.

21. A coal tar hydrogenation catalyst, which is obtained by using the preparation method described in any one of claims 1-20.

22. The coal tar hydrogenation catalyst according to claim 21, wherein, The catalyst carrier has a core-shell structure, wherein the outer layer is an alumina-silica composite material with a mesoporous pore distribution, and the core layer is alumina; based on the weight of the carrier, the alumina content in the core layer is 20% to 70%, and the alumina-silica content in the outer layer is 30% to 80%.

23. The coal tar hydrogenation catalyst according to claim 22, wherein, The silica content in the outer layer alumina-silica is 3% to l2%.

24. The coal tar hydrogenation catalyst according to claim 22, wherein, The silica content in the outer layer alumina-silica is 5% to 10%.

25. The coal tar hydrogenation catalyst according to claim 21, wherein, The properties of the coal tar hydrogenation catalyst are as follows: the specific surface area is 160 - 250 m 2 / g, the pore volume is 0.50 - 0.80 mL / g; the proportion of the mesopore volume with a pore diameter of 10 - 50 nm in the total pore volume is 70% - 98%.

26. The application of the coal tar hydrogenation catalyst described in any one of claims 21-25 in the process of coal tar hydrogenation treatment.

27. Use of the coal tar hydrogenation catalyst according to claim 26 in the process of coal tar hydrogenation treatment, wherein, The coal tar is at least one of low-temperature coal tar, medium-temperature coal tar, and high-temperature coal tar.

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