Catalytic oil slurry hydrodesulfurization catalyst and preparation method thereof

Abstract

The application discloses a catalytic oil slurry hydrodesulfurization catalyst and a preparation method thereof. The preparation method comprises the following steps: adding a helping extruding agent and a hole expanding agent into a macroporous pseudo-boehmite, mixing, then adding an acidic metal impregnation solution, kneading, shaping, drying and roasting to obtain the catalyst; the helping extruding agent comprises isosorbide and polystyrene. The method is simple in process and low in cost, the prepared catalyst has a proper pore diameter, a high desulfurization effect and asphaltene conversion capacity, and can well retain triphenyl and tetraphenyl.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of catalysts, and particularly relates to a catalytic oil slurry hydrodesulfurization catalyst and a preparation method thereof. BACKGROUND

[0002] The super high power graphite electrode takes needle coke as raw material and is used for electric arc furnace steelmaking. Compared with blast furnace steelmaking, the super high power graphite electrode can reduce carbon emission by 60%. The Ministry of Industry and Information Technology has clearly proposed to "encourage the promotion of short process steelmaking process and equipment application taking scrap steel as raw material", and the increase of the proportion of short process is expected to further increase the demand for upstream key materials such as graphite electrodes. High-quality needle coke is a key raw material for super high power graphite electrodes, and the total demand is expected to reach 800,000 tons. Under the background of "carbon neutralization", the lithium battery industry has a strong development momentum. It is predicted that the demand for negative electrode coke in China will exceed 2 million tons in 2025.

[0003] In 2020, the domestic needle coke capacity was 1.48 million tons, and the actual output was only 0.488 million tons. In 2021, the needle coke capacity was 2.21 million tons, and the actual output was only about 1 million tons. The oil-based needle coke capacity was 1.18 million tons, and the output was about 0.7 million tons. Catalytic cracking slurry is a rich by-product of catalytic cracking (FCC). Catalytic slurry contains a large amount of 2-5 ring aromatic hydrocarbons. After catalytic cracking reaction, almost all the aromatic hydrocarbons are short side chains. Low-sulfur catalytic slurry can be used as an excellent raw material for producing needle coke. However, at present, there is a lack of low-sulfur high-quality slurry suitable for producing needle coke, and it is necessary to make full use of medium and high-sulfur slurry. However, medium and high-sulfur slurry contains a large amount of sulfur, nitrogen, oxygen and other heteroatoms and asphaltene heavy components. When the sulfur content of needle coke is high (>0.8wt%), it will release rapidly during graphitization, causing irreversible volume expansion and the formation of microcracks, which reduces the quality of the electrode. The sulfur content of oil-based needle coke raw material is <0.5wt%, ash content is ≤100mg / kg, asphaltene content is ≤2wt%, and aromatic content is 35-50wt%. Therefore, it is necessary to fully utilize the existing medium and high-sulfur catalytic slurry and pretreat it by hydrogenation. In terms of raw material pretreatment, it mainly involves slurry desolidification and back process and slurry refining process. Filtration + furfural extraction or supercritical extraction is used to adjust the components of the slurry. In terms of slurry refining, a large amount of research has been conducted at home and abroad, and the main process is hydrofining, which reduces the content of sulfur, nitrogen and other impurities in the slurry. For selective hydrogenation desulfurization reaction of the slurry, the performance of the catalyst is the key. The pore structure of the catalyst carrier (specific surface area, pore volume and pore size distribution) not only has an important influence on the dispersion of the active component, but also is directly related to the diffusion and mass transfer in the reaction process. The size and type of the pore diameter affect the internal diffusion rate of the reactants and products. Most of the metal and sulfur impurities in the slurry exist in the gum and asphaltene, which are the components with the largest molecular weight and the most complex structure in the slurry components, have large diffusion resistance, and are prone to pore blockage (causing catalyst deactivation). Therefore, the pore volume of the catalyst is particularly important, and a larger pore volume is beneficial for the passage of large molecules containing impurities, the reaction inside the catalyst pore, and the maintenance of a large specific surface area, which is conducive to the desulfurization activity. Although catalytic cracking slurry is a by-product after catalytic cracking reaction, the molecular size is smaller, the side chain of the slurry molecule is shorter, and the steric hindrance effect of the side chain is smaller. It is also necessary to increase the content of 15-20nm and 20-30nm pores to promote the adsorption and desorption of large molecule sulfur compounds and asphaltene molecules in the catalyst pore for conversion.

[0004] CN101724420A discloses a method for producing needle coke raw material by treating catalytic cracking slurry oil and conventional coking feedstock by delayed coking process. In the method, the slurry oil is fed from the upper part of the coke drum, the conventional coking feedstock is fed from the bottom of the coke drum, the slurry oil is contacted with high-temperature oil gas in the coke drum to remove components unfavorable for the production of needle coke, and coking wax oil is obtained by the side line of the coking fractionating tower as needle coke raw material. However, in the method, the slurry oil does not pass through the radiation section of the heating furnace, the temperature is low, and the slurry oil is fed from the middle and upper part, and the residence time is short, which makes part of the colloid and asphaltene not fully react, and is carried to the coking wax oil by the oil gas, thereby affecting the quality of the obtained needle coke raw material; and if the sulfur content in the catalytic cracking slurry oil is high, the sulfur content in the obtained coking wax oil is difficult to meet the requirements, and therefore the application of the method is considerably limited.

[0005] CN1872963A discloses a method for pre-treating raw material for producing needle coke. The raw material oil is first subjected to vacuum distillation to remove non-ideal components, and the remaining ideal components are contacted with hydrogen and a hydrogenation catalyst, and a hydrogenation reaction stream is obtained by separation to produce needle coke raw material. The method needs separate filtration and vacuum distillation devices, and the investment is large, and the needle coke raw material obtained by the method still contains a certain amount of colloid and asphaltene, which affects the quality of the needle coke, and it is difficult to produce high-grade needle coke products.

[0006] CN103013567B introduces a method for producing needle coke raw material from catalytic cracking slurry oil. In the patent, a protection zone and a hydrogenation reaction zone are provided, the catalytic slurry oil first enters the protection zone to adsorb most of the catalyst powder, and then is mixed with hydrogen into a heating furnace, and after heating, enters the hydrogenation reaction zone for hydrogenation treatment reaction. The protection zone is filled with adsorbent capable of adsorbing catalyst powder, and the hydrogenation reaction zone is filled with protective agent, metal removal agent and desulfurization agent. Due to the presence of catalyst powder, the protection zone needs to be frequently switched, which increases the operation and management cost of the device; secondly, in order to remove sulfur in the catalytic slurry oil, a fixed-bed hydrogenation reactor is provided for hydrogenation desulfurization. Since the catalytic slurry oil contains a large amount of unsaturated hydrocarbons, these unsaturated hydrocarbons are easily polymerized in the fixed-bed hydrogenation reactor to block the catalyst bed, and then cause the bed pressure drop to rise and the device operation period to shorten.

[0007] CN108102711B provides a combined process method for producing needle coke, which is that the raw oil enters a catalytic cracking device, the catalytic oil slurry obtained after reaction and separation is mixed with hydrogen and then enters a ebullated bed reactor, the heavy liquid product obtained after separation of the ebullated bed reactor reaction effluent enters a coking device, the oil gas generated by the coking reaction is separated to obtain gas, coking gasoline, coking diesel and coking wax oil, and the needle coke generated after the reaction period ends is deposited in the coking device. In the method of the present application, a hydrogen treatment catalyst is loaded in the catalytic section of the ebullated bed reactor, the specific surface area of the special catalyst in the present application is 120m 2 / g~300m 2 / g, preferably 160m 2 / g~280m 2 / g; the pore volume is 0.2mL / g~0.8mL / g, preferably 0.4mL / g~0.6mL / g; the average pore size is 8nm~13nm, preferably 9nm~11nm and the pore size distribution is as follows: the pore volume with a diameter of 4nm~10nm accounts for 70%~80% of the total pore volume, and the pore volume with a diameter of 15nm accounts for 5%~10% of the total pore volume. The process of the present application is complex, the pore volume and pore size of the catalyst used are small, which is not conducive to the diffusion of large molecules such as asphaltene, and the hydrogenation process conditions required are harsh, although the sulfur impurities in the catalytic oil slurry can be removed, but the aromatic hydrocarbons are lost.

[0008] CN114984970A provides a method for grading desolidification catalytic oil slurry hydrogenation desulfurization catalyst and application, the grading method comprises: when the sulfur content of desolidification catalytic oil slurry is ≥0.8%, the content of three-ring and four-ring aromatic hydrocarbons is ≥55%, the reactor is loaded with selective de-aromatic catalyst, direct desulfurization catalyst and hydrogenation desulfurization catalyst from top to bottom in turn; when the sulfur content of desolidification catalytic oil slurry is 0.35~0.8%, the content of three-ring and four-ring aromatic hydrocarbons is 40~55%, the reactor is loaded with direct desulfurization catalyst and hydrogenation desulfurization catalyst from top to bottom in turn. The grading method of the present application realizes high-efficiency desulfurization while retaining as much three-ring and four-ring aromatic hydrocarbons in the desolidification catalytic oil slurry as possible, and the desolidification catalytic oil slurry is subjected to hydrogenation desulfurization reaction to obtain high-quality needle coke raw material.

[0009] CN112342059A provides a method for blending catalytic cracking slurry oil in a delayed coking device. The catalytic cracking slurry oil enters a hydrogen treatment unit, which is provided with a hydrogen reaction zone and a gas-liquid separation zone. The hydrogen reaction zone is sequentially filled with hydrogen protective agent, hydrogen demetallization agent and / or hydrogen desulfurization agent along the flow direction. The particle size of the catalyst filled at the end part of the hydrogen demetallization agent or hydrogen desulfurization agent along the flow direction is not less than 1.6 mm. The catalytic cracking slurry oil is reacted with the catalyst in the hydrogen reaction zone in the presence of hydrogen-containing gas. The reaction effluent enters the gas-liquid separation zone for separation to obtain hydrogen-rich gas and liquid phase stream. The liquid phase stream enters the delayed coking device together with the delayed coking raw material for reaction. The reaction effluent is separated to obtain coking dry gas, liquefied gas, coking gasoline, coking diesel, coking wax oil and coke.

[0010] CN106622314A discloses a high-activity hydrofining catalyst and a preparation method thereof. The method uses water as a solvent to prepare a slurry containing silicon-phosphorus-aluminum oxide. A boron-containing compound, a group VIB metal compound and a group VIII metal compound are added to the slurry. A filter cake and a filtrate are obtained by filtration. The filtrate is mixed with SB powder and a peptizing agent to obtain a binder. The binder and the filter cake are sequentially subjected to rolling, molding, drying and calcination to obtain the hydrofining catalyst. The catalyst has small pore volume and fast deactivation rate.

[0011] CN1053458C discloses a residue hydrotreating catalyst and a preparation method thereof. The catalyst uses γ-Al2O3 as a carrier and loads group VIII and group VIB metal elements. The catalyst has a pore volume of 0.30-0.60 mL / g, a specific surface area of 120-200 m2 / g, an average pore diameter of 9.0-13.0 nm, and a ratio of pore volume with a pore diameter of 7.0-13.0 nm to total pore volume of more than 80%. The catalyst prepared by the method has a large specific surface area and a small proportion of large pores, poor resistance to metal poisoning and fast deactivation.

[0012] CN1417300A discloses a hydrogenation catalyst and a preparation method thereof. The preparation method of the catalyst includes impregnating a macroporous alumina carrier with a solution containing group VIB and group VIII metal compounds. The preparation method of the alumina carrier includes extruding a mixture of pseudoboehmite, acid, water and a co-extrusion agent, rapidly drying the extruded product at 90-300°C within 35 minutes, and calcining the product in an atmosphere containing water vapor at 600-800°C for at least 0.5 hour. The obtained alumina carrier has a pore distribution in which pores with a diameter of 10-20 nm account for 70-90% of the total pore volume.

[0013] CN1103009A discloses a preparation method of a heavy oil hydrodemetallization catalyst carrier, which is formed by mixing and kneading two aluminum hydroxide precursors with different pore size distributions, adding carbon black and a surfactant as a pore expander, and then drying and calcining to form a double-pore alumina carrier. SUMMARY

[0014] The present application aims to provide a catalytic oil slurry hydrodesulfurization catalyst and a preparation method thereof, which has a simple process, low cost, suitable pore size, high desulfurization effect and asphaltene conversion capacity, and good retention of tri- and tetra-cyclic aromatics.

[0015] To achieve the above-mentioned purpose, the present application provides a preparation method of a catalytic oil slurry hydrodesulfurization catalyst, which comprises the following steps: adding a co-extrusion agent and a pore expander to a macroporous pseudo-boehmite, mixing, then adding an acidic metal impregnation solution, kneading, shaping, drying and calcining to obtain the catalyst; the pore expander comprises isosorbide and polystyrene.

[0016] The preparation method of the catalytic oil slurry hydrodesulfurization catalyst, the isosorbide is added in an amount of 0.5wt to 6wt of the alumina content in the pseudo-boehmite, preferably 2wt to 4wt; the polystyrene is added in an amount of 2wt to 8wt of the alumina content in the pseudo-boehmite, preferably 4wt to 6wt.

[0017] The preparation method of the catalytic oil slurry hydrodesulfurization catalyst, the specific surface area of the macroporous pseudo-boehmite is ≥330m 2 / g, and the pore volume is ≥1.15ml / g.

[0018] The preparation method of the catalytic oil slurry hydrodesulfurization catalyst, the acidic metal impregnation solution comprises an active metal precursor, an inorganic acid and a complexing agent.

[0019] The preparation method of the catalytic oil slurry hydrodesulfurization catalyst, the complexing agent is an amino acid substance, and the addition amount is 1wt to 15wt of the pseudo-boehmite, preferably 3wt to 10wt.

[0020] The preparation method of the catalytic oil slurry hydrodesulfurization catalyst, the complexing agent is one or more of arginine, histidine and lysine.

[0021] The preparation method of the catalytic oil slurry hydrodesulfurization catalyst, the active metal in the acid metal impregnation solution is a group VIB and / or group VIII metal, which is a hydrogenation active metal component, preferably the active metal is at least one of Mo and W and at least one of Ni and Co. The precursor of Mo element is one or more of ammonium molybdate, sodium phosphomolybdate and ammonium phosphomolybdate; the precursor of W element is ammonium tungstate, tungsten nitrate and ammonium metatungstate; the precursor of Ni element is one or more of nickel nitrate, nickel acetate and basic nickel carbonate; the precursor of Co element is one or more of cobalt nitrate, basic nickel cobalt carbonate and cobalt naphthenate. In terms of oxides, molybdenum and / or tungsten accounts for 8wt%-20wt% of the total mass of the catalyst, and nickel and / or cobalt accounts for 2wt%-5wt% of the total mass of the catalyst.

[0022] The preparation method of the catalytic oil slurry hydrodesulfurization catalyst, the inorganic acid is one or more of phosphoric acid, nitric acid and hydrochloric acid, and the amount of the inorganic acid is not particularly limited, which is used to dissolve the active metal precursor, and a person skilled in the art can adjust it according to the actual situation.

[0023] The preparation method of the catalytic oil slurry hydrodesulfurization catalyst, the extrusion aid is a cellulose substance, and the addition amount is 1wt%-6wt% of the content of alumina in pseudo-boehmite, preferably 2wt%-4wt%, the cellulose substance is a commonly used substance in the art, and specifically can be methyl cellulose, ethyl cellulose and hydroxymethyl cellulose, which is not particularly limited in the present application.

[0024] The preparation method of the catalytic oil slurry hydrodesulfurization catalyst, the forming process is carried out by a screw extruder, the extrusion pressure is 15-50Mpa, and the shape of the catalyst can be changed as needed, such as cylinder, trilobes, quadrilobes and spheres; the drying temperature in the drying process is 100-200℃.

[0025] The preparation method of the catalytic oil slurry hydrodesulfurization catalyst, the calcination temperature is 500-900℃, preferably 680-850℃, and the calcination time is 0.5-6 hours.

[0026] To achieve the above-mentioned purpose, the present application also provides a catalyst prepared by the method, the pore volume is 0.60-0.95ml / g, the pores with a diameter of 15nm-20nm account for 40%-60% of the total pore volume, and the pores with a diameter of 20-30nm account for 20%-30% of the total pore volume.

[0027] The present application has the following beneficial effects:

[0028] The method provided by the present application firstly uses large-pore pseudo-boehmite, adds isosorbide and polystyrene, the polystyrene physically expands the pores by 15-20 nm, the hydroxyl groups in the isosorbide are combined with the hydroxyl groups of the large-pore pseudo-boehmite, and the isomerization carbon chain expands the pores by 20-30 nm. The increase of the proportion of the large pores helps the catalytic reaction conversion of the asphaltene and colloid macromolecules inside the pores of the catalyst, and improves the desulfurization rate; the addition of the amino acid complexing agent improves the dispersion and acidity of the metal salt, and retains the triphenyl and tetraphenyl aromatic hydrocarbons.

[0029] The catalyst prepared according to the method provided by the present application has higher desulfurization effect and asphaltene conversion capacity, and better retains the triphenyl and tetraphenyl aromatic hydrocarbons. DETAILED DESCRIPTION

[0030] The present application is specifically described below through examples. It is necessary to point out here that the following examples are only used for further illustrating the present application, and cannot be understood as limiting the protection scope of the present application, and the skilled in the art can make some non-essential improvements and adjustments to the present application according to the above content of the present application.

[0031] Example 1

[0032] Pseudo-boehmite dry gel powder 500g (specific surface 330m 2 / g, pore volume 1.18ml / g) is weighed, 3.5g of methyl cellulose (1wt%), 1.8g of isosorbide (0.5wt%) and 7g of polystyrene (2wt%) are added, and mixed uniformly; 500ml of Mo-Ni-P solution (containing MoO3 10wt%, NiO 5wt% in the catalyst) is added and kneaded, wherein the Mo-Ni-H3PO4 solution is configured as follows: 50g of molybdenum trioxide is added to 100ml of H3PO4 solution and stirred to completely dissolve, 32g of basic nickel carbonate is added and stirred to completely dissolve, 15g of arginine is added and stirred to completely dissolve, and water is added to 500ml; then a four-leaf clover shape with a particle size of 1.4-1.6mm is extruded on a front extrusion single screw extruder, the extrusion pressure is 15MPa, 100°C drying for 3 hours, and calcination at 700°C for 6 hours, to obtain catalyst A1. The physical properties of the catalyst are shown in Table 1.

[0033] Example 2

[0034] Pseudo-boehmite dry gel powder 500g (specific surface 330m 2 / g, pore volume 1.18 ml / g), 20 g methyl cellulose (6 wt%), 20 g isosorbide (6 wt%) and 10 g polystyrene (3 wt%) were added and mixed uniformly; 500 ml Mo-Ni-P solution (containing MoO3 10 wt%, NiO 5 wt% in the catalyst) was added and kneaded, wherein the Mo-Ni-H3PO4 solution was prepared as follows: 50 g molybdenum trioxide was added into 100 ml H3PO4 solution and stirred until dissolved completely, 32 g basic nickel carbonate was added and stirred until dissolved completely, 45 g lysine was added and stirred until dissolved completely, and water was added to make up to 500 ml; then the mixture was extruded into cylindrical shape with a diameter of 1.6 mm on a front extrusion single screw extruder, the extrusion pressure was 25 MPa, the mixture was dried at 120°C for 3 hours, and then calcined at 500°C for 6 hours to obtain catalyst A3. The properties of the catalyst are shown in Table 1.

[0035] Example 3

[0036] 500 g pseudo-boehmite dry gel powder (specific surface 330 m 2 / g, pore volume 1.18 ml / g), 20 g methyl cellulose (6 wt%), 20 g isosorbide (6 wt%) and 10 g polystyrene (3 wt%) were added and mixed uniformly; 500 ml Mo-Ni-P solution (containing MoO3 10 wt%, NiO 5 wt% in the catalyst) was added and kneaded, wherein the Mo-Ni-H3PO4 solution was prepared as follows: 50 g molybdenum trioxide was added into 100 ml H3PO4 solution and stirred until dissolved completely, 32 g basic nickel carbonate was added and stirred until dissolved completely, 45 g lysine was added and stirred until dissolved completely, and water was added to make up to 500 ml; then the mixture was extruded into cylindrical shape with a diameter of 1.6 mm on a front extrusion single screw extruder, the extrusion pressure was 25 MPa, the mixture was dried at 120°C for 3 hours, and then calcined at 500°C for 6 hours to obtain catalyst A3. The properties of the catalyst are shown in Table 1.

[0037] Example 4

[0038] 500 g pseudo-boehmite dry gel powder (specific surface 330 m 2(gibbsite, specific surface 330 m2 / g, pore volume 1.18 ml / g), 10 g methyl cellulose (3 wt%), 10 g isosorbide (3 wt%) and 28 g polystyrene (8 wt%) were added and mixed well; 500 ml Mo-Ni-P solution (containing MoO310 wt%, NiO 5 wt% in the catalyst) was added and kneaded, wherein the Mo-Ni-H3PO4 solution was prepared as follows: 50 g of molybdenum trioxide was added into 200 ml of H3PO4 solution and stirred until dissolved completely, 32 g of basic nickel carbonate was added and stirred until dissolved completely, 50 g of serine was added, and water was added to make up to 500 ml; then the mixture was extruded into a trilobe shape with a diameter of 1.6 mm on a front-extrusion single-screw extruder, dried at 120°C for 3 hours, and then calcined at 850°C for 5 hours to obtain catalyst A4. The catalyst properties are shown in Table 1.

[0039] Example 5

[0040] 500 g of pseudo-boehmite dry gel powder (specific surface 330 m 2 (gibbsite, specific surface 330 m2 / g, pore volume 1.18 ml / g), 10 g methyl cellulose (3 wt%), 10 g isosorbide (3 wt%) and 28 g polystyrene (8 wt%) were added and mixed well; 500 ml Mo-Ni-P solution (containing MoO310 wt%, NiO 5 wt% in the catalyst) was added and kneaded, wherein the Mo-Ni-H3PO4 solution was prepared as follows: 50 g of molybdenum trioxide was added into 200 ml of H3PO4 solution and stirred until dissolved completely, 32 g of basic nickel carbonate was added and stirred until dissolved completely, 50 g of serine was added, and water was added to make up to 500 ml; then the mixture was extruded into a trilobe shape with a diameter of 1.6 mm on a front-extrusion single-screw extruder, dried at 120°C for 3 hours, and then calcined at 850°C for 5 hours to obtain catalyst A4. The catalyst properties are shown in Table 1.

[0041] Example 6

[0042] 500 g of pseudo-boehmite dry gel powder (specific surface 330 m 2A6. The preparation of catalyst A6 is as follows: 25 g of molybdenum trioxide and 16 g of basic nickel carbonate are added to a slurry containing silicon-containing phosphorus-containing alumina, and a filter cake and a filtrate are obtained by filtration. The filtrate is mixed with SB powder and a peptizing agent to obtain a binder. The binder and the filter cake are extruded into a trilobal shape with a diameter of 1.6 mm on a front-extrusion single-screw extruder, dried at 120°C for 3 hours, and then calcined at 800°C for 5 hours to obtain catalyst A6. The properties of the catalyst are shown in Table 1.

[0043] Comparative Example 1

[0044] According to the method described in Chinese Patent CN106622314A, 25 g of molybdenum trioxide and 16 g of basic nickel carbonate are added to a slurry containing silicon-containing phosphorus-containing alumina, and a filter cake and a filtrate are obtained by filtration. The filtrate is mixed with SB powder and a peptizing agent to obtain a binder. The binder and the filter cake are extruded into a trilobal shape with a diameter of 1.6 mm on a front-extrusion single-screw extruder, dried at 120°C for 3 hours, and then calcined at 800°C for 5 hours to obtain catalyst B1. The properties of the catalyst are shown in Table 1.

[0045] Comparative Example 2

[0046] According to the method described in Chinese Patent CN1053458C, 500 g of pseudo-boehmite dry powder is added to 80 g of an aqueous ammonia solution (containing 3% ammonia water), kneaded for 30 min, and then 240 g of an aqueous acetic acid solution is added and kneaded for 40 min. The mixture is extruded and shaped, and then calcined at 800°C to obtain a carrier. The carrier is impregnated with 150 ml of a Mo-Ni-P solution (containing 10% MoO3 and 5% NiO), wherein the Mo-Ni-H3PO4 solution is prepared as follows: 25 g of molybdenum trioxide is added to 100 ml of an H3PO4 solution and stirred until completely dissolved, 16 g of basic nickel carbonate is then added and stirred until completely dissolved, and then water is added to make up to 150 ml. After the impregnation is completed, the excess solution is filtered off, the mixture is dried at 120°C for 3 hours, and then calcined at 500°C for 4 hours to obtain catalyst B2.

[0047] Comparative Example 3

[0048] According to the method described in Chinese patent CN1417300A, 300 g of pseudo-boehmite was weighed, mixed with 3.9 g of 65 wt% nitric acid, 3 g of sesbania powder and 120 g of deionized water, and extruded into 1.6 mm clover shape on an extruder. After drying at 110°C, the dried molding was calcined at 750°C for 5 h by passing 100% water vapor to obtain the carrier. Then, 150 ml of Mo-Ni-P solution (containing 10 wt% of MoO3 and 3.5 wt% of NiO) was added for impregnation, wherein the Mo-Ni-H3PO4 solution was prepared as follows: 25 g of molybdenum trioxide was added to 100 ml of H3PO4 solution and stirred until completely dissolved, then 16 g of basic nickel carbonate was added and stirred until completely dissolved, and then water was added to 150 ml. After the impregnation was completed, the excess solution was filtered off, dried at 120°C for 3 hours, and then calcined at 500°C for 4 hours to obtain catalyst B3.

[0049] Comparative Example 4

[0050] Pseudo-boehmite dry gel powder 500 g (specific surface area 330 m 2 / g, pore volume 1.18 ml / g) was weighed, 3.5 g of methyl cellulose (1 wt%), 2 g of sorbitol (0.5 wt%) and 7 g of polystyrene (2 wt%) were added and mixed uniformly. Then, 500 ml of Mo-Ni-P solution (containing 10 wt% of MoO3 and 5 wt% of NiO in the catalyst) was added for kneading, wherein the Mo-Ni-H3PO4 solution was prepared as follows: 50 g of molybdenum trioxide was added to 100 ml of H3PO4 solution and stirred until completely dissolved, then 32 g of basic nickel carbonate was added and stirred until completely dissolved, then 15 g of arginine was added and stirred until completely dissolved, and then water was added to 500 ml. Then, the mixture was extruded into clover shape with a particle size of 1.4-1.6 mm on a front extrusion single screw extruder, the extrusion pressure was 15 MPa, and then dried at 100°C for 3 hours, and then calcined at 700°C for 6 hours to obtain catalyst B4. The catalyst properties are shown in Table 1.

[0051] Table 1 Catalyst properties

[0052]

[0053] The results in Table 1 show that the specific surface area and pore volume of the catalyst prepared by the method described in the examples of the present application are both greater than those of the comparative examples, and the content of pores with a pore size of 15-20 nm and 20-30 nm is significantly higher than that of the comparative examples.

[0054] The catalysts in Table 1 were evaluated for activity and stability, the evaluation conditions are shown in Table 2, and the evaluation results are shown in Table 3.

[0055] Table 2 Catalyst evaluation conditions

[0056] Catalytic slurry properties Density (20°C) / g-cm -3 ]] 1.078 Sulfur, wt% 0.8 Tricyclics + tetracyclics, wt% 47 Asphaltene, wt% 6.8 Process conditions Reaction temperature, °C 385 H2 partial pressure, MPa 8 volume space velocity, h -1 ]]> 0.8 H2 / oil ratio 700

[0057] Table 3 Evaluation results

[0058] Catalyst A1 A2 A3 A4 A5 A6 B1 B2 B3 B4 Sulfur content, wt% 0.39 0.34 0.38 0.36 0.37 0.35 0.40 0.39 0.41 0.41 Tricyclics + tetracyclics, wt% 46.2 47.3 46.0 46.3 45.8 46.4 41.5 42.3 41.9 44.5 Asphaltene, wt% 2.0 1.8 2.0 2.1 2.0 1.9 2.8 2.9 2.6 2.4

[0059] Of course, the present application also has other various embodiments, and those skilled in the art can make various corresponding changes and modifications according to the present application without departing from the spirit and essence of the present application, but these corresponding changes and modifications should all belong to the protection scope of the claims of the present application.

Claims

1. A method for preparing a catalytic slurry hydrodesulfurization catalyst, characterized in that, Includes the following steps: A catalyst is obtained by mixing macroporous pseudoboehmite with an extrusion aid and a pore expander, followed by the addition of an acidic metal impregnation solution, kneading, molding, drying, and calcining; the pore expander includes isosorbide and polystyrene. The catalyst has a pore volume of 0.60~0.95 ml / g, with pores of 15nm~20nm accounting for 40%~60% of the total pore volume and pores of 20~30nm accounting for 20%~30% of the total pore volume.

2. The preparation method of the catalytic slurry hydrodesulfurization catalyst according to claim 1, characterized in that, The amount of isosorbide added is 0.5wt to 6wt% of the alumina content in the boehmite; the amount of polystyrene added is 2wt% to 8wt% of the alumina content in the boehmite.

3. The method for preparing the catalytic slurry hydrodesulfurization catalyst according to claim 1, characterized in that, The specific surface area of ​​the macroporous pseudoboehmite is ≥330 μm. 2 / g, pore volume ≥1.15ml / g.

4. The method for preparing the catalytic slurry hydrodesulfurization catalyst according to claim 1, characterized in that, The acidic metal impregnation solution includes an active metal precursor, an inorganic acid, and a complexing agent.

5. The method for preparing the catalytic slurry hydrodesulfurization catalyst according to claim 4, characterized in that, The complexing agent is an amino acid-based substance, and the amount added is 1wt%~15wt% of boehmite.

6. The method for preparing the catalytic slurry hydrodesulfurization catalyst according to claim 5, characterized in that, The complexing agent is one or more of arginine, histidine, and lysine.

7. The method for preparing the catalytic slurry hydrodesulfurization catalyst according to claim 4, characterized in that, The inorganic acid is one or more of phosphoric acid, nitric acid, and hydrochloric acid.

8. The method for preparing the catalytic slurry hydrodesulfurization catalyst according to claim 4, characterized in that, The active metal is at least one of Mo and W, and at least one of Ni and Co.

9. The method for preparing the catalytic slurry hydrodesulfurization catalyst according to claim 1, characterized in that, The extrusion aid is a cellulose-based substance, and the amount added is 1wt% to 6wt% of the alumina content in the pseudoboehmite.

10. The method for preparing the catalytic slurry hydrodesulfurization catalyst according to claim 1, characterized in that, The roasting temperature is 500~900℃, and the roasting time is 0.5~6 hours.

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