Residual oil hydrogenation carbon residue removal catalyst as well as preparation method and application thereof

Abstract

The invention discloses a residual oil hydrogenation carbon residue removal catalyst as well as a preparation method and application thereof. The catalyst comprises a carrier and an active metal component, the carrier is aluminum oxide containing silicon and gallium; on the basis of the weight of the catalyst, the mass content of the carrier is 74%-83%, the content of the group VIII metal in terms of oxide is 2%-6%, and the content of molybdenum in terms of oxide is 15%-24%; the active metal component comprises Mo and a group VIII metal element; the Mo comprises + 5 valence Mo; the group VIII metal element exists in the catalyst in the form of metal phosphide. The catalyst has good hydrogenation carbon residue removal performance, can deeply remove polycyclic aromatic hydrocarbon and heterocyclic aromatic hydrocarbon in residual oil and reduce precursors of carbon residues, and has good stability.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of preparation of hydro-decarbon residue catalysts, and particularly relates to a hydro-decarbon residue catalyst for residual oil and a preparation method and application thereof. BACKGROUND

[0002] In recent years, the difficulty of crude oil exploration has increased year by year worldwide, and the conventional crude oil resources have been significantly reduced. The crude oil extracted is becoming heavier and poorer in quality. However, the demand for oil products in the modern economic society is rapidly growing, leading to an increasingly prominent contradiction between supply and demand of crude oil in China, and the number of imported crude oil has to be gradually increased, which forces the refineries in China to process more heavy and poor quality crude oil. How to solve the problem of light processing of residual oil is a technical problem that must be faced by the refineries to improve the overall economic efficiency.

[0003] The carbon residue reduction rate is an important indicator of residual oil hydrogenation process. The carbon residue value of residual oil indicates its tendency to coke during processing. Studies have shown that condensed aromatics with five rings and above are precursors of carbon residue, and the carbon residue value in resin and asphaltene is the highest, which is related to the fact that they contain a large amount of condensed aromatic and heterocyclic aromatic hydrocarbons. Therefore, in addition to improving the hydrogenation capacity of the catalyst for carbon residue precursors, the acidity of the catalyst also needs to be appropriately increased to promote the hydrogenation cracking and ring-opening, isomerization reactions of large molecules. By deep carbon residue removal treatment of residual oil, the subsequent processing properties of residual oil can be significantly changed, providing convenient conditions for the hydrogenation cracking pretreatment of residual oil.

[0004] CN117000260A discloses a hydro-decarbon residue catalyst and a preparation method thereof. The catalyst includes a catalyst body, a catalyst secondary outer layer and a large-pore alumina layer, and the catalyst body includes an alumina carrier and active components of molybdenum and nickel. The active metals of the catalyst are in a non-uniform distribution. The outermost layer of the catalyst does not contain active metals and is a layer of large-pore alumina, and the secondary outer layer contains less active metals and has larger pores. The catalyst body is prepared by impregnating a microemulsion containing active metals. The catalyst has poor acidity, which is insufficient to promote the hydrogenation cracking and ring-opening, isomerization reactions of large molecules, and the carbon residue removal performance of the catalyst still needs to be further improved.

[0005] CN103785397A discloses a kind of hydrogenation to remove residual carbon catalyst and preparation method thereof.The catalyst is with alumina as carrier, with Mo, Ni as active component, preparation method includes the following steps: (1) acidic aluminum salt aqueous solution is neutralized after being reacted with alkali metal aluminate aqueous solution, and then pH value of slurry is adjusted by passing into alkaline precipitant or alkali aluminate aqueous solution to carry out aging;(2) the material after aging of step (1) is filtered, washed, dried, and then ammonium aluminum carbonate is added to form;(3) the material after forming is loaded with active component, dried and calcined to obtain hydrogenation to remove residual carbon catalyst.The acid of the catalyst in macropore is stronger, hydrogenation reaction is more intense, and the generated carbon deposit and metal deposit are easy to block pore and cover hydrogenation active site. SUMMARY

[0006] In view of the deficiencies of the prior art, the present application provides a residual carbon removal catalyst for residue oil, a preparation method and application thereof.The residual carbon removal catalyst for residue oil has good residual carbon removal performance, can deeply remove polycyclic aromatic hydrocarbons and heterocyclic aromatic hydrocarbons in residue oil, reduce precursors of residual carbon, and has good stability.

[0007] The first aspect of the present application provides a residual carbon removal catalyst for residue oil, comprising a carrier and an active metal component;The carrier is alumina containing silicon and gallium;The mass content of the carrier is 74% to 83% based on the weight of the catalyst, the content of the group VIII metal is 2% to 6% in terms of oxide, and the content of molybdenum is 15% to 24% in terms of oxide;The active metal component includes Mo and group VIII metal elements;The Mo includes +5 valence Mo;The group VIII metal elements exist in the catalyst in the form of metal phosphide.

[0008] According to the present application, in the carrier, silicon and gallium account for 0.2% to 4.5% of the mass of alumina in terms of SiO2 and Ga2O3, and the mass ratio of silicon and gallium is 2:1 to 5:1 in terms of SiO2 and Ga2O3.

[0009] According to the present application, the properties of the catalyst are as follows: the specific surface area is 150 to 260 m 2 / g, the pore volume is 0.3 to 1.0 mL / g, the total acid amount is 0.2 to 0.6 mmol / g, and the ratio of B acid amount to L acid amount is 0.4 to 0.7.

[0010] According to the present application, the pore size distribution of the catalyst is as follows: the ratio of the pore volume of pores with a pore diameter of <10 nm to the total pore volume is 5% to 10%, the ratio of the pore volume of pores with a pore diameter of 10 to 20 nm to the total pore volume is 62% to 67%, and the ratio of the pore volume of pores with a pore diameter of >20 nm to the total pore volume is 23% to 33%.

[0011] According to the present application, the active metal component comprises Mo and Group VIII metal elements; the Mo comprises +5 valence Mo; and the Group VIII metal elements exist in the catalyst in the form of metal phosphides.

[0012] According to the present application, in the catalyst, the Mo further comprises +4 valence Mo and +6 valence Mo.

[0013] According to the present application, in the catalyst, the +5 valence Mo accounts for 50% or more of the total Mo in terms of atoms, preferably 55% to 80%. As non-limiting examples, the +5 valence Mo accounts for any one of 65%, 68%, 70%, 72%, 75%, and 78% of the total Mo in terms of atoms.

[0014] According to the present application, in the catalyst, the sum of the +4 valence Mo and the +6 valence Mo accounts for 20% to 45% of the total Mo in terms of atoms. Further preferably, in the catalyst, the +4 valence Mo accounts for 10% to 43% of the total Mo in terms of atoms; and the +6 valence Mo accounts for 2% to 10% of the total Mo in terms of atoms. As non-limiting examples, the +4 valence Mo accounts for any one of 15%, 20%, 22%, 25%, 32%, 35%, 38%, and 40% of the total Mo in terms of atoms; and the +6 valence Mo accounts for any one of 4%, 6%, 8%, and 9% of the total Mo in terms of atoms.

[0015] According to the present application, in the catalyst, the +5 valence Mo is preferably molybdenum pentachloride; the +4 valence Mo is preferably molybdenum disulfide; and the +6 valence Mo is preferably molybdenum oxide.

[0016] According to the present application, the Group VIII metal elements are selected from one or more of Fe, Co, and Ni, preferably at least one of Co and Ni, and more preferably Ni.

[0017] The second aspect of the present application provides a preparation method of the above-mentioned residual carbon removal catalyst for residual carbon removal of residual oil, comprising:

[0018] (1) mixing a molybdenum source, a sulfur source, and water to obtain a first impregnation solution, and impregnating the first impregnation solution on a carrier to obtain a catalyst intermediate I after drying;

[0019] (2) contacting and reacting the catalyst intermediate I in step (1) with chlorine to obtain a catalyst intermediate II;

[0020] (3) impregnating a second impregnation solution containing a nickel source and a phosphorus source on the catalyst intermediate II in step (2), and performing maintenance, drying, and calcination to obtain the catalyst.

[0021] According to the present application, in step (1), the preparation method of the carrier comprises:

[0022] (11) performing a precipitation reaction of the acidic aluminum salt aqueous solution and the basic aluminum salt aqueous solution in parallel flow to obtain a slurry;

[0023] (12) adding a basic solution and a water-soluble polymer to the slurry of step (11) to perform a secondary reaction, aging, drying, and obtaining material A;

[0024] (13) impregnating activated carbon with a solution containing silicon and gallium to obtain material B;

[0025] (14) kneading and molding material A obtained in step (12) and material B obtained in step (13), drying, and calcining to obtain a carrier.

[0026] According to the present application, in the preparation method of the carrier, the acidic aluminum salt in step (11) is at least one of aluminum sulfate, aluminum chloride, or aluminum nitrate, and the concentration of the acidic aluminum salt solution is 20-100 g / 100 mL in terms of Al2O3. The basic aluminum salt is at least one of sodium aluminate or potassium aluminate, and the concentration of the basic aluminum salt solution is 20-100 g / 100 mL in terms of Al2O3. The ratio of the volume rate of the acidic aluminum salt solution to the basic aluminum salt solution is 1:1-3:1. The pH value of the reaction in step (11) is controlled to be 1.2-1.8, and the pH value is adjusted by adding at least one of hydrochloric acid, nitric acid, or sulfuric acid. The concurrent flow reaction time in step (11) is 60-180 min, and the reaction temperature is 60-90°C. The reaction is preferably performed under stirring, and the stirring rate is 100-500 rad / min, preferably 150-450 rad / min.

[0027] According to the present application, in the preparation method of the carrier, the basic solution in step (12) is a solution of at least one of sodium hydroxide or sodium carbonate, and the concentration of the basic solution is 50-70 g / 100 mL. The amount of the water-soluble polymer added is 0.1%-5%, preferably 0.5%-3%, of the mass of the slurry obtained in step (11) in terms of aluminum oxide. The pH value of the secondary reaction in step (12) is controlled to be 8.5-9.7. The reaction time of the secondary reaction in step (12) is 60-120 min, and the reaction temperature is 120-180°C. The reaction is preferably performed under stirring, and the stirring rate is 100-500 rad / min, preferably 250-500 rad / min. The water-soluble polymer is at least one of polyvinyl alcohol, polyethylene oxide, or polyvinyl pyrrolidone. The weight average molecular weight of the water-soluble polymer is 10,000-40,000.

[0028] According to the present application, in the preparation method of the carrier, the aging temperature in step (12) is 200-500°C, and the aging time is 2-4 hours. After aging, washing with deionized water is preferred, and further preferred is washing at 50-90°C. The drying condition is 120-160°C, and the drying time is 2-6 hours.

[0029] According to the present application, in the preparation method of the carrier, the specific surface area of the activated carbon in step (13) is 2000-3000 m 2 / g, and the particle size is 2-15 μm.

[0030] According to the present application, in the preparation method of the carrier, the solution containing silicon and gallium in step (13) is an ethanol solution containing silicate and gallium nitrate, the silicate is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate, the concentration of silicon in the solution containing silicon and gallium is 0.1-5 g / mL as SiO2, and the mass ratio of silicon and gallium in the solution containing silicon and gallium is 2:1-5:1 as SiO2 and Ga2O3. The amount of the solution containing silicon and gallium is 30%-50% of the saturated water absorption of the activated carbon by volume. The impregnation in step (13) is preferably carried out by spraying.

[0031] According to the present application, in the preparation method of the carrier, in step (13), the silicon and gallium introduced into the activated carbon from the solution containing silicon and gallium account for 2%-9% of the mass of the activated carbon as SiO2 and Ga2O3.

[0032] According to the present application, in the preparation method of the carrier, in step (14), the mass ratio of the material A obtained in step (12) to the material B obtained in step (13) is 2:1-10:1 as Al2O3 and activated carbon.

[0033] According to the present application, in the preparation method of the carrier, in step (14), a forming agent such as a deagglomerating agent or a binder can be added in the preparation of the carrier according to the actual forming requirement. The forming can be carried out by a conventional forming method such as extrusion, tabletting, etc. The drying conditions after forming are as follows: the drying temperature is 100-160 ℃, and the drying time is 2-10 hours. The calcination conditions are as follows: the calcination temperature is 600-750 ℃, and the calcination time is 2-10 hours. The deagglomerating agent can be amaranth powder, and the amount is 1%-5% of the mass of the carrier. The binder is one or more of nitric acid, formic acid, acetic acid, citric acid, methyl cellulose and polyethylene glycol, and the amount is 0.5%-3.0% of the mass of the carrier.

[0034] According to the present application, in the preparation method of the catalyst, the molybdenum source in step (1) is selected from at least one of ammonium dimolybdate, ammonium tetramolybdate dihydrate and ammonium heptamolybdate tetrahydrate; the sulfur source is selected from at least one of thiocyanic acid, ammonium sulfide, thioacetamide and sodium thiosulfate; and the mass ratio of the molybdenum source to the sulfur source is 3-5:2-4. The mass content of the molybdenum source in the first impregnation solution is 25wt%-45wt%.

[0035] According to the present application, in the preparation method of the catalyst, the impregnation in step (1) can be carried out by spraying impregnation, and the impregnation can be carried out by saturated impregnation or supersaturated impregnation. The drying condition is 100-140℃ for 4-8h.

[0036] According to the present application, in the preparation method of the catalyst, in step (2), the purity of the chlorine gas is 96% or more by volume fraction. The flow rate of the chlorine gas is 2.7-6.8mL / (min·g catalyst intermediate I); and / or, the reaction condition is as follows: the reaction temperature is 300-400℃, and the reaction time is 40-90min.

[0037] According to the present application, in the preparation method of the catalyst, in step (3), the nickel source is a soluble salt, such as at least one of nitrate, monohydrogen phosphate, dihydrogen phosphate; and the phosphorus source is at least one of ammonium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate and phytic acid. In the second impregnation solution, the molar ratio of the nickel source (calculated as metal element) to the phosphorus source (calculated as phosphorus element) is 0.3-3:1. In the second impregnation solution, the mass content of the nickel source is 40wt%-78wt%.

[0038] According to the present application, in the preparation method of the catalyst, in step (3), the impregnation can be carried out by spraying impregnation, and the impregnation can be carried out by saturated impregnation or supersaturated impregnation.

[0039] According to the present application, in the preparation method of the catalyst, in step (3), the aging is that the impregnated sample is placed in a closed condition at 10-30℃ for 6-12h, and the pressure of the aging is not particularly limited, and can be autogenous pressure; and / or, the drying condition is 100-160℃ for 1-8h. The calcination condition is 480-550℃ for 4-8h. The drying atmosphere is an oxygen-containing atmosphere. The calcination atmosphere is selected from any one of nitrogen atmosphere, inert gas atmosphere, hydrogen / nitrogen atmosphere and hydrogen / inert gas atmosphere, wherein the hydrogen volume fraction in the hydrogen / nitrogen atmosphere and the hydrogen / inert gas atmosphere is 5%-50%.

[0040] The third aspect of the present application provides the application of the above-mentioned residual oil hydro-decarbonization catalyst or the residual oil hydro-decarbonization catalyst prepared by the above-mentioned preparation method in residual oil hydro-processing.

[0041] According to the present application, the application condition is that the reaction temperature is 350-480℃; the reaction pressure is 9-16MPa; the liquid hourly space velocity is 0.5-2.2h -1 ; and the hydrogen / oil volume ratio is 450:1-1200:1. The reaction pressure is the total pressure.

[0042] According to the present application, the catalyst needs to be sulfided before application. The process of sulfidation is that the catalyst is contacted with a sulfidation liquid and hydrogen for sulfidation. The sulfidation liquid comprises a solvent and a sulfur-containing solute; the mass content of the sulfur-containing solute in the sulfidation liquid is 4.0wt%-15.0wt%; the sulfur-containing solute has a solubility of more than 10wt% in the solvent at normal temperature, and is a sulfur-containing compound that can react with hydrogen to produce H2S under high temperature conditions. The sulfur-containing solute comprises at least one of carbon disulfide, dimethyl sulfide, dimethyl disulfide (DMDS), n-butyl mercaptan, etc. The solvent is straight-run diesel oil with a nitrogen content of not more than 200μg / g. The purity of the hydrogen is not less than 90v%.

[0043] According to the present application, the sulfidation conditions can adopt conventional sulfidation conditions. Preferably, the sulfidation conditions are as follows: the sulfidation process comprises low-temperature sulfidation and high-temperature sulfidation. The low-temperature sulfidation stage: temperature is raised to 150-230℃, and kept constant for 3-8h; the high-temperature sulfidation stage: temperature is raised to 260-310℃, and kept constant for 3-8h. The temperature raising rate for the low-temperature sulfidation stage is 8-12.0℃ / h. The temperature raising rate for the high-temperature sulfidation stage is 5-12.0℃ / h, the flow rate of the sulfidation liquid is 15-30mL / (h.g catalyst), the hydrogen pressure is 7.0-16.0MPa, and the hydrogen flow rate is 80-130mL / (min.g catalyst).

[0044] Compared with the prior art, the present application has the following advantages:

[0045] 1. The catalyst of the present application comprises a carrier and an active metal component. The carrier is alumina containing silicon and gallium; the active metal component comprises Mo and a Group VIII metal element; the Mo comprises +5 valence Mo; and the Group VIII metal element exists in the catalyst in the form of metal phosphide.

[0046] In the catalyst of the present application, the +5 valence Mo is more easily sulfided to +4 valence MoS2 in the sulfidation process, which accelerates the rate of Mo forming MoS2, and leads to the formation of more Ni-Mo-S(II) and Brim active sites with MoS2 as the skeleton and the metal nickel on the surface. In the catalyst of the present application, an appropriate amount of transition metal phosphide is also formed, which is a compound formed by the insertion of phosphorus atoms into the metal lattice, and has the characteristics of noble metals. Because the phosphorus atom is large, it is easier for the phosphorus atom to form an octahedral coordination structure around it after bonding with the transition metal, so it is located at the center position, and thus it is different from the layered structure of sulfides, and the phosphide structure is closer to a spherical shape, which exposes more active center sites in the catalytic reaction, so that the macromolecular reactants are more easily close to the active sites on the surface of the catalyst. The carrier and the active metal of the catalyst of the present application jointly act on the reaction of residual oil treatment, and have good hydrodesulfurization and hydrodecarbon performance.

[0047] 2、The catalyst of the present application is prepared by first impregnating a carrier with an impregnation solution containing a molybdenum source and a sulfur source to obtain an intermediate I, then contacting the intermediate I with chlorine to obtain an intermediate II, and finally impregnating the intermediate II with a nickel-phosphorus impregnation solution.

[0048] 3、In the preparation of the catalyst of the present application, the uniform particles are formed by controlling the process and conditions of the concurrent gelation of the acidic aqueous aluminum salt solution and the basic aqueous aluminum salt solution in the primary reaction, and the water-soluble polymer and the aluminum hydroxide sol form a physical cross-linking bridge to bind the movement of the particles and avoid the collision and adhesion of the sol-gel molecules or ions in the secondary reaction by adding a basic solution and a water-soluble polymer, so that the gel particles are arranged in an ordered crystal precipitation or a colloidal particle with a crystal structure, which is conducive to the formation of larger pseudo-boehmite particles and the pseudo-boehmite with higher crystallinity, so that the final obtained alumina carrier has a larger pore volume, pore size, concentrated pore distribution, and good mechanical strength, which is beneficial to improve the activity and stability of the catalyst.

[0049] 4、In the preparation of the catalyst of the present application, the presence of the water-soluble polymer in the active carbon containing silicon and gallium and the alumina dry gel is conducive to the formation of a well-connected pore structure when the two are kneaded and formed into a carrier, the introduction of silicon and gallium can form Si-O-Ga bonds at large pores, which can effectively prevent the formation of strong Mo(W)-O-Al bonds during the subsequent impregnation of active metals, and help the uniform distribution of active components, and Ga is a weak electron acceptor, the method of the present application can also weaken the acidity of the catalyst at large pores to some extent, improve the carbon deposition resistance and sintering resistance of the corresponding catalyst, and improve the activity and stability of the catalyst.

[0050] 5、The catalyst of the present application is suitable for residue hydroprocessing reaction, has significantly higher carbon deposition resistance and sintering resistance, high activity, and good stability. DETAILED DESCRIPTION

[0051] The technical solutions and effects of the present application are further illustrated by the following examples, but the following examples do not constitute a limitation on the method of the present application.

[0052] In the present application, % is mass fraction unless otherwise specified.

[0053] In the present application, the specific surface area, pore volume, and pore distribution are measured by an ASAP2420 full-automatic physical adsorption instrument of American Micromeritics Company.

[0054] In the present application, the operating conditions of XPS are: light source: Mg K Alpha, energy step: 0.05eV, scanning range: 220-240eV (molybdenum), 850-880eV (nickel), 280-300eV (carbon). In the analysis of the valence state of molybdenum, the binding energy at 232-233eV is the +6 valence molybdenum species, the binding energy at 230-232eV is the +5 valence molybdenum species, and the binding energy at 228-230eV is the +4 valence molybdenum species. By the peak area of the three peaks, the respective proportions of +6 valence, +5 valence and +4 valence molybdenum in total Mo can be calculated respectively.

[0055] In the present application, the catalyst composition is tested by spectrophotometry. The testing instrument is Lambda 365 ultraviolet spectrophotometer.

[0056] In the present application, the determination of total acid, L acid and B acid is carried out by infrared spectroscopy, and the instrument is Nicot Fourier infrared spectrometer-6700 of the United States.

[0057] In the present application, HDCCR is hydrogenated residual carbon removal; HDS is hydrogenated desulfurization.

[0058] Example 1

[0059] (1) Preparation of the carrier:

[0060] A 3L reaction kettle was charged with 3L of clean water and heated to 60℃, and 35g / 100mL of aluminum sulfate solution and 23g / 100mL of sodium metaaluminate were continuously added to the reaction kettle at flow rates of 30mL / min and 20mL / min respectively, and the reaction pH was controlled to be 1.4 by adding hydrochloric acid during the reaction, and the reaction time was 70min. After the reaction was completed, the temperature was adjusted to 120℃, the stirring speed was adjusted to 300rad / min, polyvinyl alcohol (molecular weight 25000) (1.2% of the content of aluminum oxide) was introduced into the reaction kettle, and then a 55g / 100mL sodium carbonate solution was introduced into the reaction kettle for secondary reaction, the reaction pH was adjusted to 9, the reaction time was 90min, and the temperature was aged at 260℃ for 2 hours. After filtration, washing with hot water at 90℃ until neutral, and drying at 130℃ for 3 hours, pseudo-boehmite was obtained.

[0061] Take 75 grams of activated carbon with a particle size of 4 μm and place it in a spray-impregnation rolling pot. While rotating, spray-impregnate the activated carbon in the rolling pot with 22.5 ml of an ethanol solution containing 3 grams of tetraethyl orthosilicate and 1.5 grams of gallium oxide in the form of gallium nitrate in an atomized manner. After impregnation, mix the activated carbon with 348 grams of pseudoboehmite (alumina mass content of 69.1%), 7.2 grams of sesbania powder, 3.58 grams of nitric acid, 2.4 grams of citric acid, and 313 grams of water, and after kneading and molding, dry at 120°C for 3 hours and calcine at 600°C for 6 hours to obtain catalyst carrier A-1.

[0062] Preparation of the catalyst:

[0063] Mix 66.9 grams of ammonium heptamolybdate tetrahydrate, 51.6 grams of ammonium sulfide, and water to obtain a first impregnation solution. In the first impregnation solution, the mass content of the molybdenum source is 29 wt%. Impregnate the first impregnation solution on the carrier A-1. The impregnation is saturated impregnation. After drying at 100°C for 6 h in an air atmosphere, a catalyst intermediate I is obtained.

[0064] (2) Contact the catalyst intermediate I with chlorine gas to obtain a catalyst intermediate II. The purity of the chlorine gas is 98 vol% as a volume fraction. The flow rate of the chlorine gas is 3.4 mL / (min·g of catalyst intermediate I). The reaction conditions are as follows: the reaction temperature is 400°C, and the reaction time is 90 min.

[0065] (3) Impregnate the catalyst intermediate II described in step (2) with a second impregnation solution of a nickel source and a phosphorus source (dissolve 53.5 grams of nickel nitrate hexahydrate and 12.2 grams of diammonium hydrogen phosphate in water, wherein the mass content of the nickel source in the second impregnation solution is 76 wt%). The impregnation is saturated impregnation. After standing for 10 h at 25°C, drying at 110°C for 6 h in an air atmosphere, and calcining at 510°C for 6 h in a nitrogen atmosphere, the catalyst C1 is prepared.

[0066] The catalyst composition, catalyst properties, and pore distribution of the catalyst are shown in Table 1. The Group VIII metal element exists in the catalyst in the form of a metal phosphide. The Mo includes +5 valence Mo, +6 valence Mo, and +4 valence Mo. That is, the Mo exists in the form of molybdenum pentachloride, molybdenum disulfide, and molybdenum oxide. The +5 valence Mo accounts for 79.3% of the total Mo in terms of atoms, the +4 valence Mo accounts for 14.3% of the total Mo in terms of atoms, and the +6 valence Mo accounts for 6.4% of the total Mo in terms of atoms.

[0067] Example 2

[0068] (1) Preparation of the carrier:

[0069] A 4L reaction kettle was charged with 4L of pure water and heated to 60℃ with stirring at 300 rad / min. 35g / 100mL of aluminum sulfate solution and 40g / 100mL of sodium metaaluminate were simultaneously and continuously added to the reaction kettle at flow rates of 45mL / min and 30mL / min, respectively. The pH of the reaction was controlled at 1.6 by adding hydrochloric acid during the reaction. After the reaction was completed, the temperature was adjusted to 140℃, the stirring rate was adjusted to 400 rad / min, and polyethylene oxide with a molecular weight of 20,000 (2.2% of the aluminum oxide content) was introduced into the reaction kettle. A 60g / 100mL sodium hydroxide solution was then introduced into the reaction kettle for a secondary reaction, the pH of the reaction was adjusted to 8.8, and the reaction time was 70 min. The product was aged at 300℃ for 4 hours, filtered, washed with hot water at 70℃ until neutral, and dried at 120℃ for 4 hours to obtain a pseudoboehmite.

[0070] 80g of activated carbon with a particle size of 10μm was placed in a spray-impregnation rolling kettle. While rotating, 32ml of an ethanol solution containing 5g of tetraethyl orthosilicate and 1.5g of gallium oxide was atomized and sprayed onto the activated carbon in the rolling kettle. The impregnated activated carbon was mixed with 418g of pseudoboehmite (alumina content of 67.8%), 8.4g of sesbania powder, 4.1g of nitric acid, 2.8g of citric acid, and 366g of water, and then formed into a shape. After drying at 120℃ for 3 hours and calcining at 600℃ for 4 hours, a catalyst carrier B-1 was obtained.

[0071] Preparation of the catalyst:

[0072] 68.4g of ammonium heptamolybdate tetrahydrate, 42.8g of thiourea, and water were mixed to obtain a first impregnation solution. In the first impregnation solution, the mass content of the molybdenum source was 36wt%. The first impregnation solution was impregnated on the carrier B-1. The impregnation was saturated impregnation. After drying at 120℃ for 4h in an air atmosphere, a catalyst intermediate I was obtained.

[0073] (2) The catalyst intermediate I was contacted with chlorine gas to obtain a catalyst intermediate II. The purity of the chlorine gas was 97v% by volume fraction. The flow rate of the chlorine gas was 4.8mL / (min.g of catalyst intermediate I). The reaction conditions were as follows: the reaction temperature was 400℃, and the reaction time was 65min.

[0074] (3) A second impregnation solution of a nickel source and a phosphorus source (49.7g of nickel nitrate hexahydrate and 13.7g of disodium hydrogen phosphate were dissolved in water, and in the second impregnation solution, the mass content of the nickel source was 71wt%) was impregnated on the catalyst intermediate II of step (2). The impregnation was saturated impregnation. After standing for 12h at 23℃, drying at 120℃ for 5h in an air atmosphere, and calcining at 495℃ for 6h in a nitrogen atmosphere, the catalyst C2 was prepared.

[0075] The catalyst composition, catalyst properties and pore distribution of the catalyst are shown in Table 1. The Group VIII metal element exists in the catalyst in the form of metal phosphide. The Mo includes +5 valence Mo, +6 valence Mo, +4 valence Mo. That is, Mo exists in the form of molybdenum pentachloride, molybdenum disulfide, molybdenum oxide. The +5 valence Mo accounts for 78.1% of the total Mo in terms of atoms, the +4 valence Mo accounts for 15.4% of the total Mo in terms of atoms, and the +6 valence Mo accounts for 6.5% of the total Mo in terms of atoms.

[0076] Example 3

[0077] (1) Preparation of the carrier:

[0078] A 3L reaction kettle was charged with 3L pure water and heated to 70°C at a stirring rate of 350 rad / min. An aluminum sulfate solution of 55g / 100mL and a sodium metaaluminate solution of 50g / 100mL were simultaneously and continuously added to the reaction kettle at flow rates of 30mL / min and 15mL / min, respectively. During the reaction, hydrochloric acid was added to control the pH of the reaction to 1.3. After the reaction was completed, the temperature was adjusted to 160°C, the stirring rate was adjusted to 500 rad / min, and polyvinylpyrrolidone (molecular weight 30000) (1.2% of the content of aluminum oxide) was introduced into the reaction kettle. Then, a sodium hydroxide solution of 55g / 100mL was introduced into the reaction kettle for a secondary reaction. The pH of the reaction was adjusted to 9.0, the reaction time was 100 min, and the aging was performed at 70°C for 3 hours. After filtration, the product was washed with hot water of 90°C until neutral, and then dried at 130°C for 2 hours to obtain a pseudoboehmite.

[0079] Active carbon of 71g with a particle size of 4μm was placed in a spray-impregnation rolling kettle. In a rotating state, an ethanol solution of 32ml containing tetraethyl orthosilicate of 4g and gallium nitrate of 1g containing gallium oxide was sprayed and impregnated on the active carbon in the kettle in an atomized manner. The impregnated active carbon was mixed with 298g of pseudoboehmite (alumina content of 68.4%), 6g of sesbania powder, 2.9g of nitric acid, 2g of citric acid and 261g of water, and then formed into a shape by kneading. After drying at 130°C for 4 hours and calcining at 670°C for 3 hours, a catalyst carrier C-1 was obtained.

[0080] Preparation of the catalyst:

[0081] A first impregnation solution was prepared by mixing 66.4g of ammonium heptamolybdate tetrahydrate, 49.8g of sodium thiosulfate and water. In the first impregnation solution, the mass content of the molybdenum source was 41wt%. The first impregnation solution was impregnated on the carrier C-1. The impregnation was saturated impregnation. After drying at 130°C for 5h in an air atmosphere, a catalyst intermediate I was obtained.

[0082] (2) The catalyst intermediate I was contacted with chlorine gas to obtain catalyst intermediate II. The purity of the chlorine gas was 98% by volume. The flow rate of the chlorine gas was 5.3 mL / (min.g catalyst intermediate I). The reaction conditions were as follows: the reaction temperature was 350°C, and the reaction time was 60 min.

[0083] (3) The catalyst intermediate II of step (2) was impregnated with a second impregnation solution of a nickel source and a phosphorus source (47.4 g of nickel nitrate hexahydrate and 14.3 g of diammonium hydrogen phosphate were dissolved in water, and the mass content of the nickel source in the second impregnation solution was 68% by weight). The impregnation was saturated impregnation. After standing for 12 h at 23°C, the catalyst was dried at 120°C in an air atmosphere for 6 h and calcined at 500°C in a nitrogen atmosphere for 7 h to obtain the catalyst C3.

[0084] The catalyst composition, catalyst properties, and pore distribution of the catalyst are shown in Table 1. The Group VIII metal element exists in the catalyst in the form of a metal phosphide. The Mo includes +5 valence Mo, +6 valence Mo, and +4 valence Mo. That is, the Mo exists in the form of molybdenum pentachloride, molybdenum disulfide, and molybdenum oxide. The +5 valence Mo accounts for 78.7% of the total Mo by atoms, the +4 valence Mo accounts for 15.3% of the total Mo by atoms, and the +6 valence Mo accounts for 6.0% of the total Mo by atoms.

[0085] Example 4

[0086] (1) Preparation of the carrier:

[0087] A reaction kettle was charged with 2.5 L of pure water and heated to 90°C at a stirring rate of 250 rad / min. An aluminum sulfate solution of 45 g / 100 mL and a sodium metaaluminate solution of 40 g / 100 mL were simultaneously and continuously added to the reaction kettle at flow rates of 36 mL / min and 30 mL / min, respectively. The pH of the reaction was controlled to be 1.3 by adding hydrochloric acid during the reaction. After the reaction was completed, the temperature was adjusted to 180°C, the stirring rate was adjusted to 400 rad / min, polyvinyl alcohol (molecular weight: 25,000) (1.2% of the content of aluminum oxide) was introduced into the reaction kettle, and a sodium bicarbonate solution with a concentration of 60 g / 100 mL was introduced into the reaction kettle to perform a secondary reaction. The pH of the reaction was adjusted to 9.5, the reaction time was 120 min, and the aging was performed at 70°C for 3 hours. After filtration, the product was washed with hot water at 90°C until neutral, and dried at 130°C for 2 hours to obtain a pseudo-boehmite.

[0088] Take 114 grams of activated carbon with a particle size of 16 μm and place it in a spray-impregnation rolling pot. While rotating, spray-impregnate the activated carbon in the rolling pot with 45 ml of an ethanol solution containing 6 grams of tetraethyl orthosilicate and 2 grams of gallium oxide in the form of gallium nitrate in an atomized manner. Mix the impregnated activated carbon with 388 grams of pseudoboehmite (alumina mass content of 69.1%), 6 grams of sesbania powder, 2.9 grams of nitric acid, 2 grams of citric acid, and 261 grams of water, and then mix and knead to form a shape. After drying at 130°C for 4 hours, calcine at 670°C for 3 hours to obtain catalyst carrier D-1.

[0089] Preparation of the catalyst:

[0090] Mix 63.9 grams of ammonium heptamolybdate tetrahydrate, 54.77 grams of thiourea, and water to obtain a first impregnation solution. In the first impregnation solution, the mass content of the molybdenum source is 40 wt%. Impregnate the first impregnation solution on the carrier D-1. The impregnation is saturated impregnation. After drying at 130°C for 5 hours in an air atmosphere, a catalyst intermediate I is obtained.

[0091] (2) Contact the catalyst intermediate I with chlorine gas to obtain a catalyst intermediate II. The purity of the chlorine gas is 99 vol% as a volume fraction. The flow rate of the chlorine gas is 3.9 mL / (min·g of catalyst intermediate I). The reaction conditions are as follows: the reaction temperature is 300°C, and the reaction time is 80 min.

[0092] (3) Impregnate the catalyst intermediate II in step (2) with a second impregnation solution of a nickel source and a phosphorus source (dissolve 43.5 grams of nickel nitrate hexahydrate and 7.9 grams of diammonium hydrogen phosphate in water, wherein the mass content of the nickel source in the second impregnation solution is 62 wt%). The impregnation is saturated impregnation. After standing for 12 hours at 23°C, drying at 120°C for 6 hours in an air atmosphere, and calcining at 500°C for 7 hours in a nitrogen atmosphere, the catalyst C4 is prepared.

[0093] The catalyst composition, catalyst properties, and pore distribution of the catalyst are shown in Table 1. The Group VIII metal element exists in the catalyst in the form of a metal phosphide. The Mo includes +5 valence Mo, +6 valence Mo, and +4 valence Mo. That is, the Mo exists in the form of molybdenum pentachloride, molybdenum disulfide, and molybdenum oxide. The +5 valence Mo accounts for 78.0% of the total Mo in terms of atoms, the +4 valence Mo accounts for 15.9% of the total Mo in terms of atoms, and the +6 valence Mo accounts for 6.1% of the total Mo in terms of atoms.

[0094] Comparative Example 1

[0095] Compared with Example 1, no secondary reaction is performed in the preparation process of the carrier; the other steps are the same as those in Example 1.

[0096] The carrier preparation process is as follows:

[0097] A 3L reaction vessel was charged with 3L of purified water and heated to 60°C with stirring at 200 rad / min. An aluminum sulfate solution (35g / 100mL) and a sodium metaaluminate solution (23g / 100mL) were simultaneously and continuously added to the reaction vessel at flow rates of 30mL / min and 20mL / min, respectively. The pH of the reaction was controlled by adding hydrochloric acid during the reaction. The reaction time was 70 min. After the reaction was completed, the temperature was adjusted to 260°C and the mixture was aged for 2 hours. The product was filtered, washed with hot water (90°C) until neutral, and dried at 130°C for 3 hours to obtain pseudoboehmite.

[0098] A 75g of activated carbon with a particle size of 4μm was placed in a spray-impregnation rolling kettle. While the kettle was rotating, 22.5ml of an ethanol solution containing 3g of tetraethyl orthosilicate and 1.5g of gallium nitrate containing gallium oxide was sprayed onto the activated carbon in an atomized manner. The impregnated activated carbon was mixed with 348g of pseudoboehmite (alumina content of 69.1%), 7.2g of sesbania powder, 3.58g of nitric acid, 2.4g of citric acid, and 313g of water, and then kneaded and formed. The product was dried at 120°C for 3 hours and calcined at 600°C for 6 hours to obtain a catalyst support DA.

[0099] A comparative hydrogenation catalyst DCA-1 was prepared. The composition, properties, and pore distribution of the catalyst are shown in Table 1.

[0100] Comparative Example 2

[0101] In comparison with Example 1, no acid was added to adjust the pH during the first reaction in the preparation of the support. The other steps were the same as in Example 1.

[0102] That is, the preparation of the support was as follows:

[0103] A 3L reaction vessel was charged with 3L of purified water and heated to 60°C with stirring at 200 rad / min. An aluminum sulfate solution (35g / 100mL) and a sodium metaaluminate solution (23g / 100mL) were simultaneously and continuously added to the reaction vessel at flow rates of 30mL / min and 20mL / min, respectively. The reaction time was 70 min. After the reaction was completed, the temperature was adjusted to 120°C, the stirring rate was adjusted to 300 rad / min, and polyvinyl alcohol (molecular weight of 25000) (1.2% of the alumina content) was added to the reaction vessel. A 55g / 100mL sodium carbonate solution was then added to the reaction vessel to perform a second reaction. The pH of the reaction was adjusted to 9 and the reaction time was 90 min. The mixture was aged at 260°C for 2 hours. The product was filtered, washed with hot water (90°C) until neutral, and dried at 130°C for 3 hours to obtain pseudoboehmite.

[0104] Take 75 grams of activated carbon with a particle size of 4 μm and place it in a spray-impregnation rolling kettle. While rotating, spray-impregnate the activated carbon in the rolling kettle with 22.5 ml of an ethanol solution containing 3 grams of tetraethyl orthosilicate and 1.5 grams of gallium nitrate containing gallium oxide, in an atomized manner. After impregnation, mix the activated carbon with 348 grams of pseudoboehmite (alumina mass content of 69.1%), 7.2 grams of sesbania powder, 3.58 grams of nitric acid, 2.4 grams of citric acid, and 313 grams of water, and then knead and shape. After drying at 120°C for 3 hours and calcining at 600°C for 6 hours, a catalyst carrier DB is obtained.

[0105] A comparative hydrogenation catalyst DCA-2 was prepared. The catalyst composition, catalyst properties, and pore distribution of the catalyst in the catalyst preparation method are shown in Table 1.

[0106] Comparative Example 3

[0107] The active metals of the catalyst in this example include molybdenum oxide and nickel oxide.

[0108] Compared with Example 1, in the catalyst preparation method, air is used instead of chlorine gas in step (2) of Example 1, i.e., catalyst intermediate I is reacted with air. The other steps are the same as those of Example 1.

[0109] A comparative hydrogenation catalyst DCA-3 was prepared.

[0110] The catalyst composition, catalyst properties, and pore distribution of the catalyst are shown in Table 1. The Mo is +6 valence Mo and +4 valence Mo, and does not contain +5 valence Mo. That is, the Mo exists in the form of molybdenum disulfide and molybdenum oxide. The +4 valence Mo accounts for 14.3% of the total Mo in terms of atoms, and the +6 valence Mo accounts for 85.7% of the total Mo in terms of atoms.

[0111] Comparative Example 4

[0112] The active metals of the catalyst in this example include molybdenum oxide and nickel oxide.

[0113] Compared with Example 1, in step (2), air is used instead of chlorine gas in Example 1, i.e., catalyst intermediate I is reacted with air. In step (3), no phosphorus source is added to the second impregnation solution. The other steps are the same as those of Example 1.

[0114] A comparative hydrogenation catalyst DCA-4 was prepared.

[0115] The catalyst composition, catalyst properties, and pore distribution of the catalyst are shown in Table 1. The Mo is +6 valence Mo and +4 valence Mo, and does not contain +5 valence Mo. That is, the Mo exists in the form of molybdenum disulfide and molybdenum oxide. The +4 valence Mo accounts for 14.6% of the total Mo in terms of atoms, and the +6 valence Mo accounts for 85.4% of the total Mo in terms of atoms.

[0116] Application Example

[0117] The catalysts obtained in the examples and comparative examples were subjected to activity evaluation experiments using the raw oil in Table 2, and the properties of the raw oil and the reaction conditions are shown in Table 2, and the evaluation results are shown in Table 3. The catalysts were sulfided before use. The sulfiding conditions were as follows: the sulfiding liquid was straight-run diesel oil containing 8.0wt% of DMDS, the flow rate of the sulfiding liquid was 20.0mL / (h·g catalyst), the hydrogen pressure was 8.5MPa, and the hydrogen flow rate was 100.0mL / (min·g catalyst). The low-temperature sulfiding stage started at 25℃, the temperature was raised at a rate of 10.0℃ / h, and after reaching 160℃, the temperature was kept constant for 6.0h; the high-temperature sulfiding stage started at 160℃, the temperature was raised at a rate of 8.0℃ / h, and after reaching 310℃, the temperature was kept constant for 4.0h, and the sulfiding was completed.

[0118] Table 1 Catalyst composition and properties of examples and comparative examples

[0119]

[0120] Table 2 Properties of raw oil and reaction conditions

[0121] Item Property Feed oil property Density (20°C) / kg m -3 ]] 997.4 S / wt% 2.8 Ni + V / μg·g -1 ]] 89 N / wt% 0.66 Reaction condition Reaction temperature / °C 355 Reaction pressure / MPa 11.2 Volume space velocity / h -1 ]] 0.52 Hydrogen / oil volume ratio 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 870

[0122] Table 3 Activity evaluation results of catalysts of each example

[0123]

[0124] The above describes the specific embodiments of the present application in detail, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A residual carbon hydrodecarbonization catalyst for residual oil, comprising a carrier and an active metal component; the carrier is an alumina containing silicon and gallium; the mass content of the carrier is 74% to 83% based on the weight of the catalyst, the content of the Group VIII metal in terms of oxide is 2% to 6%, and the content of molybdenum in terms of oxide is 15% to 24%; the active metal component comprises Mo and Group VIII metal elements; the Mo comprises +5 valence Mo; the Group VIII metal elements exist in the catalyst in the form of metal phosphides. In the carrier, the silicon and gallium account for 0.2% to 4.5% of the mass of the alumina in terms of SiO2 and Ga2O3, and the mass ratio of the silicon and gallium is 2:1 to 5:1 in terms of SiO2 and Ga2O3.

2. The catalyst of claim 1, wherein In the catalyst, the Mo further comprises +4 valence Mo and +6 valence Mo; the +5 valence Mo accounts for more than 50% of the total Mo in terms of atoms, preferably 55% to 80%; the sum of the +4 valence Mo and the +6 valence Mo accounts for 20% to 45% of the total Mo in terms of atoms.

3. The catalyst of claim 1, wherein Further preferably, in the catalyst, the +5 valence Mo is molybdenum pentachloride; the +4 valence Mo is molybdenum disulfide; and the +6 valence Mo is molybdenum oxide. And / or, the pore size distribution of the catalyst is as follows: the ratio of the pore volume of the pores with a pore diameter <10 nm to the total pore volume is 5% to 10%, the ratio of the pore volume of the pores with a pore diameter of 10 to 20 nm to the total pore volume is 62% to 67%, and the ratio of the pore volume of the pores with a pore diameter >20 nm to the total pore volume is 23% to 33%.

4. The catalyst of claim 1 wherein, The catalyst has the following properties: specific surface area of 150-260 m 2 / g, pore volume of 0.3-1.0 mL / g, total acid amount of 0.2-0.6 mmol / g, and ratio of B acid amount to L acid amount of 0.4-0.

7. The method comprises:

5. Process for the preparation of the catalyst according to any one of claims 1 to 4, characterized in that, (1) mixing a molybdenum source, a sulfur source and water to obtain a first impregnation solution, and impregnating the carrier with the first impregnation solution to obtain a catalyst intermediate I after drying; (2) contacting the catalyst intermediate I obtained in step (1) with chlorine to obtain a catalyst intermediate II; (3) impregnating the catalyst intermediate II obtained in step (2) with a second impregnation solution containing a nickel source and a phosphorus source, aging, drying and calcining to obtain the catalyst. The preparation method of the carrier comprises:

6. The preparation method according to claim 5, characterized in that: (11) performing a co-current precipitation reaction of an acidic aqueous aluminum salt solution and an alkaline aqueous aluminum salt solution to obtain a slurry; (12) adding an alkaline solution and a water-soluble polymer to the slurry obtained in step (11) to perform a secondary reaction, aging, drying to obtain material A; (13) impregnating activated carbon with a solution containing silicon and gallium to obtain material B; (14) kneading and shaping material A obtained in step (12) and material B obtained in step (13), drying and calcining to obtain the carrier. In step (11), the acidic aluminum salt is at least one of aluminum sulfate, aluminum chloride or aluminum nitrate, and the concentration of the acidic aluminum salt solution is 20 to 100 g / 100 mL in terms of Al2O3; 7. The preparation method according to claim 6, characterized in that: And / or, the alkaline aluminum salt is at least one of sodium aluminate or potassium aluminate, and the concentration of the alkaline aluminum salt solution is 20 to 100 g / 100 mL in terms of Al2O3; And / or, the ratio of the addition volume rate of the acidic aluminum salt solution to the alkaline aluminum salt solution is 1:1 to 3:1; And / or, the reaction is controlled at a pH value of 1.2 to 1.8, and the pH value is adjusted by adding at least one of hydrochloric acid, nitric acid or sulfuric acid. ​ And / or, the co-current reaction time is 60-180 min, and the reaction temperature is 60-90℃.

8. The preparation method according to claim 6, characterized in that: In step (12), the alkaline solution is a solution of at least one of sodium hydroxide or sodium carbonate, and the concentration of the alkaline solution is 50-70 g / 100 mL; And / or, the amount of the water-soluble polymer added is 0.1%-5%, preferably 0.5%-3%, of the mass of the slurry obtained in step (11) in terms of aluminum oxide; And / or, the pH value of the secondary reaction is 8.5-9.7; the reaction time of the secondary reaction is 60-120 min, and the reaction temperature is 120-180℃, and the reaction is preferably carried out under stirring, and the stirring rate is 100-500 rad / min, preferably 250-500 rad / min; And / or, the water-soluble polymer is at least one of polyvinyl alcohol, polyethylene oxide, and polyvinyl pyrrolidone; and the weight average molecular weight of the water-soluble polymer is 10,000-40,000.

9. The preparation method according to claim 6, characterized in that: In step (13), the solution containing silicon and gallium is an ethanol solution containing silicate and gallium nitrate; And / or, the silicate is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, and butyl orthosilicate; And / or, the concentration of silicon in the solution containing silicon and gallium is 0.1-5 g / mL in terms of SiO2; And / or, the mass ratio of silicon to gallium in the solution containing silicon and gallium is 2:1-5:1 in terms of SiO2 and Ga2O3; And / or, the amount of the solution containing silicon and gallium used is 30%-50% of the saturated water absorption capacity of the activated carbon in terms of volume.

10. The preparation method according to claim 6, characterized in that: In step (14), the mass ratio of material A obtained in step (12) in terms of aluminum oxide to material B obtained in step (13) in terms of activated carbon is 2:1-10:

1.

11. The preparation method according to claim 5, characterized in that: In step (1), the molybdenum source is at least one of ammonium dimolybdate, ammonium tetramolybdate dihydrate, and ammonium heptamolybdate tetrahydrate; And / or, the sulfur source is at least one of thiourea, ammonium sulfide, thioacetamide, and sodium thiosulfate; And / or, the mass ratio of the molybdenum source to the sulfur source is 3-5:2-4; and the mass content of the molybdenum source in the first impregnation solution is 25wt%-45wt%.

12. The preparation method according to claim 5, characterized in that: In step (2), the purity of the chlorine gas is 96% or more in terms of volume fraction; And / or, the flow rate of the chlorine gas is 2.7-6.8 mL / (min·g of catalyst intermediate I); And / or, the reaction conditions are as follows: the reaction temperature is 300-400℃, and the reaction time is 40-90 min.

13. The preparation method according to claim 5, characterized in that: In step (3), the nickel source is a soluble salt, such as at least one of a nitrate, monohydrogen phosphate, and dihydrogen phosphate; And / or, the phosphorus source is at least one of an ammonium phosphate salt, sodium dihydrogen phosphate, sodium hydrogen phosphate, potassium dihydrogen phosphate, potassium hydrogen phosphate, and phytic acid; And / or, in the second impregnation solution, the molar ratio of the nickel source in terms of metal elements to the phosphorus source in terms of phosphorus elements is 0.3-3:

1.

14. Use of the residue hydro-decarbon residue catalyst according to any one of claims 1-4 or prepared by the method according to any one of claims 5-13 in residue hydro-treatment.

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