A catalyst for hydrodemetallization of residual oil and a method for preparing the same

Abstract

The application discloses a catalyst for residual oil hydrodemetallization and a preparation method thereof. The preparation method of the catalyst comprises the following steps: sealing and heat-treating alumina A after immersing the alumina A in an aqueous ammonium bicarbonate solution, and then drying to obtain a carrier component B; impregnating a first active metal component on activated carbon to obtain a dispersion medium containing the first active metal component, then mixing and kneading the dispersion medium with the carrier component B to form a shape, and then roasting to obtain a carrier C; sealing and treating the carrier C after immersing the carrier C in an aqueous ammonium bicarbonate solution, and then drying to obtain a carrier D; impregnating a 'water-in-oil' impregnation solution containing a second active metal component on the carrier D, and then roasting to obtain the catalyst. When the catalyst is used for residual oil hydrodemetallization, the activity and stability of the reaction can be obviously improved.

Description

Technical Field

[0001] This invention belongs to the field of preparation technology of hydrodemetallization catalysts for residue oil, and specifically relates to a catalyst for hydrodemetallization of residue oil and its preparation method. Background Technology

[0002] Currently, the trend of crude oil becoming heavier and of lower quality is intensifying globally, making the efficient processing and utilization of heavy and residual oils extremely important. Most residual oil hydrotreating catalysts are supported hydrogenation catalysts, with the active metal components typically loaded onto the surface of the support. The pore properties of the catalyst not only affect the distribution of the active metal on the catalyst surface but also influence the catalyst's reactivity.

[0003] CN105983417A discloses a method for preparing a hydrodemetallization catalyst for residual oil, comprising the following steps: mixing one or more of alumina trihydrate, boehmite, pseudoboehmite and amorphous aluminum hydroxide with a peptizing agent, an extrusion aid, and an organic solution, then molding, drying and calcining to obtain a support; impregnating the obtained support with a solution containing nickel and molybdenum and drying and calcining to obtain the final catalyst.

[0004] CN108745392A discloses a hydrogenation demetallization catalyst with a bimodal pore distribution and its preparation method. The hydrogenation active metal component contained in the catalyst is selected from at least one group VIB metal component and at least one group VIII metal component. The specific preparation method includes mixing an alumina precursor with an extrusion aid, adding a metal salt solution containing the hydrogenation active metal component, kneading, molding, and drying, followed by hydrothermal treatment, drying, and calcination.

[0005] CN104646007A discloses a residue oil hydrodemetallization catalyst, its preparation method, and its application. The method includes: firstly, pretreating an activated carbon support with hydrochloric acid washing and nitric acid oxidation; then, mixing and extruding a composite additive, activated carbon, and alumina to prepare an activated carbon / alumina composite; finally, loading metal onto the support using a hydrotalcite method, i.e., impregnating an equal volume of a mixed solution of terephthalic acid, nickel nitrate, urea, and ammonium nitrate in a molar ratio of 2:1:(2.5-5):(1-5), crystallizing, washing several times, and drying to obtain nickel salt talc microcrystals. These microcrystals are then placed in a Mo salt solution for complete displacement, filtered, washed, and dried to obtain green solid particles, which are then dried and calcined to obtain the residue oil hydrodemetallization catalyst.

[0006] Residue oil feedstocks contain numerous large molecules, requiring residue oil hydrodemetallization catalysts to possess unobstructed pore structures. Even with sufficiently unobstructed pores, further enhancing catalyst performance necessitates a higher degree of dispersion of the active metal both within and on the catalyst surface. Currently, the impregnation method used in industrial hydrodemetallization catalyst preparation primarily relies on aqueous solution impregnation, a single-phase impregnation process where the metal is dispersed in an aqueous solution. Due to the influence of the impregnation process's spray angle and wetting conditions, the dispersion of the active metal on the catalyst surface is limited. Therefore, the activity and stability of the alumina support and hydrodemetallization catalysts prepared using the aforementioned methods still require further improvement. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a catalyst for the hydrodemetallization of residue oil and its preparation method. The residue oil hydrodemetallization catalyst provided by this invention exhibits excellent pore unobstructedness, a relatively concentrated pore distribution, and a suitable specific surface area. The residue oil hydrodemetallization catalyst prepared using the impregnation solution of this invention can improve the catalyst's hydrogenation activity and stability.

[0008] The first aspect of this invention provides a method for preparing a catalyst for hydrodemetallization of residue oil, comprising the following steps:

[0009] (1) Alumina A was immersed in a first ammonium bicarbonate aqueous solution and then sealed and heat-treated, and dried to obtain carrier component B;

[0010] (2) Impregnate activated carbon with the first active metal component to obtain a dispersion medium containing the first active metal component;

[0011] (3) Mix the carrier component B obtained in step (1) and the dispersion medium obtained in step (2) into a mold, and calcine to obtain carrier C;

[0012] (4) The carrier C obtained in step (3) is immersed in the second ammonium bicarbonate aqueous solution, sealed and dried to obtain carrier D;

[0013] (5) Impregnate the carrier D obtained in step (4) with a water-in-oil impregnation solution containing the second active metal component, and calcine to obtain the residue oil hydrodemetallization catalyst.

[0014] In step (1) of this invention, preferably, alumina A is prepared by the following method:

[0015] (1-1) Mix aluminum nitrate, urea, template agent and water to obtain solution X;

[0016] (1-2) The solution X obtained in step (1-1) is crystallized and calcined to obtain aluminum oxide A.

[0017] In this invention, all crystallization processes are carried out in a crystallization reactor.

[0018] In step (1-1) of this invention, aluminum nitrate, urea and template agent are dissolved in water (preferably deionized water) in the order of dissolving and mixing to obtain solution X.

[0019] In step (1-1) of the present invention, the molar ratio of Al(NO3)3 to the template agent is 160-240, preferably 180-220.

[0020] In step (1-1) of this invention, the molar ratio of urea to Al(NO3)3 is 7–14. Within this range, the OH- produced by the decomposition of urea... - Quantity and Al 3+ The hydrolysis rate is well-matched, and the generated aluminum hydroxide can grow uniformly on the template agent surface.

[0021] In step (1-1) of this invention, the template agent is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methylcellulose, preferably polyethylene glycol; the viscosity of the template agent (20°C) is 10-1000 mPa·s, and the viscosity of solution X (20°C) after adding the template agent and stirring evenly is 120-660 mPa·s.

[0022] In steps (1-2) of this invention, the crystallization temperature is 80-200℃ and the crystallization time is 25-35h.

[0023] In steps (1-2) of this invention, after crystallization, filtration and washing are performed according to conventional and known methods. Washing can be done with deionized water until the pH of the filtrate is close to neutral, followed by drying and calcination to obtain alumina A.

[0024] In steps (1-2) of this invention, the drying temperature is 120-200℃ and the drying time is 2-12h.

[0025] In steps (1-2) of this invention, the calcination temperature is 500-750℃, the calcination time is 2-6h, and the calcination atmosphere is air.

[0026] In step (1) of this invention, the mass percentage concentration of the first ammonium bicarbonate aqueous solution ranges from 10% to 20%. The sealing heat treatment temperature is 80 to 140°C, preferably 90 to 140°C, and the treatment time is 6 to 12 hours. The drying temperature is 120 to 180°C, and the drying time is 2 to 10 hours.

[0027] In step (2) of this invention, the load is prepared by saturation impregnation. After impregnation, the mixture is allowed to stand and then dried to obtain a dispersion medium containing the first active metal component.

[0028] In step (2) of this invention, the settling time is 4 to 12 hours.

[0029] In step (2) of this invention, the drying temperature is 20-200℃ and the drying time is 2-12h.

[0030] In step (2) of the present invention, the first active metal component includes a Group VIB metal and a Group VIII metal, wherein the Group VIB metal is preferably molybdenum, and the Group VIII metal is preferably cobalt and / or nickel, with nickel being the preferred metal.

[0031] In step (2) of this invention, when the activated carbon is impregnated with the first active metal component, an impregnation solution containing the first active metal component is used. The impregnation solution is an impregnation solution containing Mo and a Group VIII metal (preferably Ni), wherein the active metal component molybdenum is derived from one or both of molybdenum oxide and ammonium heptamolybdate, and the nickel is derived from one or both of basic nickel carbonate and nickel nitrate. The content of MoO3 and the Group VIII metal oxide in the impregnation solution containing the first active metal component is 2–30 g / 100 mL and 2–50 g / 100 mL, respectively.

[0032] In step (2) of the present invention, the amount of MoO3 introduced into the catalyst by the first active metal component is 25% to 60% of the total MoO3 loading in the catalyst, and the amount of Group VIII metal oxide introduced into the catalyst by the first active metal component is 25% to 60% of the total Group VIII metal oxide loading in the catalyst.

[0033] In step (3) of the present invention, the mass ratio of activated carbon to carrier component B in the dispersion medium obtained in step (2) is 0.12 to 0.38, for example, 0.12, 0.14, 0.16, 0.18, 0.20, 0.22, 0.24, 0.26, 0.28, 0.30, 0.32, 0.34, 0.36, 0.38, etc., and any value within the range formed by any two of these values.

[0034] In step (3) of the present invention, conventional molding aids, such as adhesives, extrusion aids, etc., can be added as needed during the molding process. The adhesive is one or more of nitric acid, sulfuric acid, and oxalic acid, preferably nitric acid; the extrusion aid is one or more of guar gum powder, cellulose, and resin, preferably guar gum powder.

[0035] In step (3) of the present invention, the amount of adhesive solvent added accounts for 0.5% to 4.0% of the mass of carrier component B, and the amount of extrusion aid added accounts for 0.1% to 5.0% of the mass of carrier component B.

[0036] In step (3) of this invention, after molding, the substrate is dried and calcined to obtain carrier C. The drying temperature is 20-200℃ and the drying time is 2-12h.

[0037] In step (3) of this invention, the calcination temperature is 500-750℃, the calcination time is 2-6h, and the calcination atmosphere is air.

[0038] In step (4) of this invention, the mass percentage concentration of the second ammonium bicarbonate aqueous solution ranges from 20% to 30%. The sealing treatment temperature is 10–60°C, preferably 20–50°C, and the treatment time is 6–12 hours. The treatment temperature in step (4) is 60–90°C lower than the heat treatment temperature in step (1). The drying temperature is 10–40°C, the drying time is 2–10 hours, and the drying method is static drying.

[0039] In step (4) of this invention, the mass concentration of the second ammonium bicarbonate aqueous solution is 8 to 15 percentage points higher than that of the first ammonium bicarbonate aqueous solution in step (1).

[0040] In step (5) of the present invention, the second active metal component includes a Group VIB metal and a Group VIII metal, wherein the Group VIB metal is preferably molybdenum and the Group VIII metal is preferably cobalt and / or nickel.

[0041] In step (5) of this invention, the preparation process of the "water-in-oil" impregnation solution containing the second active metal component includes:

[0042] (a) A surfactant is added to the oil and heated to obtain the oil phase;

[0043] (b) Mix the co-emulsifier, the Group VIB metal source, water, and optional auxiliary source, and heat to obtain a clear solution;

[0044] (c) Add a Group VIII metal source to the clear solution obtained in step (b);

[0045] (d) Add a water-soluble polymer to the mixture obtained in step (c) to obtain an aqueous phase;

[0046] (e) The aqueous phase from step (d) is added dropwise to the oil phase obtained in step (a) while the oil phase remains liquid during the dropwise addition. Simultaneously, the mixture is stirred, sheared, and homogenized to obtain the impregnation solution.

[0047] In step (a) of this invention, the surfactant is selected from glyceryl monostearate, glyceryl distearate, glyceryl monolaurate, and polyoxyethylene ether fatty alcohol (structure R-(OCC)). x -OH, where R is a straight-chain alkyl group with 12 to 15 carbon atoms, and x is 2 to 11, etc., or one or more of these. The oil may be at least one of silicone oil and vegetable oil, wherein the silicone oil is selected from at least one of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen silicone oil, and methyl phenyl silicone oil, and the vegetable oil is selected from one or more of peanut oil, coconut oil, and tea seed oil.

[0048] In step (a) of the present invention, the heating is carried out to a temperature of 40-80°C so that the oil phase presents a uniform liquid state.

[0049] In step (a) of the present invention, the mass ratio of the surfactant added to the oil is 1.0:0.1 to 10, preferably 1.0:2 to 10, for example 1.0:2.0, 1.0:2.5, 1.0:3.0, 1.0:3.5, 1.0:4.0, 1.0:4.5, 1.0:5.0, 1.0:5.5, 1.0:6.0, 1.0:6.5, 1.0:7.0, 1.0:7.5, 1.0:8.0, 1.0:8.5, 1.0:9.0, 1.0:9.5, 1.0:10.0, etc., and any value within any range formed by any two of these values.

[0050] In step (b) of the present invention, the co-emulsifier is selected from one or more of hexadecyl alcohol, octadecyl alcohol, propylene glycol, n-butanol and glycerol.

[0051] In step (b) of the present invention, the amount of the co-emulsifier is 0.5% to 5.0% of the mass of the aqueous phase obtained in step (d).

[0052] In step (b) of this invention, the Group VIB metal source may be one or more of molybdenum oxide, ammonium tetramolybdate, ammonium heptamolybdate, etc. The auxiliary agent is at least one of fluorine, phosphorus, silicon, or boron, preferably phosphorus. The phosphorus source is preferably one or more of phosphoric acid, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, etc.; the fluorine source is preferably ammonium fluoride; the silicon source is preferably silica sol; and the boron source is preferably boric acid.

[0053] In step (b) of this invention, the water is distilled water or deionized water, and the conductivity of the water should be less than 10.0 mS.

[0054] In step (b) of the present invention, the heating is carried out to a temperature of 90-120°C to ensure that the substances added in step (b) are mixed evenly to form a clear solution.

[0055] In step (c) of this invention, the Group VIII metal is Ni and / or Co. The Group VIII metal source is one or more of basic nickel carbonate, cobalt nitrate, etc.

[0056] In step (d) of this invention, the concentration of Group VIB metals (calculated as oxides) in the aqueous phase is 8–75 g / 100 mL, preferably 10–70 g / 100 mL, and the concentration of Group VIII metals (calculated as oxides) is 2–65 g / 100 mL, preferably 5–45 g / 100 mL. The concentration of the auxiliaries (calculated as oxides) is 0–10.0 g / 100 mL, preferably 0–8.0 g / 100 mL.

[0057] In step (d) of this invention, the water-soluble polymer is one or more of polyethylene glycol (molecular weight 200-600), polyvinyl alcohol (molecular weight 170,000-220,000), polyacrylamide (molecular weight 5,000,000-15,000,000), carboxymethyl cellulose, gelatin, gum arabic, and sodium polyacrylate (molecular weight less than 10,000).

[0058] In step (d) of this invention, the mass concentration of the water-soluble polymer in the aqueous phase is 4.0% to 14.0%.

[0059] In step (e) of the present invention, the oil phase is kept in a liquid state at a temperature of 45-85°C and the stirring rate is 400-800 r / min.

[0060] In step (e) of the present invention, the mass ratio of the aqueous phase to the oil phase is 0.4 to 12.0:1.0, preferably 0.5 to 9.0:1.0, for example 0.5:1.0, 0.7:1, 0.9:1.0, 1.0:1.0, 1.2:1.0, 1.3:1.0, 1.5:1.0, 2.0:1.0, 3.0:1.0, 4.0:1.0, 5.0:1.0, 6.0:1.0, 7.0:1.0, 8.0:1.0, 9.0:1.0, etc., and any value within the range formed by any two of these values.

[0061] In step (e) of this invention, the stirring-shear homogenization process is carried out at a stirring speed of 10,000 to 18,000 rpm, a shear homogenization time of 3 to 8 min, and a temperature of 50 to 85°C.

[0062] In step (5) of this invention, the saturated immersion method is used for impregnation, and the standing time after impregnation is 4 to 14 hours.

[0063] In step (5) of the present invention, the amount of MoO3 introduced into the catalyst by the second active metal component is 40% to 75% of the total MoO3 loading in the catalyst, and the amount of Group VIII metal oxide introduced into the catalyst by the second active metal component is 40% to 75% of the total Group VIII metal oxide loading in the catalyst.

[0064] In step (5) of this invention, after impregnation, the catalyst is dried and calcined to obtain the catalyst. The drying temperature is 120-200℃, and the drying time is 2-12h.

[0065] In step (5) of this invention, the calcination temperature is 350-500℃, the calcination time is 2-6h, and the calcination atmosphere is a mixture of inert atmosphere and other atmospheres, with a volume ratio of inert atmosphere to other atmospheres of 0.5-3.0:1. Among them, the inert atmosphere is mainly one or two of nitrogen and helium, and the other atmosphere is one or more of water vapor and air.

[0066] In step (5) of the present invention, the ratio of carbon content on the catalyst surface to alumina content in the support component is 0.16 to 0.50, and the ratio of activated carbon content to alumina content in the support component is 0.10 to 0.35.

[0067] A second aspect of the present invention provides a catalyst for hydrodemetallization of residual oil prepared by the above-described preparation method, comprising a support component, an active metal component, and carbon distributed on the catalyst surface, wherein the active metal component comprises molybdenum and Group VIII metals, and the support component comprises alumina and activated carbon; wherein the ratio of the carbon content distributed on the catalyst surface to the alumina content in the support component is 0.16 to 0.50, preferably 0.25 to 0.45, and the ratio of the activated carbon content to the alumina content in the support component is 0.10 to 0.35.

[0068] In this invention, the active metal component includes molybdenum and a Group VIII metal, wherein the Group VIII metal is preferably nickel.

[0069] In this invention, based on the mass of the catalyst, the content of MoO3 is 6.0% to 20.0%, and the content of Group VIII metal oxides is 1.0% to 8.0%.

[0070] In this invention, the catalyst has a specific surface area of ​​160–200 m². 2 / g, with a pore volume of 0.60~1.00mL / g.

[0071] In this invention, preferably, the catalyst has a specific surface area of ​​165–190 m². 2 / g, with a pore volume of 0.65~0.90mL / g.

[0072] In this invention, the pore distribution of the catalyst is as follows: pores with a diameter of <30nm occupy 25% to 35% of the total pore volume, pores with a diameter of 30 to 100nm occupy 30% to 45% of the total pore volume, and pores with a diameter of 100nm to 300nm occupy 20% to 45% of the total pore volume.

[0073] In this invention, the strength of the catalyst is 10.0 to 28.0 N / mm.

[0074] In this invention, the catalyst further includes an auxiliary component, which is selected from at least one of fluorine, phosphorus, silicon, or boron, preferably phosphorus. Based on the mass of the catalyst, the content of the auxiliary component, calculated as oxides, is 0-8.0%, preferably 1.0%-8.0%.

[0075] Compared with the prior art, the present invention has the following beneficial effects:

[0076] In the catalyst preparation process of this invention, firstly, alumina A with a large specific surface area and regular pore structure is prepared by uniform precipitation. After being heat-treated with ammonium bicarbonate aqueous solution and sealed, the pore properties of the support component B are adjusted, and the most probable pore size is significantly increased. Then, a portion of the active metal is impregnated onto activated carbon by saturation impregnation. After standing and drying, a dispersion medium is obtained. The obtained dispersion medium is then mixed with the support component B, shaped, and calcined to obtain a support C with more unobstructed pores and a suitable specific surface area. The shaped support C is then subjected to ammonium bicarbonate aqueous solution and sealed again to prevent the active metal component from accumulating around the pore openings. Finally, the loaded "water-in-oil" impregnation solution is impregnated by saturation impregnation to obtain the catalyst of this invention.

[0077] In the preparation of the "water-in-oil" impregnation solution of this invention, firstly, the main active metal is fully dispersed in the carrier matrix water in the form of ions using a co-emulsifier, and then the auxiliary metal is dissolved in the above solution to obtain an aqueous phase containing the main metal and the auxiliary metal. Secondly, a water-soluble polymer is added to the obtained aqueous phase as a "protective body" for the colloidal particles. During the subsequent formation of the "water-in-oil" emulsion, the water-soluble polymer adsorbs on the surface of the colloidal particles to form a "surface layer" of a certain thickness, controlling the particle size and maintaining the particle size distribution, effectively preventing collisions and aggregation between colloidal particles, and further improving the stability of the system. Thirdly, a surfactant is used to better disperse the prepared aqueous phase containing the active metal and the carrier matrix in the oil phase and the dispersion matrix, forming an impregnation solution in which the active metal is dispersed in the dispersion matrix through the carrier matrix, i.e., a "water-in-oil" type impregnation solution. Then, the catalyst support is impregnated with the above impregnation solution to prepare a catalyst with a more uniform distribution of active metal inside and on the surface of the support. Fourth, the water-soluble polymer added to the impregnation solution and the final roasting atmosphere are mixed atmosphere roasting. This process not only causes the polymer to decompose incompletely, thus forming point-distributed carbon dots, but also allows for appropriate adjustment of the catalyst's acidity, which is beneficial for weakening the interaction between the active metal and the support and promoting the dispersion of the active metal on the catalyst surface. It also makes the external pores of the catalyst unobstructed, which is beneficial for the diffusion of macromolecules during the reaction.

[0078] The method of this invention constructs a macroporous-mesoporous composite material through the comprehensive coordination of each step, which not only makes the continuous distribution of macropores more extensive, but also enhances the connectivity of the pore channels. The catalyst prepared by this method not only has large pore volume and pore size, but also has high mechanical strength and suitable specific surface area. When this catalyst is used in the hydrodemetallization reaction of residue oil, it can significantly improve the activity and stability of the hydrodemetallization reaction. Detailed Implementation

[0079] In this invention, the pore structure (SVD) and specific surface area of ​​the catalyst are characterized using the Mack ASAP-2420 physical adsorption instrument.

[0080] In this invention, the ZQJ-III intelligent particle strength tester is used to test the crushability of catalyst particles.

[0081] In this invention, the carbon / alumina mass ratio on the catalyst surface was determined using a NETZSCH STA409PC-QMS403C thermogravimetric-mass spectrometer (TG-MS).

[0082] The technical solutions and effects of the present invention will be further illustrated below with reference to the embodiments, but the invention is not limited to the following embodiments.

[0083] Example 1

[0084] (1) Weigh out appropriate amounts of aluminum nitrate, urea and template agent polyethylene glycol (viscosity 500 mPa·s), wherein the molar ratio of Al(NO3)3 to polyethylene glycol is 175 and the molar ratio of urea to Al(NO3)3 is 12. Dissolve the above substances in a certain amount of deionized water in the order of aluminum nitrate, urea and polyethylene glycol. After stirring magnetically for 5 hours to mix evenly, solution X (viscosity 360 mPa·s) is obtained.

[0085] (2) The obtained solution X was transferred to a crystallization vessel, and then the crystallization vessel was placed in an oven at 150°C. After reacting for 32 hours, the crystallization vessel was removed and cooled. A mixed slurry containing a white precipitate was obtained in the reaction vessel. The obtained white precipitate was filtered and washed several times until the pH value of the filtrate was close to 7. The white precipitate was placed in an oven to dry at 120°C for 6 hours. Then it was calcined in a muffle furnace at 600°C for 4 hours to obtain alumina A.

[0086] (3) The obtained alumina A is immersed in ammonium bicarbonate aqueous solution and then sealed and heat treated to obtain carrier component B. The mass percentage concentration of ammonium bicarbonate aqueous solution is 18%, the sealing heat treatment temperature is 90℃, the treatment time is 6h, the drying temperature is 140℃, and the drying time is 4h.

[0087] (4) Activated carbon was impregnated with an impregnation solution containing the first active metal component (MoO3 content of 25.36 g / 100 mL and NiO content of 4.64 g / 100 mL) by saturation impregnation. After impregnation, the carbon was allowed to stand at room temperature (25 °C) for 4 h and dried at 120 °C for 6 h to form a dispersion medium containing some active metal. The amount of MoO3 introduced into the catalyst by the first active metal component was 50% of the total MoO3 loading in the catalyst, and the amount of NiO was 50% of the total NiO loading in the catalyst.

[0088] (5) The carrier component B, nitric acid (68wt%), guar gum powder, dispersion medium, and deionized water are mixed, shaped, dried, and calcined to obtain carrier C; wherein, the mass content of nitric acid (68wt%) added is 2.0% of the carrier component B, the mass content of guar gum powder added is 0.8% of the carrier component B, the amount of activated carbon added in the dispersion medium is 16% of the carrier component B, the amount of deionized water added is adjusted in real time according to the material state during the shaping process, the drying temperature is 140℃, the drying time is 8h, the calcination temperature is 700℃, and the calcination time is 4h (the heating rate is 2.5℃ / min);

[0089] (6) The obtained carrier C was immersed in an ammonium bicarbonate aqueous solution and then sealed and dried to obtain carrier D. The mass percentage concentration of the ammonium bicarbonate aqueous solution was 28%, the sealing temperature was 30℃, the treatment time was 6h, the drying temperature was 30℃, the drying time was 4h, and the drying method was static drying.

[0090] (7) Prepare a water-in-oil impregnation solution containing a second active metal component:

[0091] In this example, the surfactant is glyceryl monostearate, the silicone oil is methyl silicone oil, and the mass ratio of surfactant to silicone oil is 1.5:8. The co-emulsifier is octadecyl alcohol, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, and the water-soluble polymer is polyvinyl alcohol (molecular weight 200,000). The mass ratio of co-emulsifier:molybdenum source (calculated as molybdenum oxide):phosphorus source (calculated as phosphorus oxide):nickel source (calculated as nickel oxide):water-soluble polymer:water is 20:271.4:45.3:77.2:70.3:400. The mass ratio of oil phase to water phase is 1:1.

[0092] (7-1) Add the surfactant glyceryl monostearate to the silicone oil, heat to 80°C, and wait for the silicone oil to melt to obtain the oil phase;

[0093] (7-2) Add the co-emulsifier octadecanol, molybdenum oxide and phosphoric acid to deionized water in sequence. Use a reflux condenser during the reaction. The reaction starts at 28°C. During the reaction, the stirring speed is 500 r / min. When heated to 120°C, maintain this temperature for 4 hours. Maintain a constant stirring speed until a transparent and clear solution is obtained.

[0094] (7-3) Add basic nickel carbonate to the clear solution obtained in step (7-2);

[0095] (7-4) Add water-soluble polyvinyl alcohol to the mixture obtained in step (7-3) to obtain an aqueous phase;

[0096] (7-5) The aqueous phase from step (7-4) is added dropwise to the oil phase obtained in step (7-1). During the addition process, the temperature of the oil phase is maintained at 80°C, and the mixture is stirred. The shear homogenization rate is 15000 rpm, the shear homogenization time is 5 min, and the temperature during the shear homogenization process is 60°C. After the droplets are dispersed into an emulsion, a water-in-oil impregnation solution is obtained.

[0097] (8) The support D was impregnated by a saturated impregnation method with an impregnation solution containing the second active metal component (MoO3 content of 25.36 g / 100 mL, NiO content of 4.64 g / 100 mL, and P (calculated as oxide) content in the auxiliary phosphoric acid of 5.00 g / 100 mL). The amount of MoO3 introduced into the catalyst by the second active metal component was 50% of the total MoO3 loading in the catalyst, and the amount of NiO was 50% of the total NiO loading in the catalyst. After impregnation, the sample was allowed to stand at room temperature (25 °C) for 6 h, then dried (temperature of 120 °C, drying time of 6 h), calcined at 500 °C for 4 h (heating rate of 2.0 °C / min), and calcined in a mixed atmosphere of nitrogen and air (nitrogen to air volume ratio of 3:1) to obtain the catalyst for hydrodemetallization of residue oil. The above-prepared hydrodemetallization catalyst for residue oil was named CAT-1. The physicochemical properties of the catalyst are shown in Table 1.

[0098] Example 2

[0099] The difference between this example and Example 1 is that: in step (1), the molar ratio of Al(NO3)3 to polyethylene glycol is 20:5, and the molar ratio of urea to Al(NO3)3 is 9; in step (5), the amount of activated carbon added to the dispersion medium is 24% of the carrier B; thus, CAT-2, a catalyst for hydrodemetallization of residue oil, was prepared. The physicochemical properties of the catalyst are shown in Table 1.

[0100] Example 3

[0101] The difference between this example and Example 1 is as follows: In step (3), the mass percentage concentration of the first ammonium bicarbonate aqueous solution is 15%, the sealing heat treatment temperature is 120℃, the treatment time is 6h, and the drying temperature is 140℃, the drying time is 6h; In step (6), the mass percentage concentration of the second ammonium bicarbonate aqueous solution is 25%, the sealing treatment temperature is 35℃, the treatment time is 6h, and the drying temperature is 30℃, the drying time is 8h; thus, CAT-3, a catalyst for the hydrodemetallization of residue oil, is obtained. The physicochemical properties of the catalyst are shown in Table 1.

[0102] Example 4

[0103] Similar to Example 1, except that the process of preparing the "water-in-oil" impregnation solution containing the second active metal component in step (7) is as follows:

[0104] In this example, the surfactant is glyceryl distearate, the silicone oil is ethyl silicone oil, and the mass ratio of surfactant to silicone oil is 1.45:8. The co-emulsifier is cetyl alcohol, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, and the water-soluble polymer is carboxymethyl cellulose. The mass ratio of co-emulsifier:molybdenum source (calculated as molybdenum oxide):phosphorus source (calculated as phosphorus oxide):nickel source (calculated as nickel oxide):water-soluble polymer:water is 24:271.4:45.3:77.2:90.3:400. The mass ratio of oil phase to water phase is 1:0.9.

[0105] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0106] (1) Add the surfactant glyceryl distearate to the silicone oil, heat to 75°C, and wait for the silicone oil to melt to obtain the oil phase;

[0107] (2) Add the co-emulsifier cetyl alcohol, molybdenum oxide and phosphoric acid to deionized water in sequence. A reflux condenser is used during the reaction. The reaction starts at 28°C. During the reaction, the stirring speed is 600 r / min. When the temperature is heated to 120°C, the temperature is maintained for 4 hours. The stirring speed is kept constant until a transparent and clear solution is obtained.

[0108] (3) Add basic nickel carbonate to the clear solution obtained in step (2);

[0109] (4) Add water-soluble polymer carboxymethyl cellulose to the mixture obtained in step (3) to obtain an aqueous phase;

[0110] (5) The aqueous phase from step (4) is added dropwise to the oil phase obtained in step (1). During the dropwise addition, the temperature of the oil phase is maintained at 65°C, and stirring is performed simultaneously. The shear homogenization rate is 16000 rpm, the shear homogenization time is 6 min, and the temperature during the shear homogenization process is 70°C. After the droplets are dispersed into an emulsion, a water-in-oil impregnation solution is obtained. The amount of MoO3 introduced into the catalyst by the second active metal component is 65.0% of the total MoO3 loading in the catalyst, and the amount of NiO is 65.0% of the total NiO loading in the catalyst. The hydrodemetallization catalyst CAT-4 is obtained. The physicochemical properties of the catalyst are shown in Table 1.

[0111] Example 5

[0112] Similar to Example 1, except that the process of preparing the "water-in-oil" impregnation solution containing the second active metal component in step (7) is as follows:

[0113] In this example, the surfactant is glyceryl monolaurate, the silicone oil is phenyl silicone oil, and the mass ratio of surfactant to silicone oil is 1.4:8. The co-emulsifier is propylene glycol, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, and the water-soluble polymer is sodium polyacrylate (molecular weight 8000). The mass ratio of co-emulsifier:molybdenum source (calculated as molybdenum oxide):phosphorus source (calculated as phosphorus oxide):nickel source (calculated as nickel oxide):water-soluble polymer:water is 28:271.4:45.3:77.2:111.3:400. The mass ratio of oil phase to water phase is 1:1.3.

[0114] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0115] (1) Add the surfactant glyceryl monolaurate to the silicone oil, heat to 70°C, and wait for the silicone oil to melt to obtain the oil phase;

[0116] (2) Add the co-emulsifier propylene glycol, molybdenum oxide and phosphoric acid to deionized water in sequence. A reflux condenser is used during the reaction. The reaction starts at 28°C. During the reaction, the stirring speed is 700 r / min. When the temperature is heated to 120°C, the temperature is maintained for 4 hours. The stirring speed is kept constant until a transparent and clear solution is obtained.

[0117] (3) Add basic nickel carbonate to the clear solution obtained in step (2);

[0118] (4) Add water-soluble polymer sodium polyacrylate to the mixture obtained in step (3) to obtain an aqueous phase;

[0119] (5) The aqueous phase from step (4) is added dropwise to the oil phase obtained in step (1). During the dropwise addition, the temperature of the oil phase is maintained at 55°C, and stirring is performed simultaneously. The shear homogenization rate is 17000 rpm, the shear homogenization time is 7 min, and the temperature during the shear homogenization process is 80°C. After the droplets are dispersed into an emulsion, a water-in-oil impregnation solution is obtained. The amount of MoO3 introduced into the catalyst by the second active metal component is 60.0% of the total MoO3 loading in the catalyst, and the amount of NiO is 60.0% of the total NiO loading in the catalyst. The hydrodemetallization catalyst CAT-5 is obtained. The physicochemical properties of the catalyst are shown in Table 1.

[0120] Example 6

[0121] Similar to Example 1, except that the process of preparing the "water-in-oil" impregnation solution containing the second active metal component in step (7) is as follows:

[0122] In this example, the surfactant is polyoxyethylene ether fatty alcohol (R = 12, x = 5), the silicone oil is methylphenyl silicone oil, and the mass ratio of surfactant to silicone oil is 1.35:8. The co-emulsifier is n-butanol, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, and the water-soluble polymer is gelatin. The mass ratio of co-emulsifier: molybdenum source (calculated as molybdenum oxide): phosphorus source (calculated as phosphorus oxide): nickel source (calculated as nickel oxide): water-soluble polymer: water is 28:271.4:45.3:77.2:51.3:400. The mass ratio of oil phase to water phase is 1:1.2.

[0123] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0124] (1) Add the surfactant polyoxyethylene ether fatty alcohol to the silicone oil, heat to 65°C, and wait for the silicone oil to melt to obtain the oil phase;

[0125] (2) Add the co-emulsifier n-butanol, molybdenum oxide and phosphoric acid to deionized water in sequence. A reflux condenser is used during the reaction. The reaction starts at 28°C. During the reaction, the stirring speed is 400 r / min. When the temperature is heated to 120°C, the temperature is maintained for 4 hours. The stirring speed is kept constant until a transparent and clear solution is obtained.

[0126] (3) Add basic nickel carbonate to the clear solution obtained in step (2);

[0127] (4) Add water-soluble polymer gelatin to the mixture obtained in step (3) to obtain an aqueous phase;

[0128] (5) The aqueous phase from step (4) is added dropwise to the oil phase obtained in step (1). During the dropwise addition, the temperature of the oil phase is maintained at 45°C, and stirring is performed simultaneously. The shear homogenization rate is 14000 rpm, the shear homogenization time is 4 min, and the temperature during the shear homogenization process is 50°C. After the droplets are dispersed into an emulsion, a water-in-oil impregnation solution is obtained. The amount of MoO3 introduced into the catalyst by the second active metal component is 55.0% of the total MoO3 loading in the catalyst, and the amount of NiO is 55.0% of the total NiO loading in the catalyst. The hydrodemetallization catalyst CAT-6 is obtained. The physicochemical properties of the catalyst are shown in Table 1.

[0129] Comparative Example 1

[0130] Compared with Example 1, the difference is that in step (1), the molar ratio of Al(NO3)3 to polyethylene glycol is 25:5, and the molar ratio of urea to Al(NO3)3 is 6.5. The above substances are dissolved in a certain amount of deionized water in the order of aluminum nitrate, urea, and polyethylene glycol. After being magnetically stirred for 6 hours and mixed evenly, solution X is obtained; thus, dCAT-1, a catalyst for the hydrodemetallization of residue oil, is prepared. The physicochemical properties of this catalyst are shown in Table 1.

[0131] Comparative Example 2

[0132] Compared with Example 1, the difference is that in step (6), the mass percentage concentration of the second ammonium bicarbonate aqueous solution is 32%, the sealing treatment temperature is 75°C, the treatment time is 7h, the drying temperature is 140°C, and the drying time is 8h; thus, dCAT-2, a catalyst for hydrodemetallization of residue oil, is obtained. The physicochemical properties of this catalyst are shown in Table 1.

[0133] Comparative Example 3

[0134] Compared with Example 1, the difference is that in step (4), the activated carbon was not impregnated with the first active metal component. Instead, in step (8), the support D was impregnated with the Mo-Ni-P "water-in-oil" type impregnation solution prepared according to the method of Example 1 in a saturated impregnation manner to obtain the catalyst dCAT-3 for hydrodemetallization of residue oil. The physicochemical properties of the catalyst are shown in Table 1.

[0135] Comparative Example 4

[0136] Similar to Example 1, except that the mass ratio of surfactant to silicone oil in step (7-1) is 0.56:8. The final catalyst obtained is dCAT-4. The physicochemical properties of this catalyst are shown in Table 1.

[0137] Comparative Example 5

[0138] Similar to Example 1, except that no water-soluble polymer was added to the mixture in step (7-4) (derived from step (7-3)). The final catalyst obtained was dCAT-5. The physicochemical properties of this catalyst are shown in Table 1.

[0139] Comparative Example 6

[0140] Similar to Example 1, except that in this example, the surfactant is glyceryl monostearate, the silicone oil is methyl silicone oil, the mass ratio of surfactant to silicone oil is 1.5:8, the co-emulsifier is octadecyl alcohol, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, and the water-soluble polymer is polyvinyl alcohol (molecular weight 200,000). The mass ratio of co-emulsifier: molybdenum source (calculated as molybdenum oxide): phosphorus source (calculated as phosphorus oxide): nickel source (calculated as nickel oxide): water-soluble polymer: water is 20:271.4:45.3:77.2:70.3:400. The mass ratio of oil phase to water phase is 1:1.

[0141] The method for preparing the impregnation solution in this example is as follows:

[0142] (1) Add molybdenum oxide and phosphoric acid to deionized water in sequence. A reflux condenser is used during the reaction. The reaction starts at 28°C. During the reaction, the stirring speed is 500 r / min. When the temperature is heated to 120°C, the temperature is maintained for 4 hours. The stirring speed is kept constant until a clear solution is obtained.

[0143] (2) Add basic nickel carbonate to the clear solution obtained in step (1) to obtain an aqueous phase;

[0144] (3) The surfactant glyceryl monostearate, silicone oil, co-emulsifier octadecyl alcohol, and water-soluble polymer polyvinyl alcohol were added to the aqueous phase while stirring. The shear homogenization rate was 15,000 rpm, the shear homogenization time was 5 min, and the temperature during the shear homogenization process was 60℃. After the droplets were dispersed into an emulsion, a water-in-oil impregnation solution was obtained. The final catalyst was dCAT-6. The physicochemical properties of this catalyst are shown in Table 1.

[0145] Table 1 Physicochemical properties of residue hydrodemetallization catalysts

[0146]

[0147] Table 1 (Continued) Physicochemical Properties of Residue Hydrodemetallization Catalysts

[0148]

[0149]

[0150] Evaluation test

[0151] The activity and stability tests of the residue hydrodemetallization catalysts CAT-1-CAT-6 and dCAT-1-dCAT-6 were conducted in a 200 mL fixed-bed hydrotreating experimental setup. All catalysts used were strip-shaped with a length of 2–3 mm. The reaction conditions were: reaction temperature 385 °C, hydrogen partial pressure 13.0 MPa, and liquid hourly space velocity 1.0 h⁻¹. -1 With a hydrogen-to-oil volume ratio of 750, the demetallization rate (Ni+V) of each catalyst after 1500 h of reaction is shown in Table 3. The properties of vacuum residue oil as feedstock are shown in Table 2.

[0152] Table 2 Properties of Crude Oil

[0153] <![CDATA[Density (20°C), g / cm 3 > 1.016 S, wt% 2.55 N, wt% 0.47 Ni, mg / g 62.6 V, mg / g 115.3 CCR, wt% 15.5

[0154] Table 3. Test results of residue hydrodemetallization catalysts for each example.

[0155] Catalyst number CAT-1 CAT-2 CAT-3 CAT-4 CAT-5 CAT-6 Demetallization rate, % 67.4 66.7 66.1 66.3 66.8 67.4

[0156] Table 3 continues with the test results of various residue hydrodemetallization catalysts.

[0157] Catalyst number dCAT-1 dCAT-2 dCAT-3 dCAT-4 dCAT-5 dCAT-6 Demetallization rate, % 59.2 59.5 59.4 58.7 58.3 59.4

[0158] As can be seen from Tables 1, 2 and 3, the hydrodemetallization catalyst prepared according to the method of the present invention has a more unobstructed pore structure and a suitable specific surface area. It maintains high reactivity and stability during the reaction process and can well meet the requirements of hydrodemetallization process of heavy oil, especially residue oil.

Claims

1. A method for preparing a catalyst for hydrodemetallization of residual oil, comprising the following steps: (1) Alumina A was immersed in a first ammonium bicarbonate aqueous solution and then sealed and heat-treated, and dried to obtain carrier component B; (2) Impregnate activated carbon with the first active metal component to obtain a dispersion medium containing the first active metal component; (3) Mix the carrier component B obtained in step (1) and the dispersion medium obtained in step (2) into a mold, and calcine to obtain carrier C; (4) The carrier C obtained in step (3) is immersed in the second ammonium bicarbonate aqueous solution, sealed and dried to obtain carrier D; (5) Impregnate the carrier D obtained in step (4) with a water-in-oil impregnation solution containing the second active metal component, and calcine to obtain the residue oil hydrodemetallization catalyst; In step (1), alumina A is prepared using the following method: (1-1) Mix aluminum nitrate, urea, template agent and water to obtain solution X; (1-2) Crystallize and calcine the solution X obtained in step (1-1) to obtain aluminum oxide A; In step (1-1), the molar ratio of Al(NO3)3 to the template agent is 160~240, and the molar ratio of urea to Al(NO3)3 is 7~14; In step (4), the mass percentage concentration of the second ammonium bicarbonate aqueous solution ranges from 20% to 30%. In step (4), the sealing temperature is 10~60℃ and the drying temperature is 10~40℃; In step (5), the preparation process of the "water-in-oil" impregnation solution containing the second active metal component includes: (a) Add the surfactant to the oil and heat to obtain the oil phase; (b) Mix the co-emulsifier, the Group VIB metal source, water, and optional auxiliary agent source, and heat to obtain a clear solution; (c) Add a Group VIII metal source to the clear solution obtained in step (b) to obtain a mixture; (d) Add a water-soluble polymer to the mixture obtained in step (c) to obtain an aqueous phase; (e) The aqueous phase from step (d) is added dropwise to the oil phase obtained in step (a) while the oil phase remains liquid during the dropwise addition. Simultaneously, the mixture is stirred, sheared, and homogenized to obtain the impregnation solution. In step (a), the mass ratio of the added surfactant to the mass of the oil is 1.0:0.1~10.

2. The preparation method according to claim 1, characterized in that, In step (1-1), the molar ratio of Al(NO3)3 to the template agent is 180~220.

3. The preparation method according to claim 1, characterized in that, In step (1-1), the template agent is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methylcellulose; the viscosity of the template agent at 20°C is 10~1000 mPa·s, and the viscosity of the solution after adding the template agent and stirring evenly at 20°C is 120~660 mPa·s.

4. The preparation method according to claim 1, characterized in that, In steps (1-2), the crystallization temperature is 80~200℃ and the crystallization time is 25~35h.

5. The preparation method according to claim 1, characterized in that, In step (a), the heating temperature is 40~80℃; And / or, in step (b), the heating to a temperature of 90~120°C; And / or, in step (e), the stirring-shear homogenization process is carried out at a stirring speed of 10,000 to 18,000 rpm, a shear homogenization time of 3 to 8 min, and a temperature of 50 to 85°C.

6. The preparation method according to claim 1, characterized in that, In step (a), the surfactant is selected from one or more of glyceryl monostearate, glyceryl distearate, glyceryl monolaurate, and polyoxyethylene ether fatty alcohol; and / or, the oil is selected from at least one of silicone oil and vegetable oil, wherein the silicone oil is at least one of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen silicone oil, and methyl phenyl silicone oil, and the vegetable oil is selected from one or more of peanut oil, coconut oil, and tea seed oil; And / or, in step (b), the co-emulsifier is selected from one or more of hexadecyl alcohol, octadecanol, propylene glycol, n-butanol and glycerol; And / or, in step (b), the Group VIB metal is Mo; the additive is at least one of fluorine, phosphorus, silicon or boron; in step (c), the Group VIII metal is Ni and / or Co; And / or, in step (d), the water-soluble polymer is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide, carboxymethyl cellulose, gelatin, gum arabic, and sodium polyacrylate.

7. The preparation method according to claim 6, characterized in that, In step (b), the amount of the co-emulsifier is 0.5% to 5.0% of the mass of the aqueous phase obtained in step (d). And / or, in step (d), the mass concentration of the water-soluble polymer in the aqueous phase is 4.0% to 14.0%.

8. The preparation method according to claim 1, characterized in that, In step (a), the mass ratio of the surfactant added to the oil is 1.0:2~10; And / or, in step (e), the mass ratio of the aqueous phase to the oil phase is 0.4~12.0:1.

0.

9. The preparation method according to claim 8, characterized in that, In step (e), the mass ratio of the aqueous phase to the oil phase is 0.5~9.0:1.

0.

10. The preparation method according to claim 1, characterized in that, In step (1), the mass percentage concentration of the first ammonium bicarbonate aqueous solution ranges from 10% to 20%. And / or, the mass percentage concentration of the second ammonium bicarbonate aqueous solution in step (4) is 8 to 15 percentage points higher than the mass percentage concentration of the first ammonium bicarbonate aqueous solution in step (1).

11. The preparation method according to claim 1, characterized in that, In step (1), the sealing heat treatment temperature is 80~140℃ and the treatment time is 6~12h; the drying temperature is 120~180℃ and the drying time is 2~10h. And / or, in step (4), the sealing treatment temperature is 20~50℃, the treatment time is 6~12h, and the drying time is 2~10h; And / or, the sealing treatment temperature in step (4) is 60~90°C lower than the sealing heat treatment temperature in step (1).

12. The preparation method according to claim 11, characterized in that, In step (1), the sealing heat treatment temperature is 90~140℃.

13. The preparation method according to claim 1, characterized in that, In step (2), when the activated carbon is impregnated with the first active metal component, an impregnation solution containing the first active metal component is used; the contents of MoO3 and Group VIII metal oxides in the impregnation solution are 2~30g / 100mL and 2~50g / 100mL, respectively. And / or, in step (3), the mass ratio of activated carbon to carrier component B in the dispersion medium obtained in step (2) is 0.12~0.

38.

14. The preparation method according to claim 1, characterized in that, In step (5), the calcination temperature is 350~500℃, the calcination time is 2~6h, and the calcination atmosphere is a mixture of an inert atmosphere and other atmospheres; wherein, the inert atmosphere is one or two of nitrogen and helium, and the other atmosphere is one or more of water vapor and air.

15. A catalyst for hydrodemetallization of residue oil prepared by any one of claims 1-14.

16. The catalyst according to claim 15, characterized in that, The catalyst comprises a support component, an active metal component, and carbon distributed on the catalyst surface. The active metal component includes molybdenum and Group VIII metals, and the support component includes alumina and activated carbon. The ratio of the carbon content on the catalyst surface to the alumina content in the support component is 0.16 to 0.50, and the ratio of the activated carbon content to the alumina content in the support component is 0.10 to 0.

35. And / or, based on catalyst mass, the content of MoO3 is 6.0% to 20.0% and the content of Group VIII metal oxides is 1.0% to 8.0%.

17. The catalyst according to claim 16, characterized in that, The ratio of carbon content on the catalyst surface to alumina content in the support component is 0.25~0.

45.

18. The catalyst according to claim 16, characterized in that, The catalyst includes an auxiliary component, which is selected from at least one of fluorine, phosphorus, silicon or boron.

19. The catalyst according to claim 18, characterized in that, The auxiliary agent component is phosphorus.

20. The catalyst according to claim 18, characterized in that, Based on the mass of the catalyst, the content of the auxiliary component, calculated as oxide, is 0~8.0%.

21. The catalyst according to claim 20, characterized in that, Based on the mass of the catalyst, the content of the auxiliary component, calculated as oxide, is 1.0% to 8.0%.

22. The catalyst according to claim 16, characterized in that, The catalyst has a specific surface area of ​​160~200m². 2 / g, with a pore volume of 0.60~1.00mL / g; And / or, the pore distribution of the catalyst is as follows: pores with a diameter <30 nm occupy 25%~35% of the total pore volume, pores with a diameter of 30~100 nm occupy 30%~45% of the total pore volume, and pores with a diameter of 100 nm~300 nm occupy 20%~45% of the total pore volume; And / or, the strength of the catalyst is 10.0~28.0 N / mm.

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