Residue hydrodemetallization catalyst and method for making same

Abstract

The application discloses a residual oil hydrodemetallization catalyst and a preparation method thereof. The preparation method of the catalyst comprises the following steps: (1) after alumina A is immersed in a first ammonium bicarbonate aqueous solution, the alumina A is sealed and heat-treated, and then dried to obtain a carrier component B; (2) the carrier component B obtained in the step (1) and a first active metal component source are mixed and formed, and then calcined to obtain a carrier C; (3) the carrier C obtained in the step (2) is immersed in a second ammonium bicarbonate aqueous solution, and then sealed and treated, and then dried to obtain a carrier D; and (4) the carrier D obtained in the step (3) is loaded with a second active metal component, and then calcined to obtain the residual oil hydrodemetallization catalyst. The residual oil hydrodemetallization catalyst provided by the application is used in a residual oil hydrodemetallization reaction process, and the activity and stability of the reaction are obviously improved.

Description

Technical Field

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

[0002] Currently, most traditional residue hydrotreating catalysts are supported hydrotreating catalysts, where the active metal components are typically supported on the surface of a carrier. However, in the actual reaction process, under the action of the catalyst, various metal compounds react with H₂S to form metal sulfides. These metal sulfides then deposit on the catalyst, thus being removed. Therefore, the specific surface area of ​​the catalyst not only affects the distribution of active metals when they are supported, but also further influences the catalyst's reactivity and performance.

[0003] CN105983417A discloses a method for preparing a hydrodemetallization catalyst for residual oil, comprising the following steps: mixing one or more selected from alumina trihydrate, boehmite, pseudoboehmite, and amorphous aluminum hydroxide with a peptizing agent, an extrusion aid, and an organic solution until homogeneous; then molding, drying, and calcining to obtain a support. Impregnating the obtained support with a solution containing nickel and molybdenum, followed by drying and calcining, yields the final catalyst. The catalyst obtained by this method has a pore volume of 0.80–1.20 mL / g and a specific surface area of ​​100–180 m² / g. 2 / g, the catalyst has a bimodal pore distribution, with the most probable pore size of the micropore portion of the catalyst located in the range of 10-40 nm and the most probable pore size of the macropore portion located in the range of 60-800 nm.

[0004] CN102600913A discloses a method for preparing an aqueous solution for impregnation with molybdenum, nickel, and phosphorus. The method involves first preparing an aqueous solution containing soluble molybdenum, nickel, and phosphorus, then adding a complex or organic acid. After complete dissolution, the remaining nickel is added, and the mixture is heated to boiling until completely dissolved. This method offers advantages such as adjustable molybdenum-nickel ratio, simple preparation process, large dissolution capacity, and long stability time, and can be used to prepare impregnation solutions for hydrogenation catalysts.

[0005] CN103055956B discloses an impregnation solution for a hydrogenation catalyst and a method for preparing the same. The method includes: preparing an aqueous solution A from a Group VIII metal compound and a first organic complexing agent; preparing an aqueous solution B from a Group VIB metal compound; and then mixing the aqueous solutions A and B; wherein the ligand of the first organic complexing agent contains at least a coordinating atom N.

[0006] The alumina supports prepared by the above methods not only have a limited pore size distribution, but also suffer from insufficient dispersion of active metals due to the predominantly aqueous solution impregnation process, which is detrimental to the effective hydrogenation activity of the subsequent catalyst. Therefore, the activity and stability of the alumina supports and hydrogenation demetallization catalysts prepared by the above methods still need further improvement. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a residue hydrodemetallization catalyst and its preparation method. The residue hydrodemetallization catalyst provided by this invention significantly improves both the activity and stability of the reaction during the residue hydrodemetallization process.

[0008] The first aspect of this invention provides a method for preparing a hydrodemetallization catalyst for 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) Mix the carrier component B obtained in step (1) with the first active metal component source, knead and shape them, and calcine them to obtain carrier C;

[0011] (3) The carrier C obtained in step (2) is immersed in the second ammonium bicarbonate aqueous solution, sealed and dried to obtain carrier D;

[0012] (4) Load the second active metal component onto the carrier D obtained in step (3) and calcine it to obtain the residue oil hydrodemetallization catalyst.

[0013] In step (1) of this invention, the method for preparing alumina A includes:

[0014] (I) Mix aluminum nitrate, urea, template agent and water to obtain solution X;

[0015] (II) Crystallize the solution X obtained in step (I) and calcine it to obtain aluminum oxide A.

[0016] In this invention, all crystallization processes are carried out in a crystallization reactor.

[0017] In step (I) 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.

[0018] In step (I) of this invention, the molar ratio of Al(NO3)3 to the template agent is 160 to 240.

[0019] In step (I) 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 Al3+ The hydrolysis rate is well-matched, and the generated aluminum hydroxide can grow uniformly on the template agent surface.

[0020] In step (I) of this invention, the template agent is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methylcellulose, preferably polyethylene glycol; the viscosity (20°C) of the template agent is 10-1000 mPa·s, and the viscosity (20°C) of solution X after adding the template agent and stirring evenly is 120-660 mPa·s.

[0021] In step (II) of this invention, the crystallization temperature is 80–200°C, and the crystallization time is 25–35 h. The crystallization is carried out in a crystallization reactor.

[0022] In step (II) of this invention, after crystallization, the solution is first filtered and washed using conventional and known methods, and then dried and calcined. Washing can be performed with deionized water until the pH of the filtrate is close to neutral.

[0023] In step (II) of this invention, the drying temperature is 120-200℃ and the drying time is 2-12h.

[0024] In step (II) of this invention, the calcination temperature is 500-750°C, the calcination time is 2-6 hours, and the calcination atmosphere is air.

[0025] In step (1) of this invention, the mass concentration of the first ammonium bicarbonate aqueous solution is 10%–20%. The sealing heat treatment temperature is 80–140°C, preferably 90–140°C, and the treatment time is 6–12 h. The drying temperature is 120–180°C, and the drying time is 2–10 h.

[0026] In step (2) of this invention, the first active metal component source is a molybdenum-containing compound and a Group VIII metal-containing compound. The Group VIII metal is preferably nickel.

[0027] In step (2) of this invention, the molybdenum-containing compound is at least one of molybdenum oxide and ammonium molybdate, and the group VIII metal (preferably Ni) compound is at least one of basic nickel carbonate and nickel nitrate.

[0028] In step (2) of the present invention, the amount of MoO3 introduced into the catalyst by the first active metal component is 25% to 50% 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 50% of the total Group VIII metal oxide loading in the catalyst.

[0029] In step (2) 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.

[0030] In step (2) of the present invention, the amount of adhesive solvent added (mass percentage) accounts for 1.0% to 5.0% of the carrier component B, and the amount of extrusion aid added (mass percentage) accounts for 0.2% to 5.0% of the carrier component B.

[0031] In step (2) 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.

[0032] In step (2) of this invention, the calcination temperature is 500-800℃, the calcination time is 2-6h, and the calcination atmosphere is air.

[0033] In step (3) 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 (3) is 70–80°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.

[0034] In step (3) 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).

[0035] In step (4) 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.

[0036] In step (4) of this invention, the method of loading the second active metal component preferably employs a method of impregnating the carrier D with a water-in-oil impregnation solution containing the second active metal component, wherein the preparation method of the water-in-oil impregnation solution containing the second active metal component includes:

[0037] (a) A surfactant is added to the oil and heated to obtain the oil phase;

[0038] (b) Mix the co-emulsifier, the Group VIB metal source, water, and optional auxiliary source, and heat to obtain a clear solution;

[0039] (c) Add a Group VIII metal source to the clear solution obtained in step (b);

[0040] (d) Add a water-soluble polymer to the mixture obtained in step (c) to obtain an aqueous phase;

[0041] (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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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).

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] In step (d) of this invention, the concentration of Group VIB metals (calculated as oxides) in the aqueous phase is 8–65 g / 100 mL, preferably 10–60 g / 100 mL, and the concentration of Group VIII metals (calculated as oxides) is 2–55 g / 100 mL, preferably 5–35 g / 100 mL. The concentration of the auxiliaries (calculated as oxides) is 0–8.0 g / 100 mL, preferably 0–6.0 g / 100 mL.

[0052] 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).

[0053] In step (d) of this invention, the mass concentration of the water-soluble polymer in the aqueous phase is 4.0% to 14.0%.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] In step (4) of this invention, the saturated immersion method is used for impregnation, and the standing time after impregnation is 4 to 14 hours.

[0058] In step (4) of the present invention, the amount of MoO3 introduced into the catalyst by the second active metal component is 50% 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 50% to 75% of the total Group VIII metal oxide loading in the catalyst.

[0059] In step (4) 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.

[0060] In step (4) of this invention, the calcination temperature is 350–600°C, the calcination time is 2–6 h, and the calcination atmosphere is a mixture of an inert atmosphere and other atmospheres, with a volume ratio of inert atmosphere to other atmospheres of 0.5–4.5:1. The inert atmosphere is one or both of nitrogen and helium, and the other atmosphere is one or both of water vapor and air.

[0061] The second aspect of the present invention provides a residue hydrodemetallization catalyst prepared by any of the preparation methods described in the first aspect, comprising a support containing a first active metal component, a second active metal component, and carbon distributed on the surface of the catalyst, wherein the mass ratio of the first active metal component (calculated as oxide) to the second active metal component (calculated as oxide) is 1.0:1.0 to 3.0.

[0062] In this invention, the first active metal component comprises molybdenum and a Group VIII metal, and the second active metal component comprises molybdenum and a Group VIII metal; the support is alumina. Further, in the catalyst, the mass ratio of carbon to alumina distributed on the catalyst surface is 0.15–0.45.

[0063] In this invention, the active metal component includes molybdenum and a Group VIII metal, wherein the Group VIII metal is preferably nickel.

[0064] In this invention, based on the mass of the catalyst, the content of MoO3 is 5.0% to 15.0%, and the content of Group VIII metal oxides is 1.0% to 8.0%.

[0065] In this invention, the catalyst has a specific surface area of ​​150–230 m². 2 / g, with a pore volume of 0.50~0.95mL / g.

[0066] In this invention, preferably, the catalyst has a specific surface area of ​​160–210 m². 2 / g, with a pore volume of 0.65~0.90mL / g.

[0067] In this invention, the pore distribution of the catalyst is as follows: pores with a diameter of <30 nm occupy 15% to 30% of the total pore volume, pores with a diameter of 30 to 100 nm occupy 35% to 45% of the total pore volume, and pores with a diameter of 100 nm to 300 nm occupy 25% to 50% of the total pore volume.

[0068] In this invention, the strength of the catalyst is 10.0 to 25.0 N / mm.

[0069] 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 0-5.0%, preferably 0.5%-5.0%.

[0070] Compared with the prior art, the present invention has the following beneficial effects:

[0071] Currently, for hydrodemetallization processes, catalysts with larger pore sizes and better dispersion of surface active metals are key to further enhancing catalyst performance. The inventors discovered that alumina matrices prepared by a uniform precipitation method have a large specific surface area and better pore structure. Furthermore, through processes such as post-sealing heat treatment with ammonium bicarbonate aqueous solution, mixing with some active metals, molding, drying, and calcining, a support containing some active metals with unobstructed pores and a suitable specific surface area can be obtained. Then, the obtained support is subjected to another ammonium bicarbonate aqueous solution sealing treatment. Finally, the support is impregnated with a water-in-oil type impregnation solution containing the remaining active metal components and calcined to prepare a catalyst with a more uniform distribution of active metals inside and on the surface of the support.

[0072] In the preparation of the "water-in-oil" impregnation solution of this invention, a surfactant is first used to effectively disperse the aqueous phase containing the second active metal component (containing a main metal and a co-metal) in the oil phase. Utilizing the high dispersion of the aqueous phase in the oil phase, the aqueous phase serves as the carrier matrix for the metal component. The oil phase uniformly disperses the metal in the aqueous phase on the surface and within the pores of the carrier, resulting in "water-in-oil" droplets that can penetrate deep into the pores and surface of the carrier. The aqueous phase of the "water-in-oil" impregnation solution of this invention contains a water-soluble polymer as a "protective layer" for the colloidal particles. During the subsequent formation of the "water-in-oil" emulsion, this water-soluble polymer adsorbs onto the surface of the colloidal particles, forming a surface layer of a certain thickness. This effectively hinders collisions and aggregation between the colloidal particles, controlling particle size and maintaining particle size distribution, thus improving the stability of the system. Furthermore, the water-soluble polymer added to the "water-in-oil" impregnation solution forms dotted carbon dots due to incomplete decomposition during calcination, which can appropriately adjust the acidity of the catalyst surface and weaken the interaction between the active metal and the carrier.

[0073] Through the comprehensive coordination of each step, this invention produces a catalyst that not only possesses high mechanical strength and a concentrated pore distribution, but also has suitable pore volume and pore size, resulting in significantly improved catalyst activity and stability. Using the catalyst of this invention, the demetallization rate can reach over 65% after 1500 hours of reaction, and can even reach 68.7%. Detailed Implementation

[0074] In this invention, the pore structure (SVD) and specific surface area of ​​the catalyst are characterized using the Mack ASAP-2420 physical adsorption instrument.

[0075] In this invention, the ZQJ-III intelligent particle strength tester is used to test the crushability of catalyst particles.

[0076] In this invention, the carbon / alumina mass ratio on the catalyst surface was determined using a NETZSCH STA409PC-QMS403C thermogravimetric-mass spectrometer (TG-MS).

[0077] 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.

[0078] Example 1

[0079] (I) Weigh 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 2:10, and the molar ratio of urea to Al(NO3)3 is 1:1. Dissolve the above substances in a certain amount of deionized water in the order of aluminum nitrate, urea, and polyethylene glycol. After mixing evenly by magnetic stirring for 4 hours, solution X (viscosity 290 mPa·s) is obtained.

[0080] (II) The obtained solution X is transferred to a crystallization vessel, and then the crystallization vessel is placed in an oven at 160°C. After reacting for 34 hours, the crystallization vessel is removed and cooled. A mixed slurry containing a white precipitate is obtained in the reaction vessel. The obtained white precipitate is filtered and washed several times until the pH value of the filtrate is close to 7. The white precipitate is placed in an oven to dry at 150°C for 3 hours. Then it is calcined in a muffle furnace at 650°C for 3 hours to obtain alumina A.

[0081] (1) The obtained alumina A was immersed in the first ammonium bicarbonate aqueous solution and then sealed for heat treatment to obtain carrier component B. The mass percentage concentration of the ammonium bicarbonate aqueous solution was 18%, the sealing heat treatment temperature was 90℃, the treatment time was 6h, the drying temperature was 150℃, and the drying time was 3h.

[0082] (2) The carrier component B, nitric acid (68wt%), guar gum powder, the first active metal component source (active metal source is nickel nitrate and ammonium molybdate), and deionized water are mixed, shaped, dried, and calcined to obtain carrier C; wherein, the mass content of nitric acid (68wt%) added is 1.0% of the carrier component B, and the mass content of guar gum powder added is 1.5% of the carrier component B. During the shaping process, the content of deionized water added is adjusted in real time according to the material state. The drying temperature is 160℃, the drying time is 4h, the calcination temperature is 750℃, and the calcination time is 3h (heating rate is 2.5℃ / min); wherein the amount of MoO3 introduced into the catalyst by the first active metal component is 40% of the total MoO3 loading in the catalyst, and the amount of NiO is 40% of the total NiO loading in the catalyst;

[0083] (3) The obtained carrier C was immersed in the second 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 20℃, the treatment time was 8h, the drying temperature was 30℃, the drying time was 5h, and the drying method was static drying.

[0084] Preparation of a water-in-oil impregnation solution containing a second active metal component:

[0085] 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 1:8. 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 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 20:269.2:44.9:59.8:70.3:400. The mass ratio of oil phase to water phase is 1:0.9.

[0086] (a) 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;

[0087] (b) 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 500 r / min. When the temperature is raised to 120°C, the temperature is maintained for 4 hours. The stirring speed is kept constant until a clear solution is obtained.

[0088] (c) Add basic nickel carbonate to the clear solution obtained in step (b);

[0089] (d) Add water-soluble polyvinyl alcohol to the mixture obtained in step (c) to obtain an aqueous phase;

[0090] (e) The aqueous phase from step (d) is added dropwise to the oil phase obtained in step (a). During the addition, the temperature of the oil phase is maintained at 80°C, and the mixture is stirred. The shear homogenization rate is 15,000 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.

[0091] (4) The carrier D was impregnated by a saturated impregnation method with an impregnation solution containing the second active metal component (MoO3 content of 29.05 g / 100 mL, NiO content of 4.88 g / 100 mL, and P content in the auxiliary phosphoric acid as oxide of 4.36 g / 100 mL). The amount of MoO3 introduced into the catalyst by the second active metal component was 60% of the total MoO3 loading in the catalyst, and the amount of NiO was 60% of the total NiO loading in the catalyst. After impregnation, the sample was allowed to stand at room temperature (25 °C) for 6 h, and then dried (temperature of 120 °C, drying time of 6 h). The calcination temperature was 550 °C, the calcination time was 3 h (heating rate of 2.0 °C / min), and the calcination atmosphere was a mixed atmosphere of nitrogen and air (nitrogen to air volume ratio of 3:1) to obtain the residue oil hydrodemetallization catalyst. The above-prepared residue oil hydrodemetallization catalyst was named CAT-1. The physicochemical properties of the catalyst are shown in Table 1.

[0092] Example 2

[0093] Similar to Example 1, except that in step (I), the molar ratio of Al(NO3)3 to polyethylene glycol is 2:1:5, and the molar ratio of urea to Al(NO3)3 is 1:0; in step (II), the obtained solution X is transferred to a crystallization vessel, which is then placed in an oven at 180°C. After reacting for 28 hours, the crystallization vessel is removed, and the white precipitate is dried in an oven at 120°C for 6 hours. It is then calcined in a muffle furnace at 600°C for 4 hours to obtain the residue oil hydrodemetallization catalyst CAT-2. The physicochemical properties of the catalyst are shown in Table 1.

[0094] Example 3

[0095] Similar to Example 1, except that in step (1), the mass percentage concentration of the first ammonium bicarbonate aqueous solution is 16%, the sealing heat treatment temperature is 110℃, the treatment time is 7h, and the drying temperature is 150℃ for 4h; in step (3), the mass percentage concentration of the second ammonium bicarbonate aqueous solution is 26%, the sealing treatment temperature is 40℃, the treatment time is 6h, and the drying temperature is 40℃ for 6h; thus, the residue oil hydrodemetallization catalyst CAT-3 was obtained. The physicochemical properties of the catalyst are shown in Table 1.

[0096] Example 4

[0097] Same as Example 1, except that the process for preparing the "water-in-oil" impregnation solution containing the second active metal component is as follows:

[0098] 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 0.95:8. 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 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 24:269.2:44.9:59.8:90.3:400. The mass ratio of oil phase to water phase is 1:1.

[0099] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0100] (a) Add the surfactant glyceryl distearate to the silicone oil, heat to 70°C, and wait for the silicone oil to melt to obtain the oil phase;

[0101] (b) 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 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.

[0102] (c) Add basic nickel carbonate to the clear solution obtained in step (b);

[0103] (d) Add water-soluble polymer carboxymethyl cellulose to the mixture obtained in step (c) to obtain an aqueous phase;

[0104] (e) The aqueous phase from step (d) is added dropwise to the oil phase obtained in step (a). During the addition, the oil phase temperature is maintained at 65°C while stirring. The shear homogenization rate is 16000 rpm, the shear homogenization time is 5 min, and the temperature during shear homogenization is 75°C. After the droplets disperse 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; thus, the hydrodemetallization catalyst CAT-4 is prepared. The physicochemical properties of the catalyst are shown in Table 1.

[0105] Example 5

[0106] Same as Example 1, except that the process for preparing the "water-in-oil" impregnation solution containing the second active metal component is as follows:

[0107] 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 0.9:8. 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 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 28:269.2:44.9:59.8:111.3:400. The mass ratio of oil phase to water phase is 1:1.2.

[0108] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0109] (a) Add the surfactant glyceryl monolaurate to the silicone oil, heat to 65°C, and wait for the silicone oil to melt to obtain the oil phase;

[0110] (b) Add the co-emulsifier octadecanol, 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 raised to 120°C, the temperature is maintained for 4 hours. The stirring speed is kept constant until a clear solution is obtained.

[0111] (c) Add basic nickel carbonate to the clear solution obtained in step (b);

[0112] (d) Add water-soluble sodium polyacrylate to the mixture obtained in step (c) to obtain an aqueous phase;

[0113] (e) The aqueous phase from step (d) is added dropwise to the oil phase obtained in step (a). During the addition, the oil phase temperature is maintained at 60°C while stirring. The shear homogenization rate is 17000 rpm, the shear homogenization time is 6 min, and the temperature during shear homogenization is 85°C. After the droplets disperse 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 70.0% of the total MoO3 loading in the catalyst, and the amount of NiO is 70.0% of the total NiO loading in the catalyst; thus, the hydrodemetallization catalyst CAT-5 is prepared. The physicochemical properties of the catalyst are shown in Table 1.

[0114] Example 6

[0115] Same as Example 1, except that the process for preparing the "water-in-oil" impregnation solution containing the second active metal component is as follows:

[0116] 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 0.85:8. 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 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 28:269.2:44.9:59.8:51.3:400. The mass ratio of oil phase to water phase is 1:1.3.

[0117] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0118] (a) Add the surfactant polyoxyethylene ether fatty alcohol to the silicone oil, heat to 60°C, and wait for the silicone oil to melt to obtain the oil phase;

[0119] (b) 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 400 r / min. When the temperature is raised to 120°C, the temperature is maintained for 4 h. The stirring speed is kept constant until a clear solution is obtained.

[0120] (c) Add basic nickel carbonate to the clear solution obtained in step (b);

[0121] (d) Add water-soluble polymer gelatin to the mixture obtained in step (c) to obtain an aqueous phase;

[0122] (e) The aqueous phase from step (d) is added dropwise to the oil phase obtained in step (a). During the addition, the oil phase temperature is maintained at 50°C while stirring. The shear homogenization rate is 14000 rpm, the shear homogenization time is 3 min, and the temperature during shear homogenization is 60°C. After the droplets disperse 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 75.0% of the total MoO3 loading in the catalyst, and the amount of NiO is 75.0% of the total NiO loading in the catalyst; thus, the hydrodemetallization catalyst CAT-6 is prepared. The physicochemical properties of the catalyst are shown in Table 1.

[0123] Comparative Example 1

[0124] Similar to Example 1, except that in step (I), the molar ratio of Al(NO3)3 to polyethylene glycol is 245, and the molar ratio of urea to Al(NO3)3 is 6. 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 8 hours to mix evenly, solution X is obtained; thus, the residue oil hydrodemetallization catalyst dCAT-1 is prepared. The physicochemical properties of this catalyst are shown in Table 1.

[0125] Comparative Example 2

[0126] Similar to Example 1, except that in step (3), the mass percentage concentration of the second ammonium bicarbonate aqueous solution is 35%, the sealing temperature is 70°C, the treatment time is 6 hours, the drying temperature is 120°C, and the drying time is 6 hours; thus, the residue oil hydrodemetallization catalyst dCAT-2 is obtained. The physicochemical properties of this catalyst are shown in Table 1.

[0127] Comparative Example 3

[0128] Similar to Example 1, except that no active metal is added during the mixing process in step (2), and instead, in step (4), the support D is directly impregnated with the Mo-Ni-P "water-in-oil" impregnation solution prepared according to the method of Example 1 in a saturated impregnation manner to obtain the residue oil hydrodemetallization catalyst dCAT-3. The physicochemical properties of the catalyst are shown in Table 1.

[0129] Comparative Example 4

[0130] Similar to Example 1, except that in step (a), the mass ratio of surfactant to silicone oil is 0.60:8. The final catalyst obtained is dCAT-4. The physicochemical properties of this catalyst are shown in Table 1.

[0131] Comparative Example 5

[0132] Similar to Example 1, except that no water-soluble polymer was added to the mixture in step (d) (derived from step (c)). The final catalyst obtained was dCAT-5. The physicochemical properties of this catalyst are shown in Table 1.

[0133] Comparative Example 6

[0134] Same as Example 1, except that the preparation process of the impregnation solution containing the second active metal component is as follows:

[0135] The surfactant is glyceryl monostearate, the silicone oil is methyl silicone oil, and the mass ratio of surfactant to silicone oil is 1:8. 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 polyvinyl alcohol (molecular weight 200,000). The mass ratio of co-emulsifier (calculated as molybdenum oxide): phosphorus source (calculated as phosphorus oxide): nickel source (calculated as nickel oxide): water-soluble polymer: water is 20:269.2:44.9:59.8:70.3:400. The mass ratio of oil phase to water phase is 1:0.9.

[0136] The method for preparing the impregnation solution containing the second active metal component in this example is as follows:

[0137] (a) Molybdenum oxide and phosphoric acid were added to deionized water in sequence. A reflux condenser was used during the reaction. The reaction started at 28°C. During the reaction, the stirring speed was 500 r / min. When the temperature was raised to 120°C, it was maintained for 4 h. The stirring speed was kept constant until a clear solution was obtained.

[0138] (b) Add basic nickel carbonate to the clear solution obtained in step (a) to obtain an aqueous phase;

[0139] (c) The surfactant glyceryl monostearate, silicone oil, co-emulsifier n-butanol, 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.

[0140] Table 1 Physicochemical properties of residue hydrodemetallization catalysts

[0141]

[0142]

[0143] Table 1 (Continued) Physicochemical Properties of Residue Hydrodemetallization Catalysts

[0144] Catalyst number dCAT-1 dCAT-2 dCAT-3 dCAT-4 dCAT-5 dCAT-6 <![CDATA[Specific surface area, m 2 / g]]> 152 155 158 154 165 159 <![CDATA[Pore volume, cm 3 / g]]> 0.54 0.63 0.58 0.56 0.64 0.66 Pore ​​distribution, % <30nm 42 37 36 41 39 36 30~100nm 32 37 34 38 35 41 100~300nm 26 26 30 21 26 23 Strength, N / mm 14.8 14.2 15.1 15.3 15.2 15.5 Active ingredient content <![CDATA[MoO3,wt%]]> 12.4 12.3 12.5 12.3 12.4 12.2 NiO, wt% 2.4 2.6 2.5 2.3 2.5 2.2 Additive content <![CDATA[P2O5,wt%]]> 2.3 2.1 2.3 2.2 2.4 2.3 carbon / alumina mass ratio 0.13 0.07 0.14 0.09 — 0.11

[0145] Evaluation test

[0146] 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 apparatus. All catalysts used were strip-shaped with a length of 2–3 mm. The reaction conditions were: reaction temperature 380 °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.

[0147] Table 2 Properties of Crude Oil

[0148] <![CDATA[Density (20°C), g / cm 3 > 1.014 S, wt% 2.67 N, wt% 0.52 Ni, mg / g 63.6 V, mg / g 113.4 CCR, wt% 14.5

[0149] Table 3. Test results of residue hydrodemetallization catalysts for each example.

[0150] Catalyst number CAT-1 CAT-2 CAT-3 CAT-4 CAT-5 CAT-6 Demetallization rate, % 68.7 67.6 67.5 66.4 66.7 67.3

[0151] Table 3 continues with the test results of various residue hydrodemetallization catalysts.

[0152] Catalyst number dCAT-1 dCAT-2 dCAT-3 dCAT-4 dCAT-5 dCAT-6 Demetallization rate, % 62.2 60.6 61.3 62.4 59.8 61.7

[0153] As can be seen from Tables 1, 2 and 3, the hydrodemetallization catalyst prepared according to the method of the present invention has a smooth pore structure and a large specific surface area. It exhibits 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 residue oil hydrodemetallization catalyst, 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) Mix the carrier component B obtained in step (1) with the first active metal component source, knead and shape them, and calcine them to obtain the carrier C; (3) The carrier C obtained in step (2) is immersed in the second ammonium bicarbonate aqueous solution, sealed and dried to obtain carrier D; (4) Load the second active metal component onto the carrier D obtained in step (3) and calcine it to obtain the residue oil hydrodemetallization catalyst; In step (1), the preparation method of alumina A includes: (I) Mix aluminum nitrate, urea, template agent and water to obtain solution X; (II) Crystallize and calcine the solution X obtained in step (I) to obtain aluminum oxide A; In step (I), 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 (3), the mass percentage concentration of the second ammonium bicarbonate aqueous solution ranges from 20% to 30%. In step (3), the sealing temperature is 10~60℃ and the drying temperature is 10~40℃; Step (4) describes a method for loading the second active metal component by impregnating the carrier D with a water-in-oil impregnation solution containing the second active metal component. The preparation method 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 oil is 1.0:0.1~10.

2. The preparation method according to claim 1, characterized in that, In step (I), 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 at 20°C after adding the template agent and stirring evenly is 120~660 mPa·s.

3. The preparation method according to claim 2, characterized in that, In step (I), the template agent is polyethylene glycol.

4. The preparation method according to claim 1, characterized in that, In step (II), 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 (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 is 8 to 15 percentage points higher than that of the first ammonium bicarbonate aqueous solution.

6. 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 (3), the sealing treatment time is 6~12h; the drying time is 2~10h; And / or, the sealing treatment temperature in step (3) is 70~80°C lower than the sealing heat treatment temperature in step (1).

7. The preparation method according to claim 6, characterized in that, In step (1), the sealing heat treatment temperature is 90~140℃; in step (3), the sealing treatment temperature is 20~50℃.

8. The preparation method according to claim 1, characterized in that, In step (2), the first active metal component source is a molybdenum-containing compound and a group VIII metal-containing compound, wherein the group VIII metal is nickel.

9. 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.

10. 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; 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.

11. The preparation method according to claim 1, 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). In step (d), the mass concentration of the water-soluble polymer in the aqueous phase is 4.0% to 14.0%.

12. 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.

13. The preparation method according to claim 12, characterized in that, In step (e), the mass ratio of the aqueous phase to the oil phase is 0.5~9.0:1.

0.

14. The residue oil hydrodemetallization catalyst prepared by the preparation method according to any one of claims 1-13.

15. The catalyst according to claim 14, characterized in that, The catalyst comprises a support containing a first active metal component, a second active metal component, and carbon distributed on the surface of the catalyst, wherein the mass ratio of the first active metal component (calculated as oxide) to the second active metal component (calculated as oxide) is 1.0:1.0~3.

0.

16. The catalyst according to claim 15, characterized in that, In the catalyst, the mass ratio of carbon to alumina distributed on the catalyst surface is 0.15 to 0.

45.

17. The catalyst according to claim 15, characterized in that, Based on catalyst mass, the content of MoO3 is 5.0%~15.0%, and the content of Group VIII metal oxides is 1.0%~8.0%.

18. The catalyst according to claim 15, 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 0~5.0%.

21. The catalyst according to claim 15, characterized in that, The catalyst has a specific surface area of ​​150~230m². 2 / g, with a pore volume of 0.50~0.95mL / g; And / or, the pore distribution of the catalyst is as follows: pores with a diameter <30 nm occupy 15%~30% of the total pore volume, pores with a diameter of 30~100 nm occupy 35%~45% of the total pore volume, and pores with a diameter of 100 nm~300 nm occupy 25%~50% of the total pore volume; And / or, the strength of the catalyst is 10.0~25.0 N / mm.

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