Hydrodemetallization catalyst, method for preparing the same, and use thereof

Abstract

The application discloses a kind of hydrodemetallization catalyst and its preparation method and application.The preparation method of the catalyst of the application includes the following steps: pseudo-boehmite, active carbon containing first active metal and adhesive are mixed, shaped, calcined, to obtain carrier;Mixing solution of carbon-containing precursor and water-soluble cellulose is mixed with the obtained carrier, dried, calcined, to obtain modified carrier;The modified carrier is impregnated with the "water-in-oil" type second active metal impregnation solution, calcined, to obtain the hydrodemetallization catalyst.The catalyst is used in the process of residual oil hydrodemetallization, has higher hydrodemetallization activity and metal capacity, and can ensure long-period operation of device.

Description

Technical Field

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

[0002] In recent years, crude oil resources have become increasingly scarce, and the trend of heavy and inferior crude oil has intensified. Many refineries are adapting to economic development and seeking effective methods to convert heavy oil into lighter products. Hydrotreating technology, as an important route for converting heavy oil into lighter products, also faces new challenges and problems under the current circumstances. Residue hydrotreating technology is a crucial means of converting heavy oil into lighter products in the petroleum refining process, and its development hinges on the research and development of catalysts with good activity and stability. Hydrodemetallization catalysts, positioned before hydrodesulfurization and decarbonization agents, play a vital role in removing various metallic impurities (mainly Ni and V) from the feedstock, thus ensuring the overall effectiveness of the hydrotreating process. Therefore, developing hydrodemetallization catalysts with suitable activity and good stability is particularly important.

[0003] CN1289640A discloses a method for preparing a supported hydrodemetallization catalyst. The method includes taking a macroporous δ- and / or θ-phase alumina support, placing it in a spray-impregnation boiler, preparing a Group VIB metal compound and / or Group VIII metal compound into an ammonia solution or aqueous solution, and uniformly spraying it onto the support in an atomized manner. The sprayed catalyst is then directly fed into a calcination furnace at a temperature of 300-450℃, and then gradually heated to 460-550℃, maintaining this temperature for 1-5 hours in the presence of air.

[0004] CN105709765A discloses a method for preparing a hydrodemetallization catalyst for residual oil, comprising the following steps: (1) mixing a pore-expanding agent, boehmite dry powder, extrusion aid, and adhesive solvent into a plastic body, extruding and drying; (2) spraying the unsaturated carrier after drying in step (1) with a mixed solution of phosphoric acid and ammonium oxalate, subjecting the impregnated carrier to sealed heating treatment, with the treatment pressure being the self-generated pressure under sealed conditions, the treatment temperature being 120-160℃, and the treatment time being 6-12 hours, and the treated carrier being dried and calcined to obtain an alumina carrier; (3) impregnating the alumina prepared in step (2) with active components, and after impregnation, drying and calcining to obtain an alumina carrier for the hydrodemetallization catalyst of residual oil.

[0005] The activity and stability of the hydrogenation demetallization catalysts prepared by the above methods still need to be further improved. It is necessary to further improve the hydrogenation activity and stability of the catalysts by improving the catalyst preparation method and optimizing the impregnation method of the active metal. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a hydrodemetallization catalyst, its preparation method, and its application. This catalyst, used in the hydrodemetallization process of residue oil, exhibits high hydrodemetallization activity and metal-containing capacity, ensuring long-term operation of the equipment.

[0007] The first aspect of this invention provides a method for preparing a hydrogenation demetallization catalyst, comprising the following steps:

[0008] (1) Mix boehmite, activated carbon containing the first active metal and adhesive, shape and calcine to obtain a carrier;

[0009] (2) Mix the carbon-containing precursor and water-soluble cellulose solution with the carrier obtained in step (1), dry and calcine to obtain the modified carrier;

[0010] (3) Impregnate the modified support obtained in step (2) with a water-in-oil type second active metal impregnation solution, and calcine to obtain the hydrogenation demetallization catalyst.

[0011] In step (1), the pseudoboehmite is obtained by conventional methods, such as the aluminum sulfate method, aluminum alkoxide method, sol-gel method, etc. The alumina content in the pseudoboehmite is 65.0% to 80.0% by mass.

[0012] In step (1), the adhesive can be an inorganic acid and / or an organic acid. The inorganic acid can be one or more of nitric acid, sulfuric acid, boric acid, and phosphoric acid, and the organic acid can be one or more of tartaric acid, citric acid, and oxalic acid.

[0013] In step (1), the amount of adhesive added is 0.5% to 5.0% of the total mass of boehmite (calculated as alumina) and activated carbon containing the first active metal.

[0014] In step (1), the forming method can be at least one of extrusion, sheeting, and ball forming. The formed shape can be clover-shaped, four-leaf clover-shaped, butterfly-shaped, cylindrical, spherical, or strip-shaped, etc.

[0015] In step (1), molding aids, such as at least one of extrusion aids and deionized water, can be added during the molding process according to molding requirements. The extrusion aid can be one or more of methylcellulose, ethylcellulose, guar gum, and starch. The mass of the extrusion aid added is 0.5% to 8.0% of the total mass of boehmite (calculated as alumina) and activated carbon containing the first active metal. The amount of deionized water used can be 80% to 120% of the total mass of boehmite (calculated as alumina) and activated carbon containing the first active metal.

[0016] In step (1), after molding, the substrate is dried and calcined to obtain the carrier. The drying temperature is 120–200℃, and the drying time is 2–12 h. The calcination process uses programmed temperature rise, with a heating rate of 1℃ / min–3℃ / min. The calcination temperature is 550–750℃, the calcination time is 2–8 h, and the calcination atmosphere is one or more of air, nitrogen, or water vapor, preferably air.

[0017] In step (1), the method for preparing activated carbon containing the first active metal includes:

[0018] (1-1) Activated carbon is impregnated with a first active metal impregnation solution containing a dispersing agent, dried, and calcined to obtain an activated carbon precursor containing the first active metal;

[0019] (1-2) The activated carbon precursor containing the first active metal obtained in step (1-1) is mixed with an alkaline additive, ground and dried to obtain activated carbon containing the first active metal.

[0020] In step (1-1), the dispersing agent is silica sol. The silica sol contains 20.0% to 50.0% silica by mass.

[0021] In step (1-1), the first active metal is at least one of Group VIII metals, preferably nickel, and the nickel source is selected from at least one of basic nickel carbonate, nickel nitrate, and nickel sulfate. Further, in the first active metal impregnation solution, the mass content of the first active metal, calculated as oxide, is 2.0% to 15.0%, and the mass content of the dispersing aid, calculated as silica, is 0.5% to 5.0%.

[0022] In step (1-1), the activated carbon is high-temperature activated carbon. The minimum heat resistance temperature of the high-temperature activated carbon is 750℃. The particle size of the activated carbon is 0.1~6.0μm.

[0023] In step (1-1), the impregnation method is saturated impregnation.

[0024] In step (1-1), the drying conditions are: temperature of 120–180℃ and drying time of 4–8h. The calcination conditions are: temperature of 550–750℃ and time of 3–8h, and the calcination atmosphere is one or more of air, water vapor, and nitrogen.

[0025] In step (1-1), the first active metal (Ni) is a co-active metal, which can interact with the support during the calcination process to weaken the acidity of the support, and can also work synergistically with the main active metal (Mo) in the second active metal component to facilitate the hydrogenation reaction.

[0026] In steps (1-2), the alkaline auxiliaries are one or more alkaline compounds such as sodium hydroxide, potassium hydroxide, and sodium carboxylate salts (e.g., sodium acetate, sodium formate).

[0027] In step (1-2), the mass ratio of the alkaline additive to the activated carbon used in step (1-1) is 0.01 to 0.10.

[0028] In steps (1-2), the grinding can be performed using methods such as ball milling or sand milling. The ground material not only has a more uniform metal dispersion, but the alkaline additive will also form a "first protective film" on the surface of the dried material during the molding process in step (1). After grinding, a ground sample with an average particle size of 2.0 to 8.0 μm is obtained.

[0029] In steps (1-2), the drying conditions are: temperature of 120-180℃ and drying time of 4-8h.

[0030] In step (2), the mass content of the carbon-containing precursor in the mixed solution is 8.0% to 16.0%, and the mass content of the water-soluble cellulose is 0.5% to 3.5%.

[0031] In step (2), the carbon-containing precursor is one or more of polyimide, polyfurfuryl alcohol, phenolic resin, etc.

[0032] In step (2), the water-soluble cellulose is one or more of hydroxymethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, etc.

[0033] In step (2), the ratio of the amount of the mixed solution (in mL) to the amount of the carrier obtained in step (1) (in g) is 0.8 to 1.5 mL / g.

[0034] In step (2), the drying conditions are: a drying temperature of 120–200°C and a drying time of 2.0–12.0 h. The calcination conditions are: a calcination temperature of 500–700°C and a calcination time of 2.0–8.0 h, and an inert atmosphere, wherein the inert atmosphere is one or more of nitrogen and argon.

[0035] In step (3), the second active metal 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 nickel and / or cobalt.

[0036] The preparation method of the "water-in-oil" type second active metal impregnation solution in step (3) includes:

[0037] (3-1) Add the surfactant to the oil and heat it to obtain the oil phase;

[0038] (3-2) Mix the co-emulsifier, the Group VIB metal source, water, and optional auxiliary source, and heat to obtain a clear solution;

[0039] (3-3) Add the Group VIII metal source to the clear solution obtained in step (3-2);

[0040] (3-4) Add a water-soluble polymer to the mixture obtained in step (3-3) to obtain an aqueous phase;

[0041] (3-5) The aqueous phase from step (3-4) is added dropwise to the oil phase obtained in step (3-1) in the form of droplets. During the dropwise addition, the oil phase is kept in a liquid state while being stirred, sheared and homogenized to obtain the impregnation solution.

[0042] In step (3-1), 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 (3-1), the temperature is heated to 45-85°C to make the oil phase appear as a uniform liquid.

[0044] In step (3-1), 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, but not limited to, 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 (3-2), the co-emulsifier is selected from one or more of cetyl alcohol, octadecanol, propylene glycol, n-butanol, polyvinyl alcohol, polyethylene glycol-8000 and glycerin.

[0046] In step (3-2), the amount of the co-emulsifier is 0.5% to 5.0% of the mass of the aqueous phase obtained in step (3-4).

[0047] In step (3-2), the Group VIB metal source can 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, wherein 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 (3-2), the water is distilled water or deionized water, and the conductivity of the water should be less than 10.0 mS.

[0049] In step (3-2), the temperature is heated to 90-120°C to ensure that the substances added in step (3-2) are mixed evenly to form a clear solution.

[0050] In step (3-3), the Group VIII metal is Ni and / or Co, preferably Ni. The Group VIII metal source is one or more of basic nickel carbonate, cobalt nitrate, etc.

[0051] In step (3-4), in the aqueous phase, the concentration of Group VIB metals as oxides is 8-80 g / 100 mL, preferably 10-60 g / 100 mL, the concentration of Group VIII metals as oxides is 2-50 g / 100 mL, preferably 5-30 g / 100 mL, and the concentration of additives as oxides is 0-8.0 g / 100 mL, preferably 1.0-7.0 g / 100 mL.

[0052] In steps (3-4), 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 steps (3-4), the mass concentration of the water-soluble polymer in the aqueous phase is 4.0% to 14.0%.

[0054] In steps (3-5), 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 steps (3-5), 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, 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 steps (3-5), the stirring and shearing homogenization process is carried out at a stirring speed of 10,000 to 18,000 rpm, a shearing homogenization time of 3 to 8 min, and a temperature of 50 to 85°C.

[0057] In step (3), the mass of Group VIII metals introduced into the catalyst by the second active metal impregnation solution, based on oxides, accounts for 40.0% to 70.0% of the total Group VIII metal loading in the catalyst, based on oxides.

[0058] In step (3), the impregnation method is saturated impregnation.

[0059] In step (3), after impregnation, the catalyst is first left to stand for 24 to 48 hours, and then dried and calcined to obtain the catalyst.

[0060] In step (3), the drying temperature is 120-200℃ and the drying time is 2-12h.

[0061] In step (3), the roasting process employs a two-stage roasting process. The first stage roasting temperature is 350–450℃, the roasting time is 2–6 hours, and the roasting atmosphere is one or more of air, nitrogen, or water vapor, preferably air. The second stage roasting temperature is 450–750℃, the roasting time is 2–8 hours, and the roasting atmosphere is one or more of air, nitrogen, or water vapor, preferably nitrogen. The second stage roasting temperature is 150–250℃ higher than the first stage roasting temperature.

[0062] The second aspect of the present invention provides a hydrogenation demetallization catalyst prepared by any of the preparation methods described in the first aspect.

[0063] In this invention, the catalyst includes a support and a second active metal. The support includes alumina, activated carbon and a first active metal, wherein the mass ratio of alumina to activated carbon is 4.0 to 12.0:1, preferably 6.0 to 9.0:1.

[0064] In this invention, the first active metal is at least one of Group VIII metals, preferably nickel. The second active metal includes Group VIB metals and Group VIII metals, wherein the Group VIB metal is preferably molybdenum, and the Group VIII metal is preferably nickel.

[0065] In this invention, the catalyst contains, based on catalyst mass, 9.0% to 35.0% group VIB metal oxides and 5.0% to 16.0% group VIII metal oxides.

[0066] In this invention, the mass content of Group VIII metal oxides in the first active metal of the catalyst is 30.0% to 60.0% of the total mass of Group VIII metal oxides in the catalyst, and the mass content of Group VIII metal oxides in the second active metal is 40.0% to 70.0% of the total mass of Group VIII metal oxides in the catalyst.

[0067] In this invention, the catalyst has a specific surface area of ​​150–190 m². 2 / g, with a pore volume of 0.60–1.00 mL / g; preferably, the catalyst has a specific surface area of ​​160–185 m² / g. 2 / g, with a pore volume of 0.70~0.90mL / g.

[0068] 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 2.0% to 11.0%.

[0069] The third aspect of this invention provides the application of the above-mentioned catalyst in the hydrotreating of heavy oil and residual oil.

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

[0071] In the hydrodemetallization of residual oil catalysts, hydrogenation and cracking reactions occur on the catalyst surface during the reaction. Generally, when the acidity of the catalyst surface is too strong, the hydrogenated products will continue to crack on the catalyst surface, leading to condensation and coking, which affects the catalyst activity. Through extensive research, the inventors discovered that firstly, impregnating the activated carbon surface with a first active metal (preferably Ni) in the form of metal ions, and then molding it with boehmite, can effectively reduce the interaction between the metal and the alumina support, while simultaneously reducing the acidity of the catalyst surface and lowering the overall cracking performance of the catalyst. Secondly, a second active metal is introduced onto the catalyst through saturated impregnation, which allows the catalyst to still possess strong hydrogenation performance. The first impregnation effectively controls the acidity of the catalyst surface by controlling the Ni content, while the second impregnation further regulates the hydrogenation activity of the catalyst surface. This invention introduces the active metal in two stages, not only regulating the acidity of the catalyst surface but also further controlling the hydrogenation activity of the catalyst; effectively regulating the active sites on the catalyst surface; and improving the overall performance of the catalyst while extending the operating cycle of the unit.

[0072] Conventional impregnation methods often result in metal agglomeration, leading to insufficient sulfidation and limited catalyst hydrogenation capacity. This invention employs a two-stage impregnation process to introduce the active metal. To further mitigate the interaction between the nickel flux and the dried powder during grinding and kneading, firstly, the nickel flux is impregnated onto activated carbon. A dispersing agent is introduced during this process to prevent metal agglomeration on the nickel-containing activated carbon during calcination, ensuring uniform metal distribution. Secondly, during grinding, an alkaline agent introduced onto the activated carbon forms a protective film during kneading, reducing the interaction between nickel and alumina. Next, a carbon film is applied to the Ni-containing support. This carbon film ensures that the second active metal does not contact the nickel flux or the support during subsequent impregnation, allowing for uniform dispersion of the second active metal on the carbon film. Finally, under a mixed atmosphere calcination, air removes the carbon film, leaving the second active metal uniformly dispersed on the support. This method not only further weakens the interaction between the metal and the support, but also effectively avoids the problem of uneven distribution of active metal caused by direct adsorption of the metal on the support surface during a single impregnation. Furthermore, carbon coating is applied to the support, followed by inert gas calcination. Moisture gradually evaporates, and the latex particles are gradually compressed to form a thin film containing crosslinkable groups, forming a three-dimensional network film. This film temporarily provides loading sites for the second active metal. After the catalyst is calcined in a mixed atmosphere of air and water vapor, the carbon layer is removed by air, the film disappears, and the second active metal is uniformly dispersed on the support, cooperating with the first active metal to improve the activity and stability of hydrogenation demetallization. The water vapor further ensures the unobstructed flow of the catalyst's pores.

[0073] In the second active metal preparation process, this invention utilizes a surfactant to effectively 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 via the carrier matrix, i.e., a "water-in-oil" type impregnation solution. This impregnation solution is then used to impregnate the catalyst support, resulting in a catalyst with a more uniform distribution of active metals both inside and on the surface of the support. First, this invention uses a co-emulsifier to fully disperse the main active metal in the carrier matrix water in ionic form. Then, a co-metallic metal is dissolved in the above solution to obtain an aqueous phase containing both the main active metal and the co-metallic metal. To control the particle size and maintain the particle size distribution during the subsequent "water-in-oil" emulsion formation process, a water-soluble polymer is added to the obtained aqueous phase as a "protector" for the particles. This water-soluble polymer adsorbs onto the particle surface during the subsequent "water-in-oil" emulsion formation process, forming a "surface layer" of a certain thickness, which effectively hinders collisions and aggregation between particles, further improving the stability of the system. Then, under specific conditions, the above aqueous phase is dispersed in the oil phase to obtain the hydrogenation catalyst impregnation solution.

[0074] In summary, the method of the present invention, through the comprehensive coordination of each step, significantly improves the activity and stability of the final residue oil hydrodemetallization catalyst. Detailed Implementation

[0075] 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.

[0076] In this invention, the pore structure and specific surface area of ​​the catalyst are characterized using the Mack ASAP-2420 physical adsorption instrument.

[0077] Example 1

[0078] Preparation of activated carbon containing the first active metal:

[0079] (1-1) 54.09 g of the first active metal nickel (nickel nitrate), 42.0 g of dispersant (silica sol with a silica content of 30%) and 376.0 g of water were prepared into an impregnation solution, which was then used to saturate and impregnate 297.0 g of high-temperature activated carbon. In the first active metal impregnation solution, the mass content of nickel as oxide was 3.60%, and the mass content of the dispersant as silica was 3.72%. After impregnation, the solution was dried at 120 °C for 6 h and calcined at 550 °C for 3 h to obtain an activated carbon precursor containing the first active metal.

[0080] (1-2) The activated carbon precursor containing the first active metal obtained above was mixed with 3.5g of alkaline additive (NaOH), ground (particle size after grinding was 5.0μm), and dried at 140℃ for 5h to obtain activated carbon containing the first active metal.

[0081] Preparation of hydrogenation demetallization catalysts:

[0082] (1) 364.6g of boehmite (alumina content of 72.0%), 37.5g of activated carbon containing the first active metal, 5.47g of nitric acid, 8.0g of guar gum powder, and 360.0g of deionized water were mixed and kneaded, then extruded into a four-leaf clover shape, and then dried at 150℃ for 5h and calcined at 700℃ for 4h to obtain a carrier;

[0083] (2) The carrier obtained in step (1) is subjected to surface carbon coating treatment using a mixed solution of polyimide and hydroxymethyl cellulose. The mass content of polyimide in the mixed solution is 9.0%, and the mass content of hydroxymethyl cellulose is 1.5%. The ratio of the volume of the mixed solution (mL) to the mass of the carrier obtained in step (1) (g) is 1.5 mL / g. After drying at 180℃ for 6 h, the calcination conditions are: calcination at 650℃ for 5 h under a nitrogen atmosphere. After calcination, a three-dimensional network structure film can be formed on the surface of the carrier to obtain the modified carrier.

[0084] (3) The modified support obtained in step (2) was impregnated with a water-in-oil type second active metal impregnation solution by saturation impregnation, allowed to stand for 24 h, dried at 120 °C for 6 h, and calcined to obtain the catalyst. The calcination adopted a two-stage calcination process. The first stage calcination temperature was 400 °C, the calcination time was 4 h, and the calcination atmosphere was air. The second stage calcination temperature was 650 °C, the calcination time was 6 h, and the calcination atmosphere was nitrogen. Finally, the hydrogenation demetallization catalyst CAT-1 was obtained. The physicochemical properties and composition of the catalyst are shown in Table 1.

[0085] The preparation process of the "water-in-oil" second active metal impregnation solution includes:

[0086] The surfactant is glyceryl monostearate, the silicone oil is methyl silicone oil, and the surfactant to silicone oil mass ratio is 1.0:8. The co-emulsifier is polyethylene glycol-8000, 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), and water-soluble polymer to water is 20:265:58.5:64.8:70.3:400. The oil phase to water phase mass ratio is 1:0.98.

[0087] (3-1) 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;

[0088] (3-2) Add the co-emulsifier polyethylene glycol-8000, 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.

[0089] (3-3) Add basic nickel carbonate to the clear solution obtained in step (3-2);

[0090] (3-4) Add water-soluble polymer polyvinyl alcohol to the mixture obtained in step (3-3) to obtain an aqueous phase; in the aqueous phase, the content of MoO3 is 27.70 g / 100 mL, the content of NiO is 6.13 g / 100 mL, the content of phosphoric acid as P2O5 is 6.92 g / 100 mL, and the content of polyacrylamide is 0.99 g / 100 mL;

[0091] (3-5) The aqueous phase from step (3-4) is added dropwise to the oil phase obtained in step (3-1). 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 type second active metal impregnation solution is obtained.

[0092] Example 2

[0093] Compared with Example 1, the difference is that in step (2), the support is subjected to surface carbon coating treatment using a mixed solution of polyimide and hydroxymethyl cellulose. The mass content of polyimide in the mixed solution is 12.0%, and the mass content of hydroxymethyl cellulose is 2.5%. The ratio of the mixed solution (by volume mL) to the support obtained in step (1) (by mass g) is 1.2 mL / g. The calcination conditions are: calcination at 550°C for 6 hours under a nitrogen atmosphere. After calcination, a three-dimensional network structure film can be formed on the surface of the support, thus obtaining the modified support. Finally, the hydrogenation demetallization catalyst CAT-2 was obtained. Other physicochemical properties and composition of the catalyst are shown in Table 1.

[0094] Example 3

[0095] Compared with Example 1, the difference is that in step (1), 370.4 g of boehmite (alumina mass content of 72.0%), 33.3 g of activated carbon containing the first active metal, 6.25 g of nitric acid, 6.0 g of guar gum powder, and 340.0 g of deionized water were mixed and kneaded, then extruded into a four-leaf clover shape, dried at 120°C for 8 h, and calcined at 650°C for 6 h to obtain the support. The final hydrogenation demetallization catalyst CAT-3 was obtained, and its physicochemical properties and composition are shown in Table 1.

[0096] Example 4

[0097] The difference compared to Example 1 lies in the preparation of the activated carbon containing the first active metal:

[0098] (1-1) 54.09 g of the first active metal nickel (nickel nitrate), 42.0 g of dispersant (silica sol with a silica content of 30%) and 376.0 g of water were prepared into an impregnation solution, which was then used to saturate and impregnate 297.0 g of high-temperature activated carbon. In the first active metal impregnation solution, the mass content of nickel as oxide was 3.60%, and the mass content of the dispersant as silica was 3.72%. After impregnation, the solution was dried at 160 °C for 4 h and calcined at 650 °C for 4 h to obtain an activated carbon precursor containing the first active metal.

[0099] (1-2) The activated carbon precursor containing the first active metal obtained above was mixed with 4.5g of alkaline additive (NaOH), ground (the particle size after grinding is 4.0μm), and dried at 150℃ for 4h to obtain activated carbon containing the first active metal.

[0100] The final hydrogenation demetallization catalyst CAT-4 was obtained, and its physicochemical properties and composition are shown in Table 1.

[0101] Example 5

[0102] Same as Example 1, except that the process for preparing the "water-in-oil" type second active metal impregnation solution is as follows:

[0103] 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 0.85:8. 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), and water-soluble polymer to water is 20:265:58.5:64.8:70.3:400. The mass ratio of oil phase to water phase is 1:1.2.

[0104] (3-1) 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;

[0105] (3-2) Add the co-emulsifier propylene glycol, 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.

[0106] (3-3) Add basic nickel carbonate to the clear solution obtained in step (3-2);

[0107] (3-4) Add water-soluble polymer carboxymethyl cellulose to the mixture obtained in step (3-3) to obtain an aqueous phase;

[0108] (3-5) The aqueous phase from step (3-4) is added dropwise to the oil phase obtained in step (3-1) in the form of droplets. During the dropwise addition, the temperature of the oil phase is maintained at 65°C, and the mixture is stirred. The shear homogenization rate is 14000 rpm, the shear homogenization time is 5 min, and the temperature during the shear homogenization process is 75°C. After the droplets are dispersed into an emulsion, a water-in-oil impregnation solution is obtained.

[0109] The final hydrogenation demetallization catalyst CAT-5 was obtained, and its physicochemical properties and composition are shown in Table 1.

[0110] Example 6

[0111] Same as Example 1, except that the process for preparing the "water-in-oil" type second active metal impregnation solution is as follows:

[0112] 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), and water-soluble polymer to water is 20:265:58.5:64.8:70.3:400. The mass ratio of oil phase to water phase is 1:1.3.

[0113] (3-1) 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;

[0114] (3-2) 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 600 r / min. When heated to 120°C, maintain this temperature for 4 h. Maintain a constant stirring speed until a transparent and clear solution is obtained.

[0115] (3-3) Add basic nickel carbonate to the clear solution obtained in step (3-2);

[0116] (3-4) Add water-soluble sodium polyacrylate to the mixture obtained in step (3-3) to obtain an aqueous phase;

[0117] (3-5) The aqueous phase from step (3-4) is added dropwise to the oil phase obtained in step (3-1). During the addition process, the temperature of the oil phase is maintained at 60°C, and the mixture is stirred. The shear homogenization rate is 16000 rpm, the shear homogenization time is 4 min, and the temperature during the shear homogenization process is 65°C. After the droplets are dispersed into an emulsion, a water-in-oil impregnation solution is obtained.

[0118] The final hydrogenation demetallization catalyst CAT-6 was obtained, and its physicochemical properties and composition are shown in Table 1.

[0119] Example 7

[0120] Same as Example 1, except that the process for preparing the "water-in-oil" type second active metal impregnation solution is as follows:

[0121] In this example, the surfactant is polyoxyethylene ether fatty alcohol (structure RO-(CCO)xH, where R is a 12-carbon linear alkyl group and x is 5), the silicone oil is methylphenyl silicone oil, the surfactant to silicone oil mass ratio is 0.95:8, 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, the water-soluble polymer is gelatin, and 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 20:265:58.5:64.8:70.3:400. The oil phase to water phase mass ratio is 1:1.1.

[0122] (3-1) 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;

[0123] (3-2) Add the co-emulsifier cetyl alcohol, 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 400 r / min. When heated to 120°C, maintain this temperature for 4 h. Maintain a constant stirring speed until a transparent and clear solution is obtained.

[0124] (3-3) Add basic nickel carbonate to the clear solution obtained in step (3-2);

[0125] (3-4) Add water-soluble polymer gelatin to the mixture obtained in step (3-3) to obtain an aqueous phase;

[0126] (3-5) The aqueous phase from step (3-4) is added dropwise to the oil phase obtained in step (3-1). During the addition process, the temperature of the oil phase is maintained at 50°C, and the mixture is stirred. The shear homogenization rate is 15000 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.

[0127] The final hydrogenation demetallization catalyst CAT-7 was obtained, and its physicochemical properties and composition are shown in Table 1.

[0128] Comparative Example 1

[0129] Compared with Example 1, the difference lies in the surface carbonization process in step (2), which uses a polyimide solution with a polyimide content of 9.0% by mass. The ratio of the amount of polyimide solution (by volume mL) to the amount of support obtained in step (1) (by mass g) is 1.5 mL / g. The final hydrogenation demetallization catalyst dCAT-1 was obtained, and its other physicochemical properties and composition are shown in Table 2.

[0130] Comparative Example 2

[0131] Compared with Example 1, the difference is that step (2) is omitted, i.e., the surface carbonization treatment is not performed. The final hydrogenation demetallization catalyst dCAT-2 is obtained, and other physicochemical properties and composition of the catalyst are shown in Table 2.

[0132] Comparative Example 3

[0133] Similar to Example 1, except that no water-soluble polymer was added to the mixture in steps (3-4) (derived from step (3-3)). The final catalyst obtained was dCAT-3. The physicochemical properties of this catalyst are shown in Table 2.

[0134] Comparative Example 4

[0135] Same as Example 1, except that the preparation process of the "water-in-oil" type second active metal impregnation solution is as follows:

[0136] 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), and water-soluble polymer to water is 20:265:58.5:64.8:70.3:400. The mass ratio of oil phase to water phase is 1:0.9.

[0137] The method for preparing the impregnation solution containing the second active metal component in this example is as follows:

[0138] (3-1) Add 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 clear solution is obtained.

[0139] (3-2) Add basic nickel carbonate to the clear solution obtained in step (3-1) to obtain an aqueous phase;

[0140] (3-3) 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 15000 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-4, and its physicochemical properties and composition are shown in Table 2.

[0141] Comparative Example 5

[0142] Compared with Example 1, the difference lies in the preparation process of activated carbon containing the first active metal, which includes: preparing an impregnation solution by mixing 54.09g of the first active metal nickel (nickel nitrate) and 331.8g of water, saturating 297.0g of high-temperature activated carbon, wherein the mass content of nickel in the first active metal impregnation solution is 3.60% as oxide, drying at 120°C for 6h after impregnation, and calcining at 550°C for 3h to obtain activated carbon containing the first active metal.

[0143] The final hydrogenation demetallization catalyst dCAT-5 was prepared, and its physicochemical properties and composition are shown in Table 2.

[0144] Table 1. Physicochemical properties and catalyst composition of the catalysts obtained in the examples.

[0145]

[0146] Table 2. Physicochemical properties and catalyst composition of the catalysts obtained in the comparative examples.

[0147]

[0148]

[0149] Evaluation test

[0150] The catalysts obtained in Examples 1-7 and Comparative Examples 1-5 were subjected to activity and stability tests on a 200 mL fixed-bed hydrogenation test apparatus for 2000 h. The feedstock was residual oil with a density of 987.5 kg / m³. 3(20℃), S content 2.35wt%, Ni and V contents 33.4μg / g and 59.4μg / g respectively, CCR content 12.5wt%, the demetallization rate after 2000h of operation in Example 1 was 100%, and all others were relative demetallization rates. Specific experimental conditions are shown in Table 3, and experimental results are shown in Tables 4 and 5.

[0151] Table 3 Experimental conditions

[0152] Reaction temperature, °C 380 Reaction pressure, MPa 15.7 <![CDATA[Liquid hourly space velocity, h -1 > 1.0 Hydrogen-to-oil ratio, V / V 750

[0153] Table 4 shows the test results of the catalysts obtained in the examples.

[0154]

[0155] Table 5 shows the experimental results of the catalysts obtained in the comparative examples.

[0156] Comparative numbering Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Catalyst number dCAT-1 dCAT-2 dCAT-3 dCAT-4 dCAT-5 Relative demetallization rate / % 93.7 93.1 92.7 92.5 93.2

[0157] As can be seen from Tables 1-5, the hydrodemetallization catalyst prepared according to the method of the present invention has a high specific surface area and pore volume, as well as high hydrogenation activity and stability, and can well meet the requirements of the hydrodemetallization process of residue oil.

Claims

1. A method for preparing a hydrogenation demetallization catalyst, comprising the following steps: (1) Mix boehmite, activated carbon containing the first active metal and adhesive, shape and calcine to obtain a carrier; (2) Mix the carbon-containing precursor and water-soluble cellulose solution with the carrier obtained in step (1), dry and calcine to obtain the modified carrier; (3) Impregnate the modified support obtained in step (2) with a water-in-oil type second active metal impregnation solution, and calcine to obtain the hydrogenation demetallization catalyst.

2. The preparation method according to claim 1, characterized in that, In step (1), the mass content of alumina in the pseudoboehmite is 65.0% to 80.0%; And / or, the adhesive is an inorganic acid and / or an organic acid, wherein the inorganic acid is one or more of nitric acid, sulfuric acid, boric acid, and phosphoric acid, and the organic acid is one or more of tartaric acid, citric acid, and oxalic acid; preferably, the amount of the adhesive added is 0.5% to 5.0% of the total mass of boehmite (calculated as alumina) and activated carbon containing the first active metal.

3. The preparation method according to claim 1, characterized in that, In step (1), the method for preparing activated carbon containing the first active metal includes: (1-1) Activated carbon is impregnated with a first active metal impregnation solution containing a dispersing agent, dried, and calcined to obtain an activated carbon precursor containing the first active metal; (1-2) The activated carbon precursor containing the first active metal obtained in step (1-1) is mixed with an alkaline additive, ground and dried to obtain activated carbon containing the first active metal.

4. The preparation method according to claim 3, characterized in that, In step (1-1), the dispersing agent is silica sol; preferably, the silica sol contains 20.0% to 50.0% silica by mass. And / or, in step (1-1), the first active metal is at least one of Group VIII metals, preferably nickel; preferably, in the first active metal impregnation solution, the mass content of the first active metal, calculated as oxide, is 2.0% to 15.0%, and the mass content of the dispersing aid, calculated as silica, is 0.5% to 5.0%. And / or, in step (1-1), the activated carbon is high-temperature activated carbon.

5. The preparation method according to claim 3, characterized in that, In step (1-2), the alkaline additive is one or more of sodium hydroxide, potassium hydroxide, and sodium carboxylate; preferably, the mass ratio of the alkaline additive to the activated carbon used in step (1-1) is 0.01 to 0.

10.

6. The preparation method according to claim 1, characterized in that, In step (2), the carbon-containing precursor is one or more of polyimide, polyfurfuryl alcohol, and phenolic resin; And / or, in step (2), the water-soluble cellulose is one or more of hydroxymethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl cellulose.

7. The preparation method according to claim 1, characterized in that, In step (2), the mass content of the carbon-containing precursor in the mixed solution is 8.0% to 16.0%, and the mass content of the water-soluble cellulose is 0.5% to 3.5%. And / or, in step (2), the amount of the mixed solution in mL and the amount of the carrier obtained in step (1) in g are 0.8 to 1.5 mL / g.

8. The preparation method according to claim 1, characterized in that, In step (3), the preparation method of the "water-in-oil" type second active metal impregnation solution includes: (3-1) Add the surfactant to the oil and heat it to obtain the oil phase; (3-2) Mix the co-emulsifier, the Group VIB metal source, water, and optional auxiliary source, and heat to obtain a clear solution; (3-3) Add the Group VIII metal source to the clear solution obtained in step (3-2); (3-4) Add a water-soluble polymer to the mixture obtained in step (3-3) to obtain an aqueous phase; (3-5) The aqueous phase from step (3-4) is added dropwise to the oil phase obtained in step (3-1) in the form of droplets. During the dropwise addition, the oil phase is kept in a liquid state while being stirred, sheared and homogenized to obtain the impregnation solution.

9. The preparation method according to claim 8, characterized in that, In step (3-1), the surfactant is selected from one or more of glyceryl monostearate, glyceryl distearate, glyceryl monolaurate, and polyoxyethylene ether fatty alcohol; the oil is 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; And / or, in step (3-1), the heating to a temperature of 45-85°C; And / or, in step (3-1), the mass ratio of the added surfactant to the mass of oil is 1.0:0.1 to 10, preferably 1.0:2 to 10.

10. The preparation method according to claim 8, characterized in that, In step (3-2), the co-emulsifier is selected from one or more of hexadecyl alcohol, octadecyl alcohol, propylene glycol, n-butanol, polyvinyl alcohol, polyethylene glycol-8000 and glycerin; the Group VIB metal is preferably molybdenum; the additive is at least one of fluorine, phosphorus, silicon or boron, preferably phosphorus; And / or, in step (3-2), the heating to a temperature of 90-120°C; And / or, in step (3-2), the amount of the co-emulsifier is 0.5% to 5.0% of the mass of the aqueous phase obtained in step (3-4).

11. The preparation method according to claim 8, characterized in that, In step (3-3), the Group VIII metal is nickel and / or cobalt, preferably nickel; And / or, in steps (3-4), the water-soluble polymer is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide, carboxymethyl cellulose, gelatin, gum arabic, and sodium polyacrylate; preferably, 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 8, characterized in that, In step (3-4), in the aqueous phase, the concentration of Group VIB metals as oxides is 8-80 g / 100 mL, preferably 10-60 g / 100 mL, the concentration of Group VIII metals as oxides is 2-50 g / 100 mL, preferably 5-30 g / 100 mL, and the concentration of additives as oxides is 0-8.0 g / 100 mL, preferably 1.0-7.0 g / 100 mL.

13. The preparation method according to claim 8, characterized in that, In steps (3-5), 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.

14. The preparation method according to claim 8, characterized in that, In steps (3-5), the stirring and shearing homogenization process is carried out at a stirring speed of 10,000 to 18,000 rpm, a shearing homogenization time of 3 to 8 min, and a temperature of 50 to 85°C.

15. The preparation method according to claim 1, characterized in that, In step (3), the roasting adopts a two-stage roasting process. The first stage roasting temperature is 350-450℃, the roasting time is 2-6h, and the roasting atmosphere is one or more of air, nitrogen, or water vapor, preferably air; the second stage roasting temperature is 450-750℃, the roasting time is 2-8h, and the roasting atmosphere is one or more of air, nitrogen, or water vapor, preferably nitrogen. Preferably, the second-stage roasting temperature is 150–250°C higher than the first-stage roasting temperature.

16. The hydrogenation demetallization catalyst prepared by any of the preparation methods described in claims 1-15.

17. The catalyst according to claim 16, characterized in that, The catalyst includes a support and a second active metal. The support includes alumina, activated carbon and a first active metal, wherein the mass ratio of alumina to activated carbon is 4.0 to 12.0:1, preferably 6.0 to 9.0:

1.

18. The catalyst according to claim 17, characterized in that, The first active metal is at least one of Group VIII metals, preferably nickel; the second active metal includes Group VIB metals and Group VIII metals, wherein the Group VIB metal is preferably molybdenum and the Group VIII metal is preferably nickel.

19. The catalyst according to claim 17, characterized in that, In the catalyst, based on the mass of the catalyst, the content of group VIB metal oxides is 9.0% to 35.0%, and the content of group VIII metal oxides is 5.0% to 16.0%. Preferably, in the catalyst, the mass content of Group VIII metal oxides in the first active metal is 30.0% to 60.0% of the total mass of Group VIII metal oxides in the catalyst, and the mass content of Group VIII metal oxides in the second active metal is 40.0% to 70.0% of the total mass of Group VIII metal oxides in the catalyst.

20. The catalyst according to claim 17, characterized in that, The catalyst has a specific surface area of ​​150–190 m². 2 / g, with a pore volume of 0.60–1.00 mL / g; preferably, the catalyst has a specific surface area of ​​160–185 m² / g. 2 / g, with a pore volume of 0.70~0.90mL / g.

21. The catalyst according to claim 17, characterized in that, The catalyst includes an auxiliary component, which is selected from at least one of fluorine, phosphorus, silicon or boron, preferably phosphorus; And / or, in the catalyst, the content of the auxiliary component, calculated as oxide, is 2.0% to 11.0% based on the mass of the catalyst.

22. The application of the catalyst according to any one of claims 16-21 in the hydrotreating of heavy oil and residual oil.

Images