Residue hydrodemetallization catalyst, method for preparing the same and use thereof

Abstract

The application discloses a residual oil hydrodemetallization catalyst and a preparation method and application thereof. The preparation method of the catalyst comprises the following steps: (1) mixing pseudo-boehmite, a first active metal, an alkaline additive, water and a gluey agent, shaping, and roasting to obtain an alumina carrier containing the first active metal; (2) performing surface carbon coating treatment on the carrier obtained in the step (1), and roasting to obtain an alumina carrier containing the first active metal and having a surface carbon coating film, namely, carrier B; (3) impregnating the carrier B obtained in the step (2) with an impregnation liquid containing a second active metal, and roasting to obtain the catalyst; wherein the impregnation liquid containing the second active metal comprises an aqueous phase and an oil phase covering the aqueous phase. The catalyst is used for heavy oil and residual oil hydrodemetallization reaction, has strong hydrogenation activity, and greatly improves the demetallization activity, and can ensure long-period stable operation of a device.

Description

Technical Field

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

[0002] With the increasing severity and deterioration of crude oil quality, coupled with the growing market demand for light oil products, heavy oil hydrotreating technology has gradually become a focus of attention in the petrochemical industry. Fixed-bed residue hydrotreating technology, with its advanced technology and wide range of applications, is an important means to achieve clean and efficient utilization of vacuum residue. However, due to the presence of metals and other heteroatoms in the residue, the hydrotreating catalyst is prone to deactivation during the reaction process due to the deposition of metals and carbon deposits. Since the demetallization catalyst occupies a relatively prominent position in the fixed-bed residue hydrotreating catalyst gradation system and bears a significant reaction load, developing a hydrotreating catalyst with a longer lifespan and better hydrotreating performance, especially a hydrodemetallization catalyst, is particularly important.

[0003] Currently, research on hydrodemetallization catalysts mainly focuses on the pore size of the support, such as introducing pore-expanding agents and acid treatment during support preparation. However, these methods result in uneven acidity distribution on the support surface, and the introduction of additives disrupts the original pores of the support, which is detrimental to the dispersion of active metals during subsequent impregnation. Furthermore, conventional impregnation methods are typically used for loading active metals during catalyst preparation, leading to limited dispersion of the active metal on the catalyst and resulting in poor hydrogenation performance, resistance to metal deposition, and poor resistance to carbon buildup.

[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 then drying and calcining to obtain a hydrodemetallization catalyst for residual oil.

[0005] CN104646007A discloses a residue oil hydrodemetallization catalyst and its preparation and application. First, an activated carbon support undergoes two pretreatment processes: hydrochloric acid washing and nitric acid oxidation. Then, a composite additive, activated carbon, and alumina are mixed and extruded to prepare an activated carbon / alumina composite. Finally, metal is loaded onto the support using a hydrotalcite method, i.e., an equal volume of a mixed solution of terephthalic acid, nickel nitrate, urea, and ammonium nitrate in a molar ratio of 2:1:(2.5-5):(1-5) is impregnated, crystallized, washed several times, and dried to obtain nickel salt talc microcrystals. These microcrystals are then placed in a Mo salt solution for complete displacement, filtered, washed, and dried to obtain green solid particles, which are then calcined to obtain the residue oil hydrodemetallization catalyst.

[0006] The hydrogenation activity and stability of the hydrogenation demetallization catalyst prepared by the above method need to be further improved. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a catalyst for the hydrodemetallization of heavy and residual oils, its preparation method, and its application. When used in the hydrodemetallization reaction of heavy and residual oils, this catalyst exhibits strong hydrogenation activity and significantly improved demetallization activity, ensuring long-term stable operation of the equipment.

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

[0009] (1) Mix boehmite, first active metal, alkaline additive, water (preferably deionized water) and adhesive, shape, and calcine to obtain an alumina carrier containing the first active metal.

[0010] (2) The carrier obtained in step (1) is subjected to surface carbon coating treatment and calcined to obtain an alumina carrier B containing the first active metal with a surface carbon coating film.

[0011] (3) Impregnate the carrier B obtained in step (2) with an impregnation solution containing the second active metal, and calcine to obtain the catalyst; wherein the impregnation solution containing the second active metal includes an aqueous phase and an oil phase coating the aqueous phase.

[0012] In step (3), the mass ratio of the aqueous phase to the oil phase in the impregnation solution containing the second active metal is 0.4–12.0:1.0, preferably 0.5–9.0:1.0. Further, the aqueous phase includes a second active metal source, a co-emulsifier, a water-soluble polymer, and water, as well as optional auxiliary agent sources; the second active metal includes Group VIB metals and Group VIII metals; the oil phase includes a surfactant and oil, with a surfactant to oil mass ratio of 1.0:0.1–10, preferably 1.0:2–10.

[0013] In step (3), the water-soluble polymer is one or more of polyvinyl alcohol, carboxymethyl cellulose, gelatin, gum arabic, and sodium polyacrylate; the mass concentration of the water-soluble polymer in the aqueous phase is 4.0% to 14.0%.

[0014] In step (3), the concentration of Group VIB metals as oxides in the aqueous phase is 8-80 g / 100 mL, preferably 10-70 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 1.0-7.5 g / 100 mL.

[0015] In step (3), the Group VIB metal is Mo and / or W, and the Group VIII metal is Ni and / or Co; preferably, the Group VIB metal source is one or more of ammonium molybdate, ammonium metatungstate, and molybdenum oxide, and the Group VIII metal source is one or more of basic nickel nitrate and cobalt nitrate.

[0016] In step (3), the auxiliary agent in the aqueous phase 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, and ammonium dihydrogen phosphate. The fluorine source is preferably ammonium fluoride. The silicon source is preferably silica sol. The boron source is preferably boric acid. The co-emulsifier is selected from one or more of hexadecyl alcohol, octadecyl alcohol, propylene glycol, n-butanol, polyvinyl alcohol, and glycerol. Preferably, the mass concentration of the co-emulsifier in the aqueous phase is 0.5% to 5.0%.

[0017] In step (3), the surfactant is selected from one or more of glyceryl monostearate, glyceryl distearate, glyceryl monolaurate, and polyoxyethylene ether fatty alcohol; the oil is selected from at least one of silicone oil and vegetable oil, the silicone oil is preferably 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 preferably selected from one or more of peanut oil, coconut oil, and tea seed oil.

[0018] In step (3), the particle size of the water-in-oil droplets is 5–20 nm.

[0019] In step (1), the method for preparing the alumina support containing the first active metal includes:

[0020] (1-1) Mix boehmite, the first active metal, an alkaline additive and water (preferably deionized water) to obtain solid material A;

[0021] (1-2) The solid material A obtained in step (1-1) is mixed with an adhesive, shaped, and calcined to obtain an alumina carrier containing the first active metal.

[0022] In step (1-1), the pseudoboehmite is prepared using conventional methods, such as the aluminum sulfate method, the aluminum alkoxide method, and the sol-gel method. The alumina content in the pseudoboehmite is 60.0%–75.0% by mass.

[0023] In step (1-1), the alkaline auxiliary agent is one or more alkaline compounds such as sodium hydroxide, potassium hydroxide, and sodium carboxylate (e.g., sodium acetate, sodium formate).

[0024] In step (1-1), the first active metal is at least one of Group VIII metals. Preferably, the Group VIII metal is Ni, and the Ni source is selected from at least one of basic nickel carbonate, nickel sulfate, nickel nitrate, etc.

[0025] In step (1-1), the mass ratio of pseudoboehmite (calculated as alumina), the first active metal (calculated as an oxide), the alkaline additive, and water is 200-240: 1.0-8.0: 6.0-15.0: 120-180.

[0026] In step (1-1), after mixing, the mixture is ground and filtered to obtain solid material A. The grinding can be done using ball milling, sand milling, or other methods. The ground material not only has a more uniform metal dispersion, but the alkaline additive also forms a "first protective film" on the surface of the dried material. The ground sample has an average particle size of 2.0–10.0 μm. The filtration process is a standard procedure in this field.

[0027] In step (1-1), the first active metal 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, which is beneficial to the hydrogenation reaction.

[0028] In steps (1-2), the adhesive can be an organic acid and / or an inorganic 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.

[0029] In steps (1-2), the mass of the adhesive is 0.5% to 5.0% of the mass of boehmite in step (1) based on alumina.

[0030] In steps (1-2), 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.

[0031] In steps (1-2), 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 mass of boehmite (based on alumina). The amount of deionized water used can be 80% to 120% of the mass of boehmite (based on alumina) in step (1).

[0032] In steps (1-2), after molding, the alumina carrier containing the first active metal is dried and calcined to obtain the alumina carrier. The drying temperature is 120-200℃, and the drying time is 2-12 hours.

[0033] In steps (1-2), the roasting process employs a two-stage roasting method. 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 150–300℃ higher than the first stage roasting temperature.

[0034] In step (2), the surface carbon coating treatment preferably uses a mixed solution of a carbon-containing precursor and water-soluble cellulose. In the mixed solution, the mass content of the carbon-containing precursor is 5.0%–15.0%, and the mass content of the water-soluble cellulose is 0.5%–3.0%.

[0035] In step (2), the carbon-containing precursor is one or more of polyimide, polyfurfuryl alcohol, phenolic resin, etc.

[0036] 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.

[0037] In step (2), the ratio of the amount of the mixed solution (in mL) to the amount of the alumina carrier containing the first active metal obtained in step (1) (in g) is 0.8 to 1.5 mL / g.

[0038] In step (2), after the surface carbon coating treatment is completed, the carrier B is obtained through conventional filtration, washing, drying, and calcination. The drying temperature is 120–200℃, and the drying time is 2.0–12.0 h. The calcination conditions are: temperature 500–700℃, time 2.0–8.0 h, and the calcination atmosphere is an inert atmosphere, preferably one or more of nitrogen and argon.

[0039] 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.

[0040] In step (3), the method for preparing the impregnation solution containing the second active metal includes:

[0041] (3-1) Add the surfactant to the oil and heat it to obtain the oil phase;

[0042] (3-2) Mix the co-emulsifier, the Group VIB metal source, water, and optional auxiliary source, and heat to obtain a clear solution;

[0043] (3-3) Add the Group VIII metal source to the clear solution obtained in step (3-2);

[0044] (3-4) Add a water-soluble polymer to the mixture obtained in step (3-3) to obtain an aqueous phase;

[0045] (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.

[0046] 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.

[0047] In step (3-1), the temperature is heated to 45-85°C to make the oil phase appear as a uniform liquid.

[0048] 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.

[0049] 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.

[0050] 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).

[0051] 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. 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.

[0052] 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.

[0053] 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.

[0054] In step (3-3), 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.

[0055] In step (3-4), the concentration of Group VIB metals as oxides in the aqueous phase 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 1.0-7.5 g / 100 mL.

[0056] 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).

[0057] In step (3-4), the water-soluble polymer accounts for 4.0% to 14.0% of the mass of the aqueous phase obtained in step (3-4).

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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 50.0% to 80.0% of the total Group VIII metal loading in the catalyst, based on oxides.

[0062] In step (3), the impregnation method is saturated impregnation.

[0063] In step (3), 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. The calcination temperature is 550-750℃ and the calcination time is 2-10h. The calcination is carried out in a mixed atmosphere of air and water vapor, wherein the volume ratio of air to water vapor is 0.1-5.0:1.0.

[0064] The second aspect of the present invention provides a residue oil hydrodemetallization catalyst prepared by any of the preparation methods described in the first aspect.

[0065] In this invention, the catalyst comprises an alumina support containing a first active metal and a second active metal. The mass ratio of the first active metal (calculated as oxide) to the alumina is 0.01 to 0.10:1, for example, but not limited to, 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.10:1, etc., and any value within the range formed by any two of these values.

[0066] In this invention, the first active metal is at least one of Group VIII metals, preferably nickel. The second active metal component includes Group VIB metals and Group VIII metals, preferably molybdenum from Group VIB and nickel from Group VIII.

[0067] In this invention, based on the mass of the catalyst, the content of Group VIB metal oxides is 10.0% to 28.0%, and the content of Group VIII metal oxides is 2.0% to 20.0%. In the catalyst, the mass ratio of the Group VIII metal (calculated as oxide) in the first active metal to the Group VIII metal (calculated as oxide) in the second active metal is 0.2 to 1.0:1, for example, but not limited to, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, etc., and any value within the range formed by any two of these values.

[0068] In this invention, the catalyst further includes an auxiliary agent selected from at least one of fluorine, phosphorus, silicon, or boron, preferably phosphorus. Further, based on the mass of the catalyst, the content of the auxiliary agent, calculated as oxides, is 1.0% to 6.0%.

[0069] In this invention, the catalyst has a specific surface area of ​​150–190 m². 2 / g, with a pore volume of 0.50–0.90 mL / g; preferably, the catalyst has a specific surface area of ​​160–180 m² / g. 2 / g, with a pore volume of 0.60~0.75mL / g.

[0070] The third aspect of this invention provides the application of the above-mentioned catalyst in the hydrotreating of heavy oil and residual oil.

[0071] Compared with the prior art, the present invention has the following beneficial effects:

[0072] In existing technologies, conventional active metal loading is mostly a single impregnation process, with the active metal largely distributed on the catalyst surface. This results in the actual reaction process primarily occurring on the catalyst surface, making it difficult for large molecular reactants to penetrate into the interior of the hydrogenation demetallization catalyst, thus limiting the utilization rate of the active metal. Furthermore, the aggregated active metal exhibits low metal sulfidation during the sulfidation process, limiting its hydrogenation capacity. This invention introduces a portion of the active metal (i.e., a first active metal) during the support preparation process, allowing it to first disperse within the alumina support bulk phase. During the reaction, this reduces the reaction intensity on the catalyst surface, increasing the ability of large molecules to further penetrate the catalyst interior. Simultaneously, it facilitates a higher degree of sulfidation of the active metal on the catalyst during the sulfidation process, thereby enhancing the catalyst's hydrogenation capacity. Specifically, during support preparation, the first active metal is added during grinding, resulting in more uniform dispersion. Simultaneously, the protective film formed by the introduced alkaline additive weakens the interaction between nickel and alumina during support formation. Then, the aforementioned support is subjected to a carbon coating treatment. The formation of the carbon film ensures that the second active metal (mainly the primary active metal molybdenum) does not come into contact with the already loaded and dispersed first active metal during the impregnation process, while the second active metal is uniformly dispersed on the carbon film. Finally, after calcination in a mixed atmosphere, air is introduced to remove the carbon film, and the second active metal is then uniformly dispersed on the support. This method effectively avoids the problem of uneven distribution of active metal on the support surface during a single impregnation. Furthermore, carbon coating treatment is performed on the alumina support containing the first active metal, followed by calcination in an inert gas atmosphere. 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, this film disappears, and the second active metal is uniformly dispersed on the carbon-coated alumina support B containing the first active metal, and works in conjunction with the first active metal, which is beneficial for improving the activity and stability of hydrodemetallization.

[0073] In the preparation of the second active metal impregnation solution, 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. Then, the catalyst support is impregnated using this impregnation solution, 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-metal is dissolved in the above solution to obtain an aqueous phase containing the main active metal (Group VIB metal) and a co-active metal (Group VIII 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 anti-carbon deposition performance, demetallization activity, and metal-containing capacity of the final heavy and residual oil hydrodemetallization catalyst, thus ensuring the long-term stable operation of the equipment. 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] (1) Mix 300g of boehmite (alumina content 74.0%), 9.8g of basic nickel carbonate (nickel oxide content 52.0%), 10.5g of alkaline additive NaOH, and 150g of deionized water, grind (the average particle size of the sample after grinding is 5.0μm), filter, and obtain solid material A;

[0079] (2) The solid material A obtained in step (1) is mixed with 9.4g of nitric acid, 6.0g of guar gum powder and 200g of deionized water, and then extruded into a four-leaf clover shape. It is dried at 120℃ for 6h and then calcined (the calcination process is carried out in two stages. The first stage calcination temperature is 400℃ and the calcination time is 3h. The calcination atmosphere is air. The second stage calcination temperature is 650℃ and the calcination time is 3h. The calcination atmosphere is nitrogen). After that, an alumina carrier containing some active metal Ni is obtained.

[0080] (3) The carrier obtained in step (2) 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 8.0%, and the mass content of hydroxymethyl cellulose is 0.8%. The ratio of the volume of the mixed solution (mL) to the mass of the carrier obtained in step (2) is 1.0 mL / g. After drying and calcination, the drying temperature is 150℃ and the drying time is 8h; calcination is carried out under a nitrogen atmosphere at a temperature of 650℃ for 5h. After calcination, a three-dimensional network structure film is formed on the surface of the carrier, resulting in carrier B.

[0081] (4) The carrier B obtained in step (3) was impregnated with the "water-in-oil" type second active metal impregnation solution in a saturated impregnation manner. After impregnation, the obtained sample was dried at 150°C for 4 hours and then calcined at 600°C for 4 hours. The calcination process was carried out in a mixed atmosphere with a volume ratio of air to water vapor of 1:2. Finally, the hydrogenation demetallization catalyst CAT-1 was obtained. The physicochemical properties and composition of the catalyst are shown in Table 1.

[0082] The preparation process of the "water-in-oil" second active metal impregnation solution includes:

[0083] 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.

[0084] (4-1) 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;

[0085] (4-2) 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.

[0086] (4-3) Add basic nickel carbonate to the clear solution obtained in step (4-2);

[0087] (4-4) Add water-soluble polymer polyvinyl alcohol to the mixture obtained in step (4-3) to obtain an aqueous phase; in the aqueous phase, the content of MoO3 is 29.58 g / 100 mL, the content of NiO is 6.29 g / 100 mL, the content of phosphoric acid as P2O5 is 7.26 g / 100 mL, and the content of polyacrylamide is 3.96 g / 100 mL;

[0088] (4-5) The aqueous phase from step (4-4) is added dropwise to the oil phase obtained in step (4-1). During the addition process, the temperature of the oil phase is maintained at 80°C, and the mixture is stirred. The shear homogenization rate is 15000 rpm, the shear homogenization time is 5 min, and the temperature during the shear homogenization process is 60°C. After the droplets are dispersed into an emulsion, a water-in-oil impregnation solution is obtained.

[0089] Example 2

[0090] Compared with Example 1, the difference is that in step (3), the support is subjected to surface carbonization treatment using a mixed solution of polyimide and hydroxymethyl cellulose, in which the mass content of polyimide is 10.0% and the mass content of hydroxymethyl cellulose is 1.2%. The ratio of water emulsion (by volume mL) to support (by mass g) is 1.3 mL / g. The calcination conditions are: calcination at 600℃ for 4 hours under a nitrogen atmosphere. After calcination, a three-dimensional network structure film can be formed on the surface of the support, resulting in support B. Finally, the hydrogenation demetallization catalyst CAT-2 is obtained. The physicochemical properties and composition of the catalyst are shown in Table 1.

[0091] Example 3

[0092] Compared with Example 1, the difference is that in step (1), 300g of boehmite (alumina content 74.0%), 8.5g of alkaline additive NaOH, and 180g of deionized water were mixed; in step (2), 8.8g of nitric acid, 6.6g of guar gum powder, and 240g of deionized water were extruded into a four-leaf clover shape, and then dried at 120℃ for 6h. The first stage of calcination was at 450℃ for 4h in an air atmosphere; the second stage of calcination was at 650℃ for 4h in a nitrogen atmosphere. Finally, the hydrogenation demetallization catalyst CAT-3 was obtained, and the physicochemical properties and composition of the catalyst are shown in Table 1.

[0093] Example 4

[0094] Same as Example 1, except that the process for preparing the "water-in-oil" type second active metal impregnation solution is as follows:

[0095] 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 0.90:8. 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 20:265:58.5:64.8:70.3:400. The mass ratio of oil phase to water phase is 1:1.3.

[0096] (4-1) 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;

[0097] (4-2) 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 h. Maintain a constant stirring speed until a transparent and clear solution is obtained.

[0098] (4-3) Add basic nickel carbonate to the clear solution obtained in step (4-2);

[0099] (4-4) Add water-soluble polymer carboxymethyl cellulose to the mixture obtained in step (4-3) to obtain an aqueous phase;

[0100] (4-5) The aqueous phase from step (4-4) is added dropwise to the oil phase obtained in step (4-1). During the addition process, the temperature of the oil phase is maintained at 65°C, and the mixture is stirred. The shear homogenization rate is 15000 rpm, the shear homogenization time is 4 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.

[0101] The final hydrogenation demetallization catalyst CAT-4 was obtained, and its physicochemical properties and composition are shown in Table 1.

[0102] Example 5

[0103] Same as Example 1, except that the process for preparing the "water-in-oil" type second active metal impregnation solution is as follows:

[0104] 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 0.85:8. 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 20:265:58.5:64.8:70.3:400. The mass ratio of oil phase to water phase is 1:1.1.

[0105] (4-1) 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;

[0106] (4-2) 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.

[0107] (4-3) Add basic nickel carbonate to the clear solution obtained in step (4-2);

[0108] (4-4) Add water-soluble sodium polyacrylate to the mixture obtained in step (4-3) to obtain an aqueous phase;

[0109] (4-5) The aqueous phase from step (4-4) is added dropwise to the oil phase obtained in step (4-1). 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 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.

[0110] The final hydrogenation demetallization catalyst CAT-5 was obtained, and its physicochemical properties and composition are shown in Table 1.

[0111] Example 6

[0112] Same as Example 1, except that the process for preparing the "water-in-oil" type second active metal impregnation solution is as follows:

[0113] 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 1:1.2.

[0114] (4-1) 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;

[0115] (4-2) 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.

[0116] (4-3) Add basic nickel carbonate to the clear solution obtained in step (4-2);

[0117] (4-4) Add water-soluble polymer gelatin to the mixture obtained in step (4-3) to obtain an aqueous phase;

[0118] (4-5) The aqueous phase from step (4-4) is added dropwise to the oil phase obtained in step (4-1). 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 17000 rpm, the shear homogenization time is 6 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.

[0119] The final hydrogenation demetallization catalyst CAT-6 was obtained, and its physicochemical properties and composition are shown in Table 1.

[0120] Comparative Example 1

[0121] Compared with Example 1, the difference is that the solution used for surface carbonization treatment in step (3) is a polyimide solution with a mass percentage of 8.0%, and the ratio of the amount of polyimide solution (by volume mL) to the amount of support obtained in step (2) (by mass g) is 1.0 mL / g. The final hydrogenation demetallization catalyst dCAT-1 was obtained, and its physicochemical properties and composition are shown in Table 2.

[0122] Comparative Example 2

[0123] Compared with Example 1, the difference is that the first active metal Ni is not added in step (1), and in step (4), the amount of MoO3 introduced into the catalyst by the impregnation solution containing the second active metal is 100% of the total MoO3 loading in the catalyst, and the amount of NiO introduced into the catalyst by the second impregnation solution is 100% of the total NiO loading in the catalyst. Finally, the hydrogenation demetallization catalyst dCAT-2 was obtained, and the physicochemical properties and composition of the catalyst are shown in Table 2.

[0124] Comparative Example 3

[0125] Compared with Example 1, the difference is that step (3) is omitted, i.e., the surface carbonization treatment is not performed. Finally, the hydrodemetallization catalyst dCAT-3 was obtained, and the physicochemical properties and composition of the catalyst are shown in Table 2.

[0126] Comparative Example 4

[0127] Similar to Example 1, except that no water-soluble polymer was added to the mixture in step (4-4) (derived from step (4-3)). The final catalyst obtained was dCAT-4, and its physicochemical properties and composition are shown in Table 2.

[0128] Comparative Example 5

[0129] Same as Example 1, except that the preparation process of the "water-in-oil" type second active metal impregnation solution is as follows:

[0130] The surfactant is glyceryl monostearate, the silicone oil is methyl silicone oil, and the surfactant to silicone oil mass ratio is 1:8. 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.

[0131] The method for preparing the impregnation solution containing the second active metal component in this example is as follows:

[0132] (4-1) 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.

[0133] (4-2) Add basic nickel carbonate to the clear solution obtained in step (4-1) to obtain an aqueous phase;

[0134] (4-3) The surfactant glyceryl monostearate, silicone oil, co-emulsifier polyethylene glycol-8000, 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-5, and its physicochemical properties and composition are shown in Table 2.

[0135] Table 1. Physicochemical properties and catalyst composition of each embodiment.

[0136]

[0137]

[0138] Table 2 Physicochemical properties and catalyst composition of each comparative example catalyst

[0139]

[0140] Evaluation test

[0141] The catalysts obtained in Examples 1-6 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 987.3 kg / m³. 3 (20℃), S content 2.41wt%, Ni and V contents 36.5mg / g and 63.7mg / g respectively, CCR content 12.4wt%, the demetallization rate after 2000h of operation in Example 1 was 100%, and all others are relative demetallization rates. Specific experimental conditions are shown in Table 3, and experimental results are shown in Tables 4 and 5.

[0142] Table 3 Experimental conditions

[0143]

[0144]

[0145] Table 4 Evaluation results of the hydrogenation demetallization catalysts in each example

[0146]

[0147] Table 5 Evaluation results of hydrogenation demetallization catalysts in each comparative example

[0148]

[0149] 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 heavy and residual oils.

Claims

1. A method for preparing a residue oil hydrodemetallization catalyst, comprising the following steps: (1) Mix boehmite, the first active metal, alkaline additives, water and adhesive, shape and calcine to obtain an alumina carrier containing the first active metal. (2) The carrier obtained in step (1) is subjected to surface carbon coating treatment and calcined to obtain an alumina carrier B containing the first active metal with a surface carbon coating film. (3) Impregnate the carrier B obtained in step (2) with an impregnation solution containing the second active metal, and calcine to obtain a catalyst, wherein the impregnation solution containing the second active metal includes an aqueous phase and an oil phase coating the aqueous phase.

2. The method according to claim 1, characterized in that, In step (1), the first active metal is at least one of Group VIII metals, and the Group VIII metal is preferably Ni; And / or, the alkaline auxiliary agent is one or more of sodium hydroxide, potassium hydroxide, and sodium carboxylate; And / or, the adhesive is an organic acid and / or an inorganic 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.

3. The method according to claim 1, characterized in that, In step (1), the method for preparing the alumina support containing the first active metal includes: (1-1) Mix boehmite, the first active metal, an alkaline additive and water to obtain solid material A; (1-2) The solid material A obtained in step (1-1) is mixed with an adhesive, shaped, and calcined to obtain an alumina carrier containing the first active metal.

4. The method according to claim 1 or 3, characterized in that, In step (1), the mass ratio of pseudoboehmite (calculated as alumina), the first active metal (calculated as an oxide), the alkaline additive, and water is 200–240: 1.0–8.0: 6.0–15.0: 120–180. And / or, the mass of the adhesive is 0.5% to 5.0% of the mass of boehmite based on alumina.

5. The method according to claim 1 or 3, characterized in that, In step (1), 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 150–300°C higher than the first-stage roasting temperature.

6. The method according to claim 1, characterized in that, In step (2), the surface carbon coating treatment uses a mixed solution of carbon precursor and water-soluble cellulose; Preferably, the carbon-containing precursor is one or more of polyimide, polyfurfuryl alcohol, and phenolic resin; Preferably, the water-soluble cellulose is one or more of hydroxymethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl cellulose.

7. The method according to claim 6, characterized in that, In the mixed solution, the mass content of the carbon-containing precursor is 5.0% to 15.0%, and the mass content of the water-soluble cellulose is 0.5% to 3.0%. And / or, the amount of the mixed solution in mL and the amount of the alumina carrier containing the first active metal obtained in step (1) in g are 0.8 to 1.5 mL / g.

8. The method according to claim 1, characterized in that, In step (2), the calcination conditions are: temperature of 500-700℃, time of 2.0-8.0h, and calcination atmosphere of inert atmosphere, preferably one or more of nitrogen and argon.

9. The method according to claim 1, characterized in that, In step (3), the impregnation solution containing the second active metal includes an aqueous phase comprising a second active metal source, a co-emulsifier, a water-soluble polymer and water, and an optional source of additives, and an oil phase comprising a surfactant and oil. And / or, 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.

10. The method according to claim 9, characterized in that, In step (3), the second active metal in the aqueous phase includes Group VIB metals and Group VIII metals, wherein the Group VIB metals are preferably Mo and / or W, and the Group VIII metals are preferably Ni and / or Co; the co-emulsifier is selected from one or more of hexadecyl alcohol, octadecanol, propylene glycol, n-butanol, polyvinyl alcohol, polyethylene glycol-8000, and glycerol; the water-soluble polymer is one or more of polyvinyl alcohol, carboxymethyl cellulose, gelatin, gum arabic, and sodium polyacrylate; the additive is at least one of fluorine, phosphorus, silicon, or boron, preferably phosphorus; And / or, in the oil phase, the surfactant is selected from one or more of glyceryl monostearate, glyceryl distearate, glyceryl monolaurate, and polyoxyethylene ether fatty alcohol; the oil is selected from 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.

11. The method according to claim 10, characterized in that, In step (3), the concentration of Group VIB metals as oxides in the aqueous phase is 8-80 g / 100 mL, preferably 10-70 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 1.0-7.5 g / 100 mL; And / or, in the aqueous phase, the mass concentration of the co-emulsifier is 0.5% to 5.0%; And / or, in the aqueous phase, the mass concentration of the water-soluble polymer is 4.0% to 14.0%.

12. The method according to claim 9 or 10, characterized in that, In step (3), the mass ratio of surfactant to oil in the oil phase is 1.0:0.1 to 10, preferably 1.0:2 to 10.

13. The method according to claim 1, characterized in that, In step (3), the mass of the Group VIII metal introduced into the catalyst by the impregnation solution containing the second active metal, based on oxides, accounts for 50.0% to 80.0% of the total Group VIII metal loading in the catalyst based on oxides.

14. The method according to claim 1, characterized in that, In step (3), the roasting temperature is 550-750℃, the roasting time is 2-10h, and the roasting is carried out in a mixed atmosphere of air and water vapor, wherein the volume ratio of air to water vapor is 0.1-5.0:1.

0.

15. The residue hydrodemetallization catalyst prepared by any of the preparation methods described in claims 1-14.

16. The catalyst according to claim 15, characterized in that, The catalyst comprises an alumina support containing a first active metal and a second active metal, wherein the mass ratio of the first active metal (calculated as oxide) to the alumina is 0.01 to 0.10:

1.

17. The catalyst according to claim 16, characterized in that, The first active metal is at least one of Group VIII metals, preferably nickel; the second active metal component includes Group VIB metals and Group VIII metals, preferably molybdenum and nickel.

18. 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 10.0% to 28.0%, and the content of group VIII metal oxides is 2.0% to 20.0%. And / or, in the catalyst, the mass ratio of the group VIII metal in the first active metal (calculated as oxide) to the group VIII metal in the second active metal (calculated as oxide) is 0.2 to 1.0:

1.

19. The catalyst according to claim 16, characterized in that, The catalyst includes an auxiliary agent selected from at least one of fluorine, phosphorus, silicon or boron, preferably phosphorus; Preferably, in the catalyst, the content of the auxiliary agent, calculated as oxide, is 1.0% to 6.0% based on the mass of the catalyst.

20. The catalyst according to claim 16, characterized in that, The catalyst has a specific surface area of ​​150–190 m². 2 / g, with a pore volume of 0.50–0.90 mL / g; preferably, the catalyst has a specific surface area of ​​160–180 m² / g. 2 / g, with a pore volume of 0.60~0.75mL / g.

21. The use of the catalyst according to any one of claims 15-20 in the hydrotreating of heavy oil and residual oil.

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