Preparation method of hydrogenation catalyst

Abstract

The invention discloses a preparation method of a hydrogenation catalyst. The method comprises the following steps: (1) preparing an oil phase from a surfactant and oil; (2) uniformly mixing a co-emulsifier, a VIB group metal source, water and an optional phosphorus source to prepare a clear solution; (3) adding a group VIII metal source into the settled solution, and dividing the obtained steeping liquor into two parts, namely steeping liquor A and steeping liquor B; (4) adding a water-soluble high polymer into the impregnation liquid A to obtain a water phase; (5) dropwise adding the water phase into the oil phase in the form of liquid drops, and shearing and homogenizing to obtain impregnation liquid C; (6) mixing, kneading, forming, drying and roasting the carrier dry glue powder and the steeping liquor B to obtain a catalyst intermediate; and (7) impregnating the catalyst intermediate with the impregnation liquid C, standing, then adding a polyether nonionic surfactant, and carrying out ultrasonic treatment, drying and roasting to obtain the hydrogenation catalyst. According to the residual oil hydrogenation metal catalyst prepared by adopting the impregnation liquid, the hydrogenation activity and stability of the catalyst can be improved.

Description

Technical Field

[0001] The invention relates to a method for preparing a hydrogenation impregnation liquid and a hydrogenation catalyst. Background Art

[0002] The degree of heaviness and inferiority of crude oil worldwide is becoming increasingly serious. At the same time, the market demand for light oil products is also increasing day by day. Heavy oil hydrogenation technology has gradually become the focus of increasing attention in the petrochemical industry. Fixed-bed residue oil hydrogenation technology has a wide range of applications and is an important means to achieve clean and efficient utilization of vacuum residue oil. However, due to the presence of heteroatoms such as metals in the residue oil, the residue oil hydrogenation catalyst is easily deactivated due to the deposition of metals and carbon deposits during the reaction process. The demetallized catalyst is relatively forward in the fixed-bed residue oil hydrogenation catalyst grading system and bears more reaction loads. Therefore, it is very important to develop a hydrogenation catalyst with a longer life and better hydrogenation performance.

[0003] CN102600913A discloses a method for preparing a molybdenum, nickel and phosphorus impregnation aqueous solution. The method comprises the following steps: first preparing a soluble molybdenum, nickel and phosphorus aqueous solution, then adding a complex or an organic acid, and adding the remaining nickel after all the nickel is completely dissolved, and heating and boiling the mixture until all the nickel is completely dissolved. The preparation method has the advantages of the molybdenum-nickel ratio being adjustable, the preparation process being simple, the dissolution volume being large, the stability time being long, and the like, and can be used for preparing an impregnation solution for a hydroprocessing catalyst.

[0004] CN105709765A The invention discloses a method for preparing a residual oil hydrodemetallization catalyst, comprising the following steps: (1) kneading a pore-enlarging agent, pseudo-boehmite dry glue powder, an extrusion aid and a peptizing agent into a plastic body, extruding and drying; (2) unsaturated spray impregnating a carrier dried in step (1) with a mixed solution of phosphoric acid and ammonium oxalate, sealing and heating the impregnated carrier, wherein the treatment pressure is the autogenous pressure under the sealing condition, the treatment temperature is 120-160°C, the treatment time is 6-12 hours, and the treated carrier is dried and calcined to obtain an alumina carrier; (3) impregnating the alumina prepared in step (2) with active components, and drying and calcining the impregnated alumina carrier to obtain a residual oil hydrodemetallization catalyst.

[0005] CN104646007A discloses a residual oil hydrodemetallization catalyst and its preparation and application. First, the activated carbon carrier is subjected to two pretreatment processes of hydrochloric acid washing and nitric acid oxidation; then, the composite auxiliary agent, activated carbon and alumina are mixed and extruded to prepare an activated carbon / alumina composite; finally, the carrier is loaded with metal by the hydrotalcite method, that is, equal volumes 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) are impregnated, crystallized, washed several times, dried, and nickel salt water talc microcrystals are obtained, and then placed in a Mo salt solution for full replacement, filtered and washed to obtain green solid particles, dried, and roasted to obtain a residual oil hydrodemetallization catalyst.

[0006] CN112619677A discloses a method for preparing a lubricating oil hydrorefining catalyst. The method comprises the following steps: providing a porous catalyst carrier containing alumina; preparing an auxiliary agent solution and impregnating and drying the catalyst carrier to obtain a carrier A; preparing a Mo-Ni-P solution and a W-Ni solution required for the catalyst composition; adding an oil phase, a surfactant and a co-surfactant to the Mo-Ni-P solution or the W-Ni solution, stirring, mixing evenly, and obtaining an oil-in-water type microemulsion; impregnating the carrier A with the microemulsion, drying, and calcining to obtain a catalyst semi-finished product; impregnating the catalyst semi-finished product with the W-Ni solution or the Mo-Ni-P solution, drying, and calcining to obtain the lubricating oil hydrorefining catalyst.

[0007] CN101757954A discloses a method for preparing a supported selective hydrogenation catalyst using microemulsion technology. In order to improve the hydrogenation activity and selectivity of the catalyst, the method prepares a microemulsion system containing a surfactant, a co-surfactant, an oil phase and a soluble metal salt solution in a constant temperature water bath. The components of the microemulsion system are prepared according to a certain ratio, and no obvious permeation phenomenon occurs. The microemulsion system is a microemulsion system with high interfacial film strength and stability.

[0008] At present, in the field of residual oil hydrogenation catalysts, the impregnation method used in the preparation of hydrogenation catalysts is still mainly aqueous solution impregnation, which is a single-phase impregnation in which the metal is dispersed in the aqueous solution. Due to the influence of the impregnation liquid spray angle and the wetting conditions during the impregnation process, the dispersion degree of the active metal on the surface of the prepared catalyst is limited. Although the above method also adopts a multi-phase impregnation method, the dispersion of the active metal of the obtained catalyst still needs to be improved. The dispersion of the active metal is directly related to the performance of the catalyst. Therefore, it is necessary to further optimize the impregnation method of the active metal by improving the preparation method of the catalyst, so as to further improve the hydrogenation activity and stability of the catalyst. Summary of the invention

[0009] In view of the shortcomings of the prior art, the present invention provides a method for preparing a hydrogenation catalyst. The hydrogenation catalyst prepared by the method of the present invention, especially a residual oil hydrogenation metal catalyst, can improve the hydrogenation activity and stability of the catalyst.

[0010] The first aspect of the present invention provides a method for preparing a hydrogenation catalyst, comprising:

[0011] (1) adding a surfactant to oil and heating it to obtain an oil phase;

[0012] (2) mixing the co-emulsifier, the VIB Group metal source, water and an optional phosphorus source uniformly, and heating until a clear solution is obtained;

[0013] (3) adding a Group VIII metal source to the clarified solution obtained in step (2) to obtain an active metal impregnation solution, and dividing the impregnation solution into two parts, respectively labeled as impregnation solution A and impregnation solution B;

[0014] (4) adding a water-soluble polymer to the impregnation solution A obtained in step (3) to obtain an aqueous phase;

[0015] (5) The aqueous phase of step (4) is added dropwise to the oil phase obtained in step (1) in the form of droplets, and the oil phase is kept in a liquid state during the addition process, and stirring and shearing are performed to homogenize the mixture, so as to obtain the impregnation liquid C.

[0016] (6) kneading the carrier dry rubber powder and the impregnation solution B in step (3), forming, drying and calcining to obtain a catalyst intermediate;

[0017] (7) The catalyst intermediate obtained in step (6) is impregnated with the impregnation liquid C, allowed to stand, and then a polyether nonionic surfactant is added, followed by ultrasonic treatment, drying, and calcination to obtain a hydrogenation catalyst.

[0018] In step (1), the surfactant is selected from glyceryl monostearate, glyceryl distearate, glyceryl monolaurate, polyoxyethylene ether fatty alcohol (structure is R-(OCC) x -OH, wherein R is a straight-chain alkyl with a carbon number of 12 to 15, and x is 2 to 11). The oil can be at least one of silicone oil and vegetable oil. 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. The vegetable oil is selected from one or more of peanut oil, coconut oil, and tea seed oil.

[0019] In step (1), the heating is performed to a temperature of 40 to 80° C. so that the oil phase is in a uniform liquid state.

[0020] In step (1), the mass ratio of the added mass of the surfactant to the mass ratio of the oil is 1.0:0.1-10, preferably 1.0:2-10.

[0021] In step (2), the co-emulsifier is selected from one or more of polyethylene glycol-8000, polyethylene glycol-400, hexadecanol, octadecyl alcohol, propylene glycol, n-butanol, polyvinyl alcohol and glycerol.

[0022] In step (2), the amount of the co-emulsifier used accounts for 0.5% to 5.0% of the mass of the aqueous phase obtained in step (4).

[0023] In step (2), the Group VIB metal is Mo and / or W, and the Group VIB metal source is one or more of ammonium molybdate, ammonium metatungstate, and molybdenum oxide. The phosphorus source can be one or more of phosphoric acid, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate. In step (3), the mass concentration of phosphorus in the active metal impregnation solution is 1.0% to 8.0% in terms of oxide.

[0024] In step (2), the water is distilled water or deionized water, and the conductivity of the water should be less than 10.0 mS.

[0025] In step (2), the heating temperature is 90-120° C. so that the substances added in step (2) are mixed evenly to form a clear solution.

[0026] In step (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, and the like.

[0027] In step (3), in the active metal impregnation solution, the concentration of the Group VIB metal as oxide is 8-80 g / 100 ml, preferably 10-60 g / 100 ml, and the concentration of the Group VIII metal as oxide is 2-50 g / 100 ml, preferably 5-30 g / 100 ml.

[0028] In step (3), the volume ratio of the impregnation liquid A to the impregnation liquid B is 0.1 to 6.0, preferably 0.25 to 5.0.

[0029] In step (4), the water-soluble polymer is one or more of polyvinyl alcohol (molecular weight 170,000 to 220,000), carboxymethyl cellulose, gelatin, gum arabic, and sodium polyacrylate (molecular weight less than 10,000).

[0030] In step (4), the mass concentration of the water-soluble polymer in the aqueous phase is 4.0 to 14.0%.

[0031] In step (5), the temperature at which the oil phase is kept in liquid state is 45 to 85° C., and the stirring rate is 400 to 800 r / min.

[0032] In step (5), the mass ratio of the water phase to the oil phase is 0.4-8.0:1.0, preferably 0.5-5.0:1.0.

[0033] In step (5), the stirring shear homogenization process has a stirring speed of 10000 to 18000 rpm, a shear homogenization time of 3 to 8 min, and a temperature of 50 to 85° C. during the shear homogenization process.

[0034] In step (5), the particle size of the oil-in-water droplets in the impregnation liquid C is 5 to 20 nm.

[0035] In step (6), the carrier dry rubber powder may be various dry rubber powders commonly used in the art, and may be one or more of the raw materials for preparing aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, zirconium oxide or composite carriers, preferably aluminum oxide. Materials with different average pore sizes may be selected as needed, and the shape of the catalyst after molding is no longer further limited, and may be four-leaf clover, three-leaf clover, cylindrical, etc. During the catalyst molding process, molding aids may be added, such as at least one of a peptizing agent, an extrusion aid and water. Preferably, the carrier dry rubber powder is a carrier dry rubber powder for a residual oil hydrodemetallization catalyst, and the hydrogenation catalyst is a residual oil hydrodemetallization catalyst. More preferably, the properties of the carrier dry rubber powder after high-temperature calcination (i.e., calcination at 450-700°C for 1-8 hours) are as follows: the specific surface area is 150-350m 2 / g, pore volume is 0.3~1.0cm 3 / g, and the pore volume occupied by pores with a diameter of 10 to 30 nm in the pore distribution is 30% or more of the total pore volume, preferably 40% to 80%.

[0036] In step (7), the polyether nonionic surfactant is one or more of fatty alcohol polyvinyl chloride ether, ester polyvinyl chloride ether, phenol polyvinyl chloride ether, and fatty amine polyvinyl chloride ether.

[0037] In step (7), the amount of the polyether nonionic surfactant used is 2.5% to 7.5% of the mass of the impregnation liquid C.

[0038] In step (7), the impregnation method is a conventional impregnation method or an excess impregnation method, wherein the liquid-to-solid volume ratio of the impregnation liquid C to the catalyst intermediate is 2.0 to 8.0. The sample being impregnated is allowed to stand at room temperature for 1 to 12 hours.

[0039] In step (7), the ultrasonic treatment conditions are as follows: the ultrasonic frequency is 15 to 35 kHz, the material temperature during the treatment is 35 to 75° C., and the treatment time is 15 to 60 min.

[0040] In step (7), the drying temperature is 80°C-180°C, the drying time is 2-8 hours, the calcination temperature is 450°C-700°C, the calcination time is 2-8 hours, and the calcination atmosphere is one or more of air, nitrogen, water vapor, etc., preferably air atmosphere.

[0041] The present invention also provides a hydrogenation catalyst prepared by the above method, in particular a residual oil hydrogenation demetallization catalyst.

[0042] In the hydrogenation catalyst, based on the mass of the hydrogenation catalyst, the content of the VIB group metal in terms of oxide is 6.0% to 26.0%, and the content of the VIII group metal in terms of oxide is 2.0% to 14.0%.

[0043] Compared with the prior art, the present invention has the following beneficial effects:

[0044] Conventional active metal impregnation solutions are all aqueous phases, and active metals are easily aggregated during the loading process, resulting in strong acidity on the carrier surface, strong cracking ability during the reaction, and limited improvement in the hydrogenation ability of active metals. The present invention utilizes surfactants to better disperse the prepared aqueous phase containing active metals and the carrying matrix in the oil phase and the dispersed matrix, forming an impregnation solution in which the active metals are dispersed in the dispersed matrix through the carrying matrix, that is, an "oil-in-water" type impregnation solution, and then uses the above impregnation solution to impregnate the catalyst carrier to prepare a catalyst with a more uniform distribution of active metals inside and on the surface of the carrier. First, the present invention fully disperses the main active metal in the form of ions in the carrying matrix water through an emulsifier, and then dissolves the auxiliary metal in the above solution to obtain an aqueous phase containing the main metal and the auxiliary metal. In order to control the size of the colloid particles and maintain the particle size distribution of the colloid particles in the subsequent "water-in-oil" emulsion formation process, a water-soluble polymer is added to the obtained water phase as a "protector" of the colloid particles. The water-soluble polymer will be adsorbed on the surface of the colloid particles to form a "surface layer" of a certain thickness in the subsequent "water-in-oil" emulsion formation process, which can effectively hinder the collision and aggregation between the colloid particles and further improve the stability of the system. Then, under specific conditions, the above-mentioned water phase is dispersed in the oil phase to obtain a hydrogenation catalyst impregnation solution.

[0045] The present invention adopts a two-step method to load active metals in combination with an "oil-in-water" impregnation liquid, and the active metal impregnation liquid is added during carrier kneading and during later loading. The introduction of the "oil-in-water" impregnation liquid during kneading is beneficial to first load and protect the metal, and further weakens the interaction between the metal and the alumina carrier during the drying and calcining processes. At the same time, the pores of the carrier are protected during the drying and calcining processes. The later loading of active metals uses the "oil-in-water" impregnation liquid to load the active metals. The advantage obtained is that the highly dispersed nature of the water phase in the oil phase is utilized, and the water phase is used as the carrying matrix of the metal component. The oil phase evenly disperses the metal in the water phase on the surface and pores of the carrier. The "oil-in-water" droplets in the present invention can penetrate deep into the pores and surface of the carrier. By introducing a polyether nonionic surfactant, the "surface layer" on the surface of the colloid particles can be removed. Combined with ultrasonic treatment, the water phase can be separated from the dispersed matrix mainly composed of the oil phase and evenly adsorbed in the internal pores and surface of the carrier. Finally, the impregnated carrier is dried and calcined to obtain a hydrogenation catalyst with a more even dispersion of active metals.

[0046] When the hydrogenation catalyst impregnation liquid of the present invention is used to impregnate a residual oil hydrogenation demetallization carrier to prepare a hydrogenation demetallization catalyst, the anti-carbon deposition performance, demetallization activity and metal impurity tolerance of the catalyst are greatly improved due to better dispersion of the active metal in the catalyst, thereby ensuring long-term stable operation of the device. DETAILED DESCRIPTION

[0047] The technical solutions and effects of the present invention are further described below in conjunction with embodiments, but are not limited to the following embodiments.

[0048] Example 1

[0049] In this example, the surfactant is glyceryl monostearate, the silicone oil is methyl silicone oil, the mass ratio of the surfactant to the silicone oil 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, the water-soluble polymer is polyvinyl alcohol (molecular weight of 200,000), the mass ratio of the co-emulsifier: the molybdenum source is calculated as molybdenum oxide: the phosphorus source is calculated as phosphorus oxide: the nickel source is calculated as nickel oxide: the water-soluble polymer: water is 20:265:58.5:64.8:35.2:400. The mass ratio of the oil phase to the sum of the water phase and the impregnation liquid B is 900:880. In the catalyst intermediate molding process, the mass ratio of alumina dry glue powder: glue solvent is 100:3, and the mass ratio of water powder in the extrusion process is 1.16, wherein the water is the diluted impregnation liquid B, and the volume ratio of deionized water to impregnation liquid B is 5:1.

[0050] The method for preparing the hydrodemetallization catalyst in this example is as follows:

[0051] (1) adding a surfactant, glyceryl monostearate, to silicone oil, heating the mixture to 80° C., and waiting for the silicone oil to melt to obtain an oil phase;

[0052] (2) Adding the co-emulsifier polyethylene glycol-8000, molybdenum oxide, and phosphoric acid to deionized water in order, using a condensation reflux device during the reaction, the reaction started at 28° C., and during the reaction, the stirring speed was 500 r / min and heated to 120° C., and the temperature was maintained for 4 hours, and the stirring speed was maintained at a constant level until a transparent clear solution was obtained;

[0053] (3) adding basic nickel carbonate to the clarified solution obtained in step (2) to obtain an active metal impregnation solution, and dividing it into an impregnation solution A and an impregnation solution B at a volume ratio of 1:1;

[0054] (4) adding water-soluble high polymer polyvinyl alcohol to the impregnation solution A obtained in step (3) to obtain an aqueous phase;

[0055] (5) The aqueous phase in step (4) is added dropwise to the oil phase obtained in step (1) in the form of droplets. During the addition, the temperature of the oil phase is maintained at 80°C. Stirring is performed at the same time. The shear homogenization speed is 15000 rpm. The shear homogenization time is 5 min. The temperature during the shear homogenization process is 60°C. After the droplets are dispersed into an emulsion, an "oil-in-water" type impregnation liquid C is obtained;

[0056] (6) Alumina dry glue powder (properties after high temperature calcination: specific surface area of ​​195m 2 / g, pore volume is 0.74cm 3 / g, the pore volume of pores with a diameter of 10 to 30 nm in the pore distribution accounts for 53.6% of the total pore volume), a peptizing agent, deionized water, and the impregnation solution B in step (3); the above materials are kneaded and formed, dried at 140° C. for 4 h, and calcined at 650° C. for 3 h to obtain a catalyst intermediate;

[0057] (7) The catalyst intermediate was impregnated with the impregnation solution C obtained in step (5), and allowed to stand for 18 hours. Then, fatty alcohol polyvinyl chloride ether (R is 12, x is 5) was added in an amount of 3.5% of the mass of the impregnation solution, and then ultrasonic treatment was performed for 30 minutes. The ultrasonic frequency was 25kHz. During the treatment, the material temperature was 70°C, and the water phase was separated from the oil phase, while the oil phase gradually gathered. After phase separation, it was first dried at 120°C for 6 hours and calcined at 550°C for 4 hours to obtain the residual oil hydrodemetallization catalyst CAT-1. The properties of the obtained impregnation solution and catalyst are shown in Table 1, and the test results of the catalyst are shown in Table 4.

[0058] Example 2

[0059] In this example, the surfactant is distearic acid glyceryl, the silicone oil is ethyl silicone oil, the mass ratio of the surfactant to the silicone oil is 1.2:8, the co-emulsifier is hexadecanol, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, the water-soluble polymer is carboxymethyl cellulose, and the mass ratio of the co-emulsifier: the molybdenum source is calculated as molybdenum oxide: the phosphorus source is calculated as phosphorus oxide: the nickel source is calculated as nickel oxide: the water-soluble polymer: water is 24:265:58.5:64.8:45.2:400. The mass ratio of the oil phase to the water phase and the impregnation liquid B is 920:903. In the catalyst intermediate molding process, the mass ratio of alumina dry glue powder: glue solvent is 100:3, and the water-powder ratio in the extrusion process is 1.16, wherein the water is the diluted impregnation liquid B, and the volume ratio of deionized water to impregnation liquid B is 5:1.

[0060] The method for preparing the hydrodemetallization catalyst in this example is as follows:

[0061] (1) adding a surfactant, glyceryl distearate, to silicone oil, heating the mixture to 75° C., and waiting for the silicone oil to melt to obtain an oil phase;

[0062] (2) adding the co-emulsifier hexadecanol, molybdenum oxide, and phosphoric acid to deionized water in order, using a condensation reflux device during the reaction, starting the reaction at 28° C., stirring at a speed of 600 r / min, and heating to 120° C., maintaining the temperature for 4 hours, and maintaining a constant stirring rate until a transparent clear solution is obtained;

[0063] (3) adding basic nickel carbonate to the clarified solution obtained in step (2) to obtain an active metal impregnation solution and dividing it into an impregnation solution A and an impregnation solution B at a volume ratio of 1:1;

[0064] (4) adding water-soluble polymer carboxymethyl cellulose to the impregnation solution A obtained in step (3) to obtain an aqueous phase;

[0065] (5) The aqueous phase in step (4) is added dropwise to the oil phase obtained in step (1) in the form of droplets. During the addition, the temperature of the oil phase is maintained at 65°C. Stirring is performed at the same time. The shear homogenization speed is 16000 rpm. The shear homogenization time is 6 min. The temperature during the shear homogenization process is 70°C. After the droplets are dispersed into an emulsion, an "oil-in-water" type impregnation liquid C is obtained;

[0066] (6) Alumina dry glue powder (same as in Example 1), a peptizing agent, deionized water, and the impregnation solution B in step (3) are kneaded and formed, and then dried at 140° C. for 4 h and calcined at 650° C. for 3 h to obtain a catalyst intermediate.

[0067] (7) The catalyst intermediate was impregnated with the impregnation solution C obtained in step (5), and allowed to stand for 18 hours. Then, fatty alcohol polyvinyl chloride ether (R is 12, x is 5) was added in an amount of 4.5% of the mass of the impregnation solution, and then ultrasonic treatment was performed for 40 minutes. The ultrasonic frequency was 30kHz. During the treatment, the material temperature was 60°C, and the water phase was separated from the oil phase, while the oil phase gradually gathered. After phase separation, it was first dried at 120°C for 6 hours and calcined at 550°C for 4 hours to obtain the residual oil hydrodemetallization catalyst CAT-2. The properties of the obtained impregnation solution and catalyst are shown in Table 1, and the test results of the catalyst are shown in Table 4.

[0068] Example 3

[0069] In this example, the surfactant is monolaurin, the silicone oil is phenyl silicone oil, the mass ratio of surfactant to silicone oil is 1.4:8, the co-emulsifier is propylene glycol, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, the water-soluble polymer is sodium polyacrylate (molecular weight 8000), the mass ratio of co-emulsifier: molybdenum source in molybdenum oxide: phosphorus source in phosphorus oxide: nickel source in nickel oxide: water-soluble polymer: water is 28:265:58.5:64.8:55.7:400. The mass ratio of the oil phase to the sum of the water phase and the impregnation liquid B is 940:928. In the catalyst intermediate molding process, the mass ratio of alumina dry glue powder: glue solvent is 100:3, and the water-powder ratio in the extrusion process is 1.16, wherein the water is the diluted impregnation liquid B, and the volume ratio of deionized water to the impregnation liquid is 5:1.

[0070] The method for preparing the hydrodemetallization catalyst in this example is as follows:

[0071] (1) adding the surfactant monolaurin to the silicone oil, heating to 75° C., and waiting for the silicone oil to melt to obtain an oil phase;

[0072] (2) Adding the co-emulsifier propylene glycol, molybdenum oxide, and phosphoric acid to deionized water in order, using a condensation reflux device during the reaction, the reaction started at 28° C., and during the reaction, the stirring speed was 700 r / min. When heated to 120° C., the temperature was maintained for 4 hours, and the stirring speed was maintained at a constant level until a transparent clear solution was obtained;

[0073] (3) adding basic nickel carbonate to the clarified solution obtained in step (2) to obtain an active metal impregnation solution, and dividing it into an impregnation solution A and an impregnation solution B at a volume ratio of 1:1;

[0074] (4) adding water-soluble high polymer sodium polyacrylate (molecular weight 8000) to the impregnation solution A obtained in step (3) to obtain an aqueous phase;

[0075] (5) The aqueous phase in step (4) is added dropwise to the oil phase obtained in step (1) in the form of droplets. During the addition, the temperature of the oil phase is maintained at 55° C., and stirring is performed at the same time. The shear homogenization speed is 17000 rpm, the shear homogenization time is 7 min, and the temperature during the shear homogenization process is 80° C. After the droplets are dispersed into an emulsion, an "oil-in-water" type impregnation liquid C is obtained;

[0076] (6) Alumina dry glue powder (same as in Example 1), a peptizing agent, deionized water, and the impregnation solution B in step (3) are kneaded and formed, and then dried at 140° C. for 4 h and calcined at 650° C. for 3 h to obtain a catalyst intermediate.

[0077] (7) The catalyst intermediate was impregnated with the impregnation solution C obtained in step (5), and allowed to stand for 18 hours. Then, fatty alcohol polyvinyl chloride ether (R is 12, x is 5) was added in an amount of 5.5% of the mass of the impregnation solution, and then ultrasonic treatment was performed for 50 minutes. The ultrasonic frequency was 20kHz. During the treatment, the material temperature was 50°C, and the water phase was separated from the oil phase, while the oil phase gradually gathered. After phase separation, it was first dried at 120°C for 6 hours and calcined at 550°C for 4 hours to obtain the residual oil hydrodemetallization catalyst CAT-3. The properties of the obtained impregnation solution and catalyst are shown in Table 1, and the test results of the catalyst are shown in Table 4.

[0078] Example 4

[0079] In this example, the surfactant is polyoxyethylene ether fatty alcohol (R is 12, x is 5), the silicone oil is methylphenyl silicone oil, the mass ratio of surfactant to silicone oil is 0.8:8, 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, the water-soluble polymer is gelatin, and the mass ratio of co-emulsifier: molybdenum source in terms of molybdenum oxide: phosphorus source in terms of phosphorus oxide: nickel source in terms of nickel oxide: water-soluble polymer: water is 28:265:58.5:64.8:25.7:400. The mass ratio of the oil phase to the sum of the water phase and the impregnation liquid B is 880:856. In the catalyst intermediate molding process, the mass ratio of alumina dry glue powder: glue solvent is 100:3, and the water-powder ratio in the extrusion process is 1.16, wherein the water is the diluted impregnation liquid B, and the volume ratio of deionized water to the impregnation liquid is 5:1.

[0080] The method for preparing the hydrodemetallization catalyst in this example is as follows:

[0081] (1) adding a surfactant polyoxyethylene ether fatty alcohol to silicone oil, heating to 70° C., and waiting for the silicone oil to melt to obtain an oil phase;

[0082] (2) adding the emulsifier n-butanol, molybdenum oxide and phosphoric acid to deionized water in order, using a condensation reflux device during the reaction, starting the reaction at 28° C., stirring at a speed of 400 r / min, heating to 120° C., maintaining the temperature for 4 hours, and maintaining a constant stirring rate until a transparent clear solution is obtained;

[0083] (3) adding basic nickel carbonate to the clarified solution obtained in step (2) to obtain an active metal impregnation solution, and dividing it into an impregnation solution A and an impregnation solution B at a volume ratio of 1:1;

[0084] (4) adding water-soluble high polymer gelatin to the impregnation solution A obtained in step (3) to obtain an aqueous phase;

[0085] (5) The aqueous phase in step (4) is added dropwise to the oil phase obtained in step (1) in the form of droplets. During the addition, the temperature of the oil phase is maintained at 45° C., and stirring is performed at the same time. The shear homogenization speed is 14000 rpm, the shear homogenization time is 4 min, and the temperature during the shear homogenization process is 50° C. After the droplets are dispersed into an emulsion, an "oil-in-water" type impregnation liquid C is obtained;

[0086] (6) Alumina dry glue powder (same as in Example 1), a peptizing agent, deionized water, and the impregnation solution B in step (3) are kneaded and formed, and then dried at 140° C. for 4 h and calcined at 650° C. for 3 h to obtain a catalyst intermediate.

[0087] (7) The catalyst intermediate was impregnated with the impregnation solution C obtained in step (5), and allowed to stand for 18 hours. Then, fatty alcohol polyvinyl chloride ether (R is 12, x is 5) was added in an amount of 6.5% of the mass of the impregnation solution, and then ultrasonic treatment was performed for 20 minutes. The ultrasonic frequency was 15 kHz. During the treatment, the material temperature was 40° C., and the water phase was separated from the oil phase, while the oil phase gradually gathered. After phase separation, it was first dried at 120° C. for 6 hours and calcined at 550° C. for 4 hours to obtain the residual oil hydrodemetallization catalyst CAT-4. The properties of the obtained impregnation solution and catalyst are shown in Table 1, and the test results of the catalyst are shown in Table 4.

[0088] Comparative Example 1

[0089] Same as Example 1, except that the mass ratio of surfactant to silicone oil in step (1) is 0.64:8. The final catalyst obtained is dCAT-1. The properties of the obtained impregnation solution and catalyst are shown in Table 2, and the test results of the catalyst are shown in Table 5.

[0090] Comparative Example 2

[0091] The same as Example 1, except that the temperature of the oil phase is 40° C. during the process of dripping the impregnation solution in step (1) into the oil phase in step (4). The catalyst finally obtained is dCAT-2. The properties of the obtained impregnation solution and catalyst are shown in Table 2, and the test results of the catalyst are shown in Table 5.

[0092] Comparative Example 3

[0093] Same as Example 1, except that the ultrasonic frequency in step (5) is 10 kHz, the material temperature during the treatment is 30° C., and the action time is 10 min. The catalyst finally obtained is dCAT-3. The properties of the obtained impregnation solution and catalyst are shown in Table 2, and the test results of the catalyst are shown in Table 5.

[0094] Comparative Example 4

[0095] Compared with Example 1, the method of the present invention is not adopted. The aqueous solution containing molybdenum, nickel and phosphorus is directly used as an impregnation solution (the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, and the nickel source is basic nickel carbonate) to be impregnated onto the carrier (same as Example 1). The impregnated catalyst is allowed to stand at room temperature for 18 hours, then dried at 120°C for 4 hours and calcined at 550°C for 4 hours. The final catalyst is dCAT-4. The properties of the obtained impregnation solution and catalyst are shown in Table 2, and the test results of the catalyst are shown in Table 5.

[0096] Comparative Example 5

[0097] Same as Example 1, except that no water-soluble polymer is added to the mixture in step (4) (from step (3)). The final catalyst obtained is dCAT-5. The properties of the obtained impregnation solution and catalyst are shown in Table 2, and the test results of the catalyst are shown in Table 5.

[0098] Comparative Example 6

[0099] In this example, the surfactant is glyceryl monostearate, the silicone oil is methyl silicone oil, the mass ratio of the surfactant to the silicone oil 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 mass ratio of the co-emulsifier: the molybdenum source is calculated as molybdenum oxide: the phosphorus source is calculated as phosphorus oxide: the nickel source is calculated as nickel oxide: water is 20:265:58.5:64.8:400. The mass ratio of the oil phase to the sum of the water phase and the impregnation liquid B is 900:880. In the catalyst intermediate molding process, the mass ratio of alumina dry glue powder: glue solvent is 100:3, and the water-powder mass ratio in the extrusion process is 1.16, wherein the water is the diluted impregnation liquid B, and the volume ratio of deionized water to impregnation liquid B is 5:1.

[0100] The method for preparing the hydrodemetallization catalyst in this example is as follows:

[0101] (1) adding molybdenum oxide and phosphoric acid to deionized water in order, using a condensation reflux device during the reaction, the reaction started at 28° C., and during the reaction, the stirring speed was 500 r / min and heated to 120° C., and the temperature was maintained for 4 hours, and the stirring speed was maintained at a constant level until a transparent clear solution was obtained;

[0102] (2) adding basic nickel carbonate to the clarified solution obtained in step (1) to obtain an active metal impregnation solution, and dividing it into an impregnation solution A and an impregnation solution B at a volume ratio of 1:1;

[0103] (3) Adding the surfactant glyceryl monostearate, silicone oil, and the co-emulsifier polyethylene glycol-8000 to the impregnation liquid A, stirring at the same time, the shear homogenization speed 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, an "oil-in-water" type impregnation liquid C is obtained;

[0104] (4) Alumina dry glue powder (same as in Example 1), a peptizing agent, deionized water, and the impregnation solution B in step (2) are kneaded and formed, and then dried at 140° C. for 4 h and calcined at 650° C. for 3 h to obtain a catalyst intermediate;

[0105] (5) The catalyst intermediate was impregnated with the impregnation solution C obtained in step (3), allowed to stand for 18 hours, dried at 120° C. for 6 hours, and calcined at 550° C. for 4 hours to obtain a residue hydrodemetallization catalyst dCAT-6. The properties of the obtained impregnation solution and catalyst are shown in Table 2, and the test results of the catalyst are shown in Table 5.

[0106] Comparative Example 7

[0107] Same as Example 1, except that no ultrasonic treatment was used in step (6). The catalyst finally obtained was dCAT-7. The properties of the obtained impregnation solution and catalyst are shown in Table 2, and the test results of the catalyst are shown in Table 5.

[0108] Table 1 Physicochemical properties of the impregnation solution and catalyst obtained in each embodiment

[0109]

[0110]

[0111] Table 2 Physicochemical properties of the impregnation solutions and catalysts obtained in each comparative example

[0112] Serial number Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Droplet particle size / nm 10～80 10～80 10～80 - 10～80 10～80 - Catalyst No. dCAT-1 dCAT-2 dCAT-3 dCAT-4 dCAT-5 dCAT-6 dCAT-7 <![CDATA[Specific surface area, m 2 / g]]> 159 156 154 158 152 150 151 <![CDATA[Pore volume, cm 3 / g]]> 0.53 0.57 0.54 0.51 0.47 0.52 0.48 Metal content <![CDATA[MoO3,wt%]]> 12.4 12.2 12.3 12.0 12.2 12.1 12.0 NiO, wt% 2.6 2.5 2.4 2.6 2.5 2.7 2.6 Additive content <![CDATA[P2O5,wt%]]> 3.1 2.9 2.8 3.2 3.0 3.2 3.0 Metal dispersion <![CDATA[I Mo / I Al *100]]> 5.65 5.58 5.47 5.57 5.45 5.56 5.48 <![CDATA[I Ni / I Al *100]]> 1.90 1.86 1.89 1.85 1.82 1.78 1.86

[0113] Application Examples

[0114] The activity stability test of residue hydrodemetallization catalysts CAT-1~CAT-4 and dCAT-1~dCAT-7 was carried out in a 200mL fixed bed hydrogenation test device. The catalysts used were all in strips with a length of 2~3mm. The reaction conditions were: reaction temperature 375℃, reaction pressure 15.0MPa, liquid hourly volume space velocity 1.0h -1 , the hydrogen-to-oil volume ratio is 700. After 1200h of reaction, the demetallization rate (Ni+V) of each catalyst is shown in Tables 4 and 5, and the properties of the feedstock oil are shown in Table 3.

[0115] Table 3 Raw oil properties

[0116] project <![CDATA[Density at 20 °C, kg / m 3 > 970.2 S, wt% 2.56 N, wt% 0.48 Ni, μg / g 33.5 V, μg / g 69.4 CCR, wt% 12.8

[0117] Table 4 Test results of catalysts obtained in various embodiments

[0118]

[0119] Table 5 Test results of catalysts obtained in each comparative example

[0120]

[0121] It can be seen from Tables 1-5 that the hydrodemetallization catalyst prepared by the method of the present invention has a more unobstructed pore structure and a suitable specific surface area. It maintains a high reaction activity and stability during the reaction and can well meet the hydrodemetallization process of heavy oil (especially residual oil).

Claims

1. A method for preparing a hydrogenation catalyst, comprising: (1) adding a surfactant to oil and heating it to obtain an oil phase; (2) mixing the co-emulsifier, the VIB Group metal source, water and an optional phosphorus source uniformly, and heating until a clear solution is obtained; (3) adding a Group VIII metal source to the clarified solution obtained in step (2) to obtain an active metal impregnation solution, and dividing the impregnation solution into two parts, respectively labeled as impregnation solution A and impregnation solution B; (4) adding a water-soluble polymer to the impregnation solution A obtained in step (3) to obtain an aqueous phase; (5) adding the aqueous phase of step (4) in the form of droplets to the oil phase obtained in step (1), keeping the oil phase in a liquid state during the dropping process, and stirring and shearing and homogenizing to obtain the impregnation liquid C; (6) kneading the carrier dry rubber powder and the impregnation solution B in step (3), forming, drying and calcining to obtain a catalyst intermediate; (7) The catalyst intermediate obtained in step (6) is impregnated with the impregnation liquid C, allowed to stand, and then a polyether nonionic surfactant is added, followed by ultrasonic treatment, drying, and calcination to obtain a hydrogenation catalyst.

2. The method according to claim 1, characterized in that In step (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, and the silicone oil is preferably selected from at least one of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen silicone oil, and methylphenyl silicone oil; the vegetable oil is preferably selected from one or more of peanut oil, coconut oil, and tea seed oil.

3. The method according to claim 1, characterized in that In step (1), the heating temperature is 40-80° C., and / or in step (1), the mass ratio of the added surfactant to the oil is 1.0:0.1-10, preferably 1.0:2-10.

4. The method according to claim 1, characterized in that: In step (2), the co-emulsifier is selected from one or more of polyethylene glycol-8000, polyethylene glycol-400, hexadecanol, octadecyl alcohol, propylene glycol, n-butanol, polyvinyl alcohol and glycerol; and / or, in step (2), the amount of the co-emulsifier is 0.5% to 5.0% of the mass of the aqueous phase obtained in step (4).

5. The method according to claim 1, characterized in that In step (2), the Group VIB metal is Mo and / or W, and the Group VIB metal source is one or more of ammonium molybdate, ammonium metatungstate, and molybdenum oxide; the phosphorus source is one or more of phosphoric acid, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate; preferably, in the active metal impregnation solution of step (3), the mass concentration of phosphorus in terms of oxide is 1.0% to 8.0%.

6. The method according to claim 1, characterized in that In step (2), the heating is performed to a temperature of 90 to 120°C.

7. The method according to claim 1, characterized in that In step (3), the Group VIII metal is Ni and / or Co. Preferably, in step (3), in the active metal impregnation solution, the concentration of the Group VIB metal as oxide is 8 to 80 g / 100 ml, preferably 10 to 60 g / 100 ml, and the concentration of the Group VIII metal as oxide is 2 to 50 g / 100 ml, preferably 5 to 30 g / 100 ml.

8. The method according to claim 1, characterized in that In step (3), the volume ratio of the impregnation liquid A to the impregnation liquid B is 0.1 to 6.0, preferably 0.25 to 5.

0.

9. The method according to claim 1, characterized in that: In step (4), the water-soluble polymer is one or more of polyvinyl alcohol, carboxymethyl cellulose, gelatin, gum arabic, and sodium polyacrylate; preferably, in step (4), the mass concentration of the water-soluble polymer in the aqueous phase is 4.0 to 14.0%.

10. The method according to claim 1, characterized in that In step (5), the temperature at which the oil phase is kept in liquid state is 45 to 85° C., and the stirring rate is 400 to 800 r / min.

11. The method according to claim 1, characterized in that: In step (5), the mass ratio of the water phase to the oil phase is 0.4-8.0:1.0, preferably 0.5-5.0:1.0; and / or, in step (5), the stirring shear homogenization process has a stirring speed of 10000-18000 rpm, a shear homogenization time of 3-8 min, and a temperature of 50-85°C during the shear homogenization process.

12. The method according to claim 1, characterized in that In step (5), the particle size of the oil-in-water droplets in the impregnation liquid C is 5 to 20 nm.

13. The method according to claim 1, characterized in that In step (6), the carrier dry rubber powder is a carrier dry rubber powder for a residual oil hydrodemetallization catalyst, and the hydrogenation catalyst is a residual oil hydrodemetallization catalyst; more preferably, the properties of the carrier dry rubber powder after high-temperature calcination are as follows: specific surface area of ​​150 to 350 m 2 / g, pore volume is 0.3~1.0cm 3 / g, and the pore volume occupied by pores with a diameter of 10 to 30 nm in the pore distribution is 30% or more of the total pore volume, preferably 40% to 80%.

14. The method according to claim 1, characterized in that In step (7), the polyether nonionic surfactant is one or more of fatty alcohol polyvinyl chloride ether, ester polyvinyl chloride ether, phenol polyvinyl chloride ether, and fatty amine polyvinyl chloride ether; preferably, in step (7), the amount of the polyether nonionic surfactant is 2.5% to 7.5% of the mass of the impregnation solution C.

15. The method according to claim 1, characterized in that In step (7), the impregnation method is an excess impregnation method, wherein the liquid-to-solid volume ratio of the impregnation liquid C to the catalyst intermediate is 2.0 to 8.0; and / or, in step (7), the ultrasonic treatment conditions are as follows: the ultrasonic frequency is 15 to 35 kHz, the material temperature during the treatment is 35 to 75°C, and the time is 15 to 60 min; and / or, in step (7), the drying temperature is 80°C to 180°C, and the drying time is 2 to 8 h; the calcination temperature is 450°C to 700°C, and the calcination time is 2 to 8 h.

16. A hydrogenation catalyst prepared by the method according to any one of claims 1 to 15, in particular a residue hydrodemetallization catalyst.

17. The hydrogenation catalyst according to claim 16, characterized in that In the hydrogenation catalyst, based on the mass of the hydrogenation catalyst, the content of the VIB group metal in terms of oxide is 6.0% to 26.0%, and the content of the VIII group metal in terms of oxide is 2.0% to 14.0%.

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