Hydrodemetallization catalyst and preparation method thereof

Abstract

The invention discloses a hydrodemetallization catalyst and a preparation method thereof. The preparation method comprises the following steps: preparing an aqueous solution containing active metal as an impregnation liquid B, and preparing a water-in-oil impregnation liquid C containing the active metal and a water-soluble polymer; mixing and kneading aluminum oxide I and the steeping liquor B, forming and roasting to obtain a carrier II; immersing the carrier II in an ammonium bicarbonate aqueous solution, sealing, and drying to obtain a carrier III; and impregnating the carrier III with the impregnation liquid C, standing, adding a surfactant, and carrying out ultrasonic treatment and roasting to obtain the catalyst. The catalyst disclosed by the invention is applied to a residual oil hydrodemetallization reaction, and the reaction activity and stability are obviously improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of hydrogenation catalyst preparation, and particularly relates to a hydrogenation demetallization catalyst and a preparation method thereof. BACKGROUND

[0002] It is known that most of the traditional residue hydroprocessing catalysts are supported catalysts, and the active metal components are generally supported on the surface of the carrier. Generally, under the action of the catalyst, various metal compounds react with H2S to form metal sulfides, and the generated metal sulfides are subsequently deposited on the catalyst, thereby being removed. Therefore, the specific surface area of the catalyst not only affects the distribution of the active metal when the active metal is supported, but also affects the deposition of metal impurities after the reaction.

[0003] CN103785400A discloses a preparation method of a high-activity residue hydrodemetallization catalyst. The method uses a polyhydric alcohol and / or a monosaccharide aqueous solution to impregnate an alumina carrier, performs hydrothermal carbonization treatment in a sealed container after the impregnation is completed, then loads active metal components Mo and Ni on the carrier, and finally calcines the alumina loaded with the active components in a nitrogen atmosphere, and then calcines in an air atmosphere to obtain a residue hydrodemetallization catalyst.

[0004] The pore size distribution range of the alumina carrier prepared by the above method is relatively narrow, and the role in the diffusion process of macromolecules in the residue feedstock is limited. In the process of impregnating the active metal, the aggregation of the active metal in the pores of the carrier and around the carrier cannot be avoided. Therefore, the activity and stability of the alumina carrier and the hydrogenation demetallization catalyst prepared by the above method still need to be further improved. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application provides a hydrogenation demetallization catalyst and a preparation method thereof. The hydrogenation demetallization catalyst provided by the present application is used in a residue hydrodemetallization reaction, and the reaction activity and stability are both significantly improved.

[0006] The first aspect of the present application provides a preparation method of a hydrogenation demetallization catalyst, comprising the following steps:

[0007] (0) preparing an impregnation solution, comprising:

[0008] (0-1) preparing an aqueous solution containing Group VIB metal and Group VIII metal and optional additives as impregnation solution B;

[0009] (0-2) adding a water-soluble polymer to the aqueous solution containing Group VIB metal and Group VIII metal and optional additives, i.e. impregnation A, to obtain an aqueous phase, and adding the aqueous phase to an oil phase to obtain impregnation solution C;

[0010] (1) knead the alumina I and the impregnation liquid B, shape, and calcine to obtain a carrier II;

[0011] (2) seal and treat the carrier II obtained in step (1) after immersing in an ammonium bicarbonate aqueous solution, dry to obtain a carrier III;

[0012] (3) impregnate the carrier III obtained in step (2) with the impregnation liquid C, stand, add a surfactant, treat by ultrasonic, and calcine to obtain the residual oil hydrodemetallization catalyst.

[0013] In step (0) of the present application, the impregnation liquid is prepared, preferably as follows:

[0014] (0-1) divide an active metal-containing aqueous solution containing a Group VIB metal and a Group VIII metal and optionally an additive into two parts, and mark them as impregnation liquid A and impregnation liquid B respectively;

[0015] (0-2) add a water-soluble polymer to the impregnation liquid A obtained in step (0-1) to obtain an aqueous phase, and drop the aqueous phase into an oil phase to obtain the impregnation liquid C.

[0016] In step (0-1) or step (0-2) of the present application, preferably, the co-emulsifier, the Group VIB metal source, and the water and optionally the additive source are mixed and heated to obtain a clear solution, and then the Group VIII metal source is added to the clear solution to obtain the active metal-containing aqueous solution, i.e. the impregnation liquid A or the impregnation liquid B.

[0017] In step (0-1) or step (0-2) of the present application, the co-emulsifier is selected from one or more of cetyl alcohol, stearyl alcohol, propylene glycol, n-butanol, ethylene glycol, and glycerol.

[0018] In step (0-1) or step (0-2) of the present application, the amount of the co-emulsifier is 0.5% to 5.0% of the mass of the obtained active metal-containing aqueous solution.

[0019] In step (0-1) or step (0-2) of the present application, 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 additive is at least one of fluorine, phosphorus, silicon, and boron, and is preferably phosphorus; the phosphorus source can be one or more of phosphoric acid, monobasic ammonium phosphate, and dibasic ammonium phosphate; the fluorine source is ammonium fluoride; the silicon source is silica sol; and the boron source is boric acid.

[0020] In step (0-1) or step (0-2) of the present application, the water is distilled water or deionized water, and the conductivity of the water should be less than 10.0 mS.

[0021] In the step (0-1) or step (0-2) of the present application, the temperature is heated to 90-120℃, so that the substances added in the step (0-1) or step (0-2) are mixed uniformly to form a clear solution.

[0022] In the step (0-1) or step (0-2) of the present application, the Group VIII metal is Ni and / or Co. The Group VIII metal source is one or more of nickel carbonate hydroxide, cobalt nitrate, etc.

[0023] In the aqueous solution containing active metal in the step (0-1) or step (0-2) of the present application, the concentration of the Group VIB metal is 8-75 g / 100 mL, preferably 10-60 g / 100 mL, calculated as oxide; the concentration of the Group VIII metal is 2-55 g / 100 mL, preferably 5-30 g / 100 mL, calculated as oxide; and the mass concentration of the auxiliary agent is 0-18.0 g / 100 mL, preferably 0.20-17.0 g / 100 mL, calculated as oxide.

[0024] In the step (0) of the present application, the volume ratio of the impregnation solution A to the impregnation solution B is 0.2-3.0, preferably 0.3-1.8, for example 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, etc., and any value in the range formed by any two of these values.

[0025] In the step (0-2) of the present application, the water-soluble polymer is one or more of polyvinyl alcohol (molecular weight 170-220 thousand), carboxymethyl cellulose, gelatin, gum arabic, and sodium polyacrylate (molecular weight below 10 thousand).

[0026] In the step (0-2) of the present application, the mass concentration of the water-soluble polymer in the aqueous phase is 4.0-14.0%.

[0027] In the step (0-2) of the present application, preferably, a surfactant is added to the oil, and heated to obtain an oil phase. Further, the surfactant is selected from one or more of glycerol monostearate, glycerol distearate, glycerol monolaurate, polyoxyethylene ether fatty alcohol (structure R-(O-C-C) x -OH, wherein R is a linear alkyl group with carbon number of 12-15, and x is 2-11), etc. The oil can be at least one of silicone oil and vegetable oil, wherein the silicone oil is at least one of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen-containing silicone oil, and methyl phenyl silicone oil, and the vegetable oil is one or more of peanut oil, coconut oil, and tea seed oil.

[0028] In step (0-2) of the present application, the heating is to a temperature of 40-80℃, so that the oil phase assumes the state of a uniform liquid.

[0029] In step (0-2) of the present application, the mass ratio of the surfactant to the oil is 1.0:0.1-10, preferably 1.0:2-10, for example 1.0:2.0, 1.0:2.5, 1.0:3.0, 1.0:3.5, 1.0:4.0, 1.0:4.5, 1.0:5.0, 1.0:5.5, 1.0:6.0, 1.0:6.5, 1.0:7.0, 1.0:7.5, 1.0:8.0, 1.0:8.5, 1.0:9.0, 1.0:9.5, 1.0:10.0, and any value within the range defined by any two of these values.

[0030] In step (0-2) of the present application, the temperature at which the oil phase is kept in a liquid state is 45-85℃, and the stirring rate is 400-800 r / min.

[0031] In step (0-2) of the present application, the mass ratio of the water phase to the oil phase is 0.4-1.8:1.0, preferably 0.5-1.5:1.0, for example 0.5:1.0, 0.7:1, 0.9:1.0, 1.0:1.0, 1.2:1.0, 1.3:1.0, 1.5:1.0, 2.0:1.0, 3.0:1.0, 4.0:1.0, 5.0:1.0, 6.0:1.0, 7.0:1.0, 8.0:1.0, 9.0:1.0, and any value within the range defined by any two of these values.

[0032] In step (0-2) of the present application, the water phase is added dropwise to the oil phase while stirring and shearing homogenization is performed. In the stirring and shearing homogenization, the stirring speed is 10,000-18,000 rpm, the shearing homogenization time is 3-8 min, and the temperature during shearing homogenization is 50-85℃.

[0033] In step (0-2) of the present application, the particle size of the water-in-oil droplets in the impregnation solution C is 5-20 nm.

[0034] In step (1) of the present application, the method for preparing the alumina I comprises:

[0035] (1-1) mixing aluminum nitrate, urea, a template agent, and water to obtain a solution X;

[0036] (1-2) performing first crystallization on the solution X obtained in step (1-1), and taking the lower slurry to obtain a material Y;

[0037] (1-3) mixing the material Y obtained in step (1-2), aluminum nitrate, urea, a template agent, and water to obtain a solution Z;

[0038] (1-4) crystallizing the solution Z obtained in step (1-3) for a second time and calcining the solution to obtain aluminum oxide A;

[0039] (1-5) Alumina A obtained in step (1-4) is immersed in an aqueous solution of ammonium bicarbonate, sealed and heat-treated, and dried to obtain aluminum oxide I.

[0040] In step (1-1) of the present invention, aluminum nitrate, urea and a template are dissolved in water (preferably deionized water) in this order and mixed to obtain a solution X.

[0041] In step (1-1) of the present invention, the molar ratio of Al(NO3)3 to the template is 160-240.

[0042] In step (1-1) of the present invention, the molar ratio of urea to Al(NO3)3 is 7 to 14. Within this range, the OH generated by the decomposition of urea - Amount and Al 3+ The hydrolysis rates can be well coordinated, and the generated alumina can grow uniformly on the surface of the template.

[0043] In step (1-1) of the present invention, the template agent is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methyl cellulose, preferably polyethylene glycol; the viscosity of the template agent (20°C) is 10 to 1000 mPa·s, and the viscosity of the solution X after adding the template agent and stirring evenly is 120 to 660 mPa·s (20°C).

[0044] In the present invention, the crystallization process is carried out in a crystallization kettle.

[0045] In step (1-2) of the present invention, the conditions for the first crystallization are as follows: the crystallization temperature is 90 to 140° C., and the crystallization time is 5 to 30 hours.

[0046] In step (1-3) of the present invention, material Y, aluminum nitrate, urea and template are dissolved in water (preferably deionized water) in this order and mixed to obtain solution Z.

[0047] In step (1-3) of the present invention, the molar ratio of Al(NO3)3 to the template is 160 to 240. The molar ratio of urea to Al(NO3)3 is 7 to 14.

[0048] In step (1-3) of the present invention, the amount of material Y added accounts for 10% to 40% of the total mass of material Y and urea used for the second crystallization.

[0049] In step (1-4), the second crystallization is carried out at a temperature of 100-200 DEG C for 25-35 hours.

[0050] In step (1-4), after the crystallization, the product is filtered and washed according to conventional methods, and then dried and calcined to obtain the alumina A. The washing can be carried out with deionized water until the pH of the filtrate is close to neutral.

[0051] In step (1-4), the drying is carried out at a temperature of 120-200 DEG C for 2-12 hours.

[0052] In step (1-4), the calcination is carried out at a temperature of 500-750 DEG C for 2-6 hours in an air atmosphere.

[0053] In step (1-5), the mass percentage of the ammonium bicarbonate aqueous solution is 10-20%. The sealing heat treatment is carried out at a temperature of 80-140 DEG C, preferably 85-130 DEG C, for 6-12 hours. The drying is carried out at a temperature of 120-180 DEG C for 2-10 hours.

[0054] In step (1), the amount of MoO3 introduced into the catalyst from the impregnation solution B is 35-60% of the total MoO3 loading in the catalyst, and the amount of the Group VIII metal oxide introduced into the catalyst from the impregnation solution B is 35-60% of the total Group VIII metal oxide loading in the catalyst.

[0055] In step (1), one or more conventional forming aids, such as a peptizing agent and an extrusion aid, can be added during the forming process. The peptizing agent is one or more of nitric acid, sulfuric acid and oxalic acid, and is preferably nitric acid. The extrusion aid is one or more of amaranth powder, cellulose and resin, and is preferably amaranth powder.

[0056] In step (1), the amount of the peptizing agent added is 0.5-6.0% by mass of the alumina I, and the amount of the extrusion aid added is 0.1-5.5% by mass of the alumina I.

[0057] In step (1), after the forming, the product is dried and calcined to obtain the carrier C. The drying is carried out at a temperature of 20-200 DEG C for 2-12 hours.

[0058] In step (1), the calcination is carried out at a temperature of 500-750 DEG C for 2-6 hours in an air atmosphere.

[0059] The mass percentage concentration of the ammonium bicarbonate aqueous solution in step (2) is 20% to 30%. The sealing treatment temperature is 10 to 60 DEG C, preferably 20 to 50 DEG C, and the treatment time is 6 to 12 hours. The treatment temperature in step (2) is 70 to 95 DEG C lower than the heat treatment temperature in step (1-5). The drying temperature is 10 to 40 DEG C, the drying time is 2 to 10 hours, and the drying method is static drying.

[0060] The mass concentration of the ammonium bicarbonate aqueous solution in step (2) is 8 to 15 percentage points higher than the mass concentration of the ammonium bicarbonate aqueous solution in step (1-5).

[0061] In step (3), the impregnation is performed by using a saturation impregnation method, and the static time after impregnation is 4 to 14 hours.

[0062] In step (3), the amount of MoO3 introduced into the catalyst from the impregnation solution C is 40% to 65% of the total MoO3 loading in the catalyst, and the amount of the Group VIII metal oxide introduced into the catalyst from the impregnation solution C is 40% to 65% of the total Group VIII metal oxide loading in the catalyst.

[0063] In step (3), the surfactant is one or more of polyether nonionic surfactants, fatty alcohol polyvinyl chloride ether, ester polyvinyl chloride ether, phenolic polyvinyl chloride ether, and fatty amine polyvinyl chloride ether.

[0064] In step (3), the amount of the surfactant is 2.5% to 7.5% of the mass of the impregnation solution C.

[0065] In step (3), 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 DEG C, and the time is 15 to 60 minutes.

[0066] In step (3), after the ultrasonic treatment, the catalyst is obtained by drying and calcining. The drying temperature is 120 to 200 DEG C, and the drying time is 2 to 12 hours.

[0067] In step (3), the calcination temperature is 350 to 550 DEG C, the calcination time is 2 to 6 hours, the calcination atmosphere is a mixed atmosphere of an inert atmosphere and other atmosphere, and the volume ratio of the inert atmosphere to the other atmosphere is 0.5 to 4:1. The inert atmosphere is mainly one or both of nitrogen and helium, and the other atmosphere is one or more of water vapor and air.

[0068] The second aspect of the present application provides the hydrogen demetallization catalyst prepared by the above preparation method, comprising a carrier component, an active metal component and carbon distributed on the surface of the catalyst, the active metal component comprising molybdenum and a Group VIII metal, and the carrier component being alumina; wherein the mass ratio of the carbon distributed on the surface of the catalyst to the alumina is 0.20-0.50.

[0069] In the present application, the active metal component comprises a first active metal component distributed inside the alumina and a second active metal component distributed on the surface of the alumina.

[0070] In the present application, the active metal component comprises molybdenum and a Group VIII metal, and the Group VIII metal is preferably nickel.

[0071] In the present application, the content of MoO3 is 2.0%-16.0% and the content of Group VIII metal oxide is 1.0%-5.0% based on the mass of the catalyst.

[0072] In the present application, the content of MoO3 in the first active component is 35%-60% and the content of MoO3 in the second active component is 40%-65% based on the total mass of MoO3 in the catalyst.

[0073] In the present application, the content of Group VIII metal oxide in the first active component is 35%-60% and the content of Group VIII metal oxide in the second active component is 40%-65% based on the total mass of Group VIII metal oxide in the catalyst.

[0074] In the present application, the specific surface area of the catalyst is 175-215 m 2 / g, and the pore volume is 0.75-1.00 mL / g.

[0075] In the present application, preferably, the specific surface area of the catalyst is 180-210 m 2 / g, and the pore volume is 0.75-0.95 mL / g.

[0076] In the present application, the pore distribution of the catalyst is as follows: the pore volume of pores with a pore diameter of <30 nm accounts for 25%-40% of the total pore volume, the pore volume of pores with a pore diameter of 30-100 nm accounts for 30%-40% of the total pore volume, and the pore volume of pores with a pore diameter of 100-300 nm accounts for 20%-45% of the total pore volume.

[0077] In the present application, the strength of the catalyst is 8.0-18.0 N / mm.

[0078] In the present application, the catalyst further comprises an auxiliary component selected from at least one of fluorine, phosphorus, silicon or boron, preferably phosphorus.

[0079] Compared with the prior art, the present application has the following beneficial effects:

[0080] At present, good pore structure and reasonable active metal distribution are very important for the catalytic performance of the hydrogenation demetallization catalyst. On the one hand, the catalyst should have a larger pore size; on the other hand, the active metal should be well dispersed in the interior and surface of the catalyst. The inventors have found through a large number of studies that by introducing seeds in the process of preparing the alumina carrier by the uniform precipitation method, the pore structure of the alumina carrier can be made more regular and unobstructed, and then by further adjusting the unobstructedness of the pores through the post-sealing heat treatment of the ammonium bicarbonate aqueous solution, the obtained powder is mixed and kneaded with nitric acid, sesbania powder, water phase impregnation liquid B and deionized water, and then is formed, and after drying and calcination, a carrier with large specific surface area and unobstructed pores can be obtained. The post-sealing treatment of the ammonium bicarbonate aqueous solution to the formed carrier can prevent the accumulation of active metal components around the pore mouth during impregnation. Finally, the “water-in-oil” type impregnation liquid C is impregnated, and after standing, a polyether nonionic surfactant is added, and after ultrasonic treatment and calcination, the catalyst is obtained.

[0081] In the preparation process of the impregnation liquid of the present application, the main active metal is fully dispersed in the form of ions in the water carrying matrix by means of a co-emulsifier, and then the auxiliary metal is dissolved in the above-mentioned solution to obtain an impregnation liquid containing the main metal and the auxiliary metal, which is divided into impregnation liquid A and impregnation liquid B according to a certain volume ratio. The water-soluble polymer is added to the obtained impregnation liquid A as a “protective body” of the colloidal particles to obtain an aqueous phase, and then under specific conditions, the aqueous phase is highly dispersed in an oil phase by special means to obtain a “water-in-oil” type impregnation liquid C.

[0082] The present invention introduces the active metal for the second time in the form of a "water-in-oil" impregnation liquid C for loading. Utilizing the highly dispersed nature of the aqueous phase in the oil phase, the aqueous phase serves as the carrier matrix for the metal component, and the oil phase evenly disperses the metal in the aqueous phase on the surface and pores of the carrier. The "water-in-oil" droplets are able to penetrate deep into the pores and surface of the carrier. The aqueous phase of the impregnation liquid C contains a water-soluble polymer, which can control the size of the colloid particles and maintain the particle size distribution of the colloid particles during the subsequent "water-in-oil" emulsion formation process. It acts as a "protector" for the colloid particles and is adsorbed on the surface of the colloid particles to form a "surface layer" of a certain thickness, effectively hindering collisions and aggregation between the colloid particles and further improving the stability of the system. Furthermore, by introducing a polyether-type nonionic surfactant, the "surface layer" on the surface of the colloid particles can be removed. Combined with ultrasonic treatment, the aqueous phase can be separated from the oil-based dispersion matrix and evenly adsorbed on the internal pores and surface of the carrier. In addition, the water-soluble polymer contained in the impregnation liquid C not only releases the pores and pore structure on the catalyst surface during calcination in a mixed atmosphere, thus preventing the clogging of the catalyst pores, but also causes incomplete decomposition of the polymer to form point-distributed carbon points, thereby regulating the acidity of the catalyst, weakening the interaction between the active metal and the carrier, and promoting the dispersion of the active metal on the catalyst surface.

[0083] Through comprehensive coordination of various steps, the present invention can prepare a catalyst with a more uniform distribution of active metals inside and on the surface of the carrier. The activity and stability of the prepared catalyst are significantly improved. After 1500 hours of reaction, the demetallization rate can reach more than 65%, and can further reach more than 69%. DETAILED DESCRIPTION

[0084] In the present invention, the ASAP-2420 physical adsorption instrument produced by Michael Company is used to characterize the pore structure (SVD) and specific surface area of ​​the catalyst.

[0085] In the present invention, a ZQJ-III intelligent particle strength testing machine is used to detect the crushing resistance of the catalyst particles.

[0086] In the present invention, a NETZSCH STA409PC-QMS403C thermogravimetric-mass spectrometer (TG-MS) is used to measure the carbon / alumina mass ratio on the catalyst surface.

[0087] The technical solutions and effects of the present invention are further described below with reference to the following embodiments, but are not limited to the following embodiments.

[0088] Example 1

[0089] In this example, the surfactant is glycerol monostearate, the silicone oil is methyl silicone oil, the mass ratio of surfactant to silicone oil is 3:8, the co-emulsifier is polyethylene glycol, the molybdenum source is molybdenum trioxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, the water-soluble polymer is polyvinyl alcohol, and the mass ratio of co-emulsifier: molybdenum source (calculated as molybdenum trioxide): phosphorus source (calculated as phosphorus pentoxide): nickel source (calculated as nickel oxide): water-soluble polymer: water is 20:269.2:48.7:82.9:35.2:400. The mass ratio of the aqueous phase to the oil phase is 0.8.

[0090] (0) Preparation of the impregnating solution, the steps are as follows:

[0091] (0-1) Add the surfactant glycerol monostearate to the silicone oil and heat to 70°C. When the material silicone oil is melted, an oil phase is obtained;

[0092] (0-2) Add the co-emulsifier polyethylene glycol, molybdenum trioxide, and phosphoric acid to deionized water in the order of first, second, and third. During the reaction, a condensation reflux device is used. The reaction starts at 28°C. During the reaction, the stirring speed is 500 r / min. When heated to 110°C, the temperature is maintained for 5 h. The constant stirring speed is maintained until a transparent and clear solution is obtained;

[0093] (0-3) Add the basic nickel carbonate to the clear solution obtained in step (0-2) to obtain an active metal impregnating solution (MoO3 concentration is 47.61 g / 100 mL, NiO concentration is 12.49 g / 100 mL, and P2O5 concentration is 10.15 g / 100 mL). Divide the impregnating solution into impregnating solution A and impregnating solution B in a volume ratio of 3:2;

[0094] (0-4) Add the water-soluble polymer polyvinyl alcohol to the impregnating solution A obtained in step (0-3) to obtain an aqueous phase;

[0095] (0-5) Add the aqueous phase in step (0-4) to the oil phase obtained in step (0-1) in the form of droplets. Maintain the temperature of the oil phase at 70°C during the process of adding droplets. Stir at the same time. The shearing homogenization speed is 12000 rpm. The shearing homogenization time is 6 min. The temperature during the shearing homogenization process is 80°C. After the droplets are dispersed into an emulsion, a "water-in-oil" type impregnating solution C is obtained;

[0096] (1) Take an appropriate amount of aluminum nitrate, urea, and template agent polyethylene glycol (viscosity is 500 mPa·s). The molar ratio of Al(NO3)3 to polyethylene glycol is 190, and the molar ratio of urea to Al(NO3)3 is 11. Dissolve the above substances in a certain amount of deionized water in the order of aluminum nitrate, urea, and polyethylene glycol. After magnetic stirring for 5 h, a solution X (viscosity is 330 mPa·s) is obtained;

[0097] (2) The obtained solution X is transferred to a crystallization kettle, which is then placed in an oven at 130°C. After reacting for 10 hours, the crystallization kettle is taken out and a certain amount of the slurry at the bottom of the crystallization kettle is taken out as material Y;

[0098] (3) Material Y, measured amounts of aluminum nitrate, urea, and template agent polyethylene glycol (viscosity 500 mPa·s), wherein the molar ratio of Al(NO3)3 to polyethylene glycol is 190, and the molar ratio of urea to Al(NO3)3 is 11, are weighed and dissolved in a certain amount of deionized water, wherein the mass of material Y accounts for 20% of the total mass of material Y and urea used in the second crystallization, and mixed by magnetic stirring to obtain solution Z;

[0099] (4) The solution Z obtained in step (3) is transferred to a crystallization kettle, and the crystallization kettle is placed in an oven at 160°C. After reacting for 24 hours, the crystallization kettle is taken out and cooled to obtain a mixed slurry containing a white precipitate in the reactor; the obtained white precipitate is filtered and washed several times until the pH value of the filtrate is close to 7; the white precipitate is placed in an oven to dry at a drying temperature of 140°C for a drying time of 5 hours, and then calcined in a muffle furnace at a calcination temperature of 650°C for a calcination time of 3 hours to obtain aluminum oxide A;

[0100] (5) immersing the obtained aluminum oxide A in an aqueous solution of ammonium bicarbonate and then performing a sealed heat treatment to obtain aluminum oxide I, wherein the mass percentage concentration of the aqueous solution of ammonium bicarbonate is 18%, the sealed heat treatment temperature is 120° C., the treatment time is 4 hours, and the drying temperature is 150° C., and the drying time is 6 hours;

[0101] (6) Alumina I, nitric acid (68 wt%), sesbania powder, impregnation solution B, and deionized water were kneaded and formed, and then dried and calcined to obtain carrier II; wherein the mass content of nitric acid (68 wt%) added was 1.5% of the mass content of aluminum oxide I, and the mass content of sesbania powder added was 2.5% of the mass content of aluminum oxide I. During the molding process, the content of deionized water added was adjusted in real time according to the state of the materials. The drying temperature was 120°C, the drying time was 6 h, the calcination temperature was 750°C, and the calcination time was 4 h (the heating rate was 2.5°C / min);

[0102] (7) immersing the obtained carrier II in an aqueous solution of ammonium bicarbonate, sealing the solution, and drying the solution to obtain carrier III, wherein the mass percentage concentration of the aqueous solution of ammonium bicarbonate is 28%, the sealing treatment temperature is 40° C., the treatment time is 6 h, the drying temperature is 30° C., the drying time is 5 h, and the drying method is static drying;

[0103] (8) The carrier III was impregnated with the impregnation solution C in a saturated impregnation manner; the impregnated sample was allowed to stand at room temperature (25°C) for 6 hours, and then fatty alcohol polyvinyl chloride ether (R is 12, x is 5) was added in an amount of 4.0% of the mass of the impregnation solution C. The sample was then ultrasonically treated for 35 minutes at a frequency of 30 kHz. During the treatment, the material temperature was 65°C, and the aqueous phase was separated from the oil phase, while the oil phase gradually converged. After phase separation, the sample was dried (temperature of 130°C, drying time of 5 hours), calcined at a temperature of 550°C, calcined for 3 hours (heating rate of 2.0°C / min), and calcined in a mixed atmosphere of nitrogen and air (nitrogen to air volume ratio of 3:1) to obtain the residue oil hydrodemetallization catalyst. The residue oil hydrodemetallization catalyst prepared above was named CAT-1. The physicochemical properties of the catalyst are shown in Table 1.

[0104] Example 2

[0105] The same as Example 1, except that in this example, the surfactant is glyceryl distearate, the silicone oil is ethyl silicone oil, the mass ratio of surfactant to silicone oil is 1.5:8, the co-emulsifier is cetyl alcohol, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, and the water-soluble polymer is carboxymethyl cellulose. The mass ratio of co-emulsifier: molybdenum source (as molybdenum oxide): phosphorus source (as phosphorus oxide): nickel source (as nickel oxide): water-soluble polymer: water is 24:269.2:48.7:82.9:90.3:400. The mass ratio of the aqueous phase to the oil phase is 0.7.

[0106] (0) Prepare the impregnation solution in the following steps:

[0107] (0-1) Adding surfactant glyceryl distearate to silicone oil, heating to 75°C, and waiting for the silicone oil to melt to obtain an oil phase;

[0108] (0-2) Adding the co-emulsifier hexadecanol, molybdenum oxide, and phosphoric acid to deionized water in this order, using a condensation reflux apparatus during the reaction, starting the reaction at 28° C., stirring at a speed of 600 r / min, heating to 120° C., maintaining the temperature for 4 h, and maintaining a constant stirring rate until a transparent clear solution is obtained;

[0109] (0-3) adding basic nickel carbonate to the clarified solution obtained in step (0-2) to obtain an active metal impregnation solution (MoO3 concentration of 47.61 g / 100 mL, NiO concentration of 12.49 g / 100 mL, P2O5 concentration of 10.15 g / 100 mL), and dividing the solution into impregnation solution A and impregnation solution B at a volume ratio of 11:9;

[0110] (0-4) adding water-soluble polymer carboxymethyl cellulose to the impregnation solution A obtained in step (0-3) to obtain an aqueous phase;

[0111] (0-5) The aqueous phase from step (0-4) was added dropwise to the oil phase obtained from step (0-1) in the form of droplets. During the addition, the oil phase temperature was maintained at 70°C while stirring. The shear homogenization speed was 13,000 rpm, the shear homogenization time was 5 minutes, and the temperature was maintained at 70°C during the shear homogenization. After the droplets were dispersed into an emulsion, a "water-in-oil" impregnation solution C was obtained.

[0112] The residue oil hydrodemetallization catalyst CAT-2 was obtained. The properties of the obtained catalyst are shown in Table 1, and the test results of the catalyst are shown in Table 4.

[0113] Example 3

[0114] The same as Example 1, except that in this example, the surfactant is monolaurin, the silicone oil is phenyl silicone oil, the mass ratio of surfactant to silicone oil is 2:8, the co-emulsifier is propylene glycol, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, and the water-soluble polymer is sodium polyacrylate. The mass ratio of co-emulsifier: molybdenum source (as molybdenum oxide): phosphorus source (as phosphorus oxide): nickel source (as nickel oxide): water-soluble polymer: water is 28:269.2:48.7:82.9:111.3:400. The mass ratio of the aqueous phase to the oil phase is 0.9.

[0115] (0) Prepare the impregnation solution in the following steps:

[0116] (0-1) Adding the surfactant monolaurin to the silicone oil, heating to 70°C, and waiting for the silicone oil to melt to obtain an oil phase;

[0117] (0-2) Propylene glycol, molybdenum oxide, and phosphoric acid as co-emulsifiers were added to deionized water in that order. A condensation reflux apparatus was used during the reaction. The reaction was started at 28° C. and heated to 120° C. at a stirring speed of 700 r / min. The temperature was maintained for 4 h, and the stirring speed was maintained at a constant level until a transparent, clear solution was obtained.

[0118] (0-3) adding basic nickel carbonate to the clarified solution obtained in step (0-2) to obtain an active metal impregnation solution (MoO3 concentration of 47.61 g / 100 mL, NiO concentration of 12.49 g / 100 mL, P2O5 concentration of 10.15 g / 100 mL), and dividing into impregnation solution A and impregnation solution B at a volume ratio of 1:1;

[0119] (0-4) adding a water-soluble high polymer sodium polyacrylate to the impregnation solution A obtained in step (0-3) to obtain an aqueous phase;

[0120] (0-5) The aqueous phase from step (0-4) was added dropwise to the oil phase obtained from step (1) in the form of droplets. During the addition, the oil phase temperature was maintained at 65°C while stirring. The shear homogenization speed was 14,000 rpm, the shear homogenization time was 6 minutes, and the temperature during the shear homogenization process was 75°C. After the droplets were dispersed into an emulsion, a "water-in-oil" impregnation solution C was obtained.

[0121] The residue oil hydrodemetallization catalyst CAT-3 was obtained. The properties of the obtained catalyst are shown in Table 1, and the test results of the catalyst are shown in Table 4.

[0122] Example 4

[0123] The same as Example 1, except that in this example, the surfactant is a 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 3.6:8, the co-emulsifier is n-butanol, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, and the water-soluble polymer is gelatin. The mass ratio of co-emulsifier: molybdenum source (calculated as molybdenum oxide): phosphorus source (calculated as phosphorus oxide): nickel source (calculated as nickel oxide): water-soluble polymer: water is 28:269.2:48.7:82.9:51.3:400. The mass ratio of the aqueous phase to the oil phase is 0.5.

[0124] (0) Prepare the impregnation solution in the following steps:

[0125] (0-1) Adding surfactant polyoxyethylene ether fatty alcohol to silicone oil, heating to 65°C, and waiting for the silicone oil to melt to obtain an oil phase;

[0126] (0-2) n-Butanol, molybdenum oxide, and phosphoric acid as co-emulsifiers were added to deionized water in that order. A condensation reflux apparatus was used during the reaction. The reaction was started at 28° C. and heated to 120° C. at a stirring speed of 400 r / min. The temperature was maintained for 4 h, and the stirring speed was maintained at a constant level until a transparent, clear solution was obtained.

[0127] (0-3) adding basic nickel carbonate to the clarified solution obtained in step (2) to obtain an active metal impregnation solution (MoO3 concentration of 47.61 g / 100 mL, NiO concentration of 12.49 g / 100 mL, P2O5 concentration of 10.15 g / 100 mL), and dividing it into impregnation solution A and impregnation solution B in a volume ratio of 9:11;

[0128] (0-4) adding water-soluble high polymer gelatin to the impregnation solution A obtained in step (3) to obtain an aqueous phase;

[0129] (0-5) The aqueous phase from step (0-4) was added dropwise to the oil phase obtained from step (0-1) in the form of droplets. During the addition, the oil phase temperature was maintained at 50°C while stirring. The shear homogenization speed was 15,000 rpm, the shear homogenization time was 4 minutes, and the temperature during the shear homogenization process was 55°C. After the droplets were dispersed into an emulsion, a "water-in-oil" impregnation solution C was obtained.

[0130] The residue oil hydrodemetallization catalyst CAT-4 was obtained. The properties of the obtained catalyst are shown in Table 1, and the test results of the catalyst are shown in Table 4.

[0131] Example 5

[0132] This example differs from Example 1 in that: in step (1), the molar ratio of Al(NO3)3 to polyethylene glycol is 200, and the molar ratio of urea to Al(NO3)3 is 9; in step (3), material Y accounts for 25% of the total mass of material Y and the urea used in the second crystallization; in step (4), the resulting solution Z is transferred to a crystallization kettle, which is then placed in an oven at 150°C. After reacting for 28 hours, the kettle is removed and the white precipitate is dried in an oven at 150°C for 6 hours. The precipitate is then calcined in a muffle furnace at 600°C for 4 hours to obtain a residue hydrodemetallization catalyst CAT-5. The physicochemical properties of the catalyst are shown in Table 1.

[0133] Example 6

[0134] This example differs from Example 1 in that: in step (5), the mass percentage concentration of the first ammonium bicarbonate aqueous solution is 16%, the sealed heat treatment temperature is 110° C., the treatment time is 7 h, and the drying temperature is 130° C., and the drying time is 5 h; in step (7), the mass percentage concentration of the second ammonium bicarbonate aqueous solution is 26%, the sealed treatment temperature is 30° C., the treatment time is 7 h, and the drying temperature is 30° C., and the drying time is 8 h; thus, a residue oil hydrodemetallization catalyst CAT-6 is prepared. The physicochemical properties of the catalyst are shown in Table 1.

[0135] Example 7

[0136] This example differs from Example 1 in that: in step (8), a fatty alcohol polyvinyl chloride ether (R = 12, x = 5) is added in an amount of 6.0% by mass of the impregnation solution C, and ultrasonic treatment is then performed for 40 minutes at a frequency of 25 kHz and a material temperature of 70°C to produce a hydrodemetallization catalyst CAT-7. The physicochemical properties of the catalyst are shown in Table 1.

[0137] Comparative Example 1

[0138] Compared with Example 1, the difference is that in step (1), the molar ratio of Al(NO3)3 to polyethylene glycol is 250, and the molar ratio of urea to Al(NO3)3 is 6.5. The above substances are dissolved in a certain amount of deionized water in the order of aluminum nitrate, urea, and polyethylene glycol, and mixed uniformly by magnetic stirring for 6 hours to obtain solution X; and the residue oil hydrodemetallization catalyst dCAT-1 is prepared. The physicochemical properties of the catalyst are shown in Table 1.

[0139] Comparative Example 2

[0140] Compared with Example 1, the differences are as follows: in step (7), the mass percentage concentration of the second ammonium bicarbonate aqueous solution is within the range of 35%, the sealing treatment temperature is 80°C, the treatment time is 5 hours, and the drying temperature is 140°C, and the drying time is 5 hours; thus, a residue oil hydrodemetallization catalyst dCAT-2 is prepared. The physicochemical properties of the catalyst are shown in Table 1.

[0141] Comparative Example 3

[0142] Compared with Example 1, the difference is that impregnation solution B is not added during the kneading process in step (6). Instead, in step (8), support D is directly impregnated with the Mo-Ni-P "water-in-oil" impregnation solution prepared according to the method of Example 1 (the total active metal loading is the same as in Example 1) by saturation impregnation. This produces residue oil hydrodemetallization catalyst dCAT-3. The physicochemical properties of this catalyst are shown in Table 1.

[0143] Comparative Example 4

[0144] Compared with Example 1, the difference is that the crystallization conditions for both times were the same, both crystallizations were performed at 150°C for 15 hours. The residue hydrodemetallization catalyst dCAT-4 was prepared. The physicochemical properties of the catalyst are shown in Table 1.

[0145] Comparative Example 5

[0146] The same method as Example 1 was used, except that the mass ratio of surfactant to silicone oil in step (0-1) was 0.64:8. The resulting catalyst was dCAT-5. The physicochemical properties of the catalyst are shown in Table 1.

[0147] Comparative Example 6

[0148] The same method as Example 1 was used, except that no water-soluble polymer was added to the mixture in step (0-4) (from the impregnation solution A in step (0-3)). The resulting catalyst was dCAT-6. The physicochemical properties of the catalyst are shown in Table 1.

[0149] Comparative Example 7

[0150] The same as Example 1, except that in this example, the surfactant is glyceryl monostearate, the silicone oil is methyl silicone oil, the mass ratio of surfactant to silicone oil is 3:8, the co-emulsifier is polyethylene 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 polyvinyl alcohol. The mass ratio of co-emulsifier: molybdenum source calculated as molybdenum oxide: phosphorus source calculated as phosphorus oxide: nickel source calculated as nickel oxide: water-soluble polymer: water is 20:269.2:48.7:82.9:35.2:400. The mass ratio of the aqueous phase to the oil phase is 0.8.

[0151] In this example, the steps for preparing the impregnation solution are as follows:

[0152] (0-1) Molybdenum oxide and phosphoric acid were added to deionized water in this order. A condensation reflux apparatus was used during the reaction. The reaction was started at 28° C. During the reaction, the stirring speed was 500 r / min and the mixture was heated to 110° C. The temperature was maintained for 5 h. The stirring speed was maintained at a constant rate until a transparent clear solution was obtained.

[0153] (0-2) adding basic nickel carbonate to the clarified solution obtained in step (0-1) to obtain an active metal impregnation solution, and dividing the solution into an impregnation solution A (aqueous phase) and an impregnation solution B at a volume ratio of 3:2;

[0154] (0-3) The surfactant glyceryl monostearate, silicone oil, and co-emulsifiers polyethylene glycol and polyvinyl alcohol were added to the aqueous phase while stirring. The shear homogenization process was performed at a speed of 12,000 rpm for 6 minutes at a temperature of 80°C. After the droplets dispersed into an emulsion, a "water-in-oil" impregnation solution C was obtained. The resulting catalyst was dCAT-7. The physicochemical properties of this catalyst are shown in Table 1.

[0155] Comparative Example 8

[0156] The same method as Example 1 was used, except that the ultrasonic frequency in step (8) was 10 kHz, the material temperature during the treatment was 30°C, and the treatment time was 10 min. The resulting catalyst was dCAT-8. The properties of the resulting catalyst are shown in Table 1.

[0157] Comparative Example 9

[0158] The same method as Example 1 was used, except that no ultrasonic treatment was used in step (8). The catalyst obtained was dCAT-9. The properties of the obtained catalyst are shown in Table 1.

[0159] Table 1 Physicochemical properties of residue hydrodemetallization catalyst

[0160]

[0161]

[0162] Table 1 Physical and chemical properties of residue hydrodemetallization catalysts

[0163]

[0164]

[0165] Evaluation test

[0166] The activity stability tests of residue hydrodemetallization catalysts CAT-1-CAT-7 and dCAT-1-dCAT-9 were carried out in a 200 mL fixed bed hydrogenation test device, and the catalysts used were all in the form of strips with a length of 2-3 mm. The reaction conditions were: reaction temperature 390°C, hydrogen partial pressure 13.0 MPa, liquid hourly space velocity 1.0 h -1 -1 after 1500 h of reaction, and the demetallization rates (Ni+V) of the catalysts were as shown in Table 3, with vacuum residue as the raw oil, and the properties of which were shown in Table 2.

[0167] Table 2 Properties of raw oil

[0168] Item Content Density (20°C), g / cm 3 ]] 1.010 S, wt% 2.53 N, wt% 0.45 Ni, mg / g 66.7 V, mg / g 108.6 CCR, wt% 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 14.9

[0169] Table 3 Test results of residue hydrodemetallization catalysts of various examples

[0170]

[0171]

[0172] Table 3 Test results of residue hydrodemetallization catalysts of various examples

[0173]

[0174] As can be seen from Tables 1, 2 and 3, the hydrodemetallization catalyst prepared according to the method of the present application has a smooth pore structure, and at the same time has a large specific surface area, and has high reactivity and stability in the reaction process, and can well meet the requirements of heavy oil, especially residue hydrodemetallization process.

Claims

1. A method for preparing a hydrodemetallization catalyst, comprising the following steps: (0) preparing an impregnation solution, comprising: (0-1) preparing an aqueous solution of active metal containing a Group VIB metal, a Group VIII metal, and an optional auxiliary agent as an impregnation solution B; (0-2) adding a water-soluble polymer to an aqueous solution of active metals containing a Group VIB metal and a Group VIII metal and an optional auxiliary agent, i.e., impregnation solution A, to obtain an aqueous phase, and adding the aqueous phase dropwise to the oil phase to obtain an impregnation solution C; (1) Alumina I and impregnation solution B are kneaded, formed, and calcined to obtain support II; (2) immersing the carrier II obtained in step (1) in an aqueous solution of ammonium bicarbonate, sealing the carrier, and drying the carrier III; (3) impregnating the carrier III obtained in step (2) with the impregnation solution C, allowing the carrier III to stand, adding a surfactant, ultrasonically treating the carrier, and calcining the carrier to obtain the residual oil hydrodemetallization catalyst.

2. The preparation method according to claim 1, characterized in that In step (0-1) or step (0-2), in the active metal impregnation solution, the concentration of the Group VIB metal as oxide is 8 to 75 g / 100 mL, preferably 10 to 60 g / 100 mL, the concentration of the Group VIII metal as oxide is 2 to 55 g / 100 mL, preferably 5 to 30 g / 100 mL, and the mass concentration of the additive as oxide is 0 to 18.0 g / 100 mL, preferably 0.20 to 17.0 g / 100 mL; Preferably, the Group VIB metal is Mo; the auxiliary agent is at least one of fluorine, phosphorus, silicon or boron; and the Group VIII metal is Ni and / or Co.

3. The preparation method according to claim 1, characterized in that In step (0-2), the water-soluble polymer is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide, carboxymethyl cellulose, gelatin, gum arabic, and sodium polyacrylate; preferably, the mass concentration of the water-soluble polymer in the aqueous phase is 4.0% to 14.0%.

4. The preparation method according to claim 1, characterized in that In step (0), the volume ratio of the impregnation liquid A to the impregnation liquid B is 0.2 to 3.0, preferably 0.3 to 1.8; And / or, in step (0-2), the mass ratio of the water phase to the oil phase is 0.4-1.8:1.0, preferably 0.5-1.5:1.

0.

5. The preparation method according to claim 1, characterized in that In step (1), the preparation process of aluminum oxide I includes: (1-1) Aluminum nitrate, urea, a template, and water are mixed to obtain a solution X; (1-2) crystallizing the solution X obtained in step (1-1) for the first time, removing the lower slurry layer, and obtaining material Y; (1-3) mixing the material Y obtained in step (1-2), aluminum nitrate, urea, a template, and water to obtain a solution Z; (1-4) crystallizing the solution Z obtained in step (1-3) for a second time and calcining the solution to obtain aluminum oxide A; (1-5) Alumina A obtained in step (1-4) is immersed in an aqueous solution of ammonium bicarbonate, sealed, heat-treated, and dried to obtain aluminum oxide I.

6. The preparation method according to claim 5, characterized in that In step (1-1), the molar ratio of Al(NO3)3 to the template is 160-240, and the molar ratio of urea to Al(NO3)3 is 7-14; and / or, in step (1-3), the molar ratio of Al(NO3)3 to the template is 160-240, and the molar ratio of urea to Al(NO3)3 is 7-14; and / or, in step (1-3), the amount of material Y added accounts for 10% to 40% of the total mass of the material Y and the urea used for the second crystallization.

7. The preparation method according to claim 5, characterized in that In step (1-1), the template is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methyl cellulose, preferably polyethylene glycol; and / or the viscosity of the template is 10 to 1000 mPa·s, and the viscosity of the solution X after adding the template and stirring is 120 to 660 mPa·s.

8. The preparation method according to claim 5, characterized in that The conditions for the first crystallization are as follows: crystallization temperature is 90-140° C., and crystallization time is 5-30 h; and / or, the conditions for the second crystallization are as follows: crystallization temperature is 100-200° C., and crystallization time is 25-35 h.

9. The preparation method according to claim 1 or 5, characterized in that In steps (1-5), the mass percentage concentration of the ammonium bicarbonate aqueous solution is in the range of 10% to 20%; and / or, in step (2), the mass percentage concentration of the ammonium bicarbonate aqueous solution is in the range of 20% to 30%; and or, the mass concentration of the ammonium bicarbonate aqueous solution in step (2) is 8 to 15 percentage points higher than the mass concentration of the ammonium bicarbonate aqueous solution in step (1-5).

10. The preparation method according to claim 1 or 5, characterized in that: The sealing heat treatment temperature in step (1-5) is 80-140°C, preferably 85-130°C, and the treatment time is 6-12h, and the drying temperature is 120-180°C, and the drying time is 2-10h; and / or, the sealing treatment temperature in step (2) is 10-60°C, preferably 20-50°C, and the treatment time is 6-12h, and the drying temperature is 10-40°C, and the drying time is 2-10h; and / or, the treatment temperature in step (2) is 70-95°C lower than the heat treatment temperature in step (1-5).

11. The preparation method according to claim 1, characterized in that In step (3), the surfactant is a polyether nonionic surfactant, preferably one or more of fatty alcohol polyvinyl chloride ether, ester polyvinyl chloride ether, phenol polyvinyl chloride ether, and fatty amine polyvinyl chloride ether; preferably, the amount of the surfactant is 2.5% to 7.5% of the mass of the impregnation solution C; And / or, in step (3), 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.

12. The hydrodemetallation catalyst prepared by the preparation method according to any one of claims 1 to 11.

13. The catalyst according to claim 12, characterized in that The catalyst includes a carrier component, an active metal component and carbon distributed on the catalyst surface, the active metal component includes molybdenum and a Group VIII metal, and the carrier component is aluminum oxide; wherein, in the catalyst, the mass ratio of carbon distributed on the catalyst surface to aluminum oxide is 0.20 to 0.

50.

14. The catalyst according to claim 13, characterized in that Based on the mass of the catalyst, the content of MoO3 is 2.0% to 16.0%, and the content of the Group VIII metal oxide is 1.0% to 5.0%. The Group VIII metal is preferably nickel.

15. The catalyst according to claim 13, characterized in that The specific surface area of ​​the catalyst is 175 to 215 m 2 / g, and the pore volume is 0.75~1.00mL / g.

16. The catalyst according to claim 13, characterized in that The pore distribution of the catalyst is as follows: pores with a pore diameter of less than 30 nm account for 25% to 40% of the total pore volume, pores with a pore diameter of 30 to 100 nm account for 30% to 40% of the total pore volume, and pores with a pore diameter of 100 nm to 300 nm account for 20% to 45% of the total pore volume; And / or, the catalyst has a strength of 8.0 to 18.0 N / mm.

17. The catalyst according to claim 13, characterized in that The catalyst includes an auxiliary component, which is selected from at least one of fluorine, phosphorus, silicon or boron, preferably phosphorus; and / or, based on the mass of the catalyst, the content of the auxiliary component in terms of oxide is 0-5.0%, preferably 1.5%-5.0%.

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