Hydrogenation catalyst impregnation liquid and preparation method of hydrogenation catalyst

Abstract

The invention discloses a hydrogenation catalyst impregnation liquid and a preparation method of a hydrogenation catalyst. The hydrogenation catalyst impregnation liquid comprises a water phase and an oil phase coating the water phase, the water phase comprises an active metal source, a co-emulsifier, a water-soluble high polymer, water and an optional phosphorus source, and the active metal comprises a VIB group metal and / or a VIII group metal; the oil phase comprises a surfactant and oil, and the mass ratio of the surfactant to the oil is 1.0: (0.1-10). 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 preparation method of a hydrogenation impregnation liquid and a hydrogenation catalyst. Background Art

[0002] At present, 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 is mature and widely used. It 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 hydrodemetallization catalyst is relatively forward in the fixed-bed residue oil hydrogenation catalyst grading system and bears more reaction loads. Therefore, it is particularly important to develop a hydroprocessing catalyst with longer life and better hydrogenation performance, especially a hydrodemetallization catalyst.

[0003] At present, the research on hydrogenation catalysts is basically concentrated on two aspects: carrier and active metal loading. Conventional impregnation methods and techniques are usually used for active metal loading, which leads to limited dispersion of active metals on the catalyst, poor hydrogenation performance of the catalyst, and poor resistance to metal deposition and carbon deposition.

[0004] CN102600913A discloses a method for preparing a molybdenum, nickel, and phosphorus impregnation aqueous solution. The method comprises 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 complexes or organic acids are completely dissolved, and heating and boiling until all the nickel is completely dissolved. The preparation method has the advantages of arbitrary adjustment of the molybdenum-nickel ratio, simple preparation process, large dissolution amount, long stability time, etc., and can be used to prepare an impregnation solution for a hydroprocessing catalyst.

[0005] CN104646007A discloses a residual oil hydrodemetallization catalyst and its preparation method and application. The method comprises: firstly, performing two pretreatment processes of hydrochloric acid washing and nitric acid oxidation on an activated carbon carrier; then, mixing and extruding a composite auxiliary agent, activated carbon and alumina to prepare an activated carbon / alumina composite; finally, loading a metal on the carrier by a hydrotalcite method, that is, impregnating a mixed solution of terephthalic acid, nickel nitrate, urea and ammonium nitrate in a molar ratio of 2:1:(2.5-5):(1-5) in equal volumes, crystallizing, washing several times, and drying to obtain nickel salt water talc microcrystals, then placing in a Mo salt solution for full replacement, filtering and washing to obtain green solid particles, drying, and roasting to obtain a residual oil hydrodemetallization catalyst.

[0006] CN20110317245.3 discloses an impregnation solution for a hydrogenation catalyst and a preparation method thereof. The method comprises: preparing a metal compound of group VIII and a first organic complexing agent into an aqueous solution A; preparing a metal compound of group VIB into an aqueous solution B; and then mixing the aqueous solution A and the aqueous solution B; wherein the ligand of the first organic complexing agent contains at least a coordinating atom N.

[0007] 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.

[0008] 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.

[0009] 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

[0010] In view of the shortcomings of the prior art, the present invention provides a hydrogenation catalyst impregnation liquid and a method for preparing the hydrogenation catalyst. The residual oil hydrogenation metal catalyst prepared by the impregnation liquid of the present invention can improve the hydrogenation activity and stability of the catalyst.

[0011] The first aspect of the present invention provides a hydrogenation catalyst impregnation liquid, comprising an aqueous phase and an oil phase coating the aqueous phase, wherein the aqueous phase comprises an active metal source, an emulsifier, a water-soluble polymer, water and an optional phosphorus source, and the active metal comprises a Group VIB metal and / or a Group VIII metal; the oil phase comprises a surfactant and an oil, and the mass ratio of the surfactant to the oil is 1.0:0.1 to 10, preferably 1.0:2 to 10, and more preferably 1.0:4 to 10.

[0012] In the hydrogenation catalyst impregnation liquid of the present invention, the mass ratio of the water phase to the oil phase is 0.4-12.0:1.0, preferably 0.5-9.0:1.0, for example, 0.5:1.0, 0.7:1, 0.9:1.0, 1.0:1.0, 1.5:1.0, 2.0:1.0, 3.0:1.0, 4.0:1.0, 5.0:1.0, 6.0:1.0, 7.0:1.0, 8.0:1.0, 9.0:1.0, etc., and any value in the range formed by any two of these values.

[0013] In the hydrogenation catalyst impregnation liquid of the present invention, the water-soluble polymer is one or more of polyvinyl alcohol (molecular weight 170,000-220,000), carboxymethyl cellulose, gelatin, gum arabic, sodium polyacrylate (molecular weight below 10,000).

[0014] In the hydrogenation catalyst impregnation solution of the present invention, the mass concentration of the water-soluble polymer in the water phase is 4.0% to 14.0%.

[0015] In the hydrogenation catalyst impregnation solution of the present invention, in the aqueous phase, 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.

[0016] In the hydrogenation catalyst impregnation liquid of the present invention, the Group VIB metal is Mo and / or W, and the Group VIII metal is Ni and / or Co. The Group VIB metal source is one or more of ammonium molybdate, ammonium metatungstate, and molybdenum oxide. The Group VIII metal source is one or more of basic nickel nitrate, cobalt nitrate, and the like.

[0017] In the hydrogenation catalyst impregnation solution of the present invention, the water phase also includes phosphorus, and the phosphorus source is one or more of phosphoric acid, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, etc. In the water phase, the mass concentration of phosphorus in terms of oxide is 1.0% to 8.0%.

[0018] In the hydrogenation catalyst impregnation liquid of the present invention, the auxiliary emulsifier is selected from one or more of polyethylene glycol-8000, polyethylene glycol-400, hexadecanol, octadecyl alcohol, propylene glycol, n-butanol and glycerol. In the water phase, the mass concentration of the auxiliary emulsifier is 0.5% to 5.0%.

[0019] In the hydrogenation catalyst impregnation liquid of the present invention, 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).

[0020] In the hydrogenation catalyst impregnation liquid of the present invention, the oil is selected from at least one of silicone oil and vegetable oil, and the silicone oil can be 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.

[0021] In the hydrogenation catalyst impregnation liquid of the present invention, the particle size of the water-in-oil droplets is 5 to 20 nm.

[0022] The second aspect of the present invention provides a method for preparing the above-mentioned impregnation solution, comprising:

[0023] (1) adding a surfactant to oil and heating it to obtain an oil phase;

[0024] (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;

[0025] (3) adding a Group VIII metal source to the clarified solution obtained in step (2);

[0026] (4) adding a water-soluble polymer to the mixture obtained in step (3) to obtain an aqueous phase;

[0027] (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.

[0028] 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 may 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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).

[0033] In step (2), the VIB group metal source may be one or more of molybdenum oxide, ammonium tetramolybdate, ammonium metatungstate, ammonium heptamolybdate, etc. The phosphorus source may be one or more of phosphoric acid, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, etc.

[0034] In step (2), the water is distilled water or deionized water, and the conductivity of the water should be less than 10.0 mS.

[0035] 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.

[0036] 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.

[0037] In step (4), in the aqueous phase, 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.

[0038] In step (4), the water-soluble polymer is one or more of polyvinyl alcohol, carboxymethyl cellulose, gelatin, gum arabic, and sodium polyacrylate.

[0039] In step (4), the mass concentration of the water-soluble polymer in the aqueous phase is 4.0 to 14.0%.

[0040] 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.

[0041] In step (5), the mass ratio of the water phase to the oil phase is 0.4-12.0:1.0, preferably 0.5-9.0:1.0.

[0042] 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.

[0043] The third aspect of the present invention provides a method for preparing a hydrogenation catalyst, comprising: impregnating a carrier with the impregnation solution, allowing the carrier to stand, then adding a polyether nonionic surfactant, and then subjecting the carrier to ultrasonic treatment, drying, and calcining to obtain a hydrogenation catalyst.

[0044] In the preparation method of the hydrogenation catalyst of the present invention, 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.

[0045] In the preparation method of the hydrogenation catalyst of the present invention, the usage of the polyether type nonionic surfactant is 2.5% to 7.5% of the mass of the impregnation liquid.

[0046] In the preparation method of the hydrogenation catalyst of the present invention, the carrier can be various carriers commonly used in the art, and can be one or more of aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, zirconium oxide or a composite carrier. Carrier materials with different average pore sizes can be selected as needed, and the shape of the carrier particles is no longer further limited, and can be four-leaf clover, three-leaf clover, cylindrical, etc. Preferably, the carrier is a carrier for a residual oil hydrodemetallization catalyst, and the hydrogenation catalyst is a residual oil hydrodemetallization catalyst. The carrier is preferably an alumina-based carrier with a 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 70%.

[0047] In the preparation method of the hydrogenation catalyst of the present invention, the impregnation method is an excess impregnation method, wherein the liquid-to-solid volume ratio of the hydrogenation impregnation liquid to the carrier is 2.0 to 8.0. The sample being impregnated is left to stand at room temperature for 1 to 12 hours.

[0048] In the preparation method of the hydrogenation catalyst of the present invention, 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.

[0049] In the preparation method of the hydrogenation catalyst of the present invention, the drying temperature is 80°C to 180°C, the drying time is 2 to 8 hours, the calcination temperature is 450°C to 700°C, the calcination time is 2 to 8 hours, and the calcination atmosphere is an oxygen-containing atmosphere, preferably air.

[0050] In the preparation method of the hydrogenation catalyst of the present invention, the content of the VIB group metal in the hydrogenation catalyst as oxide is 6.0% to 26.0%, and the content of the VIII group metal in the hydrogenation catalyst as oxide is 2.0% to 14.0%, based on the mass of the hydrogenation catalyst.

[0051] Compared with the prior art, the present invention has the following beneficial effects:

[0052] 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.

[0053] The hydrogenation catalyst impregnation liquid of the present invention is used, and the property of the water phase being highly dispersed in the oil phase is utilized. The water phase is used as the carrier matrix of the metal component, and the oil phase evenly disperses the metal in the water phase on the surface and pores of the carrier. The "water-in-oil" droplets of the present invention can penetrate deep into the pores and surface of the carrier. Then, by introducing a polyether-type nonionic surfactant, the "surface layer" on the surface of the colloid particles can be removed, and combined with ultrasonic treatment, the water phase can be separated from the dispersion matrix with the oil phase as the main body, and evenly adsorbed in the pores and surface of the carrier. After drying and roasting, the finally obtained impregnated carrier can obtain a hydrogenation catalyst with more evenly dispersed active metals.

[0054] When the hydrogenation catalyst impregnation liquid of the present invention is used to impregnate a residue 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

[0055] 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.

[0056] Example 1

[0057] 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 20:265:58.5:64.8:70.3:400. The mass ratio of the oil phase to the water phase is 900:880.

[0058] The method for preparing the hydrodemetallization catalyst in this example is as follows:

[0059] (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;

[0060] (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;

[0061] (3) adding basic nickel carbonate to the clear solution obtained in step (2);

[0062] (4) adding water-soluble high polymer polyvinyl alcohol to the mixture obtained in step (3) to obtain an aqueous phase;

[0063] (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 is obtained;

[0064] (6) Using the impregnation solution obtained in step (5) to impregnate the catalyst support (alumina support, with a specific surface area of ​​203 m 2 / g, pore volume is 0.81cm 3 / g, the pore volume of 10-30nm pores in the pore distribution accounts for 58.2% of the total pore volume) is impregnated at a volume ratio of 5.0, left to stand for 18 hours, and then fatty alcohol polyvinyl chloride ether (R is 12, x is 5) is added, the amount of which is 3.5% of the mass of the impregnation liquid, and then ultrasonic treatment is performed for 30 minutes, the ultrasonic frequency is 25kHz, the material temperature during the treatment is 70°C, the water phase is separated from the oil phase, and the oil phase gradually converges, after phase separation, it is first dried at 120°C for 6 hours and roasted at 550°C for 4 hours to obtain the residual oil hydrodemetallization catalyst CAT-1. The properties of the obtained impregnation liquid and catalyst are shown in Table 1, and the test results of the catalyst are shown in Table 4.

[0065] Example 2

[0066] In this example, the surfactant is glyceryl distearate, 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 24:265:58.5:64.8:90.3:400. The mass ratio of the oil phase to the water phase is 920:903.

[0067] The method for preparing the hydrodemetallization catalyst in this example is as follows:

[0068] (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;

[0069] (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;

[0070] (3) adding basic nickel carbonate to the clear solution obtained in step (2);

[0071] (4) adding water-soluble polymer carboxymethyl cellulose to the mixture obtained in step (3) to obtain an aqueous phase;

[0072] (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, and stirring is performed at the same time. The shear homogenization speed is 16000 rpm, the shear homogenization time is 6 min, and the temperature during the shear homogenization process is 70°C. After the droplets are dispersed into an emulsion, an "oil-in-water" type impregnation liquid is obtained;

[0073] (6) Using the impregnation solution obtained in step (5) to impregnate the catalyst support (alumina support, with a specific surface area of ​​203 m 2 / g, pore volume is 0.81cm 3 / g, the pore volume of 10-30nm pores in the pore distribution accounts for 58.2% of the total pore volume) is impregnated at a volume ratio of 5.0, and then left to stand for 18 hours, and then fatty alcohol polyvinyl chloride ether (R is 12, x is 5) is added, and its amount is 4.5% of the mass of the impregnation liquid, and then ultrasonic treatment is performed for 40 minutes, the ultrasonic frequency is 30kHz, and the material temperature during the treatment is 60°C, so that the water phase is separated from the oil phase, and the oil phase gradually converges. After phase separation, it is first dried at a temperature of 120°C for 6 hours and roasted at a temperature of 550°C for 4 hours to obtain the residual oil hydrodemetallization catalyst CAT-2. The properties of the obtained impregnation liquid and catalyst are shown in Table 1, and the test results of the catalyst are shown in Table 4.

[0074] Example 3

[0075] In this example, the surfactant is lauric acid monoglyceride, 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 calculated as molybdenum oxide: phosphorus source calculated as phosphorus oxide: nickel source calculated as nickel oxide: water-soluble polymer: water is 28:265:58.5:64.8:111.3:400. The mass ratio of oil phase to water phase is 940:928.

[0076] The method for preparing the hydrodemetallization catalyst in this example is as follows:

[0077] (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;

[0078] (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;

[0079] (3) adding basic nickel carbonate to the clear solution obtained in step (2);

[0080] (4) adding a water-soluble high polymer sodium polyacrylate to the mixture obtained in step (3) to obtain an aqueous phase;

[0081] (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 is obtained;

[0082] (6) Using the impregnation solution obtained in step (5) to impregnate the catalyst support (alumina support, with a specific surface area of ​​203 m 2 / g, pore volume is 0.81cm 3 / g, the pore volume of 10-30nm pores in the pore distribution accounts for 58.2% of the total pore volume) is impregnated at a volume ratio of 5.0, and then left to stand for 18 hours, and then fatty alcohol polyvinyl chloride ether (R is 12, x is 5) is added, and its amount is 5.5% of the mass of the impregnation liquid, and then ultrasonic treatment is performed for 50 minutes, the ultrasonic frequency is 20kHz, and the material temperature during the treatment is 50°C, so that the water phase is separated from the oil phase, and the oil phase gradually converges. After phase separation, it is first dried at a temperature of 120°C for 6 hours and roasted at a temperature of 550°C for 4 hours to obtain the residual oil hydrodemetallization catalyst CAT-3. The properties of the obtained impregnation liquid and catalyst are shown in Table 1, and the test results of the catalyst are shown in Table 4.

[0083] Example 4

[0084] 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 auxiliary 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 auxiliary emulsifier: molybdenum source calculated as molybdenum oxide: phosphorus source calculated as phosphorus oxide: nickel source calculated as nickel oxide: water-soluble polymer: water is 28:265:58.5:64.8:51.3:400. The mass ratio of oil phase to water phase is 880:856.

[0085] The method for preparing the hydrodemetallization catalyst in this example is as follows:

[0086] (1) adding a 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;

[0087] (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;

[0088] (3) adding basic nickel carbonate to the clear solution obtained in step (2);

[0089] (4) adding water-soluble high polymer gelatin to the mixture obtained in step (3) to obtain an aqueous phase;

[0090] (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. 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 is obtained;

[0091] (6) Using the impregnation solution obtained in step (5) to impregnate the catalyst support (alumina support, with a specific surface area of ​​203 m 2 / g, pore volume is 0.81cm 3 / g, the pore volume of 10-30nm pores in the pore distribution accounts for 58.2% of the total pore volume) is impregnated at a volume ratio of 5.0, left to stand for 18 hours, and then fatty alcohol polyvinyl chloride ether (R is 12, x is 5) is added, the amount of which is 6.5% of the mass of the impregnation liquid, and then ultrasonic treatment is performed for 20 minutes, the ultrasonic frequency is 15kHz, the material temperature during the treatment is 40°C, the water phase is separated from the oil phase, and the oil phase gradually converges, after phase separation, it is 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 liquid and catalyst are shown in Table 1, and the test results of the catalyst are shown in Table 4.

[0092] Comparative Example 1

[0093] 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.

[0094] Comparative Example 2

[0095] 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.

[0096] Comparative Example 3

[0097] 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.

[0098] Comparative Example 4

[0099] 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.

[0100] Comparative Example 5

[0101] Compared with Example 1, the difference is 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.

[0102] Comparative Example 6

[0103] 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 water phase is 900:880.

[0104] The method for preparing the hydrodemetallization catalyst in this example is as follows:

[0105] (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;

[0106] (2) adding basic nickel carbonate to the clarified solution obtained in step (1) to obtain an aqueous phase;

[0107] (3) Adding surfactant glyceryl monostearate, silicone oil, and co-emulsifier polyethylene glycol-8000 to the aqueous phase, 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 is obtained;

[0108] (4) The catalyst carrier (same as Example 1) was impregnated with the impregnation solution obtained in step (3) at a volume ratio of 5.0, left to stand for 18 hours, dried at 120° C. for 6 hours, and calcined at 550° C. for 4 hours to obtain a residual oil 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.

[0109] Comparative Example 7

[0110] 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.

[0111] Table 1 Physicochemical properties of the impregnation solution and catalyst obtained in each embodiment

[0112]

[0113]

[0114] Table 2 Physicochemical properties of the impregnation solutions and catalysts obtained in each comparative example

[0115]

[0116] Application Examples

[0117] 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 strips with a length of 2~3mm. The reaction conditions were: reaction temperature 370℃, reaction pressure 15.0MPa, liquid hourly volume space velocity 1.0h -1 , the hydrogen-to-oil volume ratio is 750. 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.

[0118] Table 3 Raw oil properties

[0119] Item <![CDATA[Density at 20 °C, kg / m 3 > 970.0 S, wt% 2.34 N, wt% 0.45 Ni, μg / g 31.1 V, μg / g 68.5 CCR, wt% 12.5

[0120] Table 4 Test results of catalysts obtained in various embodiments

[0121]

[0122] Table 5 Test results of catalysts obtained in various comparative examples

[0123]

[0124] 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 hydrogenation catalyst impregnation liquid, comprising an aqueous phase and an oil phase coating the aqueous phase, wherein the aqueous phase comprises an active metal source, an emulsifier, a water-soluble polymer, water and an optional phosphorus source, wherein the active metal comprises a Group VIB metal and / or a Group VIII metal; and the oil phase comprises a surfactant and an oil, wherein the mass ratio of the surfactant to the oil is 1.0:0.1-10, preferably 1.0:2-10.

2. The impregnation liquid according to claim 1, characterized in that The mass ratio of the water phase to the oil phase is 0.4 to 12.0:1.0, preferably 0.5 to 9.0:1.

0.

3. The impregnation liquid according to claim 1, characterized in that The water-soluble polymer is one or more of polyvinyl alcohol, carboxymethyl cellulose, gelatin, gum arabic, and sodium polyacrylate; and / or the mass concentration of the water-soluble polymer in the water phase is 4.0% to 14.0%.

4. The impregnation liquid according to claim 1, characterized in that In the aqueous phase, the concentration of the Group VIB metal in terms of oxide is 8 to 80 g / 100 ml, preferably 10 to 70 g / 100 ml, and the concentration of the Group VIII metal in terms of oxide is 2 to 50 g / 100 ml, preferably 5 to 30 g / 100 ml.

5. The impregnation liquid according to claim 1 or 4, characterized in that: The Group VIB metal is Mo and / or W, and the Group VIII metal is Ni and / or Co; preferably, the Group VIB metal source is one or more of ammonium molybdate, ammonium metatungstate, and molybdenum oxide, and the Group VIII metal source is one or more of basic nickel nitrate and cobalt nitrate.

6. The impregnation liquid according to claim 1, characterized in that In the aqueous phase, the phosphorus source is one or more of phosphoric acid, monoammonium hydrogen phosphate, and diammonium hydrogen phosphate; preferably, in the aqueous phase, the mass concentration of phosphorus in terms of oxide is 1.0% to 8.0%; and / or, the co-emulsifier is selected from one or more of polyethylene glycol-8000, polyethylene glycol-400, hexadecanol, octadecyl alcohol, propylene glycol, n-butanol and glycerol; preferably, in the aqueous phase, the mass concentration of the co-emulsifier is 0.5% to 5.0%.

7. The impregnation liquid according to claim 1, characterized in that The surfactant is selected from one or more of glyceryl monostearate, glyceryl distearate, glyceryl monolaurate, and polyoxyethylene ether fatty alcohol; and / or, the oil is selected from at least one of silicone oil and vegetable oil, the silicone oil is preferably at least one of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen silicone oil, and methyl phenyl silicone oil, and the vegetable oil is preferably selected from one or more of peanut oil, coconut oil, and tea seed oil.

8. The impregnation liquid according to claim 1, characterized in that The particle size of the oil-in-water droplets is 5 to 20 nm.

9. The method for preparing the impregnation solution according to any one of claims 1 to 8, 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); (4) adding a water-soluble polymer to the mixture 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 the phase to obtain the impregnation solution.

10. The preparation method according to claim 9, characterized in that: In step (1), the heating temperature is 40 to 80°C; and / or, in step (2), the heating temperature is 90 to 120°C; and / or, 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 preparation method according to claim 9, characterized in that: 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.

12. A method for preparing a hydrogenation catalyst, comprising: The carrier is impregnated with the impregnation liquid according to any one of claims 1 to 8, allowed to stand, and then a polyether nonionic surfactant is added, followed by ultrasonic treatment, drying, and calcination to obtain a hydrogenation catalyst.

13. The preparation method according to claim 12, characterized in that: 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, the amount of the polyether nonionic surfactant is 2.5% to 7.5% of the mass of the impregnation liquid.

14. The preparation method according to claim 12, characterized in that: The carrier is a residual oil hydrodemetallization catalyst carrier, and preferably, the hydrogenation catalyst is a residual oil hydrodemetallization catalyst.

15. The preparation method according to claim 12, characterized in that: The impregnation method is an excessive impregnation method; and / or the drying temperature is 80° C. to 180° C., the drying time is 2 to 8 hours, the roasting temperature is 450° C. to 700° C., and the roasting time is 2 to 8 hours.

16. The preparation method according to claim 14, characterized in that: 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.

17. The preparation method according to claim 14, 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%.

Images