A hydrogenation catalyst impregnation solution and a method for preparing a hydrogenation catalyst

Abstract

This invention discloses a hydrogenation catalyst impregnation solution and a method for preparing the hydrogenation catalyst. The impregnation solution comprises an inner aqueous phase, an oil phase coating the inner aqueous phase, and an outer aqueous phase. The inner aqueous phase includes a Group VIB metal source, a co-emulsifier, a water-soluble polymer, water, and optionally a phosphorus source. The outer aqueous phase includes a Group VIII metal source, a hydrophilic agent, and water. The oil phase includes a surfactant and oil. The residue oil hydrogenation demetallization catalyst prepared using the impregnation solution of this invention can improve the hydrogenation activity and stability of the catalyst.

Description

Technical Field

[0001] This invention relates to a hydrogenation impregnation solution and a method for preparing a hydrogenation catalyst. Background Technology

[0002] Heavy oil hydrotreating technology has gradually become a focus of increasing attention in the petrochemical industry. Fixed-bed residue hydrotreating technology is an important means to achieve the clean and efficient utilization of vacuum residue. However, the presence of metals and other heteroatoms in the residue makes the hydrotreating catalyst prone to deactivation during the reaction process due to the deposition of metals and carbon deposits. Since the hydrodemetallization catalyst occupies a relatively prominent position in the fixed-bed residue hydrotreating catalyst gradation system and bears a significant reaction load, developing a hydrotreating catalyst with a longer lifespan and better hydrotreating performance, especially a hydrodemetallization catalyst, is particularly important.

[0003] CN101279278A discloses a method for preparing a molybdenum, nickel, and phosphorus impregnation solution. By adding a nitrogen-containing compound to the phosphoric acid impregnation solution, the pH value is varied between 2 and 6, thereby weakening the interaction between the active component and the support. However, this solution is still a phosphoric acid-containing solution, which can damage the microstructure of the catalyst support's pores.

[0004] CN102600913A discloses a method for preparing an aqueous solution for impregnation with molybdenum, nickel, and phosphorus. The method involves first preparing an aqueous solution containing soluble molybdenum, nickel, and phosphorus, then adding a complex or organic acid. After complete dissolution, the remaining nickel is added, and the mixture is heated to boiling until completely dissolved. This method offers advantages such as adjustable molybdenum-nickel ratio, simple preparation process, large dissolution capacity, and long stability time, and can be used to prepare impregnation solutions for hydrogenation catalysts.

[0005] CN20110317245.3 discloses an impregnation solution for a hydrogenation catalyst and a method for preparing the same, comprising: preparing an aqueous solution A by combining a Group VIII metal compound and a first organic complexing agent; preparing an aqueous solution B by combining a Group VIB metal compound; and then mixing the aqueous solutions A and B; wherein the ligand of the first organic complexing agent contains at least a coordinating atom N.

[0006] CN101757954A discloses a method for preparing supported selective hydrogenation catalysts using microemulsion technology. To improve the hydrogenation activity and selectivity of the catalyst, this method prepares a microemulsion system containing surfactants, co-surfactants, an oil phase, and a soluble metal salt solution in a constant-temperature water bath. The components of this microemulsion system are prepared in a specific ratio, and no significant permeation occurs; it is a microemulsion system with high and stable interfacial film strength.

[0007] Currently, in the field of residue oil hydrotreating catalysts, the impregnation method used in catalyst preparation is still mainly aqueous solution impregnation, which involves single-phase impregnation of metals dispersed in an aqueous solution. Due to the influence of the impregnation process's spray angle and wetting conditions, the dispersion of active metals on the catalyst surface is limited. Although multiphase impregnation methods are also used, the dispersion of active metals in the resulting catalysts still needs improvement. The degree of active metal dispersion directly affects catalyst performance. Therefore, it is necessary to further optimize the impregnation method of active metals by improving catalyst preparation methods, thereby further enhancing the hydrogenation activity and stability of the catalyst. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention provides a hydrogenation catalyst impregnation solution and a method for preparing the hydrogenation catalyst. The residue oil hydrogenation demetallization catalyst prepared using the impregnation solution of this invention can improve the hydrogenation activity and stability of the catalyst.

[0009] The first aspect of the present invention provides a hydrogenation catalyst impregnation solution, comprising an inner aqueous phase, an oil phase coating the inner aqueous phase, and an outer aqueous phase, wherein the inner aqueous phase comprises a Group VIB metal source, a co-emulsifier, a water-soluble polymer, water, and optionally a phosphorus source, and the outer aqueous phase comprises a Group VIII metal source, a hydrophilic agent, and water; and the oil phase comprises a surfactant and oil.

[0010] In the impregnation solution of the hydrogenation catalyst of the present invention, the mass ratio of surfactant to oil is 1.0:0.1 to 10, preferably 1.0:2 to 10, and more preferably 1.0:4 to 10.

[0011] In the impregnation solution of the hydrogenation catalyst of the present invention, the mass ratio of the internal aqueous phase to the oil phase is 0.4 to 12.0:1.0, preferably 0.5 to 9.0:1.0, for example 0.5:1.0, 0.7:1.0, 0.9:1.0, 1.0:1.0, 1.5:1.0, 2.0:1.0, 3.0:1.0, 4.0:1.0, 5.0:1.0, 6.0:1.0, 7.0:1.0, 8.0:1.0, 9.0:1.0, etc., and any value within any range formed by any two of these values.

[0012] In the impregnation solution of the hydrogenation catalyst of the present invention, the ratio of the total mass of the inner aqueous phase / oil phase (the inner aqueous phase and the oil phase covering the inner aqueous phase) to the mass of the outer aqueous phase is 0.5 to 10.0:1.0, preferably 0.5 to 8.0:1.0, for example 0.5:1.0, 0.7:1.0, 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, etc., and any value within any range formed by any two of these values.

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

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

[0015] In the impregnation solution of the hydrogenation catalyst of the present invention, the concentration of Group VIB metals as oxides in the inner aqueous phase is 8-80 g / 100 mL, preferably 10-60 g / 100 mL; and the concentration of Group VIII metals as oxides in the outer aqueous phase is 2-50 g / 100 mL, preferably 5-30 g / 100 mL.

[0016] In the impregnation solution of the hydrogenation catalyst 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, and the Group VIII metal source is one or more of basic nickel nitrate, cobalt nitrate, etc.

[0017] In the impregnation solution of the hydrogenation catalyst of the present invention, the inner aqueous phase further includes phosphorus, and the phosphorus source is one or more selected from phosphoric acid, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate. The mass concentration of phosphorus in the inner aqueous phase, calculated as oxides, is 0–8.0%, preferably 1.0%–8.0%.

[0018] In the impregnation solution of the hydrogenation catalyst of this invention, the co-emulsifier is selected from one or more of polyethylene glycol-8000, polyethylene glycol-400, cetyl alcohol, octadecyl alcohol, propylene glycol, n-butanol, and glycerol. In the internal aqueous phase, the mass concentration of the co-emulsifier is 0.5% to 5.0%.

[0019] In the impregnation solution of the hydrogenation catalyst of this invention, the hydrophilic agent is one or more selected from polysorbate, sorbitan monolaurate, aluminum monostearate, sodium dioctyl succinate sulfonate, benzyl ammonium chloride, and hexadecanetrimethylamine bromide. The mass concentration of the hydrophilic agent in the external aqueous phase is 5.0% to 15.0%.

[0020] In the impregnation solution of the hydrogenation catalyst of this invention, the surfactant is selected from glyceryl monostearate, glyceryl distearate, glyceryl monolaurate, and polyoxyethylene ether fatty alcohol (structure R-(OCC)). x -OH, where R is a straight-chain alkyl group with 12 to 15 carbon atoms, and x is 2 to 11, etc.

[0021] In the hydrogenation catalyst impregnation solution of the present invention, the oil is selected from at least one of silicone oil and vegetable oil. The silicone oil may 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.

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

[0023] (1) Mix the surfactant and oil, and heat to obtain the oil phase;

[0024] (2) Mix the co-emulsifier, the Group VIB metal source, water and optional phosphorus source, and heat to obtain a clear solution;

[0025] (3) Add water-soluble polymer to the clear solution obtained in step (2) to obtain an inner aqueous phase;

[0026] (4) The aqueous phase from step (3) is added dropwise to the oil phase obtained in step (1) in the form of droplets. During the dropwise addition, the oil phase is kept in a liquid state, and stirring and shearing are performed to homogenize the mixture to obtain an emulsion of "aqueous phase / oil phase".

[0027] (5) Mix the group VIII metal source with water containing a hydrophilic agent to obtain an external aqueous phase;

[0028] (6) Add the “inner aqueous phase / oil phase” type emulsion obtained in step (4) to the outer aqueous phase obtained in step (5) to obtain the “inner aqueous phase / oil phase / outer aqueous phase” type impregnation solution.

[0029] In step (1), the surfactant is selected from glyceryl monostearate, glyceryl distearate, glyceryl monolaurate, and polyoxyethylene ether fatty alcohol (structure R-(OCC)). x -OH, where R is a straight-chain alkyl group with 12 to 15 carbon atoms, and x is 2 to 11, etc., or one or more of these. The oil may be at least one of silicone oil and vegetable oil, wherein the silicone oil is selected from at least one of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen silicone oil, and methyl phenyl silicone oil, and the vegetable oil is selected from one or more of peanut oil, coconut oil, and tea seed oil.

[0030] In step (1), the temperature is heated to 45-85°C to make the oil phase appear as a uniform liquid.

[0031] In step (1), the mass ratio of the added surfactant to the mass of oil is 1.0:0.1 to 10, preferably 1.0:2 to 10.

[0032] In step (2), the co-emulsifier is selected from one or more of polyethylene glycol-8000, polyethylene glycol-400, cetyl alcohol, octadecanol, propylene glycol, n-butanol, polyvinyl alcohol and glycerin.

[0033] In step (2), the amount of the co-emulsifier is 0.5% to 5.0% of the mass of the inner aqueous phase obtained in step (3).

[0034] In step (2), the Group VIB metal source can be one or more of molybdenum oxide, ammonium tetramolybdate, and ammonium heptamolybdate. The phosphorus source can be one or more of phosphoric acid, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate.

[0035] In step (2), the water is distilled water or deionized water, and the conductivity of the water should be less than 10.0 mS.

[0036] In step (2), the temperature is heated to 90-120°C to ensure that the substances added in step (2) are mixed evenly until a clear solution is obtained.

[0037] In step (3), the concentration of Group VIB metals as oxides in the internal aqueous phase is 8-80 g / 100 mL, preferably 10-60 g / 100 mL, and the concentration of phosphorus source as oxides is 0-12.0 g / 100 mL, preferably 0.5-12.0 g / 100 mL.

[0038] In step (3), the water-soluble polymer is one or more of polyvinyl alcohol, carboxymethyl cellulose, gelatin, gum arabic, and sodium polyacrylate.

[0039] In step (3), the mass concentration of the water-soluble polymer in the aqueous phase obtained in step (3) is 4.0% to 14.0%.

[0040] In step (4), the oil phase is kept in a liquid state at a temperature of 45-85°C and the stirring rate is 400-800 r / min.

[0041] In step (4), the mass ratio of the internal aqueous phase to the oil phase is 0.4 to 12.0:1.0, preferably 0.5 to 9.0:1.0.

[0042] In step (4), the stirring and shearing homogenization process is carried out at a stirring speed of 10,000 to 18,000 rpm, a shearing homogenization time of 3 to 8 min, and a temperature of 50 to 85°C.

[0043] In step (5), the Group VIII metal is Ni and / or Co. The Group VIII metal source is one or more of basic nickel carbonate, cobalt nitrate, etc.

[0044] In step (5), the hydrophilic agent is one or more of the following: polysorbate, sorbitan monolaurate, aluminum monostearate, sodium dioctyl succinate sulfonate, benzyl ammonium chloride, and hexadecanetrimethylamine bromide.

[0045] In step (5), the water is distilled water or deionized water, and the conductivity of the water should be less than 10.0 mS.

[0046] In step (5), the mass concentration of the hydrophilic agent in the external aqueous phase is 5.0% to 15.0%.

[0047] In step (5), the concentration of Group VIII metals in the external aqueous phase, calculated as oxides, is 2 to 50 g / 100 mL, preferably 5 to 30 g / 100 mL.

[0048] In step (6), the mass ratio of the "internal aqueous phase / oil phase" emulsion to the external aqueous phase is 0.5 to 10.0:1.0, preferably 0.5 to 8.0:1.0.

[0049] The third aspect of the present invention provides a method for preparing a hydrogenation catalyst, comprising: impregnating a support with the above-mentioned impregnation solution, allowing it to stand, then adding a polyether-type nonionic surfactant, followed by ultrasonic treatment, drying, and calcination to obtain a hydrogenation catalyst.

[0050] In the preparation method of the hydrogenation catalyst of the present invention, the polyether-type nonionic surfactant is preferably a fatty alcohol polyoxyethylene ether (with the structure RO-(CCO)). x -H, where R is a straight-chain alkyl group with 12 to 15 carbon atoms, and x is 2 to 11.

[0051] In the preparation method of the hydrogenation catalyst of the present invention, the amount of the polyether-type nonionic surfactant is 2.5% to 7.5% of the mass of the impregnation solution.

[0052] In the preparation method of the hydrogenation catalyst of this invention, the support can be any of the commonly used supports in the art, such as alumina, silicon dioxide, titanium dioxide, magnesium oxide, zirconium oxide, or a composite support, or one or more of these. Support materials with different average pore sizes can be selected as needed, and the shape of the support particles is not further limited; they can be clover-shaped, trefoil-shaped, cylindrical, etc. Preferably, the support is a catalyst support for the hydrodemetallization of residue oil, and the hydrogenation catalyst is a hydrodemetallization catalyst for residue oil. The support is preferably an alumina-based support with a specific surface area of ​​150–350 m². 2 / g, pore volume 0.3~1.0cm³ 3 / g, the pore volume of pores with a diameter of 10-30 nm accounts for more than 30% of the total pore volume, preferably 40%-70%.

[0053] In the preparation method of the hydrogenation catalyst of the present invention, the impregnation method is an excess impregnation method. The liquid-to-solid volume ratio of the hydrogenation impregnation solution to the support is 2.0–8.0. The impregnated sample is left to stand at room temperature (20–30°C) for 1–12 hours.

[0054] In the preparation method of the hydrogenation catalyst of the present invention, the ultrasonic treatment conditions are as follows: the ultrasonic frequency is 15-35 kHz, the material temperature is 35-75 °C, and the time is 15-60 min.

[0055] In the preparation method of the hydrogenation catalyst of the present invention, the drying temperature is 80℃~180℃, and the drying time is 2~8h. The calcination temperature is 450℃~700℃, and the calcination time is 2~8h. The calcination atmosphere is an oxygen-containing atmosphere, preferably air.

[0056] In the preparation method of the hydrogenation catalyst of the present invention, the hydrogenation catalyst contains, based on the mass of the hydrogenation catalyst, 6.0% to 26.0% of Group VIB metals as oxides and 2.0% to 14.0% of Group VIII metals as oxides.

[0057] In the preparation method of the hydrogenation catalyst of the present invention, the hydrogenation catalyst further includes phosphorus, and the content of phosphorus as oxide is 0 to 8.0% based on the mass of the hydrogenation catalyst.

[0058] Compared with the prior art, the present invention has the following beneficial effects:

[0059] Conventional active metal impregnation solutions are mostly aqueous phases. Active metals tend to aggregate during loading, leading to strong acidity on the support surface, high cracking capacity during the reaction, and limited improvement in the hydrogenation capacity of the active metal. This invention utilizes surfactants to disperse two active metals separately in an inner aqueous phase and an outer aqueous phase. The inner aqueous phase acts as a carrier for the first active metal (a Group VIB metal) dispersed in the oil phase, while the outer aqueous phase acts as a carrier for the second active metal (a Group VIII metal). This results in an impregnation solution where the active metals are dispersed in both the inner and outer aqueous phases via carrier matrices—a "bottom aqueous phase / oil phase / outer aqueous phase" type impregnation solution. This impregnation solution is then used to impregnate the catalyst support, resulting in a catalyst with a more uniform distribution of active metals both inside and on the surface of the support. In the preparation of the impregnation solution, firstly, a co-emulsifier is used to fully disperse the first active metal in ionic form within the inner aqueous phase, obtaining an inner aqueous phase containing the first active metal. To control particle size and maintain particle size distribution during the subsequent formation of the "internal aqueous / oil phase" emulsion, a water-soluble polymer is added to the obtained internal aqueous phase as a "protective layer" for the particles. This water-soluble polymer adsorbs onto the particle surface during the subsequent formation of the "internal aqueous / oil phase" emulsion, forming a surface layer of a certain thickness, which effectively hinders collisions and aggregation between particles, further improving the stability of the system. Next, the second active metal is dispersed in water containing a hydrophilic agent in ionic form to obtain the external aqueous phase. Then, under specific conditions, the above-mentioned "internal aqueous / oil phase" emulsion is further dispersed in the external aqueous phase to finally obtain the hydrogenation catalyst impregnation solution.

[0060] The hydrogenation catalyst impregnation solution of this invention utilizes the properties of high dispersion of the internal aqueous phase in the oil phase and high dispersion of the "internal aqueous phase / oil phase" in the external aqueous phase. The internal aqueous phase serves as the carrier matrix for the first active metal, while the external aqueous phase serves as the carrier matrix for the second active metal. The oil phase isolates the metals in both the internal and external aqueous phases, ensuring that the active metals diffuse deeply and distribute uniformly in sequence on the surface and within the pores of the support during impregnation. Furthermore, by introducing a polyether-type nonionic surfactant, the "surface layer" on the surface of the particles can be removed. Combined with ultrasonic treatment, the internal aqueous phase can detach from the oil-based main dispersion matrix and be uniformly adsorbed into the internal pores and surface of the support. The external aqueous phase, after dispersion in the internal aqueous phase, further enters the catalyst pores, promoting the dispersion and flow of the internal aqueous phase particles. Finally, after drying and calcination, the resulting impregnated support yields a hydrogenation catalyst with a more uniform dispersion of active metals.

[0061] When the hydrogenation catalyst impregnation solution of this invention is used to impregnate the hydrodemetallization support of residue oil to prepare a hydrodemetallization catalyst, the catalyst has better dispersion of active metals, and its anti-carbon deposition performance, demetallization activity and metal impurity tolerance are all greatly improved, which can ensure the long-term stable operation of the equipment. Detailed Implementation

[0062] The technical solutions and effects of the present invention will be further illustrated below with reference to the embodiments, but the invention is not limited to the following embodiments.

[0063] Example 1

[0064] In this example, the surfactant is glyceryl monostearate, the silicone oil is methyl silicone oil, and the surfactant-to-silicone oil mass ratio is 1:8. The co-emulsifier is polyethylene glycol-8000, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, the water-soluble polymer is polyvinyl alcohol (molecular weight 200,000), and the hydrophilic agent is polysorbate. The mass ratio of co-emulsifier:molybdenum source (calculated as molybdenum oxide):phosphorus source (calculated as phosphorus oxide):water-soluble polymer:water is 20:265:58.5:70.3:400. The mass ratio of oil phase to internal aqueous phase is 1:0.5. The mass ratio of nickel source (oxidant):hydrophilic agent:water is 65:32:400. The mass ratio of "internal aqueous phase / oil phase" emulsion to external aqueous phase is 1.0:1.

[0065] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0066] (1) Add the surfactant glyceryl monostearate to the silicone oil, heat to 80°C, and wait for the silicone oil to melt to obtain the oil phase;

[0067] (2) Add the co-emulsifier polyethylene glycol-8000, molybdenum oxide and phosphoric acid to deionized water in sequence. A reflux condenser is used during the reaction. The reaction starts at 28°C. During the reaction, the stirring speed is 500 r / min. When the temperature is heated to 120°C, the temperature is maintained for 4 hours. The stirring speed is kept constant until a transparent and clear solution is obtained.

[0068] (3) Add water-soluble polymer polyvinyl alcohol to the clear solution obtained in step (2) to obtain an inner aqueous phase;

[0069] (4) The aqueous phase from step (3) is added dropwise to the oil phase obtained in step (1). During the dropwise addition, the temperature of the oil phase is maintained at 80°C, and stirring is performed simultaneously. The shear homogenization rate is 15000 rpm, the shear homogenization time is 5 min, and the temperature during the shear homogenization process is 60°C. After the droplets are dispersed into an emulsion, an "aqueous phase / oil phase" type emulsion is obtained.

[0070] (5) Add the hydrophilic agent to the water, and then add nickel nitrate to the water containing the hydrophilic agent to obtain the external aqueous phase;

[0071] (6) Add the “inner aqueous phase / oil phase” type emulsion obtained in step (4) to the outer aqueous phase obtained in step (5) to obtain the “inner aqueous phase / oil phase / outer aqueous phase” type impregnation solution;

[0072] (7) Apply the impregnation solution obtained in step (6) to the catalyst support (alumina support, with a specific surface area of ​​216 m²). 2 / g, pore volume is 0.89cm 3 / g, the pores of 10-30nm in the pore distribution account for 60.7% of the total pore volume) are impregnated at a volume ratio of 5.0, and allowed to stand for 18h. Then, fatty alcohol polyoxyethylene ether (R is 12, x is 5) is added, the amount of which is 3.5% of the mass of the impregnation solution obtained in step (6). Then, it is ultrasonically treated for 30min at an ultrasonic frequency of 25kHz. During the treatment, the material temperature is 70℃. The inner aqueous phase and the outer aqueous phase are separated from the oil phase and loaded with metal in sequence, while the oil phase gradually accumulates. After phase separation, it is dried at 120℃ for 6h and calcined at 550℃ for 4h to obtain the residue oil hydrodemetallization catalyst CAT-1. The properties of the obtained impregnation solution and catalyst are shown in Table 1, and the test results of the catalyst are shown in Table 4.

[0073] Example 2

[0074] In this example, the surfactant is glyceryl distearate, the silicone oil is ethyl silicone oil, and the mass ratio of surfactant to silicone oil is 1.2:8. The co-emulsifier is cetyl alcohol, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, the water-soluble polymer is carboxymethyl cellulose, and the hydrophilic agent is sorbitan monolaurate. The mass ratio of co-emulsifier:molybdenum source (calculated as molybdenum oxide):phosphorus source (calculated as phosphorus oxide):water-soluble polymer:water is 24:265:58.5:90.3:400. The mass ratio of oil phase to internal aqueous phase is 1:0.7. The mass ratio of nickel source (oxidizing agent:hydrophilic agent:water) is 65:24:400. The mass ratio of "internal aqueous phase / oil phase" emulsion to external aqueous phase is 0.9:1.

[0075] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0076] (1) Add the surfactant glyceryl distearate to the silicone oil, heat to 75°C, and wait for the silicone oil to melt to obtain the oil phase;

[0077] (2) Add the co-emulsifier cetyl alcohol, molybdenum oxide and phosphoric acid to deionized water in sequence. A reflux condenser is used during the reaction. The reaction starts at 28°C. During the reaction, the stirring speed is 600 r / min. When the temperature is heated to 120°C, the temperature is maintained for 4 hours. The stirring speed is kept constant until a transparent and clear solution is obtained.

[0078] (3) Add water-soluble polymer carboxymethyl cellulose to the clear solution obtained in step (2) to obtain an inner aqueous phase;

[0079] (4) The aqueous phase from step (3) is added dropwise to the oil phase obtained in step (1) in the form of droplets. During the dropwise addition, the temperature of the oil phase is maintained at 65°C, and stirring is performed simultaneously. The shear homogenization rate 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 state, an "aqueous phase / oil phase" type emulsion is obtained.

[0080] (5) Add the hydrophilic agent to the water, and then add nickel nitrate to the water containing the hydrophilic agent to obtain the external aqueous phase;

[0081] (6) Add the “inner aqueous phase / oil phase” type emulsion obtained in step (4) to the outer aqueous phase obtained in step (5) to obtain the “inner aqueous phase / oil phase / outer aqueous phase” type impregnation solution;

[0082] (7) Apply the impregnation solution obtained in step (6) to the catalyst support (alumina support, with a specific surface area of ​​216 m²). 2 / g, pore volume is 0.89cm 3 / g, the pores of 10-30nm in the pore distribution account for 60.7% of the total pore volume) are impregnated at a volume ratio of 5.0, and allowed to stand for 18h. Then, fatty alcohol polyoxyethylene ether (R is 12, x is 5) is added, the amount of which is 4.5% of the mass of the impregnation solution obtained in step (6). Then, it is ultrasonically treated for 40min at an ultrasonic frequency of 30kHz. During the treatment, the material temperature is 60℃. The inner aqueous phase and the outer aqueous phase are separated from the oil phase and loaded with metal in sequence, while the oil phase gradually accumulates. After phase separation, it is dried at 120℃ for 6h and calcined at 550℃ for 4h to obtain the residue oil hydrodemetallization catalyst CAT-2. The properties of the obtained impregnation solution and catalyst are shown in Table 1, and the test results of the catalyst are shown in Table 4.

[0083] Example 3

[0084] In this example, the surfactant is glyceryl monolaurate, the silicone oil is phenyl silicone oil, and the mass ratio of surfactant to silicone oil is 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), and the hydrophilic agent is aluminum monostearate. The mass ratio of co-emulsifier:molybdenum source (calculated as molybdenum oxide):phosphorus source (calculated as phosphorus oxide):water-soluble polymer:water is 28:265:58.5:111.3:400. The mass ratio of oil phase to internal aqueous phase is 1:0.9. The mass ratio of nickel source (oxidizing agent):hydrophilic agent:water is 65:40:400. The mass ratio of "internal aqueous phase / oil phase" emulsion to external aqueous phase is 0.7:1.

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

[0086] (1) Add the surfactant glyceryl monolaurate to the silicone oil, heat to 70°C, and wait for the silicone oil to melt to obtain the oil phase;

[0087] (2) Add the co-emulsifier propylene glycol, molybdenum oxide and phosphoric acid to deionized water in sequence. A reflux condenser is used during the reaction. The reaction starts at 28°C. During the reaction, the stirring speed is 700 r / min. When the temperature is heated to 120°C, the temperature is maintained for 4 hours. The stirring speed is kept constant until a transparent and clear solution is obtained.

[0088] (3) Add water-soluble polymer sodium polyacrylate to the clear solution obtained in step (2) to obtain an inner aqueous phase;

[0089] (4) The aqueous phase from step (3) is added dropwise to the oil phase obtained in step (1) in the form of droplets. During the dropwise addition, the temperature of the oil phase is maintained at 55°C, and stirring is performed simultaneously. The shear homogenization rate 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 state, an "aqueous phase / oil phase" type emulsion is obtained.

[0090] (5) Add the hydrophilic agent to the water, and then add nickel nitrate to the water containing the hydrophilic agent to obtain the external aqueous phase;

[0091] (6) Add the “inner aqueous phase / oil phase” type emulsion obtained in step (4) to the outer aqueous phase obtained in step (5) to obtain the “inner aqueous phase / oil phase / outer aqueous phase” type impregnation solution;

[0092] (7) Apply the impregnation solution obtained in step (6) to the catalyst support (alumina support, with a specific surface area of ​​216 m²). 2 / g, pore volume is 0.89cm 3 / g, the pores of 10-30nm in the pore distribution account for 60.7% of the total pore volume) are impregnated at a volume ratio of 5.0, and allowed to stand for 18h. Then, fatty alcohol polyoxyethylene ether (R is 12, x is 5) is added, the amount of which is 5.5% of the mass of the impregnation solution obtained in step (6). Then, it is ultrasonically treated for 50min at an ultrasonic frequency of 20kHz. During the treatment, the material temperature is 50℃. The inner aqueous phase and the outer aqueous phase are separated from the oil phase and loaded with metal in sequence, while the oil phase gradually accumulates. After phase separation, it is dried at 120℃ for 6h and calcined at 550℃ for 4h to obtain the residue oil hydrodemetallization catalyst CAT-3. The properties of the obtained impregnation solution and catalyst are shown in Table 1, and the test results of the catalyst are shown in Table 4.

[0093] Example 4

[0094] In this example, the surfactant is polyoxyethylene ether fatty alcohol (R = 12, x = 5), the silicone oil is methylphenyl silicone oil, and the mass ratio of surfactant to silicone oil is 0.8:8. The co-emulsifier is n-butanol, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, the water-soluble polymer is gelatin, and the hydrophilic agent is sodium dioctyl succinate sulfonate. The mass ratio of co-emulsifier: molybdenum source (calculated as molybdenum oxide): phosphorus source (calculated as phosphorus oxide): water-soluble polymer: water is 28:265:58.5:51.3:400. The mass ratio of oil phase to internal aqueous phase is 1:1.0. The mass ratio of nickel source (calculated as oxide): hydrophilic agent: water is 65:36:400. The mass ratio of "internal aqueous phase / oil phase" type emulsion to external aqueous phase is 0.5:1.

[0095] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0096] (1) Add the surfactant polyoxyethylene ether fatty alcohol to the silicone oil, heat to 65°C, and wait for the silicone oil to melt to obtain the oil phase;

[0097] (2) Add the co-emulsifier n-butanol, molybdenum oxide and phosphoric acid to deionized water in sequence. A reflux condenser is used during the reaction. The reaction starts at 28°C. During the reaction, the stirring speed is 400 r / min. When the temperature is heated to 120°C, the temperature is maintained for 4 hours. The stirring speed is kept constant until a transparent and clear solution is obtained.

[0098] (3) Add water-soluble polymer gelatin to the clear solution obtained in step (2) to obtain an inner aqueous phase;

[0099] (4) The aqueous phase from step (3) is added dropwise to the oil phase obtained in step (1) in the form of droplets. During the dropwise addition, the temperature of the oil phase is maintained at 45°C, and stirring is performed simultaneously. The shear homogenization rate 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 state, an "aqueous phase / oil phase" type emulsion is obtained.

[0100] (5) Add the hydrophilic agent to the water, and then add nickel nitrate to the water containing the hydrophilic agent to obtain the external aqueous phase;

[0101] (6) Add the “inner aqueous phase / oil phase” type emulsion obtained in step (4) to the outer aqueous phase obtained in step (5) to obtain the “inner aqueous phase / oil phase / outer aqueous phase” type impregnation solution;

[0102] (7) Apply the impregnation solution obtained in step (6) to the catalyst support (alumina support, with a specific surface area of ​​216 m²). 2 / g, pore volume is 0.89cm 3 / g, the pores of 10-30nm in the pore distribution account for 60.7% of the total pore volume) are impregnated at a volume ratio of 5.0, and allowed to stand for 18h. Then, fatty alcohol polyoxyethylene ether (R is 12, x is 5) is added, the amount of which is 6.5% of the mass of the impregnation solution obtained in step (6). Then, it is ultrasonically treated for 20min at an ultrasonic frequency of 15kHz. During the treatment, the material temperature is 40℃. The inner aqueous phase and the outer aqueous phase are separated from the oil phase in sequence and loaded with metal, while the oil phase gradually accumulates. After phase separation, it is dried at 120℃ for 6h and calcined at 550℃ for 4h to obtain the residue oil hydrodemetallization catalyst CAT-4. The properties of the obtained impregnation solution and catalyst are shown in Table 1, and the test results of the catalyst are shown in Table 4.

[0103] Comparative Example 1

[0104] Similar to 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.

[0105] Comparative Example 2

[0106] Similar to Example 1, except that the temperature of the oil phase was 35°C during the dropwise addition of the aqueous phase in step (3) to the oil phase in step (4). The final catalyst obtained was 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.

[0107] Comparative Example 3

[0108] Similar to Example 1, except that the ultrasonic frequency in step (7) was 10 kHz, the material temperature was 30 °C, and the reaction time was 10 min. The final catalyst obtained was 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.

[0109] Comparative Example 4

[0110] Instead of using the method of this invention, compared with Example 1, an aqueous solution containing molybdenum, nickel, and phosphorus was directly used as the impregnation solution (molybdenum source: molybdenum oxide, phosphoric acid source: phosphoric acid, and basic nickel carbonate source) to impregnate the support (same as Example 1). After the impregnated catalyst was allowed to stand at room temperature for 18 hours, it was first dried at 120°C for 4 hours and then calcined at 550°C for 4 hours. The final catalyst obtained was 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.

[0111] Comparative Example 5

[0112] The difference from Example 1 is that no water-soluble polymer was added to the clarified solution in step (3). The final catalyst obtained was 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.

[0113] Comparative Example 6

[0114] In this example, the surfactant is glyceryl monostearate, the silicone oil is methyl silicone oil, and the mass ratio of surfactant to silicone oil is 1:8. The co-emulsifier is polyethylene glycol-8000, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, and the hydrophilic agent is polysorbate. The mass ratio of co-emulsifier:molybdenum source (calculated as molybdenum oxide):phosphorus source (calculated as phosphorus oxide):water is 20:265:58.5:400. The mass ratio of oil phase to internal aqueous phase is 1:0.5. The mass ratio of nickel source (calculated as oxide):hydrophilic agent:water is 65:32:400. The mass ratio of "internal aqueous phase / oil phase" emulsion to external aqueous phase is 1.0:1.

[0115] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0116] (1) Molybdenum oxide and phosphoric acid were added to deionized water in sequence. A reflux condenser was used during the reaction. The reaction started at 28°C. During the reaction, the stirring speed was 500 r / min. When the temperature was raised to 120°C, it was maintained for 4 hours. The stirring speed was kept constant until a transparent and clear solution was obtained, and the inner aqueous phase was obtained.

[0117] (2) Add basic nickel carbonate and a hydrophilic agent to water to obtain an external aqueous phase;

[0118] (3) Add the surfactant glyceryl monostearate, silicone oil, and co-emulsifier polyethylene glycol-8000 to the aqueous phase obtained in step (1) while stirring. The shear homogenization speed is 15000 rpm, the shear homogenization time is 5 min, and the temperature during the shear homogenization process is 60℃. After the droplets are dispersed into an emulsion, an "aqueous phase / oil phase" type emulsion is obtained.

[0119] (4) Add the “inner aqueous phase / oil phase” emulsion obtained in step (3) to the outer aqueous phase obtained in step (2) to obtain an “inner aqueous phase / oil phase / outer aqueous phase” impregnation solution;

[0120] (5) The catalyst support (same as in Example 1) was impregnated with the impregnation solution obtained in step (4) at a volume ratio of 5.0, allowed to stand for 18 hours, dried at 120°C for 6 hours, and calcined at 550°C for 4 hours to obtain the residue 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.

[0121] Comparative Example 7

[0122] Similar to Example 1, except that no ultrasonic treatment was used in step (7). The final catalyst 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.

[0123] Table 1. Physicochemical properties of the impregnation solutions and catalysts obtained in each embodiment.

[0124]

[0125] Table 2. Physicochemical properties of the impregnation solutions and catalysts obtained in each comparative example.

[0126]

[0127] Application examples

[0128] The activity and stability tests of the residue hydrodemetallization catalysts CAT-1-CAT-4 and dCAT-1-dCAT-7 were conducted in a 200 mL fixed-bed hydrotreating experimental setup. The reaction conditions were: reaction temperature 375℃, reaction pressure 15.0 MPa, and liquid hourly space velocity 1.0 h⁻¹. 1 With a hydrogen-to-oil volume ratio of 700, after a reaction of 1200 h, the demetallization rate of Example 1 was 100.0%. The relative demetallization rates (Ni+V) of other catalysts are shown in Tables 4 and 5, and the properties of the feedstock oil are shown in Table 3.

[0129] Table 3 Properties of Feed Oil

[0130] project <![CDATA[Density at 20 °C, kg / m 3 > 974.5 S, wt% 2.56 N, wt% 0.46 Ni, mg / g 33.1 V, mg / g 70.6 CCR, wt% 12.8

[0131] Table 4 shows the test results of the catalysts obtained in each example.

[0132] Example number Example 1 Example 2 Example 3 Example 4 Catalyst number CAT-1 CAT-2 CAT-3 CAT-4 Demetallization (Ni+V) rate, % 100.0 98.6 98.2 97.7

[0133] Table 5 shows the experimental results of the catalysts obtained in each comparative example.

[0134]

[0135] As can be seen from Tables 1-5, the hydrodemetallization catalyst prepared according to the method of the present invention has a more unobstructed pore structure and a suitable specific surface area. It maintains high reactivity and stability during the reaction process and can well meet the requirements of hydrodemetallization process of heavy oil (especially residue oil).

Claims

1. A hydrogenation catalyst impregnation solution comprising an inner aqueous phase, an oil phase coating the inner aqueous phase, and an outer aqueous phase, wherein the inner aqueous phase comprises a Group VIB metal source, a co-emulsifier, a water-soluble polymer, water, and optionally a phosphorus source, and the outer aqueous phase comprises a Group VIII metal source, a hydrophilic agent, and water; and the oil phase comprises a surfactant and oil.

2. The impregnation solution according to claim 1, characterized in that, The mass ratio of surfactant to oil is 1.0:0.1 to 10, preferably 1.0:2 to 10; And / or, the mass ratio of the internal aqueous phase to the oil phase is 0.4 to 12.0:1.0, preferably 0.5 to 9.0:1.0; And / or, the ratio of the total mass of the internal aqueous phase / oil phase to the mass of the external aqueous phase is 0.5 to 10.0:1.0, preferably 0.5 to 8.0:1.

0.

3. The impregnation solution 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 internal aqueous phase is 4.0% to 14.0%.

4. The impregnation solution according to claim 1, characterized in that, The co-emulsifier is selected from one or more of polyethylene glycol-8000, polyethylene glycol-400, cetyl alcohol, octadecanol, propylene glycol, n-butanol and glycerin; and / or, the mass concentration of the co-emulsifier in the inner aqueous phase is 0.5% to 5.0%.

5. The impregnation solution according to claim 1, characterized in that, The hydrophilic agent is one or more of polysorbate, sorbitan monolaurate, aluminum monostearate, sodium dioctyl succinate sulfonate, benzyl ammonium chloride, and hexadecanetrimethylamine bromide; and / or, the mass concentration of the hydrophilic agent in the external aqueous phase is 5.0% to 15.0%.

6. The impregnation solution 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, wherein the silicone oil is at least one of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen silicone oil, and methyl phenyl silicone oil, and the vegetable oil is selected from one or more of peanut oil, coconut oil, and tea seed oil.

7. The impregnation solution according to claim 1, characterized in that, The Group VIB metals are Mo and / or W, and the Group VIII metals are Ni and / or Co.

8. The impregnation solution according to claim 1 or 7, characterized in that, In the inner aqueous phase, the concentration of Group VIB metals as oxides is 8-80 g / 100 mL, preferably 10-60 g / 100 mL; in the outer aqueous phase, the concentration of Group VIII metals as oxides is 2-50 g / 100 mL, preferably 5-30 g / 100 mL.

9. The impregnation solution according to claim 1, characterized in that, The internal aqueous phase includes phosphorus; and / or, the mass concentration of phosphorus in the internal aqueous phase, calculated as oxides, is 0 to 8.0%, preferably 1.0% to 8.0%.

10. A method for preparing the impregnation solution according to any one of claims 1-9, comprising: (1) Mix the surfactant and oil, and heat to obtain the oil phase; (2) Mix the co-emulsifier, the Group VIB metal source, water and optional phosphorus source, and heat to obtain a clear solution; (3) Add water-soluble polymer to the clear solution obtained in step (2) to obtain an inner aqueous phase; (4) The aqueous phase from step (3) is added dropwise to the oil phase obtained in step (1) in the form of droplets. During the dropwise addition, the oil phase is kept in a liquid state, and at the same time, stirring and shearing are performed to homogenize the mixture to obtain an "aqueous phase / oil phase" type emulsion. (5) Mix the group VIII metal source with water containing a hydrophilic agent to obtain an external aqueous phase; (6) Add the “inner aqueous phase / oil phase” emulsion obtained in step (4) to the outer aqueous phase obtained in step (5) to obtain an “inner aqueous phase / oil phase / outer aqueous phase” impregnation solution.

11. The preparation method according to claim 10, characterized in that, In step (1), the heating temperature is 45-85°C; and / or, in step (2), the heating temperature is 90-120°C.

12. The preparation method according to claim 10, characterized in that, In step (4), the stirring and shearing homogenization process has a stirring speed of 10,000 to 18,000 rpm, a shearing homogenization time of 3 to 8 min, and a shearing homogenization temperature of 50 to 85℃.

13. A method for preparing a hydrogenation catalyst, comprising: The carrier is impregnated with the impregnation solution according to any one of claims 1-9, allowed to stand, then a polyether-type nonionic surfactant is added, followed by ultrasonic treatment, drying, and calcination to obtain a hydrogenation catalyst.

14. The preparation method according to claim 13, characterized in that, The polyether-type nonionic surfactant is a fatty alcohol polyoxyethylene ether; preferably, the amount of the polyether-type nonionic surfactant is 2.5% to 7.5% of the mass of the impregnation solution.

15. The preparation method according to claim 13, characterized in that, The support is a residue oil hydrodemetallization catalyst support, and preferably, the hydrodemetallization catalyst is a residue oil hydrodemetallization catalyst.

16. The preparation method according to claim 13, characterized in that, The impregnation method is an over-impregnation method; and / or, the drying temperature is 80℃~180℃, the drying time is 2~8h, and the calcination temperature is 450℃~700℃, the calcination time is 2~8h.

17. The preparation method according to claim 13, characterized in that, The ultrasonic treatment conditions are as follows: ultrasonic frequency is 15-35 kHz, material temperature is 35-75℃, and treatment time is 15-60 min.

18. The preparation method according to claim 13, characterized in that, In the hydrogenation catalyst, based on the mass of the hydrogenation catalyst, the content of Group VIB metals as oxides is 6.0% to 26.0%, and the content of Group VIII metals as oxides is 2.0% to 14.0%.

Images