CN115999597A - Phosphorus-containing hydrofining catalyst and preparation method thereof - Google Patents

Phosphorus-containing hydrofining catalyst and preparation method thereof Download PDF

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CN115999597A
CN115999597A CN202111234183.XA CN202111234183A CN115999597A CN 115999597 A CN115999597 A CN 115999597A CN 202111234183 A CN202111234183 A CN 202111234183A CN 115999597 A CN115999597 A CN 115999597A
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catalyst
phosphorus
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particles
nickel
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CN115999597B (en
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王海涛
徐学军
王继锋
李娟�
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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Abstract

The invention provides a phosphorus-containing hydrofining catalyst and a preparation method and application thereof. The catalyst is a granular bulk phase catalyst, and comprises core-shell composite oxide particles, wherein a shell layer is a composite oxide containing tungsten, nickel, aluminum and phosphorus, and a core phase is a composite oxide containing molybdenum, nickel and silicon. The catalyst has higher hydrodesulfurization and hydrodenitrogenation reaction performances, can avoid excessive cracking of diesel oil fraction, has good raw material adaptability, and can treat poor-quality distillate oil raw materials.

Description

Phosphorus-containing hydrofining catalyst and preparation method thereof
Technical Field
The invention relates to a hydrofining catalyst and a preparation method thereof, in particular to a phosphorus-containing bulk hydrofining catalyst and a preparation method thereof.
Background
Along with the increasing proportion of secondary processed diesel oil (catalytic diesel oil and coked diesel oil) which needs hydrofining, in order to meet the severe national VI vehicular diesel oil standard, china oil refining enterprises generally select to use a high-activity hydrogenation catalyst, and a bulk catalyst is one of hydrogenation catalysts with highest activity at present.
The research on the deep hydrodesulfurization reaction mechanism of diesel oil shows that when dibenzothiophene (such as 4, 6-DMDBT) sulfides with substituents are removed, the hydrodesulfurization path is a main reaction path of the compounds. The hydrogenation path is that one aromatic ring in 4,6-DMDBT is hydrogenated to be changed into a naphthene ring, molecules are changed into a chair-type or boat-type structure from a planar structure, so that the steric hindrance effect is weakened, and then desulfurization reaction occurs, and the desulfurization paths such as methyl transfer, methyl removal, C-C bond breakage and the like are under the action of acidity, so that methyl close to sulfur atoms in the 4,6-DMDBT is twisted, removed, transferred and the like, the steric hindrance of the sulfur atoms is reduced, the sulfur atoms are easier to contact with the active center of a catalyst to perform desulfurization reaction, and the acidity of the catalyst usually causes side reactions such as raw material cracking and the like to reduce the yield of diesel oil. The hydrodesulfurization way is a main way when the diesel oil is deeply desulfurized, but is limited by the thermodynamic equilibrium of the reaction, the reaction temperature is limited at medium pressure, and the reactions such as eliminating steric hindrance have better activity at high temperature. For inferior raw materials, the purpose of deep desulfurization can be achieved only by matching different desulfurization ways, and under higher reaction temperature, the same catalyst cannot be compatible with the desulfurization ways, so that the difficulty of deep desulfurization is increased. Therefore, how to reduce the cost and improve the raw material adaptability of the catalyst, and the desulfurization and denitrification activities can be improved, and meanwhile, the reduction of the diesel oil yield can be avoided, and the method is still a problem to be solved in the field.
The bulk phase catalyst is generally prepared by adopting a coprecipitation method, and the coprecipitation is a complex multi-substance reaction system, and different ingredients, different precipitation modes, different gel forming conditions and the like can influence the size and uniformity of precipitated particles, and simultaneously influence the interaction between different active metals in the active metal oxide of the catalyst and the coordination between the active metals and the carrier, so that the performance of the bulk phase catalyst is influenced.
CN111215094a discloses a multi-metal non-supported hydrofining catalyst, its preparation method and application. The method comprises the following steps: reacting and aging a soluble salt solution containing at least one +3 metal with an alkaline precipitant solution to obtain a colloid A containing the +3 metal; dissolving at least one soluble salt of VIII group metal and at least one soluble salt of IVB group metal into colloid A to form a solution, then adding an alkaline precipitant solution to perform precipitation reaction, filtering and washing a product to obtain a catalyst precursor B, dissolving soluble salts of two VIB group metals into water to prepare a solution, adding the catalyst precursor B to perform ion exchange reaction, filtering, washing, drying and roasting the product to obtain the multi-metal non-supported hydrofining catalyst. The method reduces the preparation cost by introducing the cheap +3 metal, and introduces the IVB metal as a dispersing auxiliary, thereby being beneficial to forming more active centers, and being capable of effectively weakening the strong interaction between the cheap +3 metal and the active metal so as to promote the hydrodesulfurization and denitrification activities of the catalyst.
CN102049295a discloses a bulk phase ultra-deep hydrodesulfurization catalyst and a preparation method thereof. The catalyst composition comprises a composite oxide Ni x W y O z 、MoO 3 Alumina and SAPO-11 molecular sieves. Adding proper amount of water-soluble nitrogen-containing compound in the process of Ni, W and Al precipitation, after gelling, adding SAPO-11 molecular sieve slurry, ageing and mixing with MoO 3 Pulping, shaping, and activating. The catalyst prepared by the method provides certain acidity for the catalyst by adding the molecular sieve, can improve the ultra-deep desulfurization activity of the catalyst, but reduces the yield of diesel products.
Disclosure of Invention
The invention provides a phosphorus-containing hydrofining catalyst and a preparation method and application thereof. The catalyst is a bulk hydrofining catalyst, has higher hydrodesulfurization and hydrodenitrogenation reaction performances, can avoid excessive cracking of diesel oil fraction, has good raw material adaptability, and can treat poor-quality distillate oil raw materials.
The first aspect of the invention provides a phosphorus-containing hydrofining catalyst which is a granular bulk phase catalyst and comprises core-shell composite oxide particles, wherein a shell layer is a composite oxide containing tungsten, nickel, aluminum and phosphorus, and a core phase is a composite oxide containing molybdenum, nickel and silicon.
In the catalyst of the invention, based on the mass of the core-shell composite oxide particles, the mass content of the composite oxide containing molybdenum, nickel and silicon is 10% -90%, preferably 15% -85%, and the mass content of the composite oxide containing tungsten, nickel, aluminum and phosphorus is 10% -90%, preferably 15% -85%.
In the catalyst of the present invention, preferably, in the core-shell composite oxide particles, the thickness of the shell accounts for 8% -83%, preferably 10% -80% of the total thickness of the core-shell.
In the catalyst of the invention, the average particle size of the core-shell composite oxide particles is 5-9 nm. Preferably, the core-shell composite oxide particles have a particle size distribution as follows: the number of particles with the particle size of less than 5nm accounts for 3% -16% of the total number of particles, the number of particles with the particle size of 5 nm-10 nm accounts for 67% -91% of the total number of particles, and the number of particles with the particle size of more than 10nm accounts for 2% -17% of the total number of particles.
In the catalyst of the invention, the mol ratio of molybdenum to nickel in the composite oxide containing molybdenum, nickel and silicon is 1: 28-12: 1, preferably 1: 22-10: 1 silicon content as SiO 2 The mass of the catalyst accounts for 2% -30%, preferably 4% -28% of the mass of the hydrofining catalyst.
In the catalyst of the invention, the mol ratio of tungsten to nickel in the composite oxide containing tungsten, nickel, aluminum and phosphorus is 1: 22-8: 1, preferably 1: 20-5: 1, aluminum content is Al 2 O 3 The calculated mass accounts for 4% -30%, preferably 5% -25% of the mass of the hydrofining catalyst, and the phosphorus content is expressed as P 2 O 5 The mass of the catalyst accounts for 2% -16% of the mass of the hydrofining catalyst, and preferably 3% -14%.
In the catalyst, the mass of NiO in the composite oxide containing molybdenum, nickel and silicon accounts for 40% -90% of the total mass of NiO in the phosphorus-containing hydrofining catalyst, and the mass of NiO in the composite oxide containing tungsten, nickel, aluminum and phosphorus accounts for 10% -60% of the total mass of NiO in the phosphorus-containing hydrofining catalyst.
In the catalyst of the invention, the phosphorus-containing hydrofining catalyst has the following properties: specific surface area of 100-700 m 2 And/g, wherein the pore volume is 0.20-0.80 mL/g.
The catalyst of the invention is (solid) granular, can be prepared by adopting a conventional molding method, and can be in various shapes conventionally used for hydrofining catalysts, such as column shape, sphere shape and the like. The sphere can be sphere, elliptic sphere, etc., and the column can be cylindrical, square column or special-shaped (such as clover, etc.) section column. The particle size of the catalyst particles is 1-10 mm. In the case of a generally cylindrical shape, the length may be 2 to 10mm and the particle diameter may be 1 to 5mm. In the case of a generally spherical shape, the particle diameter is 2 to 8mm.
The catalyst of the present invention is in the form of (solid) particles, preferably having an average pore diameter ranging from large to small from the outer surface layer of the catalyst to the central core. Preferably, the catalyst particles may be divided into an outer surface layer, an intermediate layer and a central core, the average pore diameter decreasing in a gradient, i.e. the average pore diameter of the outer surface layer is larger than the average pore diameter of the intermediate layer, which is larger than the average pore diameter of the central core. The average pore diameter of the outer surface layer is 10-18 nm, the average pore diameter of the middle layer is 7-10 nm, the average pore diameter of the central core is 2-7 nm, and the length from the outermost edge to the central point is R on the cross section of the catalyst particle. The thickness of the outer surface layer is 0.2R-0.4R, the thickness of the middle layer is 0.2R-0.5R, and the rest is the central core.
The second aspect of the invention provides a bulk hydrofining catalyst in a sulfided state, which is obtained by sulfiding the above-mentioned phosphorus-containing hydrofining catalyst.
The invention relates to a vulcanized bulk phase hydrofining catalyst, which comprises core-shell composite sulfide particles, wherein a shell layer is a composite sulfide containing tungsten, nickel, aluminum and phosphorus, and a core phase is a composite sulfide containing molybdenum, nickel and silicon.
The average particle size of the core-shell composite sulfide particles of the bulk phase hydrofining catalyst in a vulcanized state is 9-13 nm, and the particle size distribution of the core-shell composite sulfide particles is as follows: the number of particles with the particle size of less than 8nm accounts for 3% -22% of the total number of particles, the number of particles with the particle size of 8 nm-13 nm accounts for 60% -85% of the total number of particles, and the number of particles with the particle size of more than 13nm accounts for 2% -18% of the total number of particles.
The third aspect of the invention provides a method for preparing a phosphorus-containing hydrofining catalyst, comprising:
(1) Preparing a mixed solution A containing Mo, ni and Si components and preparing a mixed solution B containing W, ni and Al components;
(2) Adding the precipitant A into the mixed solution A to perform a first gel forming reaction, and aging for the first time after the reaction to obtain precipitate slurry I containing nickel, silicon and molybdenum;
(3) Adding mixed liquid of water, grease and phosphate into a reactor, then adding the mixed solution B, a precipitator B and slurry I into the reactor in parallel flow for a second gelling reaction, and aging for the second time after the reaction to generate precipitate slurry II containing nickel, molybdenum, tungsten, silicon, aluminum and phosphorus;
(4) And (3) preparing the material obtained in the step (3) into the phosphorus-containing hydrofining catalyst.
Further, in the mixed solution A of the step (1), the weight concentration of Ni in terms of NiO is 5 to 100g/L, preferably 10 to 90g/L, and Mo in terms of MoO 3 The weight concentration is 5-100 g/L, preferably 10-80 g/L, si is SiO 2 The weight concentration is 2-80 g/L, preferably 4-70 g/L.
Further, when preparing the mixed solution A, the nickel source which is generally adopted can be one or more of nickel sulfate, nickel nitrate and nickel chloride, the molybdenum source can be ammonium molybdate, and the silicon source can be one or more of sodium silicate, silica sol and the like.
Further, in the mixed solution B of step (1), W is WO 3 The weight concentration of Ni is 2-110 g/L, preferably 4-100 g/L, the weight concentration of Ni is 5-100 g/L, preferably 10-90 g/L, and the weight concentration of Al is Al 2 O 3 The weight concentration is 2-90 g/L, preferably 5-85 g/L.
Further, when preparing the mixed solution B, the nickel source which is generally adopted can be one or more of nickel sulfate, nickel nitrate and nickel chloride, and the tungsten source which is generally adopted is ammonium metatungstate; the aluminum source can be one or more of aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum acetate and the like.
Further, the precipitant A in the step (2) is an alkaline precipitant, preferably ammonia water, the weight concentration of the ammonia water is 5% -15%, and the dosage of the precipitant A can be determined by a person skilled in the art according to actual needs.
Further, the conditions of the first glue forming reaction in the step (2) are as follows: the reaction temperature is 30-90 ℃, preferably 40-85 ℃, the pH value is controlled to 7.0-11.0, preferably 7.2-10.0, and the gelling time is 0.2-2.5 hours, preferably 0.3-2.0 hours.
Further, the first aging condition in the step (2) is as follows: the aging temperature is 60-90 ℃, preferably 65-85 ℃, the pH value is controlled to 7.0-11.0, preferably 7.2-10.5 during aging, and the aging time is 0.6-3.0 hours, preferably 0.8-2.5 hours.
Further, the precipitant B in the step (3) is an alkaline precipitant, preferably one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate and potassium bicarbonate, preferably sodium carbonate and/or sodium hydroxide. The weight concentration of the precipitant solution B can be 5% -45%. The amount of precipitant B used can be determined by the person skilled in the art according to the actual requirements.
Further, the water in the step (3) is deionized water, and the volume ratio of the added water to the filter cake of the sediment slurry II of nickel, molybdenum, tungsten, silicon, aluminum and phosphorus in the step (3) is 0.2: 1-6: 1, wherein the filter cake is a material obtained by directly carrying out conventional filtration on a precipitate slurry II of nickel, molybdenum, tungsten, silicon and aluminum after second aging.
Further, the oleaginous liquid in the step (3) is unsaturated higher fatty glyceride (vegetable oil), preferably one or more of peanut oil, rapeseed oil, cottonseed oil, sunflower seed oil, soybean oil, corn oil, tea oil, and olive oil. The volume-to-volume ratio of oleaginous liquid to water is 1: 60-1: 4, preferably 1: 40-1: 6.
further, the phosphate ester in the step (3) is one or more of octadecyl ether phosphate ester (O-5P), alkylphenol ether phosphate ester (TXP-4, TXP-10), isomerate tridecyl alcohol ether phosphate ester (E-1310P), lauryl alcohol ether phosphate ester (MOA-3P, MOA-9P), castor oil phosphate ester, octadecyl phosphate ester and lauryl phosphate ester, preferably one or more of alkylphenol ether phosphate ester (TXP-4, TXP-10), isomerate tridecyl alcohol ether phosphate ester (E-1310P), lauryl alcohol ether phosphate ester (MOA-3P, MOA-9P) and castor oil phosphate ester. The molar ratio of the amount of the phosphate added to the total number of W atoms in the mixed solution B in the step (1) was 0.3: 1-3.0: 1, preferably 0.4: 1-2.5: 1.
further, the conditions of the second gelling reaction of step (3) are: the reaction temperature is 30-90 ℃, preferably 40-85 ℃, the pH value is initially controlled to be 10.0-14.0, preferably 10.5-13.5, the final pH value is 7.0-8.5, preferably 7.2-8.3 at the end, and the gel forming reaction time is 0.5-6.0 hours, preferably 0.6-5.0 hours. Preferably, the pH value can be adjusted from the initial value to the final pH value by adopting a method of gradually adjusting the pH value to the required value, and the pH value of the reaction slurry is kept constant until the next adjustment, wherein the adjustment is carried out for 2-10 times, preferably 2-8 times. Preferably, the time is constant for 0.1 to 1.2 hours after each down-regulation. The amplitude of each down-regulation may be the same or different, and preferably, when the amplitude of the decrease in pH of the down-regulation is equal to or smaller than the amplitude of the decrease in pH of the last down-regulation. The time taken for each down-regulation process is the sum of the time taken for each down-regulation and the constant time at the pH value, further, the time taken for each down-regulation is from the beginning of the next down-regulation. The time used for each down-regulation process may be the same or different, preferably the same.
Further, the second aging condition in step (3) is as follows: the aging temperature is 60-90 ℃, preferably 65-85 ℃, the pH value is controlled to 7.0-11.0, preferably 7.2-10.5 during aging, and the aging time is 2.0-6.0 hours, preferably 2.5-5.0 hours.
Further, in the step (2), the weight of the introduced Ni accounts for 40% -90%, preferably 45% -85% of the total weight of Ni in the phosphorus-containing hydrofining catalyst obtained in the step (4). In the step (3), the weight of the introduced Ni accounts for 10% -60%, preferably 15% -55% of the total weight of Ni in the phosphorus-containing hydrofining catalyst obtained in the step (4).
Further, in the step (4), the process of preparing the phosphorus-containing hydrofining catalyst from the material obtained in the step (3) may comprise: and (3) drying, molding and washing the material obtained in the step (3) for the first time, and drying and roasting the material for the second time to obtain the hydrofining catalyst.
The first drying conditions are as follows: drying at 40-150 ℃ for 1-48 hours, preferably at 50-120 ℃ for 4-36 hours. The second drying conditions are as follows: the drying conditions were as follows: drying at 60-280 ℃ for 1-48 hours. The firing of step (4) after the second drying may employ conditions conventional in the art, and the firing conditions are as follows: roasting for 1-24 hours at 350-650 ℃, and the preferable roasting conditions are as follows: roasting for 2-12 hours at 400-600 ℃.
Further, the shaping and washing described in step (4) may be performed by a method conventional in the art. Conventional molding aids, such as one or more of peptizers, extrusion aids, and the like, may be added as needed during the molding process. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like, the extrusion assisting agent is one or more of sesbania powder, carbon black, graphite powder, citric acid and the like which are favorable for extrusion molding, and the consumption of the extrusion assisting agent accounts for 1-10 wt% of the total dry matter. The washing is usually carried out by adopting deionized water or solution containing decomposable salts (such as ammonium acetate, ammonium chloride, ammonium nitrate and the like) to wash until the solution is neutral.
Further, the second drying in step (4) is preferably as follows:
a. firstly, drying the material at 60-100 ℃ for 1.0-8.5 hours, preferably at 70-90 ℃ for 2.0-8.0 hours;
b. uniformly spraying water (preferably deionized water) on the material obtained in the step a, wherein the volume ratio of water to dry material is 1:4~4:1, then drying at a temperature of 150-280 ℃, preferably 150-280 ℃ for 0.5-4.0 hours, preferably 0.6-3.5 hours;
c. and (3) repeating the step b for 2-9 times, preferably 3-8 times.
Wherein, the volume ratio of the first water adding volume to the dry material is greater than 1:1, the volume ratio of the last water adding volume to the dry material is less than 1:1, further, the volume ratio of the added water to the dried material is sequentially reduced along with the increase of the drying times.
Further, the total drying time for the second drying is preferably 5 to 40 hours, more preferably 10 to 38 hours.
Further, mo in the mixed solution A containing Mo, ni and Si components in the step (1) is expressed as MoO 3 Meter, ni in NiO and Si in SiO 2 Calculated total mass and W in the mixed solution B containing W, ni and Al components as WO 3 Ni is calculated as NiO and Al is calculated as Al 2 O 3 The ratio of the total mass is 1.2: 8.8-9.2: 0.8, preferably 1.7: 8.3-8.7: 1.3.
further, in the mixed solution A containing Mo, ni and Si components in the step (1), the mole ratio of molybdenum to nickel is 1: 28-12: 1, preferably 1: 22-10: 1 silicon content as SiO 2 The mass of the catalyst accounts for 2% -30%, preferably 4% -28% of the mass of the hydrofining catalyst obtained in the step (4).
Further, in the mixed solution B containing W, ni and Al components in the step (1), the molar ratio of tungsten to nickel is 1: 22-8: 1, preferably 1: 20-5: 1, aluminum content is Al 2 O 3 The mass of the catalyst accounts for 4-30%, preferably 5-25% of the mass of the hydrofining catalyst obtained in the step (4).
Further, the mass ratio of Ni in the mixed solution A containing Mo, ni and Si components and Ni in the mixed solution B containing W, ni and Al components in the step (1) is 4: 6-9: 1.
further, the phosphorus-containing hydrofining catalyst of the present invention is (solid) granular, can be prepared by adopting a conventional molding method, and can be in various shapes conventionally used for hydrofining catalysts, such as column shape, sphere shape and the like. The sphere can be spherical, elliptic or the like, and the column can be cylindrical, square or abnormal shape (such as clover, etc.) cross section column. In the case of a generally cylindrical shape, the length may be 2 to 10mm and the particle diameter may be 1 to 5mm. In the case of a generally spherical shape, the particle diameter is 2 to 8mm.
Further, the phosphorus-containing hydrofining catalyst obtained in the step (4) of the present invention is a bulk hydrofining catalyst in an oxidized state, in the presence ofThe vulcanization may be carried out by conventional methods prior to use. The sulfidation is the conversion of the active metal W, ni and Mo oxides to the corresponding sulfides. The vulcanization method can adopt wet vulcanization or dry vulcanization. The vulcanizing method adopted in the invention is wet vulcanization, the vulcanizing agent is a sulfur-containing substance used for conventional vulcanization, and can be an organic sulfur-containing substance or an inorganic sulfur-containing substance, such as one or more of sulfur, carbon disulfide, dimethyl disulfide and the like, the vulcanized oil is hydrocarbon and/or distillate oil, wherein the hydrocarbon is one or more of cyclohexane, cyclopentane, cycloheptane and the like, and the distillate oil is one or more of kerosene, normal-line diesel oil and the like. The amount of the vulcanizing agent is 80% -200%, preferably 100% -150% of the theoretical sulfur demand of complete vulcanization of each active metal in the hydrofining catalyst. The pre-vulcanization conditions were: the temperature is 230-370 ℃, the hydrogen pressure is 2.0-10 MPa, and the liquid hourly space velocity is 0.3-6.0 h -1 The vulcanization time is 3-24 hours, preferably: the temperature is 250-350 ℃, the hydrogen pressure is 3.0-8.0 MPa, and the liquid hourly space velocity is 1.0-3.0 h -1 And vulcanizing for 5-16 hours.
The fourth aspect of the invention provides the application of the phosphorus-containing hydrofining catalyst in diesel hydrofining reaction.
Further, the conditions of the diesel hydrofining reaction are as follows: the reaction temperature is 330-400 ℃, the reaction pressure is 2.5-12 MPa, and the hydrogen-oil volume ratio is 250: 1-1200: 1, the liquid hourly space velocity is 0.3-5.0 h -1 。
Compared with the prior art, the invention has the following advantages:
1. the invention relates to a phosphorus-containing hydrofining catalyst, which is characterized in that the distribution state of active metal is improved from the nanometer level, namely, the catalyst is mainly composed of composite oxide particles containing tungsten, nickel, aluminum and phosphorus and coated with composite oxide particles containing molybdenum, nickel and silicon, the coating structure is different from a macroscopic (such as millimeter-level) structure, the catalytic material structure is controlled from the microscopic level, the integral performance of the catalyst is broken through, the hydrodesulfurization performance of the catalyst is improved, a certain amount of acid center is formed at the joint of a core-shell structure of the catalyst, the hydrodesulfurization reaction is carried out while the steric hindrance capability of the catalyst is improved, the occurrence of side reactions such as excessive cracking is reduced, and when the distillate oil raw materials containing sulfur and nitrogen (particularly the distillate oil raw materials containing difficult removal of sulfur and nitrogen) are contacted with the hydrofining catalyst, the desulfurization and denitrification activity is obviously improved, meanwhile, the cracking reaction of diesel oil fraction is reduced, and the reduction of diesel oil yield is avoided. In addition, the catalyst can reduce the content of active metal under the condition of ensuring the desulfurization and denitrification activities, thereby reducing the preparation cost of the catalyst.
2. In the method, firstly molybdenum nickel silicon aging slurry is prepared, then the slurry is added into a reaction tank containing the existing water, grease liquid and phosphate ester mixture in parallel with tungsten nickel aluminum mixed solution and precipitant to carry out secondary colloid formation, so that tungsten nickel is uniformly and orderly precipitated on molybdenum nickel crystal grains, tungsten nickel coated molybdenum nickel nano particles with uniform particle size and good dispersion are formed, the excellent grease emulsification effect of phosphate ester is adopted, the good coordination effect between different active metals in the metal particles and between the active metals and a carrier is further improved, the particle size of core-shell composite oxide particles is reduced, and the core-shell composite oxide particles have good dispersibility, so that the prepared hydrofining catalyst is suitable for hydrofining reaction of heavy distillate oil (such as diesel oil), is particularly favorable for deep hydrodesulfurization and denitrification, and can also avoid reducing the yield of diesel oil.
3. In the method, when the second drying after forming adopts a preferred drying method, the average pore diameter is from large to small in the pore distribution of the catalyst particles from the outer surface layer of the catalyst to the central core, so that the influence of diffusion effect of reactants such as macromolecules with larger molecular diameters when entering and exiting the pore channels of the catalyst can be weakened, the diffusion performance of the catalyst on the macromolecules can be improved, and the interaction between metal components can be further improved by the preferred drying method, so that the hydrogenation active phase with higher activity can be generated.
4. In the method, when the composite oxide of tungsten, nickel, aluminum and phosphorus is formed, a method of decreasing the pH value to gel is adopted, so that the particle size of the core-shell composite oxide is more uniform, and meanwhile, the auxiliary agent P is introduced, and an intermediate formed between the auxiliary agent component and the hydrogenation active metal at the junction of the core-shell is beneficial to improving the coordination effect between the hydrogenation active metal at the junction of the core-shell, improving the coordination effect of the catalyst active metal component and further improving the hydrogenation activity of the catalyst.
Drawings
FIG. 1 is a TEM image of catalyst B obtained in example 2.
Detailed Description
In the present invention, the "cross section of the catalyst particle" refers to the entire surface exposed after cutting through the geometric center of the shape thereof along the direction of the smallest dimension of one catalyst particle. For example, when the catalyst particles are spherical, the cross section refers to the entire surface exposed after cutting through the center of the sphere along the radius or short axis of the sphere. Alternatively, when the catalyst particles are columnar, the cross section refers to the entire surface exposed after cutting through the center point of the length dimension perpendicular to the length dimension direction of the column. The outer perimeter of the exposed surface is referred to as the outermost edge of the cross-section, and the geometric center (such as the center point of the aforementioned sphere center or length dimension) is referred to as the center point on the cross-section.
In the invention, the specific surface area and pore volume are measured by adopting a low-temperature liquid nitrogen adsorption method, and the mechanical strength is measured by adopting a side pressure method. Measuring the specific surface area, pore volume and pore size distribution of the carrier by using an ASAP-2405 type BET nitrogen adsorption instrument; the crush strength of the catalyst was determined using a ZQJ-2 intelligent particle strength tester.
In the present invention, the average particle diameter (D50 particle diameter) and the particle size distribution of the core-shell composite oxide particles were measured by a nanoparticle size and Zeta potential analyzer (Zetasizer Nano ZS).
In the invention, the method for measuring the average pore diameter of the outer surface layer to the central core of the catalyst particle comprises the following steps: the pore volume, specific surface area and average pore diameter of the sample were measured by a low temperature nitrogen adsorption method (BET), and then a certain amount of the sample was taken and placed in a catalyst abrasion meter, and the sample was subjected to polishing treatment while adding a certain amount of quartz sand to increase the abrasion rate. When the sample is reduced to a certain degree by polishing the particle size, the weight loss of the sample is measured, the pore structure is measured again, the pore volume and the specific surface area of the polished part can be calculated according to the relation that the total pore volume and the specific surface area of the sample are equal to the sum of all the parts, the average pore diameter is calculated, and 20-80 samples are measured at the same time, so that the average pore diameters of different layers from the outer surface layer to the central core are measured.
In the present invention, the metal content in the composite oxide of the core and the shell and the thickness of the shell in the core-shell composite oxide particles are measured by using a TEM transmission electron microscope (JSM-2100, japan). The method for measuring the metal content in the composite oxide in the core and the shell comprises the following steps: uniformly mixing the core-shell composite oxide particles with liquid epoxy resin, adding a proper amount of curing agent, uniformly stirring, and heating and curing to form solid particles. Cutting the solid particles into slices with the thickness of 5-20nm by adopting an ultrathin slicer, and putting the obtained slices into a transmission electron microscope for observation to find a core-shell structure (cross section) with a clear interface. The diameter of the electron beam is regulated by a condenser, so that the diameter of the electron beam is basically covered with the outline of the whole core-shell structure, an energy spectrum EDS spectrum is acquired, the intensity of a main energy peak is recorded, the actual content of each element in the known feeding is corresponding to the intensity of the energy peak of each element. And adjusting the diameter of the electron beam to be smaller than or close to the size of the core or the shell, and comparing the peak intensity of energy corresponding to the element with the peak intensity and the corresponding actual value under the condition of full coverage to calculate the metal content in the composite oxide in the core and the shell. In the core-shell structure, the thickness of the shell is distinguished from the image of the transmission electron microscope and measured, and the proportion of the thickness of the shell to the total thickness of the core-shell is the average value obtained by measuring 40-100 core-shell particles.
In the invention, wt% is mass fraction and v% is volume fraction.
Example 1
Respectively adding nickel chloride, ammonium molybdate and dilute water glass solution into a dissolving tank 1 filled with deionized water to prepare a mixed solution A, wherein the weight concentration of Ni in the mixed solution A calculated by NiO is 28g/L, and Mo is calculated by MoO 3 The weight concentration is 30g/L, siO 2 The weight concentration of (C) is 22g/L. Respectively divide tungsten intoAdding ammonium acid, nickel chloride and aluminum chloride solution into a dissolving tank 2 filled with deionized water to prepare a mixed solution B, wherein W in the solution B is WO 3 The weight concentration is 56g/L, the weight concentration of Ni is 16g/L based on NiO, and Al is Al 2 O 3 The weight concentration was 32g/L. Wherein, the mass ratio of Ni in the mixed solution A to Ni in the mixed solution B used in the reaction of the embodiment is 14:8. and (3) putting the solution A into a reaction tank 1, dripping ammonia water (with the weight concentration of 10%) into the reaction tank 1 to perform a first gel forming reaction, keeping the gel forming temperature at 62 ℃, controlling the pH value at 7.8 when the reaction is finished, controlling the gel forming time at 1.0 hour, aging after the reaction is finished, controlling the aging temperature at 75 ℃, controlling the aging pH value at 7.6, and aging for 1.5 hours to obtain the precipitate slurry I containing nickel, molybdenum and silicon. Adding 500mL of deionized water, 30mL of soybean oil and castor oil phosphate with the mole ratio of 1.1 to the total W atoms in the mixed solution B into a reaction tank 2, adding 10wt% sodium hydroxide solution, nickel-containing, molybdenum-silicon precipitate slurry I and the mixed solution B into the reaction tank 2 in parallel to carry out a second gelling reaction, maintaining the gelling temperature at 60 ℃, initially controlling the pH value to be 12.8, adjusting the final pH value to be 7.8 after finishing the gelling reaction by 5 times of downward pH value adjustment, keeping the pH value of the adjusted reaction slurry constant for 10 minutes after each downward pH value adjustment, and starting aging after the second gelling reaction, wherein the aging temperature is 75 ℃, the pH value is controlled to be 8.0, and the aging time is 3.0 hours to obtain the slurry II containing tungsten, nickel-molybdenum-silicon-aluminum precipitate. Filtering the aged slurry, drying the filter cake at 100 ℃ for 7 hours, rolling, and extruding strips into a cylinder. Washing with deionized water at room temperature to neutrality. The washed wet strip is then dried as follows: firstly, drying the material at 80 ℃ for 6.0 hours, uniformly spraying deionized water on the dried material, then drying, and repeating the processes of uniformly spraying the deionized water and drying for 5 times, wherein the volume ratio of the first sprayed deionized water to the dried material is 2:1, the drying temperature is 200 ℃, the drying time is 2.5 hours, and the volume ratio of the second spraying deionized water to the dried materials is 1.5:1, the drying temperature is 220 ℃, the drying time is 2.5 hours, and the volume ratio of the third spraying deionized water to the dried materials is 1:1 drying temperature Drying at 180 ℃ for 2.0 hours, wherein the volume ratio of the fourth spraying deionized water to the dried materials is 1:2, drying temperature 180 ℃ and drying time 1.5 hours, wherein the volume ratio of the fifth spraying deionized water to the dried materials is 1:2.5, drying temperature 200 ℃ and drying time 1.5 hours. The dried material was calcined at 500℃for 4 hours to obtain catalyst A. The catalyst composition and the main properties are shown in Table 1.
Example 2
Respectively adding nickel chloride, ammonium molybdate and dilute water glass solution into a dissolving tank 1 filled with deionized water to prepare a mixed solution A, wherein the weight concentration of Ni in the mixed solution A calculated by NiO is 48g/L, and Mo is calculated by MoO 3 The weight concentration of the catalyst is 50g/L, siO 2 The weight concentration of (C) is 36g/L. Respectively adding ammonium metatungstate, nickel chloride and aluminum chloride solution into a dissolving tank 2 filled with deionized water to prepare a mixed solution B, wherein W in the solution B is WO 3 The weight concentration is 22g/L, the weight concentration of Ni is 16g/L in terms of NiO, and Al is Al 2 O 3 The weight concentration is 18g/L. Wherein, the mass ratio of Ni in the mixed solution A to Ni in the mixed solution B used in the reaction of the embodiment is 24:8. and (3) putting the solution A into a reaction tank 1, dripping ammonia water (with the weight concentration of 12%) into the reaction tank 1 to perform a first gel forming reaction, keeping the gel forming temperature at 65 ℃, controlling the pH value at 7.9 when the reaction is finished, controlling the gel forming time at 1.3 hours, aging after the reaction is finished, controlling the aging temperature at 77 ℃, controlling the aging pH value at 7.8, and aging for 1.2 hours to obtain the precipitate slurry I containing nickel, molybdenum and silicon. Adding 800mL deionized water, 60mL corn oil and alkylphenol ether phosphate (TXP-4) with the mole ratio of W atoms of 1.4 in the mixed solution B into a reaction tank 2, adding a precipitate slurry I with the concentration of 14wt% of sodium hydroxide solution, nickel, molybdenum and silicon and the mixed solution B into the reaction tank 2 in parallel to carry out a second gelling reaction, maintaining the gelling temperature at 58 ℃, initially controlling the pH value to be 13.0, adjusting the final pH value at the end to be 7.4 by 7 times of downward pH value adjustment, adjusting the pH value of the reaction slurry after adjustment to be 10 minutes constantly after each downward pH value adjustment, starting aging after the second gelling reaction is finished, controlling the pH value at 8.0 and the aging time to be 3.3 at 79 ℃ after the aging temperature of the second gelling reaction For hours, a precipitate slurry II containing tungsten, nickel, molybdenum, silicon, aluminum and phosphorus is obtained. Filtering the aged slurry, drying the filter cake for the first time, drying at 70 ℃ for 12 hours, rolling, and extruding strips into a cylinder. Washing with deionized water at room temperature to neutrality. The washed wet strip was then dried a second time as follows: firstly, drying the material at 80 ℃ for 7.0 hours, uniformly spraying deionized water on the dried material, then drying, and repeating the processes of uniformly spraying the deionized water and drying for 7 times, wherein the volume ratio of the first sprayed deionized water to the dried material is 2.0:1, the drying temperature is 190 ℃, the drying time is 2.2 hours, and the volume ratio of the second spraying deionized water to the dried materials is 1.5:1, the drying temperature is 200 ℃, the drying time is 2.0 hours, and the volume ratio of the third spraying deionized water to the dried materials is 1.2:1, the drying temperature is 220 ℃, the drying time is 1.8 hours, and the volume ratio of the fourth spraying deionized water to the dried materials is 1:1.2, drying temperature is 180 ℃, drying time is 1.5 hours, and the volume ratio of the fifth spraying deionized water to the dried materials is 1:1.6, drying temperature is 180 ℃, drying time is 1.5 hours, and the volume ratio of the sixth spray deionized water to the dried materials is 1:2.0, drying temperature 180 ℃ and drying time 2 hours, wherein the volume ratio of the seventh spraying deionized water to the dried materials is 1:2.5, drying temperature 190 ℃ and drying time 1.6 hours. The dried material was calcined at 520 ℃ for 5 hours to obtain catalyst B. The catalyst composition and the main properties are shown in Table 1.
Example 3
Respectively adding nickel chloride, ammonium molybdate and dilute water glass solution into a dissolving tank 1 filled with deionized water to prepare a mixed solution A, wherein the weight concentration of Ni in the mixed solution A calculated by NiO is 40g/L, and Mo is calculated by MoO 3 The weight concentration is 36g/L, siO 2 The weight concentration of (C) was 32g/L. Respectively adding ammonium metatungstate, nickel chloride and aluminum chloride solution into a dissolving tank 2 filled with deionized water to prepare a mixed solution B, wherein W in the solution B is WO 3 The weight concentration is 36g/L, the weight concentration of Ni is 20g/L based on NiO, and Al is Al 2 O 3 The weight concentration was 24g/L. Wherein, the mass ratio of Ni in the mixed solution A to Ni in the mixed solution B used in the reaction of the embodiment is 20:10. will bePutting the solution A into a reaction tank 1, dripping ammonia water (with the weight concentration of 11%) into the reaction tank 1 to perform a first gel forming reaction, keeping the gel forming temperature at 52 ℃, controlling the pH value at 8.4 when the reaction is finished, controlling the gel forming time at 1.2 hours, aging after the reaction is finished, controlling the aging temperature at 77 ℃, controlling the aging pH value at 7.5, and aging for 1.9 hours to obtain a precipitate slurry I containing nickel, molybdenum and silicon. Adding 1000mL of deionized water, 100mL of tea oil and lauryl ether phosphate (MOA-9P) with the mole ratio of W atoms in the total amount of mixed solution B of 0.8 into a reaction tank 2, then adding a precipitate slurry I with the concentration of 12wt% of sodium hydroxide solution, nickel, molybdenum and silicon and the mixed solution B into the reaction tank 2 in parallel to carry out a second gelling reaction, maintaining the gelling temperature at 60 ℃, initially controlling the pH value to be 12.9, adjusting the final pH value to be 7.5 after the end of the gelling reaction by 6 times of downward pH value adjustment, controlling the pH value of the reaction slurry to be constant for 10 minutes after the adjustment of each downward pH value, and after the second gelling reaction is finished, starting aging, controlling the pH value at 75 ℃, and aging time to be 3.5 hours to obtain a precipitate slurry II with tungsten, nickel, molybdenum, silicon, aluminum and phosphorus. Filtering the aged slurry, drying the filter cake for the first time, drying at 100 ℃ for 7 hours, rolling, and extruding strips into a cylinder. Washing with deionized water at room temperature to neutrality. The washed wet strip was then dried a second time as follows: firstly, drying the material at 85 ℃ for 7.0 hours, uniformly spraying deionized water on the dried material, then drying, and repeating the processes of uniformly spraying the deionized water and drying for 5 times, wherein the volume ratio of the first sprayed deionized water to the dried material is 1.7:1, the drying temperature is 200 ℃, the drying time is 2.3 hours, and the volume ratio of the second spraying deionized water to the dried materials is 1.2:1, drying temperature 180 ℃ and drying time 2.1 hours, wherein the volume ratio of the third spraying deionized water to the dried materials is 1:1.2, drying temperature 190 ℃ and drying time 1.7 hours, wherein the volume ratio of the fourth spraying deionized water to the dried materials is 1:1.5, drying temperature 180 ℃ and drying time 1.8 hours, wherein the volume ratio of the fifth spraying deionized water to the dried materials is 1:2.0, drying temperature 170 ℃ and drying time 1.7 hours. Roasting the dried material at 500 ℃ for 4 hours to obtain Catalyst C. The catalyst composition and the main properties are shown in Table 1.
Example 4
Respectively adding nickel chloride, ammonium molybdate and dilute water glass solution into a dissolving tank 1 filled with deionized water to prepare a mixed solution A, wherein the weight concentration of Ni in the mixed solution A calculated by NiO is 44g/L, and Mo is calculated by MoO 3 The weight concentration is 34g/L, siO 2 The weight concentration of (C) was 32g/L. Respectively adding ammonium metatungstate, nickel chloride and aluminum chloride solution into a dissolving tank 2 filled with deionized water to prepare a mixed solution B, wherein W in the solution B is WO 3 The weight concentration is 28g/L, the weight concentration of Ni is 28g/L and the weight concentration of Al is Al 2 O 3 The weight concentration was 24g/L. Wherein, the mass ratio of Ni in the mixed solution A to Ni in the mixed solution B used in the reaction of the embodiment is 22:14. and (3) putting the solution A into a reaction tank 1, dripping ammonia water (the weight concentration is 9%) into the reaction tank 1 to perform a first gel forming reaction, keeping the gel forming temperature at 60 ℃, controlling the pH value at 8.0 when the reaction is finished, controlling the gel forming time at 1.0 hour, aging after the reaction is finished, controlling the aging temperature at 74 ℃, controlling the aging pH value at 8.6, and aging for 1.5 hours to obtain the precipitate slurry I containing nickel, molybdenum and silicon. Adding 700mL of deionized water, 50mL of peanut oil and the isomeric tridecanol ether phosphate (E-1310P) with the mole ratio of W atoms in the total amount of the mixed solution B of 0.6 into a reaction tank 2, adding 9wt% sodium hydroxide solution, nickel-containing, molybdenum-containing and silicon precipitate slurry I and the mixed solution B into the reaction tank 2 in parallel to carry out a second gelling reaction, maintaining the gelling temperature at 70 ℃, initially controlling the pH value to be 12.8, adjusting the final pH value at the end to 8.0 by 4 times of downward pH value adjustment, wherein the pH value of each downward pH value is 1.2, after each downward pH value adjustment, keeping the pH value of the adjusted reaction slurry constant for 15 minutes, after the second gelling reaction is finished, starting aging, controlling the pH value at 79 ℃, and aging time to be 3.7 hours to obtain tungsten-containing, nickel-molybdenum-containing, silicon-aluminum-phosphorus precipitate slurry II. Filtering the aged slurry, drying the filter cake at 90 ℃ for 8 hours, rolling, and extruding strips into a cylinder. Washing with deionized water at room temperature to neutrality. The washed wet strip is then dried as follows: the material was dried at 70 c for 7.5 hours, Evenly spraying deionized water on the dried material, then drying, and repeating the evenly spraying deionized water and the drying process for 5 times, wherein the volume ratio of the first sprayed deionized water to the dried material is 2:1, the drying temperature is 190 ℃, the drying time is 2.2 hours, and the volume ratio of the second spraying deionized water to the dried materials is 1.1:1, drying temperature 180 ℃ and drying time 1.8 hours, wherein the volume ratio of the third spraying deionized water to the dried materials is 1:1.5, drying temperature 200 ℃, drying time 2.0 hours, and the volume ratio of the fourth spraying deionized water to the dried materials is 1:1.8, drying temperature 170 ℃ and drying time 1.9 hours, wherein the volume ratio of the fifth spraying deionized water to the dried materials is 1:2.4, drying temperature 170 ℃ and drying time 1.6 hours. The dried material was calcined at 540 ℃ for 5 hours to obtain catalyst D. The catalyst composition and the main properties are shown in Table 1.
Example 5
Respectively adding nickel chloride, ammonium molybdate and dilute water glass solution into a dissolving tank 1 filled with deionized water to prepare a mixed solution A, wherein the weight concentration of Ni in the mixed solution A calculated by NiO is 40g/L, and Mo is calculated by MoO 3 The weight concentration of the catalyst is 32g/L, siO 2 The weight concentration of (C) is 36g/L. Respectively adding ammonium metatungstate, nickel chloride and aluminum chloride solution into a dissolving tank 2 filled with deionized water to prepare a mixed solution B, wherein W in the solution B is WO 3 The weight concentration is 40g/L, the weight concentration of Ni is 16g/L in terms of NiO, and Al is Al 2 O 3 The weight concentration was 22g/L. Wherein, the mass ratio of Ni in the mixed solution A to Ni in the mixed solution B used in the reaction of the embodiment is 20:8. and (3) putting the solution A into a reaction tank 1, dripping ammonia water (with the weight concentration of 10%) into the reaction tank 1 to perform a first gel forming reaction, keeping the gel forming temperature at 55 ℃, controlling the pH value at 7.7 when the reaction is finished, controlling the gel forming time at 1.3 hours, aging after the reaction is finished, controlling the aging temperature at 76 ℃, controlling the aging pH value at 7.9, and aging for 1.6 hours to obtain the precipitate slurry I containing nickel, molybdenum and silicon. 800mL deionized water, 70mL soybean oil and alkylphenol ether phosphate (TXP-10) with the mole ratio of W atoms of 0.9 in the mixed solution B are added into a reaction tank 2, and then 12wt% sodium hydroxide solution, nickel-containing solution,And (3) adding the molybdenum and silicon precipitated slurry I and the mixed solution B into a reaction tank 2 in parallel to carry out a second gelling reaction, maintaining the gelling temperature at 65 ℃, initially controlling the pH value to be 13.0, adjusting the final pH value to be 7.4 after finishing the final pH value by 7 times of downward adjustment of the pH value, wherein the pH value of each downward adjustment is 0.8, after each downward adjustment to the adjustment value, keeping the pH value of the adjusted reaction slurry constant for 8 minutes, starting aging after finishing the second gelling reaction, controlling the aging temperature at 78 ℃, controlling the pH value at 8.3, and aging time to be 3.6 hours to obtain the tungsten, nickel, molybdenum, silicon, aluminum and phosphorus-containing precipitate slurry II. Filtering the aged slurry, drying the filter cake at 110 ℃ for 7 hours, rolling, and extruding strips into a cylinder. Washing with deionized water at room temperature to neutrality. The washed wet strips were then dried at 140℃for 8.0 hours. The dried material was calcined at 520 ℃ for 6 hours to obtain catalyst E. The catalyst composition and the main properties are shown in Table 1.
Example 6
Respectively adding nickel chloride, ammonium molybdate and dilute water glass solution into a dissolving tank 1 filled with deionized water to prepare a mixed solution A, wherein the weight concentration of Ni in the mixed solution A calculated by NiO is 38g/L, and Mo is calculated by MoO 3 The weight concentration is 36g/L, siO 2 The weight concentration of (C) is 28g/L. Respectively adding ammonium metatungstate, nickel chloride and aluminum chloride solution into a dissolving tank 2 filled with deionized water to prepare a mixed solution B, wherein W in the solution B is WO 3 The weight concentration is 34g/L, the weight concentration of Ni is 24g/L in terms of NiO, and Al is Al 2 O 3 The weight concentration was 24g/L. Wherein, the mass ratio of Ni in the mixed solution A and Ni in the mixed solution B used in the reaction of the embodiment is 19:12. and (3) putting the solution A into a reaction tank 1, dripping ammonia water (with the weight concentration of 12%) into the reaction tank 1 to perform a first gel forming reaction, keeping the gel forming temperature at 50 ℃, controlling the pH value at 8.5 when the reaction is finished, controlling the gel forming time at 1.0 hour, aging after the reaction is finished, controlling the aging temperature at 79 ℃, controlling the aging pH value at 7.6, and aging for 1.7 hours to obtain the precipitate slurry I containing nickel, molybdenum and silicon. 700mL of deionized water, 40mL of sunflower seed oil and laureth phosphate (MOA-3P) with the mole ratio of 1.1 of total W atoms in the mixed solution B are added into a reaction tank 2, and then 12wt% sodium hydroxide solution is added And (3) adding the precipitate slurry I containing nickel, molybdenum and silicon and the mixed solution B into a reaction tank 2 in parallel to carry out a second gelling reaction, keeping the gelling temperature at 57 ℃, initially controlling the pH value to be 11.5, adjusting the final pH value to be 7.5 after finishing by 5 times of downward adjustment of the pH value, wherein the pH value of the reaction slurry with negligence is constant for 15 minutes after each downward adjustment of the pH value to be 0.8, starting aging after finishing the second gelling reaction, controlling the aging temperature at 77 ℃, controlling the pH value to be 8.0 and aging time to be 3.0 hours, thus obtaining the precipitate slurry II containing tungsten, nickel, molybdenum, silicon, aluminum and phosphorus. Filtering the aged slurry, drying the filter cake at 130 ℃ for 10 hours, rolling, and extruding strips into a cylinder. Washing with deionized water at room temperature to neutrality. The washed wet strips were then dried at 150℃for 12.0 hours. The dried material was calcined at 550℃for 4 hours to obtain catalyst F. The catalyst composition and the main properties are shown in Table 1.
Comparative example 1
The catalyst composition of example 1 was prepared by dissolving nickel chloride, ammonium metatungstate, ammonium molybdate, aluminum chloride, and water glass in deionized water to prepare a mixed solution having Ni at a weight concentration of 44g/L in terms of NiO and W in terms of WO 3 The weight concentration of Mo is 56g/L, and Mo is MoO 3 The weight concentration is 30g/L, al is calculated as Al 2 O 3 The weight concentration of the catalyst is 40g/L, siO 2 The weight concentration of (C) is 30g/L. 500mL of deionized water is added into a reaction tank, ammonia water with the concentration of 10wt% and the mixed solution are added into the reaction tank in parallel flow for gelling, the gelling temperature is kept at 62 ℃, the pH value is controlled at 7.8 at the end, the gelling time is controlled at 1.0 hour, and precipitate slurry containing nickel and tungsten is generated. Then aging for 2.0 hours, wherein the aging temperature is 75 ℃, the pH value is controlled to be 7.6 when aging, the reaction slurry is filtered after the aging is finished, the filter cake is dried for 8 hours at 120 ℃, rolled and extruded into a cylinder. Washing with deionized water at room temperature to neutrality. The wet strips were then dried at 80℃for 10 hours and calcined at 500℃for 4 hours to give catalyst G. The catalyst composition and the main properties are shown in Table 1.
Comparative example 2
According to the preparation method disclosed in CN1951558A, a reference catalyst H is prepared, and the preparation method is as follows:
adding deionized water into a dissolving tank, adding nickel chloride, ammonium metatungstate and aluminum chloride for dissolving, preparing an acidic working solution A, wherein the weight concentration of Ni in the solution A calculated by NiO is 74.8g/L, and W is WO 3 The weight concentration is 48.6g/L, al is Al 2 O 3 The weight concentration was 44g/L and the pH of solution A was 1.8. 350mL of water was added to the reaction vessel and the temperature was raised to 62 ℃. Under the condition of stirring, adding the solution A and 10wt% ammonia water into a reaction tank in parallel flow for gelling, wherein the gelling temperature is 62 ℃, the gelling time is 1 hour, and the pH value of slurry in the gelling process is 8.5. Aging for 2 hours after the gel forming is finished, wherein the aging temperature is 75 ℃, and the pH value is controlled at 7.6 during aging. Then filtering, adding 600mL deionized water and 32.6g molybdenum trioxide into the filter cake, pulping and stirring uniformly, filtering, drying the filter cake at 120 ℃ for 8 hours, rolling, and extruding strips to form a cylinder. Washing with deionized water at room temperature to neutrality. Then the wet strips were dried at 80℃for 10 hours and calcined at 500℃for 4 hours to give catalyst H. The catalyst composition and the main properties are shown in Table 1.
Comparative example 3
Reference I, identical in composition to the catalyst of example 1, was prepared according to the method disclosed in CN102049295a, as follows:
after 1000mL of water is added into a dissolution tank, nickel chloride, ammonium metatungstate and aluminum chloride solution are sequentially added, and the mixture is prepared after uniform stirring. Wherein the weight concentration of Ni in terms of NiO is 44g/L, and W in terms of WO 3 The weight concentration is 56g/L, al is calculated as Al 2 O 3 The weight concentration was 54g/L. 160g of ammonium bicarbonate was prepared as an aqueous solution having a molar concentration of 2.5 mol/L. Then the mixed solution, ammonium bicarbonate aqueous solution and precipitator 10% ammonia water are added into a reaction tank filled with deionized water simultaneously in parallel flow for gelling, the pH value of the gelling is 7.8, and the gelling temperature is 62 ℃. After the gel formation is finished, the slurry containing the SAPO-11 molecular sieve is added and aged for 2 hours. Filtering after aging, adding 600mL of deionized water and 30 g of molybdenum trioxide into a filter cake, pulping and stirring uniformly, filtering, drying the obtained filter cake at 120 ℃ for 8 hours, extruding strips into cylinders, washing with deionized water to be neutral, drying wet strips at 80 ℃ for 10 hours, and roasting at 500 ℃ for 4 hours to obtain the final catalyst I, wherein the composition and main properties are shown in Table 1.
The SAPO-11 molecular sieve used in the comparative example was that used in CN102049295a, and can be synthesized by conventional methods, such as hydrothermal crystallization, and has the following properties: siO (SiO) 2 /Al 2 O 3 The molar ratio is 0.85, the infrared acid amount is 0.9mmol/g, the pore volume is 0.24mL/g, and the specific surface area is 250m 2 And/g, particle size of 450nm and crystallinity of 85%.
Comparative example 4
Reference J was prepared according to the procedure of example 1 (no grease or phosphate was added to the tank during the second gel formation).
Respectively adding nickel chloride, ammonium molybdate and dilute water glass solution into a dissolving tank 1 filled with deionized water to prepare a mixed solution A, wherein the weight concentration of Ni in the mixed solution A calculated by NiO is 28g/L, and Mo is calculated by MoO 3 The weight concentration is 30g/L, siO 2 The weight concentration of (C) is 30g/L. Respectively adding ammonium metatungstate, nickel chloride and aluminum chloride solution into a dissolving tank 2 filled with deionized water to prepare a mixed solution B, wherein W in the solution B is WO 3 The weight concentration is 56g/L, the weight concentration of Ni is 16g/L based on NiO, and Al is Al 2 O 3 The weight concentration is 40g/L. Wherein, the mass ratio of Ni in the mixed solution A and Ni in the mixed solution B used in the reaction of the comparative example is 14:8. and (3) putting the solution A into a reaction tank 1, dripping ammonia water (with the weight concentration of 10%) into the reaction tank 1 to perform a first gel forming reaction, keeping the gel forming temperature at 62 ℃, controlling the pH value at 7.8 when the reaction is finished, controlling the gel forming time at 1.0 hour, aging after the reaction is finished, controlling the aging temperature at 75 ℃, controlling the aging pH value at 7.6, and aging for 1.5 hours to obtain the precipitate slurry I containing nickel, molybdenum and silicon. Adding 500mL deionized water into a reaction tank 2, adding a 12wt% sodium hydroxide solution, a nickel-containing, molybdenum-containing and silicon-containing precipitated slurry I and a mixed solution B into the reaction tank 2 in parallel to perform a second gelling reaction, maintaining the gelling temperature at 60 ℃, initially controlling the pH value to be 12.8, adjusting the final pH value at the end to be 7.8 by 5 times of downward adjustment of the pH value, wherein the pH value of each downward adjustment is 1.0, keeping the pH value of the adjusted reaction slurry constant for 10 minutes after each downward adjustment of the pH value, and starting aging after the second gelling reaction is finished, and the aging is performed The melting temperature is 75 ℃, the pH value is controlled to be 8.0, and the aging time is 3.0 hours, so that the precipitate slurry II containing tungsten, nickel, molybdenum, silicon and aluminum is obtained. Filtering the aged slurry, drying the filter cake at 100 ℃ for 7 hours, rolling, and extruding strips into a cylinder. Washing with deionized water at room temperature to neutrality. The washed wet strip is then dried as follows: firstly, drying the material at 80 ℃ for 6.0 hours, uniformly spraying deionized water on the dried material, then drying, and repeating the processes of uniformly spraying the deionized water and drying for 5 times, wherein the volume ratio of the first sprayed deionized water to the dried material is 2:1, the drying temperature is 200 ℃, the drying time is 2.5 hours, and the volume ratio of the second spraying deionized water to the dried materials is 1.5:1, the drying temperature is 220 ℃, the drying time is 2.5 hours, and the volume ratio of the third spraying deionized water to the dried materials is 1:1, drying temperature 180 ℃ and drying time 2.0 hours, wherein the volume ratio of the fourth spraying deionized water to the dried materials is 1:2, drying at 180 ℃ for 1.5 hours, and roasting the dried material at 500 ℃ for 4 hours to obtain the catalyst J. The catalyst composition and the main properties are shown in Table 1.
Comparative example 5
Reference K was prepared following the procedure of example 1 (no silicon was added when preparing the mixed solution a).
Respectively adding nickel chloride, ammonium molybdate and aluminum chloride solution into a dissolving tank 1 filled with deionized water to prepare a mixed solution A, wherein the weight concentration of Ni in the mixed solution A calculated by NiO is 28g/L, and Mo is calculated by MoO 3 The weight concentration is 30g/L, al is calculated as Al 2 O 3 The weight concentration was 22g/L. Respectively adding ammonium metatungstate, nickel chloride and aluminum chloride solution into a dissolving tank 2 filled with deionized water to prepare a mixed solution B, wherein W in the solution B is WO 3 The weight concentration is 56g/L, the weight concentration of Ni is 16g/L based on NiO, and Al is Al 2 O 3 The weight concentration was 32g/L. Wherein, the mass ratio of Ni in the mixed solution A and Ni in the mixed solution B used in the reaction of the comparative example is 14:8. putting the solution A into a reaction tank 1, dripping ammonia water (with the weight concentration of 10%) into the reaction tank 1 to perform a first gel forming reaction, keeping the gel forming temperature at 62 ℃, and controlling the pH value at 7.8 when the reaction is finishedThe gel forming time is controlled to be 1.0 hour, after the reaction is finished, the aging is carried out, the aging temperature is 75 ℃, the aging pH value is controlled to be 7.6, and the aging is carried out for 1.5 hours, so that the precipitate slurry I containing nickel, molybdenum and aluminum is obtained. Adding 500mL of deionized water, 30mL of soybean oil and castor oil and phosphate with the mole ratio of 1.1 to the total W atoms in the mixed solution B into a reaction tank 2, adding a precipitate slurry I with the concentration of 12wt% of sodium hydroxide solution, nickel, molybdenum and aluminum and the mixed solution B into the reaction tank 2 in parallel to carry out a second gelling reaction, maintaining the gelling temperature at 60 ℃, initially controlling the pH value to be 12.8, adjusting the final pH value at the end to be 7.8 through 5 times of downward pH value adjustment, wherein the pH value of the reaction slurry after each downward pH value adjustment is 1.0, keeping the pH value of the reaction slurry after adjustment constant for 10 minutes, and after the second gelling reaction is finished, starting aging, controlling the pH value at 8.0 at the aging temperature of 75 ℃ for 3.0 hours to obtain the precipitate slurry II with tungsten, nickel, molybdenum and aluminum. Filtering the aged slurry, drying the filter cake at 100 ℃ for 7 hours, rolling, and extruding strips into a cylinder. Washing with deionized water at room temperature to neutrality. The washed wet strip is then dried as follows: firstly, drying the material at 80 ℃ for 6.0 hours, uniformly spraying deionized water on the dried material, then drying, and repeating the processes of uniformly spraying the deionized water and drying for 5 times, wherein the volume ratio of the first sprayed deionized water to the dried material is 2:1, the drying temperature is 200 ℃, the drying time is 2.5 hours, and the volume ratio of the second spraying deionized water to the dried materials is 1.5:1, the drying temperature is 220 ℃, the drying time is 2.5 hours, and the volume ratio of the third spraying deionized water to the dried materials is 1:1, drying temperature 180 ℃ and drying time 2.0 hours, wherein the volume ratio of the fourth spraying deionized water to the dried materials is 1:2, drying temperature 180 ℃ and drying time 1.5 hours, wherein the volume ratio of the fifth spraying deionized water to the dried materials is 1:3, drying at 200 ℃ for 1.5 hours. Roasting the dried material at 500 ℃ for 4 hours to obtain the catalyst K. The catalyst composition and the main properties are shown in Table 1.
Example 7
This example is an evaluation experiment of the activity of the catalyst of the present invention and is compared with a comparative catalyst. The catalyst A, B, C, E and the catalyst G, H, I, J, K of the invention and the catalyst G, H, I, J, K of the comparative example are respectively adopted, a comparison evaluation test is carried out on a 200mL small hydrogenation device, and mixed diesel (the weight ratio of straight-run diesel to coked diesel to catalytic diesel is 30:20:50) is used as a test raw material, and the main properties of the raw materials are shown in Table 5. The evaluation process conditions and the evaluation results of the catalyst activity are shown in Table 6. The type of sulfide in the hydrofinished oil was detected by a gas chromatograph-atomic emission spectroscopy detector (GC-AED), and the results are shown in table 7.
As can be seen from the evaluation results, compared with the catalyst of the comparative example, the catalyst of the invention shows high hydrodesulfurization activity when removing the refractory 4,6-DMDBT macromolecular sulfides, has excellent ultra-deep hydrodesulfurization activity, and simultaneously has good yield of diesel products. When the activity evaluation reaction space velocity is increased, the catalyst still has excellent ultra-deep desulfurization activity by increasing the reaction temperature, and compared with the evaluation result of the catalyst of the comparative example, the catalyst effectively reduces the influence of the thermodynamic equilibrium of a high-temperature hydrogenation path and has good temperature adaptability. The catalyst of the invention is used for processing light distillate oil, especially for processing poor diesel oil fraction, and has excellent ultra-deep hydrodesulfurization and denitrification performances.
Table 1 composition and properties of the catalysts prepared in examples and comparative examples
Catalyst numbering A B C D E F
NiO，wt% 22 32 30 36 28 31
WO 3 ，wt% 28 11 18 14 20 17
MoO 3 ，wt% 15 25 18 17 16 18
SiO 2 ，wt% 11 18 16 16 18 14
Al 2 O 3 ，wt% 16 9 12 12 11 12
P 2 O 5 ，wt% 8 5 6 5 7 8
Specific surface area, m 2 /g 255 247 241 264 225 220
Pore volume, mL/g 0.366 0.354 0.348 0.380 0.339 0.330
Catalyst particle size, mm 1.63 1.75 1.30 1.73 1.32 1.96
Cross section of catalyst particles catalyst of different layer thicknesses, R being the catalyst particle size
Outer surface layer 0.34R 0.30R 0.28R 0.36R 0.33R 0.28R
Intermediate layer 0.37R 0.45R 0.42R 0.36R 0.38R 0.41R
Central core layer 0.29R 0.25R 0.30R 0.28R 0.29R 0.31R
Average pore diameter of outer surface layer, nm 13.2 12.9 13.7 14.2 5.2 5.3
Average pore diameter of intermediate layer, nm 8.6 8.3 7.9 9.0 5.2 5.3
Central core average pore diameter, nm 6.0 5.7 5.6 6.2 5.2 5.3
The thickness of the shell accounts for the proportion of the total thickness of the core shell, percent 52 23 37 36 37 41
The catalyst compositions and properties prepared in examples and comparative examples of Table 1 are shown below
Catalyst numbering G H I J K
NiO，wt% 22 37.4 22 22 22
WO 3 ，wt% 28 24.3 28 28 28
MoO 3 ，wt% 15 16.3 15 15 15
SiO 2 ，wt% 15 - 5 15 -
Al 2 O 3 ，wt% 20 22 30 20 27
P 2 O 5 ，wt% - - - - 8
Specific surface area, m 2 /g 188 174 205 201 249
Pore volume, mL/g 0.284 0.301 0.245 0.304 0.358
Catalyst particle size, mm 1.62 1.63 1.61 1.63 1.65
Cross section of catalyst particles catalyst of different layer thicknesses, R being the catalyst particle size
Outer surface layer 0.33R 0.31R 0.32R 0.29R 0.32R
Intermediate layer 0.40R 0.40R 0.41R 0.40R 0.38R
Central core layer 0.27R 0.29R 0.27R 0.31R 0.30R
Average pore diameter of outer surface layer, nm 4.3 4.5 4.6 11.2 13.3
Average pore diameter of intermediate layer, nm 4.3 4.5 4.6 7.0 8.5
Central core average pore diameter, nm 4.3 4.5 4.6 5.1 5.9
The thickness of the shell accounts for the proportion of the total thickness of the core shell, percent - - - - 52
Note that: wherein, catalysts G-K are tested with reference to the relative thicknesses of the outer skin, middle and center cores of catalysts A-F when testing the average pore diameters of the outer skin, middle and center cores.
TABLE 2 composition of composite oxides in core and shell of the catalysts obtained in each example (based on the mass of the catalyst)
Catalyst numbering A B C D E F
Composite oxide composition in core
NiO，wt% 14 24 20 22 20 19
MoO 3 ，wt% 15 25 18 17 16 18
SiO 2 ，wt% 11 18 16 16 18 14
WO 3 ，wt% - - - - - -
Al 2 O 3 ，wt% - - - - - -
P 2 O 5 ，wt% - - - - - -
Composite oxide composition in shell
NiO，wt% 8 8 10 14 8 12
WO 3 ，wt% 28 11 18 14 20 17
Al 2 O 3 ，wt% 16 9 12 12 11 12
P 2 O 5 ，wt% 8 5 6 5 7 8
MoO 3 ，wt% - - - - - -
SiO 2 ，wt% - - - - - -
Table 2 shows the composition of the composite oxide in the core and shell of the catalyst obtained (based on the mass of the catalyst)
Catalytic reactionAgent numbering J K
Composite oxide composition in core
NiO，wt% 10 14
MoO 3 ，wt% 8 15
SiO 2 ，wt% 9 -
WO 3 ，wt% 12 -
Al 2 O 3 ，wt% 8 11
P 2 O 5 ，wt% - -
Composite oxide composition in shell
NiO，wt% 12 8
WO 3 ，wt% 16 28
Al 2 O 3 ，wt% 12 16
MoO 3 ，wt% 7 -
SiO 2 ，wt% 6 -
P 2 O 5 ，wt% - 8
Table 3 average particle diameter and particle diameter distribution of core-shell composite oxide particles of the catalysts obtained in each example
Catalyst numbering A B C D E
Average particle diameter, nm, of core-shell composite oxide particles 6.8 7.0 6.9 7.2 7.6
Particle size distribution of core-shell composite oxide particles,%
Particle size of less than 5nm 9.29 9.20 9.26 9.13 9.01
Particle diameter of 5nm-10nm 83.76 83.52 83.68 83.44 83.28
Particle size of more than 10nm 6.95 7.28 7.06 7.43 7.71
Table 3 shows the average particle diameter and particle diameter distribution of the core-shell composite oxide particles of the catalyst obtained in each example
Catalyst numbering F G H I J K
Average particle diameter, nm, of core-shell composite oxide particles 7.5 28.6 19.6 23.2 22.5 7.2
Particle size distribution of core-shell composite oxide particles,%
Particle size of less than 5nm 9.03 1.12 1.53 1.08 2.36 9.11
Particle diameter of 5nm-10nm 83.36 4.82 8.01 6.09 6.02 83.49
Particle size of more than 10nm 7.61 94.06 90.46 92.83 91.62 7.40
Table 4 average particle diameter and particle diameter distribution of the core-shell composite sulfide particles of the catalysts obtained in each example
Catalyst numbering A B C D E
Average particle diameter, nm, of core-shell composite sulfide particles 9.7 10.0 9.9 10.2 10.6
Particle size distribution of core-shell composite sulfide particles, percent
Particle size of less than 8nm 13.55 13.28 13.37 13.24 13.12
Particle diameter of 8nm-13nm 78.35 78.02 78.22 77.95 77.76
Particle size of greater than 13nm 8.10 8.70 8.41 8.81 9.12
Table 4 shows the average particle diameter and particle diameter distribution of the core-shell composite sulfide particles of the catalyst obtained in each example
Catalyst numbering F G H I J K
Average particle diameter, nm, of core-shell composite sulfide particles 10.4 38.3 25.4 29.5 28.2 10.2
Particle size distribution of core-shell composite sulfide particles, percent
Particle size of less than 8nm 12.17 0.92 1.25 1.13 1.21 12.26
Particle diameter of 8nm-13nm 78.81 2.53 3.89 3.36 3.42 78.99
Particle size of greater than 13nm 9.02 96.55 94.86 95.51 95.37 8.75
TABLE 5 Main Properties of raw oil
Project Analysis results
Density (20 ℃), g/cm 3 0.8879
Distillation range, DEG C 178-377
S，µg/g 12300
N，µg/g 890
TABLE 6 evaluation of catalyst Process conditions and Activity evaluation results
Catalyst numbering A B C E G I
Reaction conditions
Hydrogen partial pressure/MPa 6.4 6.4 6.4 6.4 6.4 6.4
Liquid hourly space velocity/h -1 2.0 2.0 2.0 2.0 2.0 2.0
Hydrogen to oil volume ratio 500:1 500:1 500:1 500:1 500:1 500:1
Reaction temperature/. Degree.C 365 365 365 365 365 365
Oil density (20 ℃ C.) g/cm was produced 3 0.8635 0.8636 0.8637 0.8637 0.8698 0.8671
Distillation range, DEG C 166-365 165-365 169-366 168-366 176-374 168-370
S，µg/g 6.7 6.9 7.5 8.7 148.6 28.8
N，µg/g 2.8 3.0 3.4 3.9 61.5 12.6
Yield of diesel oil, percent 99.3 99.4 99.0 99.2 94.0 85.3
Table 6 shows the evaluation process conditions and the activity evaluation results of the catalyst
Catalyst numbering J K H H A A
Reaction conditions
Hydrogen partial pressure/MPa 6.4 6.4 6.4 6.4 6.4 6.4
Liquid timeVolume space velocity/h -1 2.0 2.0 2.0 2.0 2.5 2.5
Hydrogen to oil volume ratio 500:1 500:1 500:1 500:1 500:1 500:1
Reaction temperature/. Degree.C 365 365 380 387 380 387
Oil density (20 ℃ C.) g/cm was produced 3 0.8708 0.8652 0.8667 0.8665 0.8647 0.8640
Distillation range, DEG C 177-373 169-369 169-370 172-371 170-367 168-366
S，µg/g 154.6 29.4 43.8 40.7 15.1 7.6
N，µg/g 59.7 10.2 22. 5 21.9 6.9 3.8
Yield of diesel oil, percent 94.4 99.1 98.9 99.0 99.2 99.1
TABLE 7 content of different sulfides in hydrofined oils
Catalyst numbering A B C E G I
Reaction conditions
Hydrogen partial pressure/MPa 6.4 6.4 6.4 6.4 6.4 6.4
Liquid hourly space velocity/h -1 2.0 2.0 2.0 2.0 2.0 2.0
Hydrogen to oil volume ratio 500:1 500:1 500:1 500:1 500:1 500:1
Reaction temperature/. Degree.C 365 365 365 365 365 365
Sulfur content in hydrorefining oil, mug/g 6.7 6.9 7.5 8.7 148.6 28.8
C 1 -DBT，µg/g 0 0 0 0 12.1 0
4- MDBT，µg/g 1.8 1.9 2.0 2.3 30.2 8.7
6-MDBT，µg/g 1.9 1.9 2.1 2.4 40.6 9.8
4，6- DMDBT，µg/g 3.0 3.1 3.4 4.0 65.7 10.3
Table 7 shows the content of various sulfides in hydrofined oils
Catalyst numbering J K H H A A
Reaction conditions
Hydrogen partial pressure/MPa 6.4 6.4 6.4 6.4 6.4 6.4
Liquid hourly space velocity/h -1 2.0 2.0 2.0 2.0 2.5 2.5
Hydrogen to oil volume ratio 500:1 500:1 500:1 500:1 500:1 500:1
Reaction temperature/. Degree.C 365 365 380 387 380 387
Sulfur content in hydrorefining oil, mug/g 154.6 29.4 43.8 40.7 15.1 7.6
C 1 -DBT，µg/g 12.4 0 0 0 0 0
4- MDBT，µg/g 31.1 7.8 12.3 12.1 3.5 2.3
6-MDBT，µg/g 40.7 8.7 11.6 9.8 3.7 2.3
4，6- DMDBT，µg/g 70.4 12.9 19.9 18.8 7.9 4.2

Claims (25)

1. A hydrofining catalyst containing phosphorus is a granular bulk phase catalyst, and comprises core-shell composite oxide particles, wherein a shell layer is a composite oxide containing tungsten, nickel, aluminum and phosphorus, and a core phase is a composite oxide containing molybdenum, nickel and silicon.
2. The phosphorus-containing hydrofinishing catalyst of claim 1, wherein: based on the mass of the core-shell composite oxide particles, the mass content of the composite oxide containing molybdenum, nickel and silicon is 10% -90%, and the mass content of the composite oxide containing tungsten, nickel, aluminum and phosphorus is 10% -90%.
3. The phosphorus-containing hydrofinishing catalyst of claim 1, wherein: in the core-shell composite oxide particles, the thickness of the shell accounts for 8% -83% of the total thickness of the core-shell, and is preferably 10% -80%.
4. A phosphorus-containing hydrofinishing catalyst according to any one of claims 1-3, characterized in that: the average particle size of the core-shell composite oxide particles is 5-9 nm.
5. The phosphorus-containing hydrofining catalyst according to claim 4, wherein: the particle size distribution of the core-shell composite oxide particles is as follows: the number of particles with the particle size of less than 5nm accounts for 3% -16% of the total number of particles, the number of particles with the particle size of 5 nm-10 nm accounts for 67% -91% of the total number of particles, and the number of particles with the particle size of more than 10nm accounts for 2% -17% of the total number of particles.
6. The phosphorus-containing hydrofinishing catalyst of claim 1, wherein: in the composite oxide containing molybdenum, nickel and silicon, the mole ratio of molybdenum to nickel is 1: 28-12: 1 silicon content as SiO 2 The mass of the catalyst accounts for 2% -30% of the mass of the hydrofining catalyst.
7. The phosphorus-containing hydrofinishing catalyst of claim 1, wherein: in the composite oxide containing tungsten, nickel, aluminum and phosphorus, the molar ratio of tungsten to nickel is 1: 22-8: 1, aluminum content is Al 2 O 3 The calculated mass accounts for 4% -30% of the hydrofining catalyst mass, and the content of phosphorus is P 2 O 5 The mass of the catalyst accounts for 2% -16% of the mass of the hydrofining catalyst, and preferably 3% -14%.
8. The phosphorus-containing hydrofinishing catalyst of claim 1, wherein: the mass of NiO in the composite oxide containing molybdenum, nickel and silicon accounts for 40% -90% of the total mass of NiO in the phosphorus-containing hydrofining catalyst, and the mass of NiO in the composite oxide containing tungsten, nickel, aluminum and phosphorus accounts for 10% -60% of the total mass of NiO in the phosphorus-containing hydrofining catalyst.
9. The phosphorus-containing hydrofinishing catalyst of claim 1, wherein: the properties of the phosphorus-containing hydrofining catalyst are as follows: specific surface area of 100-700 m 2 And/g, wherein the pore volume is 0.20-0.80 mL/g.
10. The phosphorus-containing hydrofinishing catalyst of claim 1, wherein: the particle size of the catalyst particles is 1-10 mm.
11. The phosphorus-containing hydrofinishing catalyst of claim 1, wherein: from the catalyst outer surface layer to the central core, the average pore diameter is from large to small;
Preferably, the catalyst particles are divided into an outer surface layer, an intermediate layer and a central core, the average pore diameter of the outer surface layer is reduced in a gradient manner, the average pore diameter of the outer surface layer is 10-18 nm, the average pore diameter of the intermediate layer is 7-10 nm, and the average pore diameter of the central core is 2-7 nm.
12. A bulk hydrofinishing catalyst in the sulfided state, characterized by: obtained by sulfiding the phosphorus-containing hydrofinishing catalyst of any one of claims 1-11.
13. The bulk hydrofinishing catalyst in the sulfided state of claim 12, wherein: the average particle size of the core-shell composite sulfide particles of the bulk phase hydrofining catalyst in a vulcanized state is 9-13 nm, and the particle size distribution of the core-shell composite sulfide particles is as follows: the number of particles with the particle size of less than 8nm accounts for 3% -22% of the total number of particles, the number of particles with the particle size of 8 nm-13 nm accounts for 60% -85% of the total number of particles, and the number of particles with the particle size of more than 13nm accounts for 2% -18% of the total number of particles.
14. A process for preparing a phosphorus-containing hydrofinishing catalyst as claimed in any one of claims 1 to 11, comprising:
(1) Preparing a mixed solution A containing Mo, ni and Si components and preparing a mixed solution B containing W, ni and Al components;
(2) Adding the precipitant A into the mixed solution A to perform a first gel forming reaction, and aging for the first time after the reaction to obtain precipitate slurry I containing nickel, silicon and molybdenum;
(3) Adding mixed liquid of water, grease and phosphate into a reactor, then adding the mixed solution B, a precipitator B and slurry I into the reactor in parallel flow for a second gelling reaction, and aging for the second time after the reaction to generate precipitate slurry II containing nickel, molybdenum, tungsten, silicon, aluminum and phosphorus;
(4) And (3) preparing the material obtained in the step (3) into the phosphorus-containing hydrofining catalyst.
15. The method of claim 14, wherein: in the mixed solution A in the step (1), the weight concentration of Ni in terms of NiO is 5-100 g/L, and Mo in terms of MoO 3 The weight concentration is 5-100 g/L, si is SiO 2 The weight concentration of the meter is 2-80 g/L;
in the mixed solution B, W is WO 3 The weight concentration of Ni is 2-110 g/L, the weight concentration of Ni is 5-100 g/L, and Al is Al 2 O 3 The weight concentration of the meter is 2-90 g/L.
16. The method of claim 14, wherein: the conditions of the first glue forming reaction in the step (2) are as follows: the reaction temperature is 30-90 ℃, preferably 40-85 ℃, the pH value is controlled to 7.0-11.0, preferably 7.2-10.0, and the gelling time is 0.2-2.5 hours, preferably 0.3-2.0 hours.
17. The method of claim 14, wherein: the first aging condition in the step (2) is as follows: the aging temperature is 60-90 ℃, preferably 65-85 ℃, the pH value is controlled to 7.0-11.0, preferably 7.2-10.5 during aging, and the aging time is 0.6-3.0 hours, preferably 0.8-2.5 hours.
18. The method of claim 14, wherein: in the step (3), the volume ratio of water to the volume of the filter cake of the sediment slurry II of nickel, molybdenum, tungsten, silicon, aluminum and phosphorus in the step (3) is 0.2: 1-6: 1.
19. the method of claim 14, wherein: the oleaginous liquid in the step (3) is unsaturated higher fatty glyceride, preferably one or more of peanut oil, rapeseed oil, cottonseed oil, sunflower seed oil, soybean oil, corn oil, tea oil and olive oil; the volume-to-volume ratio of oleaginous liquid to water is 1: 60-1: 4, preferably 1: 40-1: 6.
20. the method of claim 14, wherein: the conditions of the second gelling reaction of step (3) are: the reaction temperature is 30-90 ℃, the pH value is initially controlled to be 10.0-14.0, the final pH value is 7.0-8.5 at the end, the gel forming reaction time is 0.5-6.0 hours, and preferably 0.6-5.0 hours; preferably, the pH value is adjusted from an initial value to a final pH value by adopting a method of gradually adjusting down for 2-10 times, preferably 2-8 times; preferably, the time is constant for 0.1-1.2 hours after each down-regulation.
21. The method of claim 14, wherein: the second aging conditions described in step (3) are as follows: the aging temperature is 60-90 ℃, preferably 65-85 ℃, the pH value is controlled to 7.0-11.0, preferably 7.2-10.5 during aging, and the aging time is 2.0-6.0 hours, preferably 2.5-5.0 hours.
22. The method of claim 14, wherein: the phosphate in the step (3) is one or more of octadecyl ether phosphate, alkylphenol ether phosphate, isomeric tridecyl alcohol ether phosphate, lauryl alcohol ether phosphate, castor oil phosphate, octadecyl phosphate and lauryl phosphate, preferably one or more of alkylphenol ether phosphate, isomeric tridecyl alcohol ether phosphate, lauryl alcohol ether phosphate and castor oil phosphate; the molar ratio of the amount of the phosphate added to the total number of W atoms in the mixed solution B in the step (1) was 0.3: 1-3.0: 1, preferably 0.4: 1-2.5: 1.
23. the method of claim 14, wherein: in the step (4), the process of preparing the phosphorus-containing hydrofining catalyst from the material obtained in the step (3) comprises the following steps: the material obtained in the step (3) is dried, molded and washed for the first time, and then dried and roasted for the second time to obtain the hydrofining catalyst;
the first drying conditions are as follows: drying at 40-150 ℃ for 1-48 hours; the second drying conditions are as follows: drying at 60-280 ℃ for 1-48 hours; the roasting conditions are as follows: roasting for 1-24 hours at 350-650 ℃.
24. The method of claim 23, wherein: the second drying in the step (4) is as follows:
a. firstly, drying the material at 60-100 ℃ for 1.0-8.5 hours, preferably at 70-90 ℃ for 2.0-8.0 hours;
b. uniformly spraying water on the material obtained in the step a, wherein the volume ratio of water to dry material is 1:4~4:1, then drying at a temperature of 150-280 ℃, preferably 150-280 ℃ for 0.5-4.0 hours, preferably 0.6-3.5 hours;
c. repeating the step b for 2-9 times, preferably 3-8 times;
wherein, the volume ratio of the first water adding volume to the dry material is greater than 1:1, the volume ratio of the last water adding volume to the dry material is less than 1:1, preferably, the volume ratio of the added water to the dried material decreases in sequence with the increase of the number of times of drying.
25. A process for hydrofining diesel oil, characterized in that a phosphorus-containing hydrofining catalyst according to any one of claims 1 to 11 or a bulk hydrofining catalyst in the sulfided state according to any one of claims 12 to 13 or a phosphorus-containing hydrofining catalyst prepared by a preparation process according to any one of claims 14 to 24 is used.
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