CN115999573A

CN115999573A - Hydrofining catalyst and preparation method thereof

Info

Publication number: CN115999573A
Application number: CN202111234243.8A
Authority: CN
Inventors: 王继锋; 陈�光; 李娟�; 王海涛; 徐学军
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2021-10-22
Filing date: 2021-10-22
Publication date: 2023-04-25
Anticipated expiration: 2041-10-22
Also published as: CN115999573B

Abstract

The invention provides a hydrofining catalyst and a preparation method thereof. The method comprises the following steps: (1) Preparing a mixed solution A containing Mo, ni and an organic auxiliary agent component, and preparing a mixed solution B containing W, ni and an Al component; (2) Mixing the precipitator A, the alkaline solution containing silicon and the mixed solution A for a first gel forming reaction, and performing first aging to obtain slurry I; (3) Adding mixed liquid of water and grease into a reaction tank, then adding the mixed solution B, a precipitator B and slurry I into the reaction tank in parallel flow for a second gelling reaction, and aging for the second time after the reaction to generate slurry II; (4) And (3) preparing the hydrofining catalyst from the material obtained in the step (3). The catalyst has higher hydrodesulfurization and hydrodenitrogenation reaction performances, can avoid excessive cracking of diesel oil fraction, and can treat poor-quality distillate oil raw materials.

Description

Hydrofining catalyst and preparation method thereof

Technical Field

The invention relates to a hydrofining catalyst and a preparation method thereof, in particular to a bulk hydrofining catalyst and a preparation method thereof, wherein the hydrofining catalyst is used in processes of hydrodesulfurization, denitrification and the like of distillate oil.

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, domestic 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 hydrofining catalyst and a preparation method 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 present invention provides a method for producing a hydrofining catalyst, comprising:

(1) Preparing a mixed solution A containing Mo, ni and an organic auxiliary agent component, and preparing a mixed solution B containing W, ni and an Al component;

(2) Mixing the precipitant A, the alkaline solution containing silicon and the mixed solution A for 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 and grease into a reaction tank, then adding the mixed solution B, a precipitator B and slurry I into the reaction tank 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 and aluminum;

(4) And (3) preparing the hydrofining catalyst from the material obtained in the step (3).

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.

Further, in preparing the mixed solution a, the nickel source generally used may be one or more of nickel sulfate, nickel nitrate and nickel chloride, and the molybdenum source may be ammonium molybdate.

Further, in the step (1), the organic auxiliary agent is a polyoxyethylene nonionic surfactant, and may be one or more selected from fatty alcohol polyoxyethylene ether (C16-18 alcohol polyoxyethylene ether, C12-14 alcohol polyoxyethylene ether, oleyl alcohol polyoxyethylene ether, isomeric decanyl alcohol polyoxyethylene ether, octyl phenol polyoxyethylene ether, castor oil polyoxyethylene ether), alkylphenol polyoxyethylene (4, 6, 7, 9, 10, 15) ether, dodecylamine polyoxyethylene ether, and the like. The molar ratio of the mole number of the organic auxiliary agent to the mole number of Mo in the mixed solution A is 0.3-2.5: 1, preferably 0.4 to 1.8:1.

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 alkaline solution containing silicon in the step (2) may be one or more of water glass, silica sol and the like. Si in alkaline solution containing silicon as SiO ₂ The weight concentration is 5-90 g/L, preferably 6-85 g/L.

In the step (2), the mixed solution A and the precipitator A are preferably subjected to concurrent reaction, when the volume of the mixed solution A is still 1/5-1/2, the mixed solution A is kept stand for 10-30 minutes, and then the remaining mixed solution A and the alkaline solution containing silicon are continuously subjected to concurrent precipitation.

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 gel forming reaction time (excluding the standing 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 is deionized water, and the volume ratio of the added water to the filter cake volume of the sediment slurry II of nickel, molybdenum, tungsten, silicon and aluminum 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. The oleaginous liquid 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 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% -80%, preferably 45% -75% of the total Ni weight in the hydrofining catalyst obtained in the step (4). In the step (3), the weight of the introduced Ni accounts for 20% -60% of the total weight of Ni in the hydrofining catalyst obtained in the step (4), and is preferably 25% -55%.

Further, in the step (4), the process of preparing the hydrofining catalyst from the material obtained in the step (3) may include: 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 after the molding in the step (4) 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. spraying water (preferably deionized water) on the material obtained in the step a, wherein the volume ratio of the added water to the dried material is 1:4~4:1, then drying at a temperature of 150-280 ℃, preferably 150-250 ℃ 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 the organic auxiliary agent component in the step (1) is expressed as MoO ₃ Based on the total mass of Ni in terms of NiO, and W in the mixed solution B containing W, ni and Al components in terms of WO ₃ Ni is calculated as NiO and Al is calculated as Al ₂ O ₃ The ratio of the total mass is 1:9~9:1, preferably 1.5: 8.5-8.5: 1.5.

Further, in the mixed solution A containing Mo, ni and the organic additive component in the step (1), the atomic ratio of molybdenum to nickel is 1: 26-14: 1, preferably 1: 24-12: 1.

further, in the mixed solution B containing W, ni and Al components in the step (1), the atomic 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 5% -38%, preferably 7% -35% 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 the organic additive component in the step (1) to Ni in the mixed solution B containing W, ni and Al components is 4: 6-8: 2.

the silicon content added in the step (2) is SiO ₂ The mass of the catalyst accounts for 2% -32%, preferably 4% -30% of the mass of the hydrofining catalyst obtained in the step (4).

Further, the hydrofining catalyst of the present invention is (solid) granular, can be prepared by a conventional molding method, and can be in various shapes conventionally used for hydrofining catalysts, such as column shape, sphere shape, etc. 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 hydrofining catalyst obtained in the step (4) is an oxidized bulk hydrofining catalyst, and can be vulcanized by a conventional method before use.

The second aspect of the present invention provides a hydrofining catalyst prepared by the above method, the catalyst is a granular bulk hydrofining catalyst comprising core-shell composite oxide particles, the core is a composite oxide containing molybdenum, nickel and silicon, and the shell is a composite oxide containing tungsten, nickel and aluminum.

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 and aluminum 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, the average particle size of the core-shell composite oxide particles is 6-10 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% -17% of the total number of particles, the number of particles with the particle size of 5 nm-10 nm accounts for 69% -90% of the total number of particles, and the number of particles with the particle size of more than 10nm accounts for 2% -19% of the total number of particles.

In the catalyst of the invention, the mole 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% -32% of the mass of the hydrofining catalyst, and preferably 4% -30%.

In the catalyst of the invention, the mole ratio of tungsten to nickel in the composite oxide containing tungsten, nickel and aluminum is 1: 22-8: 1, preferably 1: 20-5: 1, aluminiumContent of Al in ₂ O ₃ The mass of the catalyst accounts for 5% -38%, preferably 7% -35% of the mass of the hydrofining catalyst.

In the catalyst, the mass of NiO in the composite oxide containing molybdenum, nickel and silicon accounts for 40-80% of the total mass of NiO in the hydrofining catalyst, and the mass of NiO in the composite oxide containing tungsten, nickel and aluminum accounts for 20-60% of the total mass of NiO in the hydrofining catalyst.

In the catalyst of the invention, the 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 6mm. In the case of a generally spherical shape, the particle diameter is 2 to 10mm.

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 are 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.

In a third aspect, the present invention provides a sulfided bulk hydrofining catalyst obtained by sulfiding the hydrofining catalyst.

The invention relates to a bulk hydrofining catalyst in a vulcanized state, which comprises core-shell composite sulfide particles, wherein the core is a composite sulfide containing molybdenum, nickel and silicon, and the shell is a composite sulfide containing tungsten, nickel and aluminum.

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 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 use of the hydrofining catalyst in a 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. in the method, firstly, molybdenum nickel silicon aging slurry is prepared, then, the slurry is added into a reaction tank of the existing water and grease liquid mixture in parallel flow with tungsten nickel aluminum mixed solution and precipitant to carry out secondary gel forming, so that tungsten nickel is uniformly and orderly deposited on molybdenum nickel crystal grains, thereby forming tungsten nickel coated molybdenum nickel nano particles with uniform particle size and good dispersion, different active metals in the metal particles and between the active metals and a carrier have good coordination effect, and the core-shell composite oxide particles have good dispersibility, and the prepared hydrofining catalyst is suitable for hydrofining reaction of heavy distillate oil (such as diesel oil), and is particularly beneficial to deep hydrodesulfurization and denitrification, and can also avoid reducing the yield of the diesel oil.

2. 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.

3. In the method, when the composite oxide of tungsten, nickel and silicon is formed, the quantity of acid centers at the junction of the core and the shell is better controlled by adjusting the adding mode of the silicon, and meanwhile, the addition of the organic aid promotes the dispersion of the silicon in the core, so that the acid centers formed at the junction of the core-shell structure are more uniformly dispersed.

4. In the method, when the composite oxide of tungsten, nickel and aluminum is formed, the method of decreasing the pH value to form gel is adopted, so that the particle size of the core-shell composite oxide is more uniform.

5. The hydrogenation refined catalyst prepared by the method is characterized in that the distribution state of active metals is improved from the nanometer level, namely, the catalyst is mainly composed of composite oxide particles containing tungsten, nickel and aluminum 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 centers are 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 hydrogenation refined catalyst, the desulfurization and denitrification activities are obviously improved, meanwhile, the cracking reaction of diesel oil fraction is reduced, and the reduction of the 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.

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 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, 20-80 samples are measured at the same time, and the average pore diameter is calculated. The average pore diameter of the different layers from the outer surface layer to the central core was thus determined.

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 oleyl alcohol polyoxyethylene ether into a dissolution 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 calculated weight concentration is 30g/L, and the mole ratio of the oleyl alcohol polyoxyethylene ether to the Mo in the mixed solution A is 0.8. 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 to Ni in the mixed solution B used in the reaction of the embodiment is 14:8. the mixed solution A and ammonia water (10% by weight concentration) were added dropwise to the reaction tank 1 in parallel to carry out the first gelling reaction, and when the remaining volume of the mixed solution A was 1/3, the gelling was stopped and left standing for 15 minutes, and then the remaining mixed solution A and a dilute water glass Solution (SiO) ₂ The weight concentration of (2) is 30 g/L) is continuously carried out parallel flow gel forming until the reaction is finished, the gel forming temperature is kept at 62 ℃, the pH value is controlled at 7.8 when the reaction is finished, the gel forming reaction time is controlled at 1.0 hour (excluding the standing time), the aging is carried out after the reaction is finished, the aging temperature is 75 ℃, the aging pH value is controlled at 7.6, and the aging is carried out for 1.5 hours, thus obtaining the precipitate slurry I containing nickel, molybdenum and silicon. Adding 500mL of deionized water and 30mL of soybean oil mixture into a reaction tank 2, adding 12wt% sodium hydroxide solution, nickel-containing, molybdenum-containing and silicon-containing precipitate slurry I and 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 to be 7.8 after finishing 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 to be 1.0, starting aging after finishing the second gelling reaction, controlling the aging temperature at 75 ℃, controlling the pH value to be 8.0, and aging time to be 3.0 hours to obtain the tungsten-containing, nickel-containing, molybdenum-containing, silicon-containing and aluminum-containing precipitate slurry II. Filtering the aged slurry, drying the filter cake at 100deg.C for 7 hr, rolling, and extruding The strips are cylindrical. 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. 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 castor oil polyoxyethylene ether 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 24g/L, and Mo is calculated by MoO ₃ The calculated weight concentration is 32g/L, and the mole ratio of the castor oil polyoxyethylene ether to the Mo in the mixed solution A is 1.0. 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 (WO) ₃ The weight concentration is 48g/L, the weight concentration of Ni is 24g/L in terms of NiO, and Al is Al ₂ O ₃ The weight concentration is 36g/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 12:12. the solution A and ammonia water (10% by weight concentration) were added in parallel to the reaction tank 1 to carry out the first gelling reaction, and when the remaining volume of the mixed solution A was 2/5, the gelling was stopped and left to stand for 20 minutes, and then the remaining mixed solution A and the diluted water glass Solution (SiO) ₂ Concentration of 36 g/L) by weightAnd (3) parallel flow gelling is carried out until the reaction is finished, the gelling temperature is kept at 50 ℃, the pH value is controlled at 7.9 when the reaction is finished, the gelling time is controlled at 1.3 hours, aging is carried out after the reaction is finished, the aging temperature is 75 ℃, the aging pH value is controlled at 8.2, and the aging is carried out for 1.5 hours, so that the precipitate slurry I containing nickel, molybdenum and silicon is obtained. Adding 800mL of deionized water and 60mL of tea oil into a reaction tank 2, adding 13wt% sodium hydroxide solution, nickel-containing, molybdenum-silicon precipitated slurry I and mixed solution B into the reaction tank 2 in parallel to carry out a second gelling reaction, keeping the gelling temperature at 55 ℃, initially controlling the pH value to be 12.4, adjusting the final pH value to be 7.6 after finishing by 6 times of downward adjustment of the pH value, adjusting the pH value of the reaction slurry to be 0.8 each time, keeping the pH value of the adjusted reaction slurry constant for 15 minutes after each time of downward adjustment of the pH value to be 0.8, starting aging after finishing the second gelling reaction, controlling the aging temperature at 78 ℃, controlling the pH value to be 7.9, and aging time to be 3.4 hours to obtain the tungsten-containing, nickel-molybdenum-silicon-aluminum precipitated slurry II. Filtering the aged slurry, drying the filter cake for the first time, drying at 80 ℃ for 11 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 75 ℃ 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 1.6:1, the drying temperature is 170 ℃, the drying time is 1.8 hours, and the volume ratio of the second spraying deionized water to the dried materials is 1:1, the drying temperature is 150 ℃, the drying time is 2.0 hours, and the volume ratio of the third spraying deionized water to the dried materials is 1:1.8, drying temperature 160 ℃, drying time 1.8 hours, and the volume ratio of the fourth spraying deionized water to the dried materials is 1:2.2, drying temperature 170 ℃ and drying time 1.5 hours, wherein the volume ratio of the fifth spraying deionized water to the dried materials is 1:2.6, drying temperature 160 ℃ and drying time 1.8 hours. The dried material was calcined at 540 ℃ for 5 hours to obtain catalyst B. The catalyst composition and the main properties are shown in Table 1.

Example 3

Respectively polymerizing nickel chloride, ammonium molybdate and octylphenolAdding oxyvinyl ether 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 34g/L, and Mo is calculated by MoO ₃ The calculated weight concentration is 28g/L, and the mole ratio of the mole number of the octyl phenol polyoxyethylene ether to the mole number of Mo in the mixed solution A is 0.7. 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 26g/L in terms of NiO, and Al is Al ₂ O ₃ The weight concentration is 36g/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 17:13. the solution A and ammonia water (9% by weight concentration) were added dropwise to the reaction tank 1 in parallel to carry out the first gelling reaction, and when the remaining volume of the mixed solution A was 1/4, the gelling was stopped and left standing for 18 minutes, and then the remaining mixed solution A and the diluted water glass Solution (SiO) ₂ The weight concentration of (2) is 40 g/L) is continuously carried out parallel flow gel forming until the reaction is finished, the gel forming temperature is kept at 60 ℃, the pH value is controlled at 8.3 when the reaction is finished, the gel forming time is controlled at 0.8 hour, the aging is carried out after the reaction is finished, the aging temperature is 78 ℃, the aging pH value is controlled at 7.7, and the aging is carried out for 1.6 hours, thus obtaining the precipitate slurry I containing nickel, molybdenum and silicon. Adding 900mL of deionized water and 60mL of peanut oil into a reaction tank 2, adding a 12wt% sodium hydroxide solution, nickel-containing, molybdenum-silicon precipitated slurry I and a mixed solution B into the reaction tank 2 in parallel to perform a second gel forming reaction, maintaining the gel forming temperature at 50 ℃, initially controlling the pH value to be 12.9, adjusting the final pH value to be 7.9 after finishing by 5 times of downward adjustment of the pH value, adjusting the pH value of each downward adjustment to be 1.0, controlling the pH value of the reaction slurry to be constant for 13 minutes after each downward adjustment of the pH value, starting aging after finishing the second gel forming reaction, controlling the pH value to be 7.9 at the aging temperature of 78 ℃, and aging for 3.2 hours to obtain the tungsten-containing, nickel-molybdenum-silicon-aluminum precipitated slurry II. Filtering the aged slurry, drying the filter cake for the first time, drying at 100 ℃ for 8 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: the material was first dried at 75 c for 7.0 hours, Evenly spraying deionized water on the dried material, then drying, and repeating the evenly spraying deionized water and the drying process for 7 times, wherein the volume ratio of the first sprayed deionized water to the dried material is 2.5:1, the drying temperature is 210 ℃, the drying time is 2.4 hours, and the volume ratio of the second spraying deionized water to the dried materials is 1.8:1, drying temperature 180 ℃ and drying time 2.0 hours, wherein the volume ratio of the third spraying deionized water to the dried materials is 1.2:1, the drying temperature is 170 ℃, the drying time is 1.8 hours, and the volume ratio of the fourth spraying deionized water to the dried materials is 1:1.3, drying temperature is 180 ℃, drying time is 1.8 hours, and the volume ratio of the fifth spraying deionized water to the dried materials is 1:1.8, drying temperature 180 ℃ and drying time 1.5 hours, wherein the volume ratio of the sixth spray deionized water to the dried materials is 1:2.2, drying temperature 180 ℃ and drying time 1.8 hours, wherein the volume ratio of the seventh spraying deionized water to the dried materials is 1:2.7, drying temperature 180 ℃ and drying time 1.8 hours. The dried material was calcined at 520 ℃ for 5 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 isodecanol polyoxyethylene ether 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 32g/L, and Mo is calculated by MoO ₃ The calculated weight concentration is 36g/L, and the mole ratio of the mole number of the isomeric decaol polyoxyethylene ether to the mole number of Mo in the mixed solution A is 1.3. 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 20g/L in terms of NiO, and Al is Al ₂ O ₃ The weight concentration of the meter is 38g/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 16:10. the solution A and ammonia water (13% by weight concentration) were added dropwise to the reaction tank 1 in parallel to carry out the first gelling reaction, and when the remaining volume of the mixed solution A was 9/20, the gelling was stopped and left standing for 20 minutes, and then the remaining mixed solution A and the diluted water glass Solution (SiO) ₂ 34 g/L) of the mixture is continuously carried out and parallel-flow gel is formedAnd (3) keeping the gel forming temperature at 65 ℃ until the reaction is finished, controlling the pH value at 8.0 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 78 ℃, controlling the aging pH value at 8.3, and aging for 1.8 hours to obtain the precipitate slurry I containing nickel, molybdenum and silicon. Adding 1000mL of deionized water and 90mL of corn oil into a reaction tank 2, adding 13wt% sodium hydroxide solution, nickel-containing, molybdenum-silicon precipitate slurry I and mixed solution B into the reaction tank 2 in parallel to perform a second gel forming reaction, maintaining the gel forming temperature at 68 ℃, initially controlling the pH value to be 12.5, adjusting the final pH value to be 8.0 after finishing the reaction by 5 times of downward adjustment of the pH value, wherein the pH value of the reaction slurry after adjustment is constant for 11 minutes after each downward adjustment of the pH value to be 0.9, starting aging after the second gel forming reaction, controlling the pH value to be 8.0 at 79 ℃, and aging time to be 3.0 hours to obtain the tungsten-containing, nickel-molybdenum-silicon-aluminum precipitate slurry II. Filtering the aged slurry, drying the filter cake at 130 ℃ for 6 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 75 ℃ 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 2.5:1, drying temperature 180 ℃ and drying time 2.8 hours, wherein the volume ratio of the second spraying deionized water to the dried materials is 1.8:1, drying temperature 180 ℃ and drying time 2 hours, wherein the volume ratio of the third spraying deionized water to the dried materials is 1.2:1, the drying temperature is 170 ℃, the drying time is 1.8 hours, and the volume ratio of the fourth spraying deionized water to the dried materials is 1:1.5, drying temperature 180 ℃ and drying time 1.6 hours, wherein the volume ratio of the fifth spraying deionized water to the dried materials is 1:2.2, drying temperature 160 ℃ and drying time 1.5 hours. The dried material was calcined at 520 ℃ for 5 hours to obtain catalyst D. The catalyst composition and the main properties are shown in Table 1.

Example 5

Adding nickel chloride, ammonium molybdate and alkylphenol polyoxyethylene (9) ether into deionized waterA solution tank 1 is used for preparing 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 calculated weight concentration was 40g/L, and the molar ratio of the alkylphenol ethoxylate (9) to the Mo in the mixed solution A was 1.4. 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 30g/L, the weight concentration of Ni is 18g/L in terms of NiO, and Al is Al ₂ O ₃ The weight concentration is 36g/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 19:9. putting the solution A into a reaction tank 1, dripping the solution A and ammonia water (with the weight concentration of 10%) into the reaction tank 1 in parallel flow for carrying out a first gel forming reaction, stopping gel forming and standing for 18 minutes when the residual volume of the mixed solution A is 2/5, and then adding the residual mixed solution A and a dilute water glass Solution (SiO) ₂ The weight concentration of (3) is 38 g/L) is continuously carried out parallel flow gel forming until the reaction is finished, the gel forming temperature is kept at 65 ℃, the pH value is controlled at 8.2 when the reaction is finished, the gel forming time is controlled at 1.0 hour, the aging is carried out after the reaction is finished, the aging temperature is 77 ℃, the aging pH value is controlled at 7.8, and the aging is carried out for 1.5 hours, thus obtaining the precipitate slurry I containing nickel, molybdenum and silicon. Adding 800mL of deionized water and 40mL of olive oil into a reaction tank 2, adding a 12wt% sodium hydroxide solution, a nickel-containing, molybdenum-silicon 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 55 ℃, initially controlling the pH value to be 12.8, adjusting the final pH value to be 7.9 after finishing the final pH value by 7 times of downward adjustment of the pH value, wherein the pH value of the reaction slurry after adjustment is constant for 15 minutes after each downward adjustment of the pH value to be 0.7, starting aging after the second gelling reaction, controlling the pH value to be 8.0 at the aging temperature of 78 ℃, and aging for 3.3 hours to obtain a tungsten-containing, nickel-molybdenum-silicon-aluminum precipitated slurry II. 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 strips were then dried at 160℃for 8.0 hours. The dried material was calcined at 530℃for 5 hours to give catalyst E. Catalyst composition The main properties are shown in Table 1.

Example 6

Respectively adding nickel chloride, ammonium molybdate and C18 alcohol polyoxyethylene ether 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 calculated weight concentration is 26g/L, and the mole ratio of the mole number of the C18 alcohol polyoxyethylene ether to the mole number of Mo in the mixed solution A is 1.0. Respectively adding ammonium metatungstate, nickel chloride and aluminum chloride solution into a dissolution tank 2 provided 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 of the meter was 42g/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 22:10. the solution A and ammonia water (14% by weight concentration) were added dropwise to the reaction tank 1 in parallel to carry out the first gelling reaction, and when the remaining volume of the mixed solution A was 7/20, the gelling was stopped and left standing for 18 minutes, and then the remaining mixed solution A and a dilute water glass Solution (SiO) ₂ The weight concentration of (2) is 32 g/L) is continuously carried out parallel flow gel forming until the reaction is finished, the gel forming temperature is kept at 55 ℃, the pH value is controlled at 8.5 when the reaction is finished, the gel forming time is controlled at 1.2 hours, the aging is carried out after the reaction is finished, the aging temperature is 77 ℃, the aging pH value is controlled at 8.0, and the aging is carried out for 1.7 hours, thus obtaining the precipitate slurry I containing nickel, molybdenum and silicon. 700mL of deionized water and 70mL of rapeseed oil are added into a reaction tank 2, then a precipitate slurry I with concentration of 12wt% of sodium hydroxide solution, nickel, molybdenum and silicon and a mixed solution B are added into the reaction tank 2 in parallel to carry out a second gelling reaction, the gelling temperature is kept at 60 ℃, the pH value is initially controlled to be 13.3, the final pH value at the end is adjusted to be 7.9 through 6 times of downward pH value adjustment, the pH value of each downward pH value adjustment is 0.9, the pH value of the reaction slurry after adjustment is constant for 15 minutes after each downward pH value adjustment, aging is started after the second gelling reaction is finished, the aging temperature is 75 ℃, the pH value is controlled to be 7.7, and the aging time is 3.6 hours, thus obtaining the precipitate slurry II with tungsten, nickel, molybdenum, silicon and aluminum. Filtering the aged slurry, drying the filter cake at 110 ℃ for 10 hours, rolling, and extruding strips into a cylinder. Washing with deionized water at room temperature Washing to neutrality. The washed wet strips were then dried at 180℃for 8.0 hours. The dried material was calcined at 500℃for 4 hours to obtain catalyst F. The catalyst composition and the main properties are shown in Table 1.

Comparative example 1

Reference G, identical in composition to the catalyst of example 1, was prepared as follows:

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. Old after the end of the gel formationThe mixture was aged for 2 hours at a temperature of 75℃and the pH at the time of aging was controlled at 7.6. 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 was added to the tank during the second step of gelling) and catalyst composition.

Respectively adding nickel chloride, ammonium molybdate and oleyl alcohol polyoxyethylene ether into a dissolution 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 calculated weight concentration is 30g/L, and the mole ratio of the oleyl alcohol polyoxyethylene ether to the Mo in the mixed solution A is 0.8. 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. the solution A and ammonia water (10% by weight concentration) were added dropwise to the reaction tank 1 in parallel to carry out the first gelling reaction, and when the remaining volume of the mixed solution A was 1/3, the gelling was stopped and left standing for 15 minutes, and then the remaining mixed solution A and the diluted water glass Solution (SiO) ₂ The weight concentration of (2) is 30 g/L) is continuously carried out parallel flow gel forming until the reaction is finished, the gel forming temperature is kept at 62 ℃, the pH value is controlled at 7.8 when the reaction is finished, the gel forming time is controlled at 1.0 hour, the aging is carried out after the reaction is finished, the aging temperature is 75 ℃, the aging pH value is controlled at 7.6, and the aging is carried out for 1.5 hours, thus obtaining the precipitate slurry I containing nickel, molybdenum and silicon. Adding 500mL of deionized water into a reaction tank 2, adding a 12wt% sodium hydroxide solution, a nickel-containing, molybdenum-containing and silicon-containing precipitate 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 to be 7.8 after finishing the final pH value by 5 times of downward adjustment, wherein the pH value of the reaction slurry after each downward adjustment is 1.0, keeping the pH value of the reaction slurry after adjustment constant for 10 minutes after each downward adjustment, starting aging after the second gelling reaction, controlling the pH value at 8.0 at the aging temperature of 75 ℃, and performing aging for 3.0 hours to obtain a tungsten-containing, nickel-containing, molybdenum-containing, silicon-containing and aluminum-containing precipitate slurry II. 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: will first Drying the material at 80 ℃ for 6.0 hours, spraying deionized water on the dried material, then drying, repeatedly 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. The dried material was calcined at 500 ℃ for 4 hours to obtain 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, aluminum chloride solution and oleyl alcohol polyoxyethylene ether into a dissolution 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 calculated weight concentration is 30g/L, and the mole ratio of the oleyl alcohol polyoxyethylene ether to the Mo in the mixed solution A is 0.8. 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. the solution A is put into a reaction tank 1, the mixed solution A and ammonia water (the weight concentration is 10%) are added into the reaction tank 1 in parallel to carry out a first gel forming reaction, the gel forming temperature is kept at 62 ℃, the pH value is controlled at 7.8 when the reaction is finished, the gel forming time is controlled at 1.0 hour, and after the reaction is finished, the aging is carried out, the aging temperature is 75 ℃, and the aging is carried outThe pH value is controlled at 7.6, and the aging is carried out for 1.5 hours, thus obtaining the precipitate slurry I containing nickel, molybdenum and aluminum. Adding 500mL of deionized water and 30mL of soybean oil into a reaction tank 2, adding a sodium hydroxide solution with the concentration of 12wt%, nickel-containing, molybdenum-containing and aluminum precipitate slurry I and a mixed solution B into the reaction tank 2 in parallel to perform a second gel forming reaction, maintaining the gel forming temperature at 60 ℃, initially controlling the pH value to be 12.8, adjusting the final pH value to be 7.8 after finishing by 5 times of downward adjustment of the pH value, keeping the pH value of the adjusted reaction slurry constant for 10 minutes after each downward adjustment of the pH value to be 1.0, starting aging after finishing the second gel forming reaction, controlling the aging temperature at 75 ℃, controlling the pH value to be 8.0, and aging for 3.0 hours to obtain the slurry II containing tungsten, nickel, molybdenum and 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 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 4. The evaluation process conditions and the evaluation results of the catalyst activity are shown in Table 5. 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 6.

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 can still obtain diesel oil with the sulfur content smaller than 10 mu g/g 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	24	30	26	28	32
WO ₃ ，wt%	28	24	18	20	15	18
							MoO ₃ ，wt%	15	16	14	18	20	13
SiO ₂ ，wt%	15	18	20	17	19	16
							Al ₂ O ₃ ，wt%	20	18	18	19	18	21
Specific surface area, m ² /g	252	239	248	261	225	222
							Pore volume, mL/g	0.364	0.345	0.356	0.378	0.328	0.322
Catalyst particle size, mm	1.63	1.74	1.28	1.65	1.95	1.74
							Cross section of catalyst particles catalyst of different layer thicknesses, R being the catalyst particle size
Outer surface layer	0.31R	0.29R	0.30R	0.32R	0.32R	0.29R
							Intermediate layer	0.40R	0.39R	0.40R	0.38R	0.37R	0.42R
Central core layer	0.29R	0.32R	0.30R	0.30R	0.31R	0.29R
							Average pore diameter of outer surface layer, nm	13.5	12.9	13.2	14.4	5.4	5.3
Average pore diameter of intermediate layer，nm	8.6	8.0	8.4	9.2	5.4	5.3
							Central core average pore diameter, nm	5.8	5.5	5.6	6.1	5.4	5.3
The thickness of the shell accounts for the proportion of the total thickness of the core shell, percent	46	44	40	40	31	39

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	35
Specific surface area, m ² /g	188	174	205	214	250
						Pore volume, mL/g	0.284	0.301	0.245	0.318	0.360
Catalyst particle size, mm	1.62	1.63	1.61	1.63	1.64
						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	0.30R	0.33R
						Intermediate layer	0.40R	0.40R	0.41R	0.41R	0.37R
Central core layer	0.27R	0.29R	0.27R	0.29R	0.30R
						Average pore diameter of outer surface layer, nm	4.3	4.5	4.6	11.5	13.4
Average pore diameter of intermediate layer, nm	4.3	4.5	4.6	7.4	8.3
						Central core average pore diameter, nm	4.3	4.5	4.6	5.3	5.7
The thickness of the shell accounts for the proportion of the total thickness of the core shell, percent	-	-	-	-	46

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	12	17	16	19	22
							MoO ₃ ，wt%	15	16	14	18	20	13
SiO ₂ ，wt%	15	18	20	17	19	16
							WO ₃ ，wt%	-	-	-	-	-	-
Al ₂ O ₃ ，wt%	-	-	-	-	-	-
							Composite oxide composition in shell
NiO，wt%	8	12	13	10	9	10
							WO ₃ ，wt%	28	24	18	20	15	18
Al ₂ O ₃ ，wt%	20	18	18	19	18	21
							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)

Catalyst numbering	J	K
			Composite oxide composition in core
NiO，wt%	10	14
			MoO ₃ ，wt%	10	15
SiO ₂ ，wt%	8	-
			WO ₃ ，wt%	8	-
Al ₂ O ₃ ，wt%	7	15
			Composite oxide composition in shell
NiO，wt%	12	8
			WO ₃ ，wt%	20	28
Al ₂ O ₃ ，wt%	13	20
			MoO ₃ ，wt%	5	-
SiO ₂ ，wt%	7	-

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	7.6	7.9	8.1	8.0	8.3
Particle size distribution of core-shell composite oxide particles,%
						Particle size of less than 5nm	10.21	9.99	9.23	9.52	9.14
Particle diameter of 5nm-10nm	80.36	79.87	79.21	79.32	79.06
						Particle size of more than 10nm	9.43	10.14	11.56	11.16	11.80

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	8.0	28.6	19.6	23.2	21.0	7.8
Particle size distribution of core-shell composite oxide particles,%
							Particle size of less than 5nm	9.58	1.12	1.53	1.08	2.92	10.05
Particle diameter of 5nm-10nm	79.38	4.82	8.01	6.09	8.32	79.96
							Particle size of more than 10nm	11.04	94.06	90.46	92.83	88.76	9.99

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	10.4	10.7	11.2	11.0	11.5
Particle size distribution of core-shell composite sulfide particles, percent
						Particle size of less than 8nm	12.85	12.49	12.04	12.23	11.86
Particle diameter of 8nm-13nm	77.67	77.32	76.29	76.41	76.15
						Particle size of greater than 13nm	9.48	10.19	11.67	11.36	11.99

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	10.9	38.3	25.4	29.5	27.1	10.6
Particle size distribution of core-shell composite sulfide particles, percent
							Particle size of less than 8nm	12.20	0.92	1.25	1.13	2.09	12.48
Particle diameter of 8nm-13nm	77.07	2.53	3.89	3.36	8.35	77.45
							Particle size of greater than 13nm	10.73	96.55	94.86	95.51	89.56	10.07

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 timeVolume 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	0.8639	0.8640	0.8640	0.8641	0.8698	0.8671
							Distillation range, DEG C	170-366	168-366	166-366	174-366	176-374	168-371
S，µg/g	6.0	6.4	6.6	7.6	148.6	28.8
							N，µg/g	2.8	3.0	3.2	3.5	61.5	12.6
Yield of diesel oil, percent	99.0	99.2	99.0	99.4	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 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
Oil density (20 ℃ C.) g/cm was produced ³	0.8703	0.8655	0.8667	0.8665	0.8647	0.8642
							Distillation range, DEG C	178-372	164-370	169-370	172-371	170-368	168-366
S，µg/g	135.8	32.6	43.8	40.7	16.4	7.9
							N，µg/g	49.2	11.9	22. 5	21.9	7.1	3.7
Yield of diesel oil, percent	94.0	99.1	98.9	99.0	99.1	99.2

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	6.0	6.4	6.6	7.6	148.6	51.8
							C ₁ -DBT，µg/g	0	0	0	0	12.1	3.4
4- MDBT，µg/g	1.6	1.7	1.7	2.0	30.2	11.3
							6-MDBT，µg/g	1.8	1.9	2.0	2.2	40.6	13.8
4，6- DMDBT，µg/g	2.6	2.8	2.9	3.4	65.7	23.3

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
							ReactionTemperature/. Degree.C	365	365	380	387	380	387
Sulfur content in hydrorefining oil, mug/g	135.8	32.6	43.8	40.7	16.4	7.9
							C ₁ -DBT，µg/g	9.9	0	0	0	0	0
4- MDBT，µg/g	26.7	8.8	12.3	12.1	4.6	2.0
							6-MDBT，µg/g	38.3	8.1	11.6	9.8	4.0	2.2
4，6- DMDBT，µg/g	60.9	15.7	19.9	18.8	7.8	3.7

Claims

1. A method for preparing a hydrofining catalyst, comprising:

2. A method according to claim 1, characterized in that: in the step (1), the organic auxiliary agent is a polyoxyethylene nonionic surfactant; one or more selected from fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether and dodecylamine polyoxyethylene ether; the molar ratio of the mole number of the organic auxiliary agent to the mole number of Mo in the mixed solution A is 0.3-2.5: 1, preferably 0.4 to 1.8:1.

3. a method according to claim 2, characterized in that: the fatty alcohol polyoxyethylene ether is one or more selected from C16-18 alcohol polyoxyethylene ether, C12-14 alcohol polyoxyethylene ether, oleyl alcohol polyoxyethylene ether, isomeric decayl alcohol polyoxyethylene ether, octyl phenol polyoxyethylene ether and castor oil polyoxyethylene ether.

4. A method according to claim 1, characterized in that: 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; and/or the number of the groups of groups,

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.

5. A method according to claim 1, characterized in that: the alkaline solution containing silicon in the step (2) is one or more of water glass and silica sol; si in alkaline solution containing silicon as SiO ₂ The weight concentration of the meter is 5-90 g/L.

6. A method according to claim 1, characterized in that: in the step (2), the mixed solution A and the precipitator A are subjected to parallel flow reaction, when the volume of the mixed solution A is still 1/5-1/2, the mixed solution A is kept stand for 10-30 minutes, and then the rest mixed solution A and the alkaline solution containing silicon are continuously subjected to parallel flow precipitation.

7. A method according to claim 1, characterized in that: the conditions of the first glue forming reaction in the step (2) are as follows: the reaction temperature is 30-90 ℃, the pH value is controlled to be 7.0-11.0, and the gel forming reaction time is 0.2-2.5 hours; and/or the number of the groups of groups,

the first aging condition in the step (2) is as follows: the aging temperature is 60-90 ℃, the pH value is controlled to 7.0-11.0 during aging, and the aging time is 0.6-3.0 hours.

8. A method according to claim 1, characterized in that: in the step (3), the volume ratio of the water to the volume of the filter cake of the sediment slurry II of nickel, molybdenum, tungsten, silicon and aluminum in the step (3) is 0.2: 1-6: 1.

9. a method according to claim 1, characterized in that: the oleaginous liquid is unsaturated higher fatty glyceride, preferably one or more of peanut oil, rapeseed oil, cotton seed 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.

10. a method according to claim 1, characterized in that: 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, and the gel forming reaction time is 0.5-6.0 hours; preferably, the pH value is adjusted downwards from an initial value to a final pH value in a fractional manner, wherein the number of times of the adjustment is 2-10 times, preferably 2-8 times; preferably, the time is constant for 0.1-1.2 hours after each down-regulation.

11. A method according to claim 1, characterized in that: the second aging conditions described in step (3) are as follows: the aging temperature is 60-90 ℃, the pH value is controlled to 7.0-11.0 during aging, and the aging time is 2.0-6.0 hours.

12. A method according to claim 1, characterized in that: in the step (4), the process of preparing the hydrofining catalyst from the material obtained in the step (3) comprises the following steps: drying, molding and washing the material obtained in the step (3), and drying and roasting for the second time to obtain a hydrofining catalyst;

the first drying conditions are as follows: drying at 40-150 ℃ for 1-48 hours;

the second drying conditions are as follows: the drying conditions were as follows: drying at 60-280 ℃ for 1-48 hours;

the roasting 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 ℃.

13. The method of claim 12, wherein: the second drying in the step (4) is as follows:

b. spraying water on the material obtained in the step a, wherein the volume ratio of the water to the dry material is 1:4~4:1, then drying at a temperature of 150-280 ℃, preferably 150-250 ℃ 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 ratio of the volume of water added to the volume of the dry material decreases in sequence with increasing drying times.

14. A hydrofinished catalyst prepared according to the process of any one of claims 1-13.

15. A diesel hydrofining method, characterized in that the hydrofining catalyst prepared by the method of any one of claims 1-13 is adopted.

16. The method of claim 15, wherein: the reaction conditions of the diesel hydrofining 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 。