阅读说明：本技术 体相加氢精制催化剂及其制备方法 (Bulk phase hydrofining catalyst and preparation method thereof ) 是由 王海涛 方向晨 王继锋 徐学军 刘东香 李娟� 于 2019-04-18 设计创作，主要内容包括：本发明公开了一种体相加氢精制催化剂及其制备方法。加氢精制催化剂为体相加氢精制催化剂,包括加氢活性金属组分WO<Sub>3</Sub>、NiO和MoO<Sub>3</Sub>以及氧化铝,经硫化后,MoS<Sub>2</Sub>/WS<Sub>2</Sub>的平均堆积层数为6.3~9.5层,MoS<Sub>2</Sub>/WS<Sub>2</Sub>的片层平均晶片片层长度为2.0~3.9nm。制备方法包括：(1)配制含Ni、W组分的溶液A,配制含W、Mo、Al组分的溶液B；(2)将溶液A、有机助剂和偏铝酸钠碱性溶液并流成胶,生成浆液Ⅰ,进行老化、过滤；(3)将滤饼与溶液B混合均匀,得到混合物A,然后向混合物A中滴加氨水进行成胶反应,生成浆液Ⅱ；(4)所得的物料经干燥、成型,再经干燥、焙烧得到体相加氢精制催化剂。该催化剂具有较高加氢脱硫和加氢脱氮反应性能,适宜在柴油馏分超深度加氢脱硫、脱氮反应中应用。(The invention discloses a bulk phase hydrofining catalyst and a preparation method thereof. The hydrofining catalyst is bulk hydrofining catalyst and comprises a hydrogenation active metal component WO 3 NiO and MoO 3 And alumina, after sulfidation, MoS 2 /WS 2 The average number of stacked layers of (2) is 6.3 to 9.5 layers, MoS 2 /WS 2 The average wafer length of the wafer is 2.0 to 3.9 nm. The preparation method comprises the following steps: (1) preparing a solution A containing Ni and W components and preparing a solution B containing W, Mo and Al components; (2) the solution A, the organic auxiliary agent and the sodium metaaluminate alkaline solution are mixed to form glue in parallel, and slurry is generatedAging and filtering the solution I; (3) uniformly mixing the filter cake with the solution B to obtain a mixture A, and then dropwise adding ammonia water into the mixture A to perform gelling reaction to generate slurry II; (4) drying and molding the obtained material, and then drying and roasting to obtain the bulk phase hydrofining catalyst. The catalyst has high hydrodesulfurization and hydrodenitrogenation reaction performance, and is suitable for application in ultra-deep hydrodesulfurization and denitrogenation reactions of diesel oil fractions.)

1. A hydrofining catalyst is a bulk hydrofining catalyst, which is characterized in that: the composition comprises a hydrogenation active metal component WO₃NiO and MoO₃The total content of Ni, W and Mo in terms of oxides is 40-95% and the content of alumina is 5-60% on the basis of the weight of the oxidation state hydrofining catalyst; the molar ratio of W/Mo is 1: 10-8: 1, the molar ratio of Ni/(Mo + W) is 1: 12-12: 1; after vulcanization, MoS₂/WS₂The average number of stacked layers of (2) is 6.3 to 9.5 layers, MoS₂/WS₂The average wafer length of the wafer is 2.0 to 3.9 nm.

2. The hydrofinishing catalyst according to claim 1, characterized in that: after vulcanization, MoS₂/WS₂The number of stacked layers is distributed as follows: the average stacking layer number is 6.3-9.5, and the number of the laminated layers with the stacking layer number of 6.0-10.0 accounts for 68-90% of the total laminated layers; the average length of the lamella is 2.0-3.9 nm, and the number of the lamellas with the lamella length of 2.0-3.5 nm accounts for 60.0-90.0% of the total number of the lamellas.

3. The hydrofinishing catalyst according to claim 1, characterized in that: after vulcanization, MoS₂/WS₂The distribution of the number of stacked layers is specifically as follows: the number of the layers of the composite material is less than 3.0 and accounts for 1-6% of the total number of the layers of the composite material, the number of the layers of the composite material is 3.0-6.0 and accounts for 2-10% of the total number of the layers of the composite material, the number of the layers of the composite material is 6.0-10.0 and accounts for 68-90% of the total number of the layers of the composite material, and the number of the layers of the composite material is more than 10.0 and accounts for 3-18% of the total.

4. The hydrofinishing catalyst according to claim 1, characterized in that: after vulcanization, MoS₂/WS₂The lamella length distribution is specifically as follows: the number of the lamella with the length of less than 2.0nm accounts for 3.0-15.0% of the total number of the lamellae, the number of the lamella with the length of 2.0-less than 3.5nm accounts for 80-90.0% of the total number of the lamellae, the number of the lamella with the length of 3.5-5.0 nm accounts for 1.0-10.0% of the total number of the lamellae, and the number of the lamella with the length of more than 5.0nm accounts for 0.2-5.0% of the total number of the lamellae.

5. The hydrofinishing catalyst according to claim 1, characterized in that: the specific surface area is 180-550 m²The pore volume is 0.20 to 0.85 mL/g.

6. A method for preparing a bulk phase hydrofining catalyst is characterized by comprising the following steps: (1) preparing a solution A containing Ni and W components and preparing a solution B containing W, Mo and Al components; (2) adding the solution A, the organic assistant and the sodium metaaluminate alkaline solution into a reaction tank in a concurrent flow manner for gelling reaction to generate slurry I containing Ni, W and Al precipitates, and aging and filtering the obtained slurry I; (3) uniformly mixing the filter cake obtained in the step (2) with the solution B to obtain a mixture A, then dropwise adding ammonia water into the mixture A to perform gelling reaction to generate slurry II containing Ni, Mo, W and Al precipitates, and then aging; (4) and (4) drying, forming and washing the material obtained in the step (3), and then drying and roasting to obtain the bulk phase hydrofining catalyst.

7. The method of claim 6, wherein: in the solution A in the step (1), the mass concentration of Ni in NiO is 3-90 g/L, and the mass concentration of W in WO₃The measured mass concentration is 2-70 g/L; in solution B, W is as WO₃The mass concentration is 2-70 g/L, and Mo is MoO₃The mass concentration is 3-80 g/L, Al is Al₂O₃The mass concentration is 2-60 g/L.

8. The method of claim 6, wherein: the organic auxiliary agent in the step (2) is a carboxylic acid polymer and/or organic phosphonic acid; the molecular weight of the carboxylic acid polymer is 400-5000, and the carboxylic acid polymer is selected from one or more of polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid, polyepoxysuccinic acid, acrylic acid-hydroxypropyl acrylate copolymer or maleic acid-acrylic acid copolymer; the organic phosphonic acid is selected from one or more of ethylenediamine tetramethylene phosphonic acid, hydroxyethylidene diphosphonic acid, polyalcohol phosphonate, polyaminopolyether methylene phosphonic acid, 1,2, 4-tricarboxylic acid-2-phosphonic butane, hydroxyphosphonoacetic acid, aminotrimethylene phosphonic acid or diethylenetriamine pentamethylene phosphonic acid.

9. The method of claim 6, wherein: the molar ratio of the addition amount of the organic auxiliary agent in the step (2) to W in the solution A is 0.8: 1-3: 1, preferably 1: 1-2.5: 1.

10. the method of claim 6, wherein: step (2) in the step (2), the weight of the hydrogenation active metal introduced into the bulk phase hydrofining catalyst through the solution A accounts for 35-80% of the weight of the hydrogenation active metal in the bulk phase hydrofining catalyst.

11. The method of claim 6, wherein: step (2) the concentration of the sodium metaaluminate alkaline solution in the step (2) is Al₂O₃The amount is 2-60 g/L.

12. The method of claim 6, wherein: step (2) the gelling reaction conditions are as follows: the reaction temperature is 20-90 ℃, the pH value is 6.0-9.0, and the gelling time is 0.2-2.0 hours.

13. The method of claim 6, wherein: the aging conditions in the step (2) are as follows: the aging temperature is 40-90 ℃, the pH value during aging is 6.0-8.0, and the aging time is 0.1-1.0 hour.

14. The method of claim 6, wherein: the gelling reaction conditions in the step (3) are as follows: the reaction temperature is 20-90 ℃, the pH value is 7.5-11.0, and the gelling time is 0.5-4.0 hours.

15. The method of claim 6, wherein: the aging conditions in the step (3) are as follows: the aging temperature is 40-90 ℃, the pH value during aging is 7.5-11.0, and the aging time is 1.5-6.0 hours; the aged pH of step (3) is at least 0.5 higher than the aged pH of step (2).

16. The method of claim 6, wherein: the bulk phase hydrofining catalyst obtained in the step (4) is an oxidation state bulk phase hydrofining catalyst, and is vulcanized by a conventional method before use, wherein the conditions are as follows: 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^-1And the vulcanization time is 3-24 h.

Technical Field

The invention relates to a hydrogenation catalyst and a preparation method thereof, in particular to a high-activity bulk-phase hydrofining catalyst and a preparation method thereof.

Background

The bulk phase catalyst is usually prepared by a coprecipitation method, active metal components are taken as main components, the active metal components are usually VIB group metal elements (Mo and W) and VIII group metal elements (Ni), active metal atoms are mutually staggered to form channels, generated vacancy defects are crossed or mixed and stacked, and the vacancy defects of the active metals provide reaction active centers for reactant molecules. The bulk phase catalyst with excellent hydrodesulfurization, hydrodenitrogenation and hydrogenation saturation performances is mainly characterized in that the catalytic activity of the bulk phase catalyst is greatly improved by increasing the density of the active centers on the catalyst. The hydrogenation activity of the bulk phase catalyst has a great relationship with the hydrogenation active phase morphology, and the good active phase morphology can generate more active centers.

The active metal content of the bulk phase hydrogenation catalyst prepared by the coprecipitation method can reach more than 60 percent, the limitation of the metal content can be eliminated, the activity of the catalyst is greatly increased compared with that of a supported catalyst, and the bulk phase catalyst has excellent hydrogenation activity, can produce ultra-low sulfur diesel, can resist severe operating environment and ensures the operating period of the device.

CN1951561A discloses a method for preparing hydrogenation catalyst by coprecipitation, the catalyst adopts active metal acid solution to react with precipitator to generate precipitate containing active metal, MoO is added into the slurry of the precipitate₃To obtain a bulk catalyst.In the process of preparing bulk catalyst by the method, molybdenum oxide and Ni_xW_yO_zThe composite oxide is directly pulped and mixed, so that the active metal is excessively accumulated, the number of active phases is reduced, and the utilization rate of the active metal is reduced.

CN103861609A discloses a preparation method of a non-supported high-activity hydrogenation catalyst. The method comprises the steps of firstly preparing an acidic solution A containing a metal compound and an alkaline solution B containing at least one silicon source or aluminum source, reacting the two solutions to obtain slurry, and carrying out aging, suction filtration, washing, drying, molding and roasting treatment on the slurry to obtain the catalyst. The method does not change the active metal dispersibility of the bulk phase catalyst, the number of active phases is not obviously increased, and the utilization rate of the metal is not improved.

CN106311259A discloses a gasoline selective hydrodesulfurization bulk phase catalyst, which is prepared by carrying out coprecipitation reaction on a soluble salt solution containing VIII group metal and a solution of an alkaline precipitator to obtain a catalyst precursor of hydroxyl salt or basic carbonate with a layered structure, carrying out anion exchange reaction on a soluble salt solution of VIB group metal and the obtained slurry of the catalyst precursor, and separating, drying and roasting to obtain a mixed metal oxide, wherein the obtained catalyst has a layered structure, but still has the defects of uneven dispersion of active metal, few effective active centers and poor utilization rate of the active metal.

In the existing technology for preparing bulk phase catalyst by coprecipitation method, the dispersion of active metal of bulk phase catalyst is regulated and controlled by adjusting the gel-forming and aging conditions in the preparation process and adding inorganic auxiliary agent or organic auxiliary agent to improve the activity of catalyst. However, the adjustment of different conditions was carried out on the active phase (MoS) in the bulk catalyst after the catalyst had been sulfided₂/WS₂) The influence of the morphology of (a) shows a significant difference, resulting in a significant difference in the number of hydrogenation active centers that can be provided by bulk catalysts prepared under different conditions.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a bulk phase hydrofining catalyst and a preparation method thereof. The catalyst prepared by the method is a bulk phase hydrofining catalyst, has more effective active phases, stronger promotion function among the active phases and higher hydrodesulfurization and hydrodenitrogenation reaction performances, is suitable for application in ultra-deep hydrodesulfurization and denitrogenation reactions of diesel fractions, and is particularly used for treating diesel raw materials with high nitrogen and high sulfur content.

The hydrofining catalyst is a bulk hydrofining catalyst and comprises a hydrogenation active metal component WO₃NiO and MoO₃And alumina, after sulfidation, MoS₂/WS₂The average number of stacked layers of (2) is 6.3 to 9.5 layers, preferably 6.5 to 9.5 layers, MoS₂/WS₂The average wafer length of the wafer is 2.0 to 3.9nm, preferably 2.0 to 3.5 nm.

In one aspect, the hydrofining catalyst provided by the invention is an oxidation state hydrofining catalyst.

The hydrofining catalyst provided by the invention is a sulfide-state bulk hydrofining catalyst, and comprises W, Ni hydrogenation active metal components, Mo, alumina and MoS₂/WS₂The average number of stacked layers of (2) is 6.3 to 9.5 layers, MoS₂/WS₂The average length of the lamella is 2.0-3.9 nm; the following are preferred: MoS₂/WS₂The average number of stacked layers of (2) is 6.5 to 9.5 layers, MoS₂/WS₂The average length of the lamella is 2.0-3.5 nm.

The vulcanized hydrofining catalyst provided by the invention can be obtained by vulcanizing the oxidized hydrofining catalyst. The hydrofining catalyst provided by the invention has the total content of Ni, W and Mo in terms of oxides of 40-95%, preferably 50-85%, and the content of alumina of 5-60%, preferably 15-50%, based on the weight of the oxidation state hydrofining catalyst.

In the hydrofining catalyst of the invention, the molar ratio of W/Mo is 1: 10-8: 1, preferably 1: 8-5: 1, the molar ratio of Ni/(Mo + W) is 1: 12-12: 1, preferably 1: 8-8: 1.

according to the invention, the sulfurization is to convert the active metal component W, Ni and the oxide of Mo into corresponding sulfide, so as to obtain the sulfurized hydrofining catalyst, and the sulfurization degree of each active metal W, Ni and Mo in the catalyst is not lower than 80%.

The hydrogenation refining catalyst of the invention, after being vulcanized, MoS₂/WS₂The number of stacked layers is distributed as follows: the average stacking layer number is 6.3-9.5, preferably 6.5-9.5, and the number of sheets with the stacking layer number of 6.0-10.0 accounts for 68-90%, preferably 70-85% of the total number of sheets; the average length of the lamella is 2.0-3.9 nm, preferably 2.0-3.5 nm, and the number of the lamellas with the lamella length of 2.0-3.5 nm accounts for 60.0% -90.0%, preferably 65.0% -87.0% of the total number of the lamellas.

The hydrogenation refining catalyst of the invention, after being vulcanized, MoS₂/WS₂The distribution of the number of stacked layers is specifically as follows: the number of the layers of the composite material is less than 3.0 and accounts for 1-6% of the total number of the layers of the composite material, the number of the layers of the composite material is 3.0-6.0 and accounts for 2-10% of the total number of the layers of the composite material, the number of the layers of the composite material is 6.0-10.0 and accounts for 68-90% of the total number of the layers of the composite material, and the number of the layers of the composite material is more than 10.0 and accounts for 3-18% of the total.

The hydrogenation refining catalyst prepared by the method of the invention is sulfurized and then MoS₂/WS₂The lamella length distribution is specifically as follows: the number of the lamella with the length of less than 2.0nm accounts for 3.0-15.0% of the total number of the lamellae, the number of the lamella with the length of 2.0-less than 3.5nm accounts for 80-90.0% of the total number of the lamellae, the number of the lamella with the length of 3.5-5.0 nm accounts for 1.0-10.0% of the total number of the lamellae, and the number of the lamella with the length of more than 5.0nm accounts for 0.2-5.0% of the total number of the lamellae.

The hydrofining catalyst has the following properties: the specific surface area is 180-550 m²The pore volume is 0.20 to 0.85 mL/g.

The preparation method of the hydrofining catalyst comprises the following steps:

(1) preparing a solution A containing Ni and W components and preparing a solution B containing W, Mo and Al components;

(2) adding the solution A, the organic assistant and the sodium metaaluminate alkaline solution into a reaction tank in a concurrent flow manner for gelling reaction to generate slurry I containing Ni, W and Al precipitates, and aging and filtering the obtained slurry I;

(3) uniformly mixing the filter cake obtained in the step (2) with the solution B to obtain a mixture A, then dropwise adding ammonia water into the mixture A to perform gelling reaction to generate slurry II containing Ni, Mo, W and Al precipitates, and then aging;

(4) and (4) drying, forming and washing the material obtained in the step (3), and then drying and roasting to obtain the bulk phase hydrofining catalyst.

In the method, in the solution A in the step (1), the mass concentration of Ni in NiO is 3-90 g/L, preferably 5-80 g/L, and W in WO₃The mass concentration is 2-70 g/L, preferably 5-60 g/L. In solution B, W is as WO₃The mass concentration is 2-70 g/L, preferably 4-60 g/L, Mo is MoO₃The mass concentration is 3-80 g/L, preferably 2-60 g/L, Al is Al₂O₃The mass concentration is 2-60 g/L, preferably 3-50 g/L. When preparing the solution A, the commonly adopted nickel source can be one or more of nickel sulfate, nickel nitrate and nickel chloride; the tungsten source generally employed is ammonium metatungstate. When preparing the solution B, the tungsten source generally used is ammonium metatungstate, the molybdenum source is ammonium molybdate, and the aluminum source may be one or more of aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum acetate, and the like.

In the method, the organic auxiliary agent in the step (2) is a carboxylic acid polymer and/or an organic phosphonic acid. The molecular weight of the carboxylic acid polymer is 400-5000, and the carboxylic acid polymer is selected from one or more of polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid, polyepoxysuccinic acid, acrylic acid-hydroxypropyl acrylate copolymer or maleic acid-acrylic acid copolymer, and preferably one or more of polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid or polyepoxysuccinic acid. The organic phosphonic acid is selected from one or more of ethylenediamine tetramethylene phosphonic acid, hydroxyethylene diphosphonic acid, polyol phosphonate, polyaminopolyether methylene phosphonic acid, 1,2, 4-tricarboxylic acid-2-phosphonobutane, hydroxyphosphonoacetic acid, aminotrimethylene phosphonic acid or diethylenetriamine pentamethylene phosphonic acid, preferably one or more of ethylenediamine tetramethylene phosphonic acid, hydroxyethylene diphosphonic acid or aminotrimethylene phosphonic acid. The molar ratio of the added amount of the organic auxiliary agent to W in the solution A is 0.8: 1-3: 1, preferably 1: 1-2.5: 1. the organic auxiliary agents can be added separately and concurrently or can be added when preparing the solution A.

In the method of the invention, the weight of the hydrogenation active metal introduced into the bulk hydrofining catalyst through the solution A in the step (2) accounts for 35-80%, preferably 51-75% of the weight of the hydrogenation active metal in the bulk hydrofining catalyst. In the step (3), the weight of the hydrogenation active metal introduced into the bulk phase hydrofining catalyst through the solution B accounts for 20-65%, preferably 25-49% of the weight of the hydrogenation active metal in the bulk phase hydrofining catalyst.

In the method, the concentration of the sodium metaaluminate alkaline solution in the step (2) is Al₂O₃The amount is 2 to 60g/L, preferably 3 to 50 g/L.

In the method, the reaction conditions of the gelling reaction in the step (2) are as follows: the reaction temperature is 20-90 ℃, preferably 30-70 ℃, the pH value is controlled to be 6.0-9.0, preferably 6.5-8.2, and the gelling time is 0.2-2.0 hours, preferably 0.3-1.5 hours.

In the method of the present invention, the aging conditions in step (2) are as follows: the aging temperature is 40-90 ℃, preferably 50-80 ℃, the pH value during aging is controlled to be 6.0-8.0, preferably 6.5-7.5, and the aging time is 0.1-1.0 hour, preferably 0.2-0.8 hour. The aging is generally carried out with stirring.

In the method, the mass percentage concentration of the ammonia water in the step (3) is 5-15%.

In the method, the reaction conditions of the gelling reaction in the step (3) are as follows: the reaction temperature is 20-90 ℃, preferably 30-80 ℃, the pH value is controlled to be 7.5-11.0, preferably 7.5-9.5, and the gelling time is 0.5-4.0 hours, preferably 1.0-3.0 hours.

In the method of the present invention, the aging conditions in step (3) are as follows: the aging temperature is 40-90 ℃, preferably 50-80 ℃, the pH value during aging is controlled to be 7.5-11.0, preferably 7.5-9.5, and the aging time is 1.5-6.0 hours, preferably 2.0-5.0 hours. The pH of the aging of step (3) is at least 0.5 higher, preferably at least 1.0 higher than the pH of the aging of step (2). The aging is generally carried out with stirring.

In the method of the present invention, the drying, shaping and washing in step (4) may be carried out by a method conventional in the art. The drying conditions were as follows: drying at 40-250 ℃ for 1-48 hours, preferably at 50-180 ℃ for 4-36 hours. In the forming process, conventional forming aids, such as one or more of peptizers, extrusion aids, and the like, can be added as required. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like, the extrusion aid is a substance which is beneficial to extrusion forming, such as one or more of sesbania powder, carbon black, graphite powder, citric acid and the like, and the amount of the extrusion aid accounts for 1-10 wt% of the total dry basis of the materials. The washing is generally carried out by washing with deionized water or a solution containing decomposable salts (such as ammonium acetate, ammonium chloride, ammonium nitrate, etc.) until the solution is neutral.

In the method of the present invention, after the step (4) is formed, the drying and baking may be performed by using the conditions conventional in the art, and the drying conditions are as follows: drying for 1-48 hours at 40-250 ℃, wherein the roasting conditions are as follows: roasting at 350-650 ℃ for 1-24 hours, preferably drying under the following conditions: drying for 4-36 hours at 50-180 ℃, wherein the roasting conditions are as follows: roasting at 400-600 ℃ for 2-12 hours.

In the process of the present invention, the catalyst may be in the form of a sheet, a sphere, a cylindrical strip or a shaped strip (clover ), preferably a cylindrical strip or a shaped strip (clover ) as required. The catalyst may be in the form of fine strands of 0.8-2.0 mm diameter and coarse strands > 2.5mm diameter.

In the method of the present invention, the bulk phase hydrofining catalyst obtained in step (4) is an oxidized bulk phase hydrofining catalyst, and before use, the bulk phase hydrofining catalyst can be sulfurized by a conventional method. The sulfidation is the conversion of the active metal W, Ni and Mo oxide to the corresponding sulfide. The vulcanization method can adopt wet vulcanization or dry vulcanization. The sulfurization method adopted in the invention is wet sulfurization, the sulfurization agent is a sulfur-containing substance used in conventional sulfurization, can be an organic sulfur-containing substance, and can also be an inorganic sulfur-containing substance, such as one or more of sulfur, carbon disulfide, dimethyl disulfide and the like, the sulfurized 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, common first-line diesel oil, common second-line diesel oil and the like. The vulcanizing agent is used in such an amount that the degree of vulcanization of each active metal in the hydrorefining catalyst is not less than 80 percent, can be adjusted according to the actual situation, and the dosage of the vulcanizing agent can be 80 to 200 percent, preferably 100 to 150 percent of the theoretical sulfur demand of the complete vulcanization of each active metal in the hydrofining catalyst. The prevulcanization conditions are as follows: 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^-1The vulcanization time is 3-24 h, and the preferable selection is as follows: 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^-1And the vulcanization time is 5-16 h.

In the hydrorefining catalyst of the invention, MoS₂/WS₂The stacking is high in layer number and small in length, particularly the stacking is concentrated on 6.3-9.5 layers, the length of each sheet layer is 2.0-3.9 nm, more effective active phases are generated, the promoting effect between the effective active phases is stronger, the activity is higher, meanwhile, the pore distribution is proper, the mechanical strength is high, the hydrodesulfurization and hydrodenitrogenation reaction performance is higher, and the method is suitable for being applied to ultra-deep hydrodesulfurization and denitrogenation reactions of diesel fractions, especially for treating a diesel raw material with high nitrogen content.

The invention firstly carries out the previous precipitation under the condition that partial W and Ni are used as an aluminum source and a precipitator in an alkaline solution of sodium metaaluminate and organic auxiliaries are added, active metals and the organic auxiliaries are chelated to form a macromolecular reticular complex, so that the particles of precipitates containing W, Ni and Al after the first initial aging are larger and regularly arranged, certain anchoring effect is provided for the hydrogenation active metals which are deposited later, different hydrogenation active metals are orderly deposited, and the growth speed of metal oxide particles and the probability of mutual contact among the active metals are controlled. Meanwhile, in the second step of reaction, ammonia water is dripped into the mixture containing the first primarily aged precipitate and the solution B, the primary precipitate adsorbs transition metal ions, and WO is added under the action of ammonia water₃And MoO₃The product has proper particle size and well-controlled distribution, and increases MoS in bulk catalyst₂/WS₂The stacking layer number, the lamella length are reduced, the morphology of the active phase is optimized, more effective active phases are generated, and the mutual promotion effect is stronger. The method also enables the catalyst to form a more appropriate pore structure, the pore distribution is reasonable, and the specific surface area and the pore volume of the catalyst are improved.

The catalyst is particularly suitable for ultra-deep hydrodesulfurization and denitrification reactions of light distillate oil, has higher hydrodesulfurization and hydrodenitrogenation activities, and particularly has higher hydrodenitrogenation and desulfurization activities when processing heavy diesel oil with high nitrogen and high sulfur content. The sulfur content in the heavy diesel fraction is 1000-20000 mug/g, wherein the sulfur content in thiophene and derivatives thereof accounts for 60-85 wt% of the total sulfur content of the raw material, the nitrogen content is 200-2000 mug/g, and the nitrogen content in carbazole and derivatives thereof accounts for 60-80 wt% of the total nitrogen content of the raw material.

Detailed Description

In the present invention, the specific surface area and the pore volume are measured by a low-temperature liquid nitrogen adsorption method, and the mechanical strength is measured by a side pressure method. In the present invention, MoS in bulk catalyst₂/WS₂The number of stacked layers and the length of the lamella are measured by a transmission electron microscope, wherein in the case of the W-Ni-Mo catalyst, after being vulcanized, the active phase MoS can form the stacked layers₂And WS₂In the invention, MoS is used₂/WS₂Formally representing the active phase. The hydrofining catalyst is vulcanized, namely a non-vulcanized hydrofining catalyst is vulcanized into a vulcanized hydrofining catalyst, namely a vulcanized hydrofining catalyst.

In the present invention, wt% is a mass fraction and v% is a volume fraction. In the invention, the degree of vulcanization is measured by an X-ray photoelectron spectrometer (XPS), and the percentage of the content of the active metal in a vulcanized state in the total content of the active metal is the degree of vulcanization of the active metal.