阅读说明：本技术 一种加氢催化剂及其制备方法 (Hydrogenation catalyst and preparation method thereof ) 是由 刘璐 朱慧红 金浩 杨光 杨涛 于 2019-10-29 设计创作，主要内容包括：本发明公开了一种加氢催化剂及其制备方法,所述催化剂制备方法首先制备湿滤饼物料,然后与工业拟薄水铝石原料混合,加入助挤剂混捏后经干燥、焙烧得到加氢催化剂载体；进一步负载活性金属组分后,经干燥、焙烧后得到加氢催化剂。本发明方法制备的加氢催化剂具有良好的机械性能,强度高,耐磨性能好,尤其适用于沸腾床加氢工艺。所述加氢催化剂的制备方法工艺简单,能耗低,适合于沸腾床催化剂的大规模生产。(The invention discloses a hydrogenation catalyst and a preparation method thereof, wherein the preparation method of the catalyst comprises the steps of firstly preparing a wet filter cake material, then mixing the wet filter cake material with an industrial pseudo-boehmite raw material, adding an extrusion aid, kneading, drying and roasting to obtain a hydrogenation catalyst carrier; and further loading an active metal component, drying and roasting to obtain the hydrogenation catalyst. The hydrogenation catalyst prepared by the method has good mechanical property, high strength and good wear resistance, and is particularly suitable for a fluidized bed hydrogenation process. The preparation method of the hydrogenation catalyst has simple process and low energy consumption, and is suitable for large-scale production of the fluidized bed catalyst.)

1. A method for preparing a hydrogenation catalyst, the method comprising:

(1) adding bottom water into a first-stage reaction kettle, then adding an aluminum-containing alkaline solution and an aluminum-containing acidic solution in a concurrent flow manner for reaction, controlling the pH value of a system to be 4.0-6.0, and dividing reaction effluent into two parts, namely a1 st material flow and a 2 nd material flow;

(2) adding bottom water into a secondary reaction kettle, then enabling the 1 st material flow obtained in the step (1) and alkali liquor to enter the secondary reaction kettle, and controlling the pH value of a system to be 7.0-10.0;

(3) carrying out primary aging treatment on a reaction product obtained in the secondary reaction kettle in the step (2), and filtering to obtain primary filtrate and a primary filter cake;

(4) mixing and pulping the 2 nd material flow obtained in the step (1) and the primary filter cake obtained in the step (3), carrying out secondary aging treatment, filtering to obtain secondary filtrate and a secondary filter cake, and further washing the secondary filter cake to obtain a wet filter cake material;

(5) mixing the wet filter cake material obtained in the step (4) with an industrial pseudo-boehmite raw material, adding an extrusion aid, kneading, drying and roasting to obtain a hydrogenation catalyst carrier;

(6) and (5) loading the active metal component on the catalyst carrier obtained in the step (5), and drying and roasting to obtain the hydrogenation catalyst.

2. The process for producing a hydrogenation catalyst according to claim 1, wherein: the volume of the bottom water in the first-stage reaction kettle in the step (1) is 1/5-1/3 of the volume of the first-stage reaction kettle.

3. The process for producing a hydrogenation catalyst according to claim 1, wherein: the aluminum-containing alkaline solution in the step (1) is alkali metalThe metaaluminate solution of (a), in particular sodium metaaluminate and/or potassium metaaluminate; the concentration of the aluminum-containing alkaline solution is 50-100gAl₂O₃L, a causticity ratio of 1.35 to 2.50, preferably 1.35 to 2.00.

4. The process for producing a hydrogenation catalyst according to claim 1, wherein: the aluminum-containing acidic solution in the step (1) is one or more of aluminum sulfate, aluminum chloride and aluminum nitrate, preferably aluminum sulfate; the concentration of the aluminum-containing acidic solution is 50-100gAl₂O₃/L。

5. The process for producing a hydrogenation catalyst according to claim 1, wherein: the reaction conditions of the first-stage reaction kettle in the step (1) are as follows: the reaction temperature is 60-90 ℃, and the pH is 4.0-6.0.

6. The process for producing a hydrogenation catalyst according to claim 1, wherein: the volume of the 1 st stream in step (1) is from 1/2 to 4/5, preferably from 2/3 to 4/5, based on the volume of the total stream.

7. The process for producing a hydrogenation catalyst according to claim 1, wherein: and (3) the volume of the bottom water in the secondary reaction kettle in the step (2) is 1/5-1/3 of the volume of the second reactor.

8. The process for producing a hydrogenation catalyst according to claim 1, wherein: the alkali liquor in the step (2) is inorganic alkali liquor, specifically one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate and the like, and the concentration of the alkali liquor is 5wt% -10 wt%.

9. The process for producing a hydrogenation catalyst according to claim 1, wherein: the reaction conditions of the secondary reaction kettle in the step (2) are as follows: the reaction temperature is 60-90 ℃, and the pH is 7.0-10.0.

10. The process for producing a hydrogenation catalyst according to claim 1, wherein: the primary aging temperature in the step (3) is 60-100 ℃; the primary aging time is 0.5-6 h.

11. The process for producing a hydrogenation catalyst according to claim 1, wherein: the secondary aging temperature in the step (4) is 60-100 ℃; the secondary aging time is 0.5-6 h.

12. The process for producing a hydrogenation catalyst according to claim 1, wherein: and (4) the dry basis content of the washed wet filter cake material in the step (4) is 20-40 wt%.

13. The process for producing a hydrogenation catalyst according to claim 1, wherein: the drying condition in the step (5) is drying for 2-6h at the temperature of 110-150 ℃; the roasting temperature is 500-950 ℃, and the roasting time is 2-6 h.

14. The process for producing a hydrogenation catalyst according to claim 1, wherein: the industrial pseudo-boehmite powder in the step (5) accounts for 80-95wt% of the kneaded material, preferably 80-90 wt%.

15. The process for producing a hydrogenation catalyst according to claim 1, wherein: the dry basis content of the mixed material of the wet filter cake material obtained in the step (5) and the industrial pseudo-boehmite raw material is 30-40 wt%.

16. The process for producing a hydrogenation catalyst according to claim 1, wherein: in the step (5), the extrusion aid is one or more of sesbania powder, cellulose, citric acid and the like.

17. The process for producing a hydrogenation catalyst according to claim 1, wherein: the method for loading the active metal component in the step (6) adopts an impregnation method and a kneading method, and preferably adopts an impregnation method.

18. The process for producing a hydrogenation catalyst according to claim 1, wherein: the method for loading the active metal component in the step (6) adopts a spray dipping method, a saturated dipping method or a supersaturated dipping method.

19. The process for producing a hydrogenation catalyst according to claim 1, wherein: the method for loading the hydrogenation active metal component on the carrier in the step (6) is an impregnation method, and comprises the steps of preparing a solution containing a hydrogenation active metal compound, impregnating the carrier with the solution, and then drying, roasting or not roasting, wherein the hydrogenation active metal component is one or more of VIB group metals and/or VIII group metals, the concentration of the hydrogenation active metal compound in the solution and the dosage of the solution are such that the content of the VIII group metals in the final catalyst is 1.5-10.0 wt%, preferably 2.0-8.0 wt%, and the content of the VIB group metals is 5.0-25.0 wt%, preferably 10.0-20.0 wt%, calculated by oxides and based on the catalyst.

20. The process for preparing a hydrogenation catalyst as claimed in claim 19, wherein: and (3) the solution of the hydrogenation active metal compound in the step (6) contains a dispersing agent, wherein the dispersing agent refers to one or more of polyethylene glycol, polyvinyl alcohol and Tween.

21. A hydrogenation catalyst, characterised in that it is prepared by a process according to any one of claims 1 to 20.

22. A hydrogenation catalyst as claimed in claim 21, wherein: the hydrogenation catalyst properties were as follows: the pore volume is 0.50-0.80mL/g, the specific surface area is 150-280m²The pore volume of pores with the pore diameter of 6-15nm accounts for 40-70% of the total pore volume, and the pore volume of pores with the pore diameter of more than 100nm accounts for more than 15% of the total pore volume; lateral pressure strength thereof>10N/mm。

Technical Field

The invention belongs to the field of catalytic materials, and particularly relates to a hydrogenation catalyst and a preparation method thereof.

Background

Heavy oil or residual oil contains a large amount of macromolecular aromatic hydrocarbon, and a catalyst is required to have a larger pore passage in the hydrotreating process so as to meet the requirement that the macromolecular aromatic hydrocarbon enters a reaction active region. Usually, macroporous pseudo-boehmite is used as a raw material of a residual oil hydrogenation catalyst carrier, but the carrier prepared by a macroporous material has poor mechanical property and low compressive strength, and in an increasingly important residual oil hydrogenation boiling bed treatment process, the back-mixing flow also puts higher requirements on the wear resistance of the catalyst. However, the macroporous pseudo-boehmite prepared by the existing pseudo-boehmite production process has low peptization index and poor cohesiveness, and when the pseudo-boehmite is used as a hydrotreating catalyst material, the mechanical strength of the catalyst is weak.

CN104646070A discloses a preparation method of a supported hydrotreating catalyst carrier, which enhances the strength of the catalyst carrier by enhancing the bonding force between the catalyst carriers by using a high concentration organic acid as a binder. This method uses high concentration organic acid instead of traditional nitric acid, reducing NOx emissions during calcination, but still requires additional high concentration of acid during support preparation.

CN101450327A discloses a method for preparing an alumina carrier, which focuses on improving the mechanical strength of the alumina carrier. The method is that the monohydrate alumina is heat treated at low temperature, the calcined alumina is mixed with graphite, sodium stearate or aluminum stearate, etc., and water is added to knead evenly. The method adds a step of heat treatment before the preparation of the common carrier, and simultaneously, an auxiliary agent is added, so that the preparation step of the carrier is complicated.

CN101085935A discloses a preparation method of a coal liquefaction oil boiling bed hydrogenation catalyst carrier, wherein the carrier contains 3-10wt% of alumina fiber, and nano-silica can be added, which is mainly used for enhancing the mechanical strength and wear resistance of the carrier and improving the stability of the catalyst taking the carrier as a carrier. The chemical components added in the method are the same as the components of the carrier, no extra substances are introduced, but the alumina fiber needs to be prepared separately or purchased.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a hydrogenation catalyst and a preparation method thereof. The preparation method of the hydrogenation catalyst has simple process and low energy consumption, and is suitable for large-scale production of the fluidized bed catalyst.

In a first aspect, the present invention provides a method for preparing a hydrogenation catalyst, the method comprising the following steps:

(1) adding bottom water into a first-stage reaction kettle, then adding an aluminum-containing alkaline solution and an aluminum-containing acidic solution in a concurrent flow manner for reaction, controlling the pH value of a system to be 4.0-6.0, and dividing reaction effluent into two parts, namely a1 st material flow and a 2 nd material flow;

(2) adding bottom water into a secondary reaction kettle, then enabling the 1 st material flow obtained in the step (1) and alkali liquor to enter the secondary reaction kettle, and controlling the pH value of a system to be 7.0-10.0;

(3) carrying out primary aging treatment on a reaction product obtained in the secondary reaction kettle in the step (2), and filtering to obtain primary filtrate and a primary filter cake;

(4) mixing and pulping the 2 nd material flow obtained in the step (1) and the primary filter cake obtained in the step (3), carrying out secondary aging treatment, filtering to obtain secondary filtrate and a secondary filter cake, and further washing the secondary filter cake to obtain a wet filter cake material;

(5) mixing the wet filter cake material obtained in the step (4) with an industrial pseudo-boehmite raw material, adding an extrusion aid, kneading, drying and roasting to obtain a hydrogenation catalyst carrier;

(6) and (5) loading the active metal component on the catalyst carrier obtained in the step (5), and drying and roasting to obtain the hydrogenation catalyst.

In the preparation method of the hydrogenation catalyst, the volume of the bottom water in the first-stage reaction kettle in the step (1) is 1/5-1/3 of the volume of the first-stage reaction kettle.

In the preparation method of the hydrogenation catalyst, the aluminum-containing alkaline solution in the step (1) is an alkali metal metaaluminate solution, and specifically can be sodium metaaluminate and/or potassium metaaluminate; the concentration of the aluminum-containing alkaline solution is50-100gAl₂O₃L, a caustic ratio (molar ratio of alkali metal oxide to alumina) of 1.35 to 2.50, preferably 1.35 to 2.00.

In the preparation method of the hydrogenation catalyst, the aluminum-containing acidic solution in the step (1) is one or more of aluminum sulfate, aluminum chloride and aluminum nitrate, preferably aluminum sulfate; the concentration of the aluminum-containing acidic solution is 50-100gAl₂O₃/L。

In the preparation method of the hydrogenation catalyst, the reaction conditions of the first-stage reaction kettle in the step (1) are as follows: the reaction temperature is 60-90 ℃, and the pH is 4.0-6.0.

In the above method for preparing a hydrogenation catalyst, the volume of the 1 st stream in the step (1) accounts for 1/2-4/5, preferably 2/3-4/5 of the volume of the total stream.

In the preparation method of the hydrogenation catalyst, the volume of the bottom water in the secondary reaction kettle in the step (2) is 1/5-1/3 of the volume of the second reactor.

In the preparation method of the hydrogenation catalyst, the alkali liquor in the step (2) is inorganic alkali liquor, specifically one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate and the like, and the concentration of the alkali liquor is 5wt% -10 wt%.

In the preparation method of the hydrogenation catalyst, the reaction conditions of the secondary reaction kettle in the step (2) are as follows: the reaction temperature is 60-90 ℃, and the pH is 7.0-10.0.

In the preparation method of the hydrogenation catalyst, the primary aging temperature in the step (3) is 60-100 ℃; the primary aging time is 0.5-6 h.

In the preparation method of the hydrogenation catalyst, the secondary aging temperature in the step (4) is 60-100 ℃; the secondary aging time is 0.5-6 h.

In the preparation method of the hydrogenation catalyst, the dry-basis content of the washed wet filter cake material in the step (4) is 20-40 wt%.

In the preparation method of the hydrogenation catalyst, the drying condition in the step (5) is drying at 110-150 ℃ for 2-6 h; the roasting temperature is 500-950 ℃, and the roasting time is 2-6 h.

In the preparation method of the hydrogenation catalyst, the industrial pseudo-boehmite powder in the step (5) accounts for 80-95wt% of the kneaded material, preferably 80-90 wt%. The dry basis content of the mixed material of the wet filter cake material obtained in the step (5) and the industrial pseudo-boehmite raw material is 30-40 wt%.

In the preparation method of the hydrogenation catalyst, the extrusion aid in the step (5) is one or more of sesbania powder, cellulose, citric acid and the like, and accounts for 1-5wt%

In the preparation method of the hydrogenation catalyst, the kneading in the step (5) can be carried out firstly, and then the drying and roasting treatment is carried out, wherein the molding can be carried out by adopting the existing molding method in the field, and can be cylindrical strip, spherical, dentate spherical, leafy grass and the like.

In the above-mentioned preparation method of the hydrogenation catalyst, the method for supporting the active metal component in the step (6) may be an impregnation method, a kneading method, or the like, and preferably an impregnation method is used. The carrier is prepared by a conventional impregnation method by adopting an impregnation method to load the active metal component, and can adopt a spray impregnation method, a saturated impregnation method or a supersaturated impregnation method. If the method for loading the hydrogenation active metal component on the carrier is an impregnation method, the method comprises the steps of preparing a solution containing a hydrogenation active metal compound and impregnating the carrier with the solution, and then drying, roasting or not roasting, wherein the hydrogenation active metal component is one or more of VIB group metals and/or VIII group metals, calculated by oxides and based on the catalyst, and the concentration of the hydrogenation active metal containing compound in the solution and the dosage of the solution enable the content of the VIII group metals in the final catalyst to be 1.5-10.0 wt%, preferably 2.0-8.0 wt%, and the content of the VIB group metals to be 5.0-25.0 wt%, preferably 10.0-20.0 wt%. The drying conditions include: the temperature is 90-120 ℃, and the time is 1-10 h; the roasting conditions include: the temperature is 300-600 ℃, and the time is 1-10 h.

In the preparation method of the hydrogenation catalyst, the solution of the compound of the hydrogenation active metal in the step (6) contains a dispersant, wherein the dispersant refers to one or more of polyethylene glycol (molecular weight 200-1000), polyvinyl alcohol (molecular weight 100-1000) and tween (tween 60 and tween 80), and the content of the dispersant is 5-15wt% of the oxide formed by the VIB group metal.

In the preparation method of the hydrogenation catalyst, the metal element in the active metal component in the step (6) is from VIII group and/or VIB group, the VIII group active metal is one or more of Ni and Co, and the VIB group active metal is one or more of Mo and W.

The hydrogenation catalyst prepared by the method comprises a carrier and an active metal component, wherein alumina is used as the carrier, the metal element in the active metal component is from VIII group and/or VIB group, the VIII group active metal is one or more of Ni and Co, and the VIB group active metal is one or more of Mo and W. The group VIII metal is present in an amount of 1.5 wt.% to 10.0 wt.%, preferably 2.0 wt.% to 8.0 wt.%, and the group VIB metal is present in an amount of 5.0 wt.% to 25.0 wt.%, preferably 10.0 wt.% to 20.0 wt.%.

The hydrogenation catalyst obtained above had the following properties: the pore volume is 0.50-0.80mL/g, the specific surface area is 150-280m²The pore volume of pores with the pore diameter of 6-15nm accounts for 40-70% of the total pore volume, and the pore volume of pores with the pore diameter of more than 100nm accounts for more than 15% of the total pore volume; lateral pressure strength thereof>10N/mm, the diameter of the catalyst is less than 1.5 mm.

Compared with the prior art, the hydrogenation catalyst and the preparation method thereof have the following advantages:

1. in the preparation method of the hydrogenation catalyst, the carrier is prepared by kneading the industrial pseudo-boehmite and the self-made wet filter cake, the obtained carrier has better mechanical property, high side pressure strength of the carrier and good wear resistance, the self-made filter cake is directly used as part of raw materials for preparing the carrier, the filter cake is not required to be dried, and the energy consumption for preparing the carrier is reduced.

2. In the preparation method of the hydrogenation catalyst, the slurry in the first-stage reaction kettle is further dispersed on large particles formed by primary aging through secondary aging, so that the surface hydroxyl is increased, the peptization of a self-made filter cake is improved, and simultaneously two carrier materials with pore size distribution are formed.

3. In the preparation method of the hydrogenation catalyst, the dispersing agent of the impregnating solution contains an electron-donating group, which can be coordinated with metal ions in the Mo-Ni-P-O impregnating solution to form a complex, and then the complex is coordinated with A1 in the carrier through a polar group³⁺The ions act to promote the dispersion of the metal ions.

Detailed Description

The technical solution of the present invention will be further described below by way of examples and comparative examples, but the present invention is not limited to the following examples. The industrial pseudo-boehmite raw material in the embodiment and the comparative example of the invention is a commercial product, and the specific surface area is 320 m²The volume of pores is 0.98 mL/g, the peptization index is 25 percent, and the dry basis is 70 percent by weight.

Example 1

(1) Preparation of pseudo-boehmite filter cake

Bottom water of reactor volume 1/5 was added to the first order reactor followed by co-current addition of caustic ratio of 1.35 and concentration of 100gAl₂O₃L of sodium metaaluminate solution and 50gAl₂O₃The reaction is carried out on the aluminum sulfate solution/L, the pH value of the system is controlled to be 4.0, the reaction temperature is controlled to be 60 ℃, the reaction effluent is divided into two parts, namely a1 st material flow and a 2 nd material flow, and the 1 st material flow accounts for 2/3 of the reaction effluent; adding bottom water into a secondary reaction kettle, feeding the 1 st material flow and 5.0wt% of sodium carbonate solution into the secondary reaction kettle, and controlling the pH value of the system to be 10.0 and the temperature to be 90 ℃; carrying out primary aging treatment on a reaction product obtained in the secondary reaction kettle at 100 ℃ for 0.5h, and filtering to obtain primary filtrate and a primary filter cake; and mixing and pulping the 2 nd material flow of the first-stage reaction kettle and the primary filter cake, carrying out secondary aging treatment at 100 ℃ for 0.5h, filtering to obtain secondary filtrate and a secondary filter cake, further washing the secondary filter cake, and drying to obtain a wet filter cake material with a dry basis of 32.0 wt%.

(2) Catalyst preparation

Weighing 900g of wet filter cake material (32 wt% on a dry basis) and 100g of industrial pseudo-boehmite raw material, mixing, adding 2.0wt% of sesbania powder, kneading, extruding, molding, drying at 110 ℃ for 6h, and roasting at 700 ℃ for 4h to finally obtain the cylindrical strip-shaped hydrogenation catalyst carrier with the diameter of 1.05mm and the length of 3-6 mm.

53.29g of molybdenum oxide (with the content of 99%), 24.42g of basic nickel carbonate (with the content of 54 wt%), 19.62g of phosphoric acid and 2005.33 g of polyethylene glycol were weighed and heated to prepare 500mL of impregnation solution.

The carrier is impregnated by an isometric impregnation method, and the hydrogenation catalyst A is obtained after drying at 100 ℃ for 10 hours and roasting at 500 ℃ for 2 hours, and the physicochemical properties of the obtained catalyst are shown in Table 1.

Example 2

The other conditions were the same as in example 1, except that the bottom water of the first-stage reactor was adjusted to 1/4, the pH of the second-stage reactor was adjusted to 7.0, the aging temperature of the second-stage aging apparatus was adjusted to 80 ℃, the dry basis of the wet cake material was adjusted to 28wt%, the solid weighing of polyethylene glycol 200 was changed to 7.99g, and catalyst B was obtained, and the physicochemical properties of the obtained catalyst are shown in Table 1.

Example 3

The other conditions are the same as example 1, only the bottom water of the first-stage reaction kettle is adjusted to 1/3 of the volume of the reactor, the aging temperature of the first-stage aging device is adjusted to 60 ℃, the aging time is adjusted to 2.0h, the weighing of the wet filter cake material is changed to 850g, the weighing of the industrial pseudo-boehmite raw material is changed to 150g, the weighing of the polyethylene glycol 200 is changed to 400, the mass of the molybdenum oxide is changed to 100.95g, the mass of the basic nickel carbonate is changed to 34.37g, and the mass of the phosphoric acid is changed to 26.55g, so that the catalyst C is obtained, and the physicochemical properties of the obtained catalyst are listed in Table 1.

Example 4

(1) Preparation of pseudo-boehmite filter cake

Bottom water of reactor volume 1/4 was added to the first order reactor followed by co-current addition of caustic ratio of 2.0 and 50gAl concentration₂O₃Per liter sodium metaaluminate solution and 100gAl₂O₃The reaction is carried out on the aluminum sulfate solution/L, the pH value of the system is controlled to be 6.0, the reaction temperature is controlled to be 90 ℃, the reaction effluent is divided into two parts, namely a1 st material flow and a 2 nd material flow, and the 1 st material flow accounts for 4/5 of the reaction effluent; adding bottom water, feeding the 1 st material flow and 10.0wt% sodium carbonate solution into a secondary reaction kettle, and controlling the pH value of the system to be 8.5 and the temperature to be 60 ℃; the reaction product obtained from the second-stage reaction kettle is subjected to primary aging treatment at the temperature of 90 DEG CFiltering for 6h to obtain primary filtrate and primary filter cake; and mixing and pulping the 2 nd material flow of the first-stage reaction kettle and the primary filter cake, carrying out secondary aging treatment at 60 ℃ for 3 hours, filtering to obtain secondary filtrate and a secondary filter cake, further washing the secondary filter cake, and drying to obtain a wet filter cake material with a dry basis of 25.0 wt%.

(2) Catalyst preparation

Weighing 800g of wet filter cake material (dry basis is 25%) and 200g of industrial pseudo-boehmite raw material, mixing, adding 2.0wt% of sesbania powder, kneading, extruding, molding, drying at 100 ℃ for 8h, and roasting at 600 ℃ for 4h to finally obtain the cylindrical strip-shaped hydrogenation catalyst carrier with the diameter of 1.05mm and the length of 3-6 mm.

38.79g of molybdenum oxide (with the content of 99 percent), 17.78g of basic nickel carbonate (with the content of 54 percent by weight), 14.28g of phosphoric acid and 3.10g of polyethylene glycol 200 solid are weighed and heated to prepare 500ml of impregnation liquid.

The carrier is impregnated by an isometric impregnation method, and the hydrogenation catalyst D is obtained after drying at 100 ℃ for 10 hours and roasting at 500 ℃ for 2 hours, and the physicochemical properties of the obtained catalyst are shown in Table 1.

Example 5

The other conditions are the same as example 4, except that the concentration of the prepared sodium metaaluminate solution is changed to 80g Al₂O₃The caustic ratio of the sodium metaaluminate solution is changed to 1.5, the dry basis of the wet filter cake material is changed to 22%, the weight of the polyethylene glycol 200 is changed to 5mL of Tween 80, the weight of the molybdenum oxide is changed to 139.26g, the weight of the basic nickel carbonate is changed to 25.53g, and the weight of the phosphoric acid is changed to 39.88g, so that a hydrogenation catalyst E is obtained, and the physicochemical properties of the obtained catalyst are listed in Table 1.

Comparative example 1

Weighing 1000g of industrial pseudo-boehmite raw material (dry basis is 70 wt%), mixing, adding 2.0wt% of sesbania powder, kneading, extruding, molding, drying at 110 ℃ for 6h, and roasting at 700 ℃ for 4h to finally obtain a cylindrical strip-shaped hydrogenation catalyst carrier with the diameter of 1.05mm and the length of 3-6 mm;

53.29g of molybdenum oxide (with the content of 99 percent), 24.42g of basic nickel carbonate (with the content of 54 percent by weight), 19.62g of phosphoric acid and 5.33g of polyethylene glycol 200 solid are weighed and heated to prepare 500ml of impregnation liquid.

The carrier is impregnated by an isometric impregnation method, and the hydrogenation catalyst F is obtained after drying at 100 ℃ for 10 hours and roasting at 500 ℃ for 2 hours, and the physicochemical properties of the obtained catalyst are shown in Table 1.

Comparative example 2

The other conditions were the same as in example 1 except that no polyethylene glycol 200 was added during the impregnation solution preparation to obtain a hydrogenation catalyst G, and the physicochemical properties of the obtained catalyst are shown in Table 1.

TABLE 1 physicochemical Properties of the catalyst

As can be seen from table 1: the hydrogenation catalyst prepared by the method has higher lateral pressure strength and good metal dispersion, and is particularly suitable for being used as a heavy oil or residue oil boiling bed hydrogenation catalyst.

The catalyst is subjected to activity evaluation on a Continuous Stirred autoclave (CSTR), the catalyst is filled to 100mL, and the fluidized bed Reactor and the Continuous Stirred Tank Reactor (CSTR) are similar to each other, have good full back-mixing performance and have equivalent reaction kinetic characteristics. Therefore, the CSTR can be used instead of the ebullated bed reactor for catalyst performance evaluation. The properties and evaluation conditions of the raw oil are shown in Table 2. The results of other evaluations, which were compared with the activity of comparative example 1, are shown in Table 3, taking the activity of comparative example 1 as 100.

TABLE 2 Properties and evaluation conditions of the stock oils

TABLE 3 evaluation results of catalysts

In table 3, HDS means hydrodesulfurization, HDCCR means hydrodecarbonization, and HDM (Ni + V) means hydrodemetallization (Ni + V).

As can be seen from table 3: compared with the catalyst prepared by a comparative example, the hydrogenation catalyst prepared by the research increases the impurity removal rate and the conversion rate, and is particularly suitable for being used as a heavy oil or residue oil boiling bed hydrogenation catalyst.