CN109926077B

CN109926077B - Inferior raw material hydro-conversion catalyst and preparation method thereof

Info

Publication number: CN109926077B
Application number: CN201711353763.4A
Authority: CN
Inventors: 朱慧红; 金浩; 孟兆会; 葛海龙; 杨光; 孙素华; 杨涛
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: 2017-12-15
Filing date: 2017-12-15
Publication date: 2021-10-08
Anticipated expiration: 2037-12-15
Also published as: CN109926077A

Abstract

The invention provides an inferior raw material hydro-conversion catalyst and a preparation method thereof, wherein the catalyst comprises an active component and a carrier; the active component is VIB group and/or VIII group metal, and the carrier is alumina. The preparation method comprises the steps of firstly preparing pseudo-boehmite, then obtaining a carrier through molding, drying and roasting, and finally loading active metal components. The catalyst prepared by the method has larger pore volume and specific surface area, and has higher hydrogenation impurity removal activity and conversion rate.

Description

Inferior raw material hydro-conversion catalyst and preparation method thereof

Technical Field

The invention belongs to the field of oil refining, relates to a catalytic material and a preparation method thereof, and particularly relates to a hydroconversion catalyst and a preparation method thereof.

Background

In recent years, crude oil has become increasingly heavier, and market demand for middle distillate products has increased, and demand for residual oil fuels has decreased, making it increasingly attractive to hydroconvert the residual oil to produce high quality products. The boiling bed residual oil hydrogenation process technology has the advantage of dual functions, and the technology can achieve good hydrogenation capacity and can also achieve higher hydrogenation conversion level of residual oil.

The ebullated-bed reactor should have good dynamic balance to maintain the expansion and fluidization uniformity of the catalyst bed to achieve the catalytic hydrogenation reaction balance. This requires that the catalyst should have certain special physicochemical properties, and that the catalyst also has certain requirements on the bulk density, particle shape and particle size distribution, and it is generally considered that the more suitable particle shape is a spherical shape with fine particle size. Spherical particles flow easily and have no corners where sharp asperities are easily broken as in other shapes.

When the boiling bed processes inferior raw materials, such as vacuum residuum, the reactant is mostly a larger molecular compound, and the catalyst should have a sufficiently large pore volume and a suitable pore size distribution so that the reactant molecules can enter the inside of the catalyst and contact with the active center of the inner surface to improve the diffusion performance and contain more impurities. If the pore size is relatively small, the catalyst pore openings will be rapidly plugged, causing catalyst deactivation. If the large holes are large, the surface area is too low, and the abrasion resistance is difficult to meet the requirement. Slightly different from a fixed bed, the boiling bed has higher reaction temperature, and the viscosity of residual oil is obviously reduced, so that the residual oil can more easily enter a catalyst pore channel for reaction, and therefore, the proper pore size distribution is very important for the residual oil hydrogenation of the boiling bed. The property of the carrier material directly determines the pore size distribution of the ebullated bed residue oil hydrogenation catalyst, and therefore, the development of a low-cost carrier material suitable for the ebullated bed residue oil hydrogenation catalyst is a research target.

CN201310495647.1 discloses a preparation method of an ebullated bed catalyst. The patent adopts a carbonization method to prepare the pseudoboehmite, and the reaction is carried out in an impinging stream reactor to strengthen mass transfer. The pseudo-boehmite prepared by the patent does not solve the problem of uneven particles in the gelling process, and the prepared pseudo-boehmite raw material has non-centralized hole distribution.

CN201510306899.4 discloses a carbonization reaction synthesis system and application thereof in the aspect of preparing pseudo-boehmite and a preparation method thereof, comprising the steps of preparing aluminum hydroxide precipitate by a continuous carbonization reaction kettle, aging, washing, filtering and drying, wherein the aluminum hydroxide precipitation system prepared by the continuous carbonization reaction kettle is formed by connecting two or more micro unit carbonization reaction kettles in series, and an aluminum-containing alkaline solution for preparing pseudo-boehmite forms baffling, back mixing and CO in the micro unit carbonization reaction kettles due to resistance force₂And carrying out carbonization reaction on the mixed gas of the slurry and air, and enabling the generated slurry to flow into the next micro unit carbonization reaction kettle from the outlet, repeating the steps and realizing continuous carbonization reaction process. Although the process realizes the continuity of the preparation process, the process is more complex.

CN201010188611.5 discloses a hydrated alumina and its preparation method. The hydrated alumina contains pseudo-boehmite and basic ammonium aluminum carbonate. The method comprises the steps of carrying out contact reaction on sodium metaaluminate and/or sodium aluminate and an acidic solution, and aging mixed slurry obtained after the contact reaction in the presence of an aging agent; the conditions of the contact reaction include: the reaction pH value is 4.5-9, and the reaction temperature is 15-75 ℃; the aging conditions include: the temperature is 20-60 ℃, and the time is 2-6 hours; the aging agent is ammonium carbonate and/or ammonium bicarbonate. The aging process in the process of preparing the aluminum oxide by the patent is complicated.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides an inferior raw material hydro-conversion catalyst and a preparation method thereof. In the method for preparing the hydro-conversion catalyst, two-stage reaction is adopted and a treating agent is introduced when the pseudo-boehmite is prepared, so that the obtained pseudo-boehmite has the characteristics of equal-grain-size crystal grains and high cohesiveness, and the catalyst prepared by taking the alumina prepared by taking the pseudo-boehmite as a precursor as a carrier has the advantages of large pore volume, centralized pore distribution, low abrasion, good hydrogenation performance and the like.

The invention provides a first aspect of a hydroconversion catalyst, which comprises an active component and a carrier; the active component is VIB group metal and/or VIII group metal, based on the weight of the catalyst, the content of the VIB group metal is 8.0-18.0 wt%, preferably 9.0-15.0 wt% calculated by oxide, and the content of the VIII group metal is 1.0-8.0 wt%, preferably 2.0-5.0 wt% calculated by oxide.

In the hydro-conversion catalyst, the VIB group metal is W and/or Mo, and the VIII group metal is Co and/or Ni.

In the hydro-conversion catalyst, the active components are Mo and Ni.

The hydroconversion catalyst of the invention has the following properties: the pore volume is 0.55-0.70 mL/g, the specific surface area is 150-220 m²A concentration of 150 to 200m per gram²/g。

The pore distribution of the hydroconversion catalyst of the invention is as follows: the pore volume of the pores with the pore diameter of less than 8nm accounts for less than 15 percent of the total pore volume, preferably less than 10 percent of the total pore volume, the pore volume of the pores with the pore diameter of 8-15 nm accounts for 60-80 percent of the total pore volume, preferably 70-80 percent of the total pore volume, and the pore volume of the pores with the pore diameter of more than 15nm accounts for 15-25 percent of the total pore volume, preferably 18-25 percent of the total pore volume.

The molar ratio of the surface hydroxyl density of the hydroconversion catalyst to the surface hydroxyl density of the catalyst prepared from the SB powder is 1.1-1.6, preferably 1.2-1.5. The SB powder is a standard sample provided by Sasol company of Germany. The pore volume of the SB powder was 0.5 mL/g.

The particle size of the hydro-conversion catalyst is 0.8-2.0 mm, and the abrasion of the catalyst is less than 1.5wt%, preferably less than 1.0 wt%. In the invention, the abrasion is measured by a fluidized abrasion strength tester. The catalyst can be one or more of spherical, honeycomb, bird nest, tablet or bar (clover, butterfly, cylinder, etc.), and is preferably spherical.

In a second aspect, the present invention provides a preparation method of the above hydroconversion catalyst, including the following steps:

(1) adding water into a first reactor, then adding an alkaline aluminate solution and a first acidic aluminate solution in a continuous parallel flow mode, adjusting the pH value of the solutions to be 3-6.5, preferably 4-6, and obtaining slurry after reaction;

(2) continuously introducing the slurry and the treating agent A into a second reactor, then adding an alkaline solution and a second acidic aluminate solution in a parallel flow manner, adjusting the pH value of the solution to 7-10, preferably 7.5-9, and reacting to obtain a suspension;

(3) filtering, washing and drying the suspension obtained in the step (2) to obtain pseudo-boehmite;

(4) forming, drying and roasting the pseudo-boehmite obtained in the step (3) to obtain a carrier;

(5) and (4) carrying active components on the carrier obtained in the step (4), and drying and roasting to obtain the catalyst.

In the preparation method of the hydroconversion catalyst, the adding amount of water in the first reactor in the step (1) is 1/4-1/2, preferably 1/4-1/3 of the volume of the first reactor.

In the preparation method of the hydro-conversion catalyst, the alkaline aluminate in the step (1) is one or more of sodium metaaluminate and potassium metaaluminate, and preferably sodium metaaluminate.

In the preparation method of the hydro-conversion catalyst, the concentration of the alkaline aluminate solution in the step (1) is 100-250 gAl₂O₃Preferably 150-200 gAl₂O₃The flow rate is 0.5-1L/h.

In the preparation method of the hydro-conversion catalyst, the first acidic aluminate in the step (1) is one or more of aluminum sulfate, aluminum nitrate and aluminum chloride, and preferably aluminum sulfate.

In the preparation method of the hydroconversion catalyst, the concentration of the first acidic aluminate solution in the step (1) is 40-100 gAl₂O₃Preferably 50-80 gAl₂O₃and/L, controlling the flow rate to be 1-2L/h.

In the preparation method of the hydrogenation and hydrogenation conversion of the invention, the alkaline solution in the step (2) is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate, and sodium carbonate is preferred.

In the preparation method of the hydrogenation and hydrogenation conversion, the concentration of the alkaline solution in the step (2) is 0.5-2.0 mol/L, and the flow rate is controlled to be 1.0-2.0L/h.

In the preparation method of the hydro-conversion catalyst, the second acidic aluminate in the step (2) is one or more of aluminum sulfate, aluminum nitrate, aluminum chloride and the like, and preferably aluminum sulfate.

In the preparation method of the hydroconversion catalyst, the concentration of the second acidic aluminate solution in the step (2) is 20-50 gAl₂O₃Preferably 20-40 gAl₂O₃and/L, controlling the flow rate to be 0.4-1.0L/h.

In the preparation method of the hydroconversion catalyst, the concentration of the first acidic aluminate solution is 20-80 gAl higher than that of the second acidic aluminate solution₂O₃a/L, preferably 40 to 60gAl higher₂O₃/L。

In the preparation method of the hydroconversion catalyst, the treating agent A in the step (2) is one or more of triethanolamine, isopropanolamine, polyacrylamide, ammonium lauryl ether sulfate, hexadecyltrimethylammonium chloride and octadecyl trimethylammonium chloride, preferably one or more of triethanolamine, isopropanolamine and polyacrylamide, and further preferably triethanolamine.

In the preparation method of the hydro-conversion catalyst, the concentration of the treating agent A in the step (2) is 0.5-5 wt%, and the flow rate is controlled to be 1.0-2.0L/h.

In the preparation method of the hydroconversion catalyst, the treating agent A in the step (2) is added before the concurrent flow of the alkaline solution and the second acidic aluminate solution, and is preferably introduced into the second reactor simultaneously with the slurry obtained in the step (1).

In the preparation method of the hydroconversion catalyst, the alkaline solution and the second acidic aluminate solution are added simultaneously in the step (2).

In the preparation method of the hydro-conversion catalyst, when an alkaline solution and a second acidic aluminate solution are added in the step (2) in a concurrent flow manner, a treating agent B is preferably added, wherein the treating agent B is one or more of polyethylene glycol, OP-20, span and Tween, and the molecular weight of the polyethylene glycol is not less than 10000.

In the preparation method of the hydroconversion catalyst, the addition amount of the treating agent B in the step (2) is 2-8 wt%, preferably 3-5 wt% of the content of alumina in the second acidic aluminate.

In the preparation method of the hydroconversion catalyst, the treating agent B and the second acidic aluminate solution are added simultaneously in the step (2).

In the preparation method of the hydroconversion catalyst, the reaction temperature in the step (1) is 50-95 ℃, preferably 60-95 ℃, and more preferably 65-85 ℃.

In the preparation method of the hydroconversion catalyst, the reaction temperature in the step (2) is 50-95 ℃, preferably 60-95 ℃, and more preferably 65-85 ℃.

In the preparation method of the hydro-conversion catalyst, the washing in the step (3) is carried out at the temperature of 50-70 ℃, and water can be adopted for washing. Drying conditions are as follows: drying for 2-6 hours at 100-150 ℃, preferably 110-130 ℃, and drying for 4-6 hours.

In the preparation method of the hydro-conversion catalyst, an auxiliary agent, such as SiO, can be added in the preparation process of the pseudo-boehmite according to actual needs₂、P₂O₅、B₂O₃、TiO₂One or more precursors, which are added in the form of water-soluble inorganic substances, can be added together with the alkaline aluminate solution or can be added separately. The auxiliary agent precursor can be one or more of silicate, phosphoric acid, boric acid, titanium sulfate and titanium nitrate. The addition amount of the auxiliary agent can be added according to the requirement.

In the preparation method of the hydroconversion catalyst, the forming process of the pseudo-boehmite in the step (4) can be completed by adding a forming auxiliary agent, wherein the forming auxiliary agent is an adhesive, a peptizing agent or an extrusion aid and the like, such as one or more of sesbania powder methyl cellulose, silica sol, ammonium dihydrogen phosphate and the like, and the adding amount is 2-8% of the content of alumina, preferably 2-5%. Drying conditions are as follows: drying for 2-6 hours at 100-150 ℃, preferably 110-130 ℃, and drying for 4-6 hours. Roasting conditions are as follows: roasting at 500-800 ℃ for 2-6 hours, preferably at 600-750 ℃ for 3-6 hours. The carrier of the hydroconversion catalyst provided by the invention can be made into various easy-to-operate molded products according to different requirements, such as spheres, honeycombs, bird nests, tablets or strips (clovers, butterflies, cylinders and the like), and the spheres are preferred. The shaping is carried out in a conventional manner, for example, by one or a combination of extrusion, spheronization, tabletting and extrusion.

In the preparation method of the hydroconversion catalyst of the present invention, the method for loading the active component on the carrier in the step (5) may be any method existing in the art, and the loading method is not particularly limited, and preferably an impregnation method is used, on the premise that the active component can be supported on the carrier. The preparation method comprises the steps of preparing an impregnation solution of a compound containing the metal, impregnating the carrier with the impregnation solution, and drying and roasting to obtain the catalyst. The impregnation method is a conventional method, and for example, the impregnation method can be excess liquid impregnation and pore saturation impregnation. The active component is a VIB group metal and/or a VIII group metal, the metal component compound containing the VIB group is selected from one or more soluble compounds of the VIB group metal and the VIB group metal, such as one or more of molybdenum oxide, molybdate and paramolybdate, and molybdenum oxide, ammonium molybdate and paramolybdate in the soluble compounds are preferred; one or more of tungstate, metatungstate and ethyl metatungstate, preferably ammonium metatungstate and ethyl metatungstate. The compound containing the group VIII metal component is selected from one or more soluble compounds thereof, such as one or more soluble complexes of cobalt nitrate, cobalt acetate, basic cobalt carbonate, cobalt chloride and cobalt, preferably cobalt nitrate and basic cobalt carbonate; one or more of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and soluble complex of nickel, preferably nickel nitrate and basic nickel carbonate.

In the preparation method of the hydroconversion catalyst of the present invention, the drying conditions in step (5) are as follows: drying for 2-6 hours at 100-150 ℃, preferably 110-130 ℃, and drying for 4-6 hours. Roasting conditions are as follows: roasting at 400-600 ℃ for 2-6 hours, preferably at 450-600 ℃ for 3-6 hours.

In a third aspect of the present invention, a method for hydrogenating an inferior raw material is provided, wherein under a hydroconversion reaction condition, a poor raw material of a hydrocarbon oil and hydrogen are contacted with the hydroconversion catalyst to react. The reaction conditions for the hydroconversion are not particularly limited, and preferably the hydroconversion reaction conditions are: the reaction temperature is 380-450 ℃, preferably 400-440 ℃, the hydrogen partial pressure is 4-25 MPa, preferably 13-20 MPa, and the liquid volume space velocity (LHSV) is 0.3-5.0 h^-1Preferably 0.3 to 2.0 hours^-1The volume ratio of hydrogen to oil is 200-2500, preferably 500-1000.

In the hydrogenation method of the inferior raw material, the inferior raw material can be one or more of atmospheric residue oil, vacuum residue oil, light deasphalted oil and heavy deasphalted oil.

In the hydrogenation method for the inferior raw material, the device for carrying out hydrogenation reaction can be one or more of a fixed bed reactor, a moving bed reactor, a suspension bed reactor or a boiling bed reactor, and is particularly suitable for the boiling bed reactor.

The hydroconversion catalyst is presulfided either ex-situ or in-situ to convert the active metal component it supports to a metal sulfide component, according to methods conventional in the art, and any means known in the art to effect sulfidation of hydroprocessing catalysts may be employed, such operation and selection being readily determinable by one skilled in the art.

The hydroconversion catalyst provided by the invention can be used alone or in combination with other catalysts, and is particularly suitable for hydroconversion of heavy oil, particularly inferior residual oil, so that residual oil is effectively converted.

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

1. the preparation method of the hydro-conversion catalyst comprises the steps of firstly preparing the pseudo-boehmite with large pore volume, concentrated pore distribution, low apparent density and good cohesiveness, wherein the hydro-conversion catalyst taking the alumina prepared from the pseudo-boehmite as a carrier has the advantages of large pore volume, concentrated pore size distribution, high hydrogenation activity, good wear resistance, high surface hydroxyl density, and capability of forming more active phases and high hydrogenation activity.

2. According to the preparation method of the pseudo-boehmite, two steps of reactions are set during the preparation of the pseudo-boehmite, wherein a first acidic aluminate solution with relatively high concentration is adopted in the first step of reaction, the pseudo-boehmite slurry is synthesized with an alkaline aluminate solution in a liquid-liquid continuous parallel flow mode, the obtained slurry is acidic under the control of reaction conditions, a treating agent A is introduced when the slurry enters a second reactor, the treating agent A can be combined with complete grains in the slurry obtained in the first step, the complete grains are protected, and more second acidic aluminate solution with relatively low concentration is ensured to continue to react on the incomplete grains to obtain a product identical to the complete grains. The preparation method solves the technical problems that when the pseudo-boehmite is prepared by adopting a conventional continuous parallel flow mode, due to the reason of liquid stirring back mixing, the retention time of reaction materials is different, so that generated complete and incomplete crystal grains flow out together, and due to the change of microenvironment among particles, the incomplete crystal grains are reduced or dissolved in the subsequent gelling reaction, so that the obtained pseudo-boehmite crystal grains are different in size, poor in cohesiveness and influence the properties of subsequent alumina products.

3. In the preparation method of the hydro-conversion catalyst, the pseudo-boehmite is prepared by adopting two-stage reaction, introducing different treating agents, different reaction conditions and different concentrations of acidic aluminate solution under the combined action of a plurality of means, so that the aging step in the traditional preparation process can be saved, the process flow is shortened, the whole preparation process is more energy-saving, and the preparation method is more suitable for large-scale industrial production from the economic aspect.

4. In the preparation method of the hydro-conversion catalyst, two stages of crystal nucleus generation and growth exist in the preparation process of the pseudo-boehmite, a first acidic aluminate solution is adopted to react with sodium metaaluminate in the first step, pseudo-boehmite crystal nuclei are generated rapidly and grow slowly, complete or incomplete crystal grains appear due to material back mixing, a treating agent solution A, a second acidic aluminate solution and an alkaline solution are added in the second step, the concentration of the slurry is reduced, the incomplete crystal grain growth is facilitated under the alkaline condition, and meanwhile, in the second reaction process, the second acidic aluminate is mixed with a treating agent B, so that the complete particles generated by the incomplete particles do not aggregate and grow.

Detailed Description

The technical solution of the present invention is further illustrated by the following examples, but is not limited to the following examples. In the invention, the specific surface area, the pore volume and the pore distribution are measured by adopting a low-temperature liquid nitrogen adsorption method.

The method for measuring the surface hydroxyl density of the catalyst comprises the following steps: 0.5g of the catalyst sample was weighed and ground to particlesSamples with a degree of less than 1 micron were ready for use. Weighing 10mg of sample, tabletting, transferring to an in-situ cell of an in-situ infrared spectrometer under a vacuum degree of 10^-3And heating the sample in the in-situ cell under the Pa condition, wherein the heating rate is 10 ℃/min, heating to 500 ℃, keeping the temperature for 2h, and then cooling to room temperature under the vacuum condition. Collecting a spectrum by using an in-situ infrared spectrometer, wherein the peak position is 3600-3850 cm^-1The catalyst prepared by the invention and the catalyst prepared by SB powder under the same conditions are respectively used for measuring the surface hydroxyl peak area, the ratio of the two graphic peak areas is the molar ratio of the surface hydroxyl density of the two catalyst samples, the SB powder is provided by German Sasol company, and the pore volume is 0.5 mL/g.

Example 1

150mL of water are added to the first reactor (500 mL capacity) followed by continuous co-current addition of sodium metaaluminate solution (180 gAl)₂O₃L), a flow rate of 1.1L/h and a first acidic aluminium sulphate solution (80 gAl)₂O₃L), the flow rate is 1.8L/h, the pH value of the solution is adjusted to 6.5, and the gelling temperature of the first reactor is controlled to be 75 ℃. After the reaction, 0.7% triethanolamine liquid was added to the resulting slurry at a flow rate of 1.8L/h, and the mixture was fed into a second reactor (500 mL capacity). Then 1.5mol/L sodium carbonate solution with a flow rate of 0.6L/h and second acid aluminium sulphate (30 gAl) were added co-currently₂O₃L) solution with flow rate of 0.7L/h and polyethylene glycol (molecular weight 20000) of 0.75g/h, adjusting the pH value of the solution to 8.0, and controlling the gelling temperature of the second reactor to 55 ℃. After the reaction, the obtained suspension is washed under water at 60 ℃ and dried for 4 hours at 120 ℃ to obtain the pseudoboehmite A.

Weighing 200g of prepared pseudoboehmite A, adding 4.2g of sesbania powder and 200g of purified water, uniformly mixing, forming balls, drying the samples at 120 ℃ for 3, and roasting at 700 ℃ for 3h to obtain the spherical carrier with the granularity of 0.8-1.0 mm. The spherical carrier is impregnated with Mo-Ni-P (12-3.0-1.3%) solution, dried at 120 deg.C for 4 hours, and calcined at 480 deg.C for 3 hours to obtain catalyst S-A, the properties of which are shown in Table 1, and the evaluation results of which are shown in Table 4.

For determination of the surface hydroxyl group density of the catalyst, a reference catalyst was prepared according to the above preparation method except that the pseudoboehmite A was replaced with 200gSB powder, and the SB powder was supplied from Sasol, Germany, and the pore volume was 0.5 mL/g. The surface hydroxyl group densities of the catalysts described in the following examples and comparative examples were all tested by the same method by replacing the pseudo-boehmite in the examples and comparative examples with SB powder.

Example 2

The other preparation conditions were the same as example 1 except that the pH of the solution in the first reactor was adjusted to 6, the gelling temperature in the first reactor was 80 ℃, the concentration of the treating agent A was 0.9%, and the flow rate was 1.0L/h, thereby obtaining pseudoboehmite B and the catalyst S-B. The catalyst properties are shown in Table 1, and the catalyst evaluation results are shown in Table 4.

Example 3

The other conditions were the same as in example 1 except that the treating agent A was changed to a polyacrylamide liquid, the pH of the solution in the second reactor was adjusted to 10, and the gelling temperature in the second reactor was 40 ℃ to prepare pseudoboehmite C. The prepared microsphere carrier is soaked in Mo-Ni (15-3.5-1.5%) solution, dried for 3 hours at 120 ℃, and calcined for 3 hours at 550 ℃ to obtain the catalyst S-C, wherein the properties of the catalyst are shown in Table 1, and the evaluation results of the catalyst are shown in Table 4.

Example 4

Other conditions were prepared as in example 1 except that treatment B was changed to Tween, and second acidic aluminum sulfate (40 gAl) was added in an amount of 2.5g/h₂O₃and/L) solution, adjusting the pH value of the solution in the second reactor to 8 at the flow rate of 0.8L/h, and preparing to obtain pseudo-boehmite D at the gelling temperature of 70 ℃ in the second reactor, wherein 2g of methylcellulose and 2.4g of ammonium dihydrogen phosphate are added in the preparation process of the carrier to prepare a spherical carrier with the particle size of 1.0-1.5 mm, and finally the catalyst S-D is prepared. The catalyst properties are shown in Table 1, and the catalyst evaluation results are shown in Table 4.

Example 5

Preparation of pseudo-boehmite E and catalyst S-E were prepared under otherwise the same conditions as in example 1, except that treating agent B was not added.

Example 6

200mL of water were added to the first reactor (500 mL capacity) followed by continuous co-current addition of sodium metaaluminate solution (150 gAl)₂O₃/L), a flow rate of 1.0L/h and a first acidic aluminum nitrate solution (60 gAl)₂O₃L), the flow rate is 1.5L/h, the pH value of the solution is adjusted to 5.5, and the gelling temperature of the first reactor is controlled to be 80 ℃. After the reaction, 0.5% isopropanolamine liquid is added into the slurry at a flow rate of 1.0L/h, and the slurry enters a second reactor (the volume is 500 mL). Then 0.7mol/L sodium carbonate solution is added in parallel at a flow rate of 0.9L/h and a second acid aluminium sulphate (20 gAl)₂O₃L), the flow rate is 0.8L/h, the OP-20 solution is 0.64g/h, the pH value of the solution is adjusted to 9.0, and the gelling temperature of the second reactor is controlled to be 50 ℃. And washing the obtained suspension at 60 ℃ under washing water after reaction, and drying at 130 ℃ for 4 hours to obtain the pseudoboehmite F.

Weighing 200g of prepared pseudoboehmite F, adding 1g of sesbania powder, 1g of methylcellulose and 190g of purified water, uniformly mixing, forming balls, drying the samples at 110 ℃ for 4 hours, and roasting at 750 ℃ for 4 hours to obtain the spherical carrier with the granularity of 1.6-2.0 mm. The spherical carrier is impregnated with Mo-Ni-P (12-3.0-1.3%) solution, dried at 120 deg.C for 6 hours, and calcined at 580 deg.C for 3 hours to obtain catalyst S-F, the properties of which are shown in Table 1, and the evaluation results of which are shown in Table 4.

Comparative example 1

150mL of water are added to the first reactor (500 mL capacity) followed by continuous co-current addition of sodium metaaluminate solution (180 gAl)₂O₃L), a flow rate of 1.1L/h and a first acidic aluminium sulphate solution (80 gAl)₂O₃L), the flow rate is 1.8L/h, the pH value of the solution is adjusted to 6.5, and the gelling temperature of the first reactor is controlled to be 75 ℃. After the reaction, the obtained slurry enters a second reactor (the volume is 500 mL). Then 1.5mol/L sodium carbonate solution with a flow rate of 0.6L/h and second acid aluminium sulphate (30 gAl) were added co-currently₂O₃/L) solution with the flow rate of 0.7L/h, adjusting the pH value of the solution to 8.0 and controlling the gelling temperature of the second reactor to be 55 ℃. After the reaction, the obtained suspension is washed under water at 60 ℃ and dried for 4 hours at 120 ℃ to obtain the pseudoboehmite G.

Weighing 200G of prepared pseudoboehmite G, adding 4.2G of sesbania powder and 200G of purified water, uniformly mixing, balling and forming, drying the sample at 120 ℃ for 3, and roasting at 700 ℃ for 3h to obtain a spherical carrier with the granularity of 0.8-1.0 mm. The spherical carrier is impregnated with Mo-Ni-P (12-3.0-1.3%) solution, dried at 120 deg.C for 4 hours, and calcined at 480 deg.C for 3 hours to obtain catalyst S-A, the properties of which are shown in Table 1, and the evaluation results of which are shown in Table 4.

Comparative example 2

150mL of water are added to the first reactor (500 mL capacity) followed by continuous co-current addition of sodium metaaluminate solution (180 gAl)₂O₃L), a flow rate of 1.1L/h and a first acidic aluminium sulphate solution (80 gAl)₂O₃L), the flow rate is 1.8L/h, the pH value of the solution is adjusted to 6.5, and the gelling temperature of the first reactor is controlled to be 75 ℃. After the reaction, the obtained slurry enters a second reactor (the volume is 500 mL). Then 1.5mol/L sodium carbonate solution with a flow rate of 0.6L/h and second acid aluminium sulphate (30 gAl) were added co-currently₂O₃L) solution with flow rate of 0.7L/h and polyethylene glycol (molecular weight 20000) of 0.75g/h, adjusting the pH value of the solution to 8.0, and controlling the gelling temperature of the second reactor to 55 ℃. After the reaction, the obtained suspension is washed under water at 60 ℃ and dried for 4 hours at 120 ℃ to obtain the pseudoboehmite H.

Weighing 200g of prepared boehmite A, adding 4.2g of sesbania powder and 200g of purified water, uniformly mixing, balling and forming, drying the sample at 120 ℃ for 3, and roasting at 700 ℃ for 3h to obtain a spherical carrier with the granularity of 0.8-1.0 mm. The spherical carrier is impregnated with Mo-Ni-P (12-3.0-1.3%) solution, dried at 120 deg.C for 4 hours, and calcined at 480 deg.C for 3 hours to obtain catalyst S-H, the properties of which are shown in Table 1, and the evaluation results of which are shown in Table 4.

Comparative example 3

150mL of water are added to the first reactor (500 mL capacity) followed by continuous co-current addition of sodium metaaluminate solution (180 gAl)₂O₃L), a flow rate of 1.1L/h and a first acidic aluminium sulphate solution (80 gAl)₂O₃L), the flow rate is 1.8L/h, the pH value of the solution is adjusted to 6.5, and the gelling temperature of the first reactor is controlled to be 75 ℃. After the reaction, 0.7% triethanolamine liquid was added to the resulting slurry at a flow rate of 1.8L/h, and the mixture was fed into a second reactor (500 mL capacity). Then 1.5mol/L sodium carbonate solution with the flow rate of 0.6L/h and second acid aluminum sulfate (80 gAl) are added in parallel₂O₃/L) solution flow rate 0.7L0.75g/h of polyethylene glycol (molecular weight is 20000), the pH value of the solution is adjusted to 8.0, and the gelling temperature of the second reactor is controlled to be 55 ℃. After the reaction, the obtained suspension is washed under water at 60 ℃ and dried for 4 hours at 120 ℃ to obtain the pseudoboehmite I.

Weighing 200g of prepared boehmite A, adding 4.2g of sesbania powder and 200g of purified water, uniformly mixing, balling and forming, drying the sample at 120 ℃ for 3, and roasting at 700 ℃ for 3h to obtain a spherical carrier with the granularity of 0.8-1.0 mm. The spherical carrier is impregnated with Mo-Ni-P (12-3.0-1.3%) solution, dried at 120 deg.C for 4 hours, and calcined at 480 deg.C for 3 hours to obtain catalyst S-I, the properties of which are shown in Table 1, and the evaluation results of which are shown in Table 4.

Comparative example 4

150mL of water are added to the first reactor (500 mL capacity) followed by continuous co-current addition of sodium metaaluminate solution (180 gAl)₂O₃L), a flow rate of 1.1L/h and a first acidic aluminium sulphate solution (30 gAl)₂O₃L), the flow rate is 1.8L/h, the pH value of the solution is adjusted to 6.5, and the gelling temperature of the first reactor is controlled to be 75 ℃. After the reaction, 0.7% triethanolamine liquid was added to the resulting slurry at a flow rate of 1.8L/h, and the mixture was fed into a second reactor (500 mL capacity). Then 1.5mol/L sodium carbonate solution with a flow rate of 0.6L/h and second acid aluminium sulphate (30 gAl) were added co-currently₂O₃L) solution with flow rate of 0.7L/h and polyethylene glycol (molecular weight 20000) of 0.75g/h, adjusting the pH value of the solution to 8.0, and controlling the gelling temperature of the second reactor to 55 ℃. After the reaction, the obtained suspension is washed under water at 60 ℃ and dried for 4 hours at 120 ℃ to obtain the pseudoboehmite J.

Weighing 200g of prepared boehmite A, adding 4.2g of sesbania powder and 200g of purified water, uniformly mixing, balling and forming, drying the sample at 120 ℃ for 3, and roasting at 700 ℃ for 3h to obtain a spherical carrier with the granularity of 0.8-1.0 mm. The spherical carrier was impregnated with a Mo-Ni-P (12-3.0-1.3%) solution, dried at 120 ℃ for 4 hours, and calcined at 480 ℃ for 3 hours to obtain the catalyst S-J, the properties of which are shown in Table 1, and the evaluation results of which are shown in Table 4.

TABLE 1 Properties of the catalysts

As can be seen from the data in the table: the hydrotreating catalyst prepared by the method has large pore volume, concentrated pore size distribution, low abrasion and high surface hydroxyl molar ratio.

The catalysts were measured out to 200mL each, and the activity of the catalyst was evaluated in an autoclave, and the properties of the residue feedstock used are shown in Table 2, the evaluation conditions are shown in Table 3, and the evaluation results are shown in Table 4.

TABLE 2 Properties of the feed oils

Table 3 evaluation of Process conditions

TABLE 4 evaluation results of different catalysts

From the evaluation results, it can be seen that: when the poor-quality raw material hydroconversion catalyst prepared by the method is used for processing poor-quality vacuum residue, the catalyst shows higher hydrogenation impurity removal activity, and the residue is effectively converted.

Claims

1. A hydroconversion catalyst comprising an active component and a support; the active component is VIB group metal and/or VIII group metal, based on the weight of the catalyst, the content of the VIB group metal is 8.0-18.0 wt% calculated by oxides, the content of the VIII group metal is 1.0-8.0 wt% calculated by oxides, and the molar ratio of the surface hydroxyl density of the hydroconversion catalyst to the surface hydroxyl density of the catalyst prepared from SB powder is 1.1-1.6;

the preparation method of the hydroconversion catalyst comprises the following steps:

(1) adding water into a first reactor, then adding an alkaline aluminate solution and a first acidic aluminate solution in a continuous parallel flow mode, adjusting the pH value of the solutions to be 3-6.5, and obtaining a slurry after reaction, wherein the concentration of the first acidic aluminate solution is 40-100 gAl₂O₃/L；

(2) Continuously introducing the slurry and the treating agent A into a second reactor, then adding an alkaline solution and a second acidic aluminate solution in a parallel flow manner, adjusting the pH value of the solution to 7-10, and obtaining a suspension after reaction, wherein the concentration of the second acidic aluminate solution is 20-50 gAl₂O₃The treating agent A is one or more of triethanolamine, isopropanolamine, polyacrylamide, ammonium lauryl ether sulfate, hexadecyl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride;

2. The hydroconversion catalyst of claim 1, characterized in that: based on the weight of the catalyst, the content of VIB group metal is 9.0wt% -15.0 wt% calculated by oxide, and the content of VIII group metal is 2.0wt% -5.0 wt% calculated by oxide.

3. The hydroconversion catalyst of claim 1, characterized in that: the VIB group metal is W and/or Mo, and the VIII group metal is Co and/or Ni.

4. The hydroconversion catalyst of claim 1, characterized in that: the active components are Mo and Ni.

5. The hydroconversion catalyst of claim 1, characterized in that: the well capacity is 0.55-0.70 mL-g, the specific surface area is 150-220 m²/g。

6. The hydroconversion catalyst of claim 1, characterized in that: the pore volume is 0.55-0.70 mL/g, the specific surface area is 150-200 m²/g。

7. The hydroconversion catalyst of claim 1, characterized in that: the pore distribution of the hydroconversion catalyst is as follows: the pore volume of pores with the pore diameter less than 8nm accounts for less than 15 percent of the total pore volume, the pore volume of pores with the pore diameter of 8-15 nm accounts for 60-80 percent of the total pore volume, and the pore volume of pores with the pore diameter more than 15nm accounts for 15-25 percent of the total pore volume.

8. The hydroconversion catalyst of claim 1, characterized in that: the pore distribution of the hydroconversion catalyst is as follows: the pore volume of pores with the pore diameter less than 8nm accounts for less than 10 percent of the total pore volume, the pore volume of pores with the pore diameter of 8-15 nm accounts for 70-80 percent of the total pore volume, and the pore volume of pores with the pore diameter more than 15nm accounts for 18-25 percent of the total pore volume.

9. The hydroconversion catalyst of claim 1, characterized in that: the molar ratio of the surface hydroxyl density of the hydro-conversion catalyst to the surface hydroxyl density of the catalyst prepared from the SB powder is 1.2-1.5.

10. The hydroconversion catalyst of claim 1, characterized in that: the particle size of the hydro-conversion catalyst is 0.8-2.0 mm, and the abrasion of the catalyst is less than 1.5 wt%.

11. The hydroconversion catalyst of claim 1, characterized in that: the particle size of the hydro-conversion catalyst is 0.8-2.0 mm, and the abrasion of the catalyst is less than 1.0 wt%.

12. A process for the preparation of a hydroconversion catalyst as claimed in any of claims 1 to 11, comprising:

(1) feeding into the first reactorAdding water, adding an alkaline aluminate solution and a first acidic aluminate solution in a continuous parallel flow mode, adjusting the pH value of the solutions to be 3-6.5, and obtaining slurry after reaction, wherein the concentration of the first acidic aluminate solution is 40-100 gAl₂O₃/L；

13. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: adding water into the first reactor, then adding an alkaline aluminate solution and a first acidic aluminate solution in a continuous parallel flow mode, adjusting the pH value of the solutions to be 4-6, and obtaining slurry after reaction.

14. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: and continuously introducing the slurry and the treating agent A into a second reactor, then adding an alkaline solution and a second acidic aluminate solution in a parallel flow manner, adjusting the pH value of the solution to 7.5-9, and reacting to obtain a suspension.

15. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: in the step (1), the adding amount of water in the first reactor is 1/4-1/2 of the volume of the first reactor.

16. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: in the step (1), the adding amount of water in the first reactor is 1/4-1/3 of the volume of the first reactor.

17. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: in the step (1), the alkaline aluminate is one or more of sodium metaaluminate and potassium metaaluminate.

18. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: in the step (1), the alkaline aluminate is sodium metaaluminate.

19. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the concentration of the alkaline aluminate solution in the step (1) is 100-250 gAl₂O₃/L。

20. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the concentration of the alkaline aluminate solution in the step (1) is 150-200 gAl₂O₃/L。

21. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the first acidic aluminate in the step (1) is one or more of aluminum sulfate, aluminum nitrate and aluminum chloride.

22. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the first acidic aluminate in the step (1) is aluminum sulfate.

23. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the concentration of the first acidic aluminate solution in the step (1) is 50-80 gAl₂O₃/L。

24. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the alkaline solution in the step (2) is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate.

25. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the alkaline solution in the step (2) is sodium carbonate.

26. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the concentration of the alkaline solution in the step (2) is 0.5-2.0 mol/L.

27. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the second acidic aluminate in the step (2) is one or more of aluminum sulfate, aluminum nitrate and aluminum chloride.

28. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the second acidic aluminate in the step (2) is aluminum sulfate.

29. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the concentration of the second acidic aluminate solution in the step (2) is 20-40 gAl₂O₃/L。

30. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the concentration of the first acidic aluminate solution is 20-80 gAl higher than that of the second acidic aluminate solution₂O₃/L。

31. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: of a first acidic aluminate solutionThe concentration of the second aluminate solution is 40-60 gAl higher than that of the second aluminate solution₂O₃/L。

32. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the treating agent A in the step (2) is one or more of triethanolamine, isopropanolamine and polyacrylamide.

33. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the treating agent A in the step (2) is triethanolamine.

34. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: in the step (2), the concentration of the treating agent A is 0.5-5 wt%.

35. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: and (3) when an alkaline solution and a second acidic aluminate solution are added in parallel in the step (2), adding a treating agent B, wherein the treating agent B is one or more of polyethylene glycol, OP-20, span and Tween, and the molecular weight of the polyethylene glycol is not less than 10000.

36. A process for preparing a hydroconversion catalyst as claimed in claim 35, wherein: the addition amount of the treating agent B in the step (2) is 2-8 wt% of the content of alumina in the second acidic aluminate.

37. A process for preparing a hydroconversion catalyst as claimed in claim 35, wherein: the addition amount of the treating agent B in the step (2) is 3-5 wt% of the content of alumina in the second acidic aluminate.

38. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the reaction temperature in the step (1) is 50-95 ℃.

39. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the reaction temperature in the step (1) is 60-95 ℃.

40. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the reaction temperature in the step (1) is 65-85 ℃.

41. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: in the step (2), the reaction temperature is 50-95 ℃.

42. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: in the step (2), the reaction temperature is 60-95 ℃.

43. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: in the step (2), the reaction temperature is 65-85 ℃.

44. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: washing in the step (3) at the temperature of 50-70 ℃, and washing with water; drying conditions are as follows: drying for 2-6 hours at 100-150 ℃.

45. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: washing in the step (3) at the temperature of 50-70 ℃, and washing with water; drying conditions are as follows: drying at 110-130 ℃ for 4-6 hours.

46. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the method for loading the active component on the carrier in the step (5) adopts an impregnation method, and comprises the steps of preparing an impregnation solution of a compound containing the active component, impregnating the carrier with the impregnation solution, and drying and roasting to obtain the catalyst.

47. A process for preparing a hydroconversion catalyst as claimed in claim 46, wherein: the active component is VIB group metal and/or VIII group metal, the metal component compound containing VIB group is selected from one or more soluble compounds of the metal component compound, and the compound containing VIII group metal component is selected from one or more soluble compounds of the metal component compound.

48. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the drying conditions in the step (5): drying for 2-6 hours at 100-150 ℃, wherein the roasting condition is as follows: roasting at 400-600 ℃ for 2-6 hours.

49. A process for preparing a hydroconversion catalyst as claimed in claim 12, characterized in that: the drying conditions in the step (5): drying for 4-6 hours at 110-130 ℃; roasting conditions are as follows: roasting at 450-600 ℃ for 3-6 hours.

50. A hydrogenation method for inferior raw materials is characterized in that: the catalyst of any one of claims 1 to 11 is used for contacting a poor-quality hydrocarbon oil raw material with hydrogen to react under the condition of a hydrogenation conversion reaction.

51. The method of claim 50, wherein: the hydroconversion reaction conditions are as follows: the reaction temperature is 380-450 ℃, the hydrogen partial pressure is 4-25 MPa, and the liquid volume space velocity is 0.3-5.0 h^-1The volume ratio of hydrogen to oil is 200-2500.

52. The method of claim 50, wherein: the hydroconversion reaction conditions are as follows: the reaction temperature is 400-440 ℃, the hydrogen partial pressure is 13-20 MPa, and the liquid volume space velocity is 0.3-2.0 h^-1The volume ratio of hydrogen to oil is 500-1000.