Residue hydroprocessing catalyst, method for making and use thereof

Abstract

The application discloses a residual oil hydrogenation catalyst and a preparation method and application thereof. The preparation method of the catalyst comprises the following steps: impregnating an active metal solution C1 into a polyimide carrier, drying and calcining to obtain a metal / polyimide material; putting the obtained metal / polyimide material into a gelatinization solution, synthesizing a silicon and carbon-containing pseudo-boehmite wet filter cake, drying the silicon and carbon-containing pseudo-boehmite wet filter cake to obtain a silicon and carbon-containing pseudo-boehmite; shaping the obtained silicon and carbon-containing pseudo-boehmite, drying to obtain an intermediate; mixing the obtained intermediate with an active metal solution C2 for second impregnation, drying, and calcining in an oxygen-containing atmosphere to obtain the catalyst. The catalyst provided by the application is applied to residual oil hydrogenation treatment, and exhibits excellent catalytic performance in the desulfurization and denitrification processes, and also exhibits good catalytic capacity in the removal of residual carbon and metals.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of hydrogenation catalyst and its preparation method and application, specifically relates to a kind of residue hydrogenation catalyst and its preparation method and application. BACKGROUND

[0002] Residue hydrogenation catalyst is mainly metal supported catalyst, more with alumina and / or silicon dioxide as carrier, Ni, Mo, Co etc. as active metal component. In the existing method, when active metal loading is larger, metal particle agglomeration or uneven distribution phenomenon is easily generated. In addition, in the calcination process, due to the strong interaction between metal and carrier, metal-oxygen-aluminum bond is formed, which affects the catalytic efficiency of the catalyst, ultimately leading to the decrease of hydrogenation activity of the catalyst.

[0003] There are many types of alumina, such as γ-Al2O3, η-Al2O3, θ-Al2O3, δ-Al2O3 and α-Al2O3, etc. Among them, γ-Al2O3 has a very wide application in the field of catalysis, especially in the field of catalytic hydrogenation, due to its large specific surface area, adjustable pore structure and good thermal stability. The usual method for preparing γ-Al2O3 is to first prepare pseudo-boehmite, and then calcine it at a certain temperature to convert it into γ-Al2O3. In industry, pseudo-boehmite is generally prepared by aluminum chloride method, aluminum sulfate method and carbonization method, etc. Among them, the pseudo-boehmite produced by aluminum chloride method cannot meet the current environmental protection requirements due to poor operating environment and high ammonia and nitrogen emissions during washing process. The pseudo-boehmite produced by aluminum sulfate method contains sulfate ions, which decomposes into sulfur trioxide during the calcination process, especially during high temperature calcination, causing environmental pollution and equipment corrosion. Only the carbonization method for preparing pseudo-boehmite is green and environmentally friendly, and the prepared pseudo-boehmite has no corrosive impurities.

[0004] CN103055908A discloses a preparation method of a hydroprocessing catalyst. First, aluminum hydroxide or alumina is slurried to form a slurry, and concentrated phosphoric acid is added to react to obtain a sol; then the sol is used as a binder, and the alumina carrier is obtained by mixing, kneading, shaping, drying and calcining with macroporous alumina and microporous alumina; then the alumina carrier is impregnated with an active metal component impregnation solution, and the hydroprocessing catalyst is prepared by drying and calcining. This method is complex, the introduction of acid sites will promote the bonding between active metal and carrier, and the use of a large amount of concentrated acid will cause environmental pollution, and industrial production is more dangerous.

[0005] CN105582945A discloses a preparation method of a hydroprocessing catalyst. The method is first to impregnate an alumina carrier with a urea aqueous solution, then to spray impregnate the alumina carrier with a polyol or a monosaccharide aqueous solution in the order of decreasing concentration, so that the concentration of the polyol and / or the monosaccharide forms a gradient distribution from low to high from the outside to the inside on the carrier, and then to load an active metal component. The method needs multiple steps of spray impregnation to form a polymeric carbon shell layer, and has a high requirement for the solution concentration, and the actual operation process is relatively complex.

[0006] CN101618886A discloses an aluminum hydroxide and a preparation method thereof, specifically comprising: adding a small amount of an organic pore-expanding agent and a defoaming agent into a sodium aluminate solution, then introducing a mixed gas of air and CO2, stirring with the mixed gas, one-time gelation, generating pseudo-boehmite with uniform crystal grains, and obtaining alumina with large pore volume, large pore size and concentrated pore distribution through calcination. In order to obtain suitable and uniform pseudo-boehmite particle size and alumina with large pore volume, large pore size and concentrated pore distribution, the organic components added in the method will have an impact on the environment.

[0007] CN101172631A discloses a pseudo-boehmite preparation method, which comprises: introducing carbon dioxide with a volume concentration of 20% to 50% into a sodium aluminate solution with an Al2O3 content of 20 to 60 g / L at a temperature of 15 to 45 ℃ for carbonization, then performing slurry separation after the carbonization is completed, and then adding the filter cake into washing water for mixing and beating, and then aging at 80 to 100 ℃ to obtain pseudo-boehmite. The preparation process of the method is relatively complex. SUMMARY

[0008] In view of the deficiencies of the prior art, the present application provides a method for synthesizing pseudo-boehmite by carbonization, and a preparation method and application of a residual oil hydrogenation catalyst. The pseudo-boehmite prepared by the present application has concentrated and uniform particle size, and the alumina obtained by calcination has suitable large pore size and pore volume. The catalyst provided by the present application has high metal loading and uniform dispersion, high mechanical strength, and suitable surface acidity, and is suitable for use in residual oil hydroprocessing.

[0009] The first aspect of the present application provides a preparation method of a residual oil hydrogenation catalyst, comprising the following steps:

[0010] (1) impregnating an active metal solution C1 into a polyimide carrier, drying and calcining to obtain a metal / polyimide material;

[0011] (2) preparing a silicon and carbon-containing pseudo-boehmite wet filter cake, and drying to obtain a silicon and carbon-containing pseudo-boehmite;

[0012] (3) shaping the silicon and carbon-containing pseudo-boehmite obtained in step (2), and drying to obtain an intermediate;

[0013] (4) mixing the intermediate prepared in step (3) with an active metal solution C2 to perform a second impregnation, drying, and calcining in an oxygen-containing atmosphere to prepare the catalyst;

[0014] The silicon-containing and carbon-containing pseudo-boehmite wet cake in step (2) is prepared by the following method:

[0015] (A) adding the aluminum-containing alkaline solution I into a carbonization reactor I, introducing a carbon dioxide-containing mixed gas to perform a carbonization reaction, and controlling the pH value of the reaction material;

[0016] (B) adding the reaction material obtained in step (A) and a mixed solution of the aluminum-containing alkaline solution II and water glass into the main reactor in parallel flow, and controlling the pH value of the slurry in the main reactor;

[0017] (C) adding the slurry obtained in step (B) into the carbonization reactor II, and introducing carbon dioxide to perform a carbonization reaction, and controlling the pH value of the reaction material;

[0018] (D) replacing the carbonization material obtained in step (A) in step (B) with the reaction material obtained in step (C) to repeat steps (B) and (C);

[0019] (E) adjusting the pH value of the material obtained in step (D), adding the metal / polyimide material obtained in step (1) to perform an adsorption reaction, filtering and washing to obtain the silicon-containing and carbon-containing pseudo-boehmite wet cake.

[0020] In the method, in step (A), the aluminum-containing alkaline solution I is one or both of sodium metaaluminate solution or potassium metaaluminate solution, and preferably sodium metaaluminate solution; the concentration of the aluminum-containing alkaline solution I is 40-100 g Al2O3 / L, and preferably 50-80 g Al2O3 / L, calculated as Al2O3; and the caustic ratio of the aluminum-containing alkaline solution I is 1.15-1.45, and preferably 1.20-1.40.

[0021] In the method, in step (A), the volume fraction of carbon dioxide in the carbon dioxide-containing mixed gas is 35%-65%. In step (A), the time for introducing the carbon dioxide-containing mixed gas is 10-45 min, and the pH value of the obtained reaction material is 5.5-6.5.

[0022] In the method, in step (B), the pH value of the slurry in the main reactor is controlled by adjusting the flow rate of the aluminum-containing alkaline solution, and the pH value of the slurry is 11.5-12.5.

[0023] In the method, in step (B), the modulus of the water glass is 2.5-3.0, and the concentration of the water glass in the mixed solution is 5-95 g SiO2 / L, calculated as SiO2.

[0024] In the method of the present application, in step (B), the basic solution containing aluminum II is one or both of sodium meta-aluminate solution or potassium meta-aluminate solution, preferably sodium meta-aluminate solution, and the concentration of the basic solution containing aluminum II is 90-220 g Al2O3 / L, preferably 150-190 g Al2O3 / L, calculated as Al2O3.

[0025] In the method of the present application, in step (B), the reaction time is 20-50 min.

[0026] In the method of the present application, in step (C), the volume fraction of carbon dioxide in the mixed gas containing carbon dioxide is 35%-65%. In step (C), the time for passing the mixed gas containing carbon dioxide is 5-25 min, and the pH value of the obtained reaction material is 7.5-9.5.

[0027] In the method of the present application, the carbonization reactor I and the carbonization reactor II can be the same reactor.

[0028] In the method of the present application, the number of repetitions of step (D) is 1-4 times.

[0029] In the method of the present application, in step (E), the adjustment of the pH value of the material obtained in step (D) and the addition of the metal / polyimide material obtained in step (1) are not limited in sequence.

[0030] In the method of the present application, in step (E), the amount of the metal / polyimide material added is 10%-40% of the total amount of the basic solution containing aluminum II, calculated as aluminum oxide; and the adsorption reaction is carried out under stirring.

[0031] In the method of the present application, in step (E), the adjustment of the pH value of the material obtained in step (D) is 10-10.5.

[0032] In the method of the present application, in step (E), the washing can be carried out by using a conventional washing method in the art, and preferably using deionized water at 50-80°C.

[0033] In the method of the present application, in step (1), the synthesis of the polyimide carrier comprises:

[0034] (a) dissolving p-diaminobenzene in a N,N-dimethylformamide solution, then adding pyromellitic dianhydride, stirring, and preparing a viscous solution;

[0035] (b) transferring the above solution to a reactor, heating and reacting, then cooling, washing with an organic solvent, drying, and grinding;

[0036] (c) calcining the obtained powder sample under inert gas protection to obtain the polyimide carrier.

[0037] In the method of the present application, in step (a), the concentration of the p-phenylenediamine in the N,N-dimethylformamide solution is 0.005-0.1 g / mL, preferably 0.01-0.05 g / mL.

[0038] In the method of the present application, in step (a), the concentration of the pyromellitic dianhydride in the N,N-dimethylformamide solution is 0.01-0.2 g / mL, preferably 0.02-0.1 g / mL.

[0039] In the method of the present application, in step (a), the stirring time is 2-24 h, preferably 6-10 h.

[0040] In the method of the present application, in step (b), the heating temperature is 130-300 ℃, preferably 160-190 ℃, and the time is 4-15 h.

[0041] In the method of the present application, in step (b), the organic solvent is one of N,N-dimethylformamide or toluene, preferably N,N-dimethylformamide, and the washing times are 2-6 times.

[0042] In the method of the present application, in step (b), the drying temperature is 100-120 ℃, and the time is 2-5 h.

[0043] In the method of the present application, in step (c), the inert atmosphere is at least one selected from Ar, He, and N2; the calcination temperature is 250-600 ℃, preferably 300-400 ℃, and the time is 4-15 h.

[0044] In the method of the present application, in step (1), the active metal in the active metal solution C1 is at least one selected from group VIII metals cobalt and nickel, preferably nickel; the loading is 30%-50% of the total active metal oxide in the catalyst; and the concentration of the active metal oxide in the active metal solution C1 is 0.02-0.4 g / mL. The active component introduced into the catalyst by the active metal solution C1 is the first active component.

[0045] In the method of the present application, in step (1), the drying temperature is 100-120 ℃, and the time is 2-5 h; the calcination temperature is 400-450 ℃, and the time is 2-3 hours under the protection of an inert atmosphere selected from at least one of Ar, He, and N2.

[0046] In the method of the present application, in step (2), the drying temperature is 60-150 ℃, and the drying time is 4-10 h. The dry basis content of the pseudo-boehmite obtained after drying is 75%-85%.

[0047] In the method, in step (3), the forming can adopt extrusion forming. An extrusion aid can be added in the forming process, and the extrusion aid can be amaranth powder, and the amount of the extrusion aid is 1% to 6% of the mass of the silicon-containing and carbon-containing pseudo-boehmite.

[0048] In the method, in step (3), the drying temperature is 80 to 120 ℃, and the drying time is 4 to 6 hours.

[0049] In the method, in step (4), the impregnation adopts saturation impregnation; the active metal in the active metal solution C2 is selected from at least one of group VIB metals and at least one of group VIII metals, wherein the group VIB metal is preferably at least one of Mo and W, and more preferably Mo, and the group VIII metal is preferably at least one of Co and Ni, and more preferably Ni; wherein the concentration of the group VIB metal in the active metal solution C2 is 0.05 to 0.5 g / mL in terms of oxide, and the concentration of the group VIII metal is 0.01 to 0.2 g / mL in terms of oxide.

[0050] In the method, the amount of the group VIII active metal introduced into the catalyst from step (4) accounts for 50% to 70% of the total active metal oxide mass of the group VIII in the catalyst in terms of oxide. The active component introduced into the catalyst from the active metal solution C2 is the second active component.

[0051] In the method, in step (4), the drying temperature is 80 to 120 ℃, the drying time is 2 to 5 hours, the calcination temperature is 600 to 900 ℃, and the calcination time is controlled to be 3 to 5 hours, and the calcination is performed in an oxygen-containing atmosphere (such as air).

[0052] The second aspect of the application provides a residue hydroprocessing catalyst prepared by the above preparation method.

[0053] In the application, the catalyst comprises an active component and an alumina component containing silicon and carbon, and the mass content of silicon is 3% to 95% based on the mass of the alumina component, preferably 5% to 20%, the mass content of carbon is 2% to 90%, preferably 4% to 15%, and further preferably 5.0% to 6.5%.

[0054] In the application, the active component comprises a first active component and a second active component, wherein the first active component is selected from at least one of group VIII metals Co and Ni, and preferably Ni; and the second active component is selected from at least one of group VIB metals and at least one of group VIII metals, and the group VIB metal in the second active component is preferably at least one of Mo and W, and more preferably Mo, and the group VIII metal is preferably at least one of Co and Ni, and more preferably Ni.

[0055] In the present application, the content of the Group VIB metal oxide in the catalyst is 15% to 25% based on the mass of the catalyst, and the content of the Group VIII metal oxide is 3% to 8%.

[0056] In the present application, the catalyst also contains N, and the content of N is 0.8% to 1.3% based on the mass of the catalyst.

[0057] In the present application, the content of the Group VIII metal oxide in the first active component is 30% to 50% based on the mass of the total Group VIII metal oxide in the catalyst, and the content of the Group VIII metal oxide in the second active component is 50% to 70%.

[0058] In the present application, the dispersion of the active metal in the catalyst is: I VIB / I Al (×100) is 2 to 10, preferably 5.1 to 6.0, I VIII / I Al (×100) is 2 to 6.

[0059] In the present application, the specific surface area of the catalyst is 110 to 235 m 2 / g, preferably 195 to 220 m 2 / g, the pore volume is 0.6 to 1.4 cm 3 / g, the mechanical strength is 15 to 28 N / mm, preferably 21 to 24 N / mm, the pore volume of pores with a pore diameter of 15 to 80 nm accounts for 11% to 32% of the total pore volume, and the pore volume of pores with a pore diameter of 8 nm or less accounts for 5.0% or less, preferably 2.0% to 4.5%, of the total pore volume.

[0060] In the present application, the acid amount of the catalyst is 0.50 to 0.95 mmol / g, preferably 0.60 to 0.75 mmol / g, and the ratio C B / C L of the acid amount of the B acid to the acid amount of the L acid is 0.025 to 0.095, preferably 0.060 to 0.085.

[0061] The third aspect of the present application provides the use of the above-mentioned residue oil hydrogenation catalyst in a residue oil hydrogenation process.

[0062] In the present application, residue oil and hydrogen-containing gas are contacted under hydrogenation reaction conditions in the presence of the above-mentioned residue oil hydrogenation catalyst or the residue oil hydrogenation catalyst obtained according to the above-mentioned preparation method.

[0063] In the above-mentioned residue oil hydrogenation reaction, the residue oil material is selected from one of atmospheric residue oil, vacuum residue oil, and high-temperature coal tar.

[0064] In the above-mentioned residue hydrogenation reaction, the hydrogen-containing gas is hydrogen or a mixture of hydrogen and other gases, the volume content of hydrogen in the mixture is generally not less than 80%, preferably not less than 85%, and more preferably not less than 95%.

[0065] In the above-mentioned residue hydrogenation process, the operating conditions of the residue hydrogenation are as follows: the reaction pressure is 5-20 MPaG, the reaction temperature is 280-400℃, the liquid hourly space velocity is 0.1-3.0 h -1 , and the hydrogen / oil volume ratio is 100-1000.

[0066] Compared with the prior art, the present application has the following beneficial effects:

[0067] In the preparation method of the residue oil hydrogenation catalyst, the high molecular polymer polyimide contains C, N and O elements, after calcination, the organic carbon material has an opened band gap and becomes a semiconductor material, in the first metal impregnation process, the active phase VIII group metal is first loaded on the polyimide, a metal-semiconductor heterojunction is formed on the contact interface between the VIII group metal and the polyimide, the heterojunction accelerates the rate of electron migration from the VIII group metal to the polyimide, and at the same time, the interaction force between the two is enhanced, which not only improves the metal dispersion and increases the metal loading, but also greatly weakens the electron migration efficiency between the active metal and the silicon and carbon-containing pseudo-boehmite, so that the adsorption and bonding between the two are weakened, and the synthesized catalyst has higher activity in the residue oil hydrogenation process. Further, the metal / polyimide material is added in the gelation process by using a one-pot method, which is simple to operate, since the Si element is also contained in the gelation solution, and the preparation method of the present application uses a control end-point pH value carbonization method in the later stage, which slowly decreases the pH value of the main reaction kettle, provides time for the generated pseudo-boehmite to change from a metastable state to a stable state, and at the same time, ensures that the polymer polyimide carrier is in full contact with the Si element in the gelation solution, so that part of the silicon carbide semiconductor can be formed in the subsequent calcination process, and the carbon element will not be removed due to calcination in oxygen, and the presence of silicon carbide also plays a role in transferring electrons and promoting metal dispersion. Compared with pure silicon pseudo-boehmite, the silicon and carbon pseudo-boehmite has a larger pore volume, which provides a guarantee for the activity of the subsequent hydrogenation catalyst. In addition, the present application uses a carbonization reaction outside the main reaction kettle, and the low-pH value slurry after carbonization is returned to the high-pH value solution in the main reaction kettle, wherein the incomplete or defective crystal grains after carbonization are dissolved in the high-pH solution, while the complete crystal grains grow as the crystal nucleus for preparing the pseudo-boehmite, and such a carbonization cycle makes the slurry swing between acidity and alkalinity, so as to increase the grain size, concentrate the particle size, and increase the crystallinity of the prepared pseudo-boehmite, and the alumina obtained after calcination has a large pore volume and pore size, which meets the requirements of the residue oil hydrogenation catalyst carrier. The preparation method of the present application overcomes the influence of the product grain size, grain concentration, and pore structure in the traditional carbonization method for preparing pseudo-boehmite, and the process is simple and easy to operate.

[0068] The residue oil hydrogenation catalyst provided by the present application has a high metal loading and uniform dispersion, high mechanical strength, suitable pore distribution and specific surface area, and suitable surface acidity, and has excellent catalytic performance in the processes of desulfurization and denitrification, and also has good catalytic ability in the processes of removing residual carbon and removing metal. DETAILED DESCRIPTION

[0069] In the present application, the nitrogen adsorption-desorption curve of the sample is tested at-196℃ by using the ASAP2020 full-automatic physical adsorption instrument of the American Micromeritics Company, and the specific surface area, pore volume and pore size distribution are determined.

[0070] In the present application, the mechanical strength is tested by using the ZQJ-III intelligent particle strength tester manufactured by the Dalian Zhiqu Testing Machine Factory, and the average mechanical strength of a group of samples with a length of 4-6mm is determined.

[0071] In the present application, the metal dispersion is measured by using XRS (the instrument is Kratos Axis Ultra DLD model) to measure the XPS peak intensity ratio of the active metal and aluminum element.

[0072] In the present application, the infrared acid amount is determined by using the Nicolet 870 Fourier transform infrared spectrometer of the American Nicolet Company.

[0073] The technical solutions and effects of the present application will be further illustrated by the following examples, but are not limited to the following examples.

[0074] Example 1

[0075] (1) 100mmol of p-diaminobenzene is dissolved in 60mL of N,N-dimethylformamide solution, and 2.2g of pyromellitic dianhydride is added at the same time, and the solution is stirred quickly for 8h until the solution is viscous. Then the above solution is transferred to a hydrothermal reaction kettle, heated at 180℃ for 10h, after cooling, washed with N,N-dimethylformamide solvent for 3 times, dried at 110℃ for 4h, and ground for use. The powder sample is calcined under nitrogen protection for 8h, and the calcination temperature is 350℃, to obtain a polyimide carrier;

[0076] 80mL of active metal solution with a NiO content of 0.135g / mL is impregnated into 100g of polyimide carrier, and dried at 110℃ for 4h, and then calcined at 430℃ for 3h under nitrogen atmosphere protection, to obtain a metal / polyimide material, wherein the amount of Ni introduced into the catalyst accounts for 31.3% of the total Ni in the catalyst in terms of the mass of the oxide;

[0077] (2) Preparation of silicon and carbon-containing pseudo-boehmite

[0078] (A) A sodium metaaluminate mixed solution with a caustic ratio of 1.35 and a concentration of 65g Al2O3 / L is added to carbonization reaction kettle I, and a mixed gas containing 55% carbon dioxide and air by volume fraction is introduced from the bottom of the carbonization reaction kettle, and the reaction is carried out for 15min, and the pH value of the carbonization reaction material is controlled to be 6.0;

[0079] (B) to the main reactor, the reaction material obtained in step (A) is added in parallel with a mixed solution of water glass with a modulus of 2.8 and a concentration of 50 g SiO2 / L and sodium metaaluminate solution with a concentration of 180 g Al2O3 / L and a caustic ratio of 1.25, and the reaction is carried out for 25 min, and the pH value of the slurry in the main reactor is controlled to be 12 by adjusting the flow rate of the sodium metaaluminate solution;

[0080] (C) to the carbonization reactor II, the slurry obtained in step (B) is added, and a mixed gas containing carbon dioxide with a volume fraction of 55% and air is introduced from the bottom of the carbonization reactor, and the reaction is carried out for 10 min, and the pH value of the carbonization reaction material is controlled to be 8.0;

[0081] (D) the carbonization material obtained in step (A) in step (B) is replaced with the reaction material obtained in step (C), and steps (B) and (C) are repeated 3 times;

[0082] (E) the pH value of the material obtained in step (D) is adjusted to 10, and 100 g of the metal / polyimide material obtained in step (1) is added for adsorption reaction, and washed with deionized water at a temperature of 70°C until neutral, and after filtration, a wet filter cake containing silicon and carbon pseudo-boehmite with a solid content of 55% is obtained, and dried at 120°C for 6 hours to obtain the silicon and carbon pseudo-boehmite required by the present application;

[0083] (3) 600 g (dry basis 80%) of the silicon and carbon pseudo-boehmite sample obtained in step (2) and 15 g of sesbania powder are mixed and extruded, and dried at 120°C for 4 hours to obtain an intermediate;

[0084] (4) an impregnation solution containing MoO3 at 0.309 g / mL and NiO at 0.058 g / mL is prepared to saturate impregnate the catalyst intermediate obtained in step (3), and after complete impregnation, dried at 120°C for 5 hours, and calcined at 650°C for 3 hours to obtain the final hydrogenation catalyst A, and the physicochemical properties are shown in Table 1.

[0085] Example 2

[0086] Compared with Example 1, the only difference is that the amount of metal / polyimide material added in the preparation process of the silicon and carbon pseudo-boehmite in step (2) is changed to 200 g, and the final hydrogenation catalyst B is obtained, and the physicochemical properties are shown in Table 1.

[0087] Example 3

[0088] The difference from Example 1 is only that the concentration of NiO in the impregnation solution in step (1) is changed to 0.206 g / mL; the concentration of MoO3 in the impregnation solution in step (4) is changed to 0.312 g / mL, the concentration of NiO is 0.045 g / mL, the calcination temperature after impregnation is changed to 450°C, and the concentration of SiO2 in the mixed solution in the preparation of the pseudo-boehmite is changed to 95 g / L, to obtain the final hydrogenation catalyst C (see Table 1 for the physical and chemical properties), wherein the amount of Ni introduced into the catalyst by the first impregnation accounts for 46.9% of the total Ni in the catalyst, in terms of the mass of the oxides.

[0089] Example 4

[0090] The difference from Example 1 is only that in step (2) the silica- and carbon-containing pseudo-boehmite is prepared by adding the water glass with a modulus of 2.8 and a concentration of 10 g SiO2 / L in step (B) in a parallel flow; the product in step (4) is washed with deionized water at 80°C until neutral, and dried at 140°C for 8 hours, to obtain the silica- and carbon-containing pseudo-boehmite required by the present application. The final hydrogenation catalyst D is obtained, and its physical and chemical properties are shown in Table 1.

[0091] Comparative Example 1

[0092] The difference from Example 1 is only that the carrier used is activated carbon powder, and the final hydrogenation catalyst E is obtained, and its physical and chemical properties are shown in Table 1.

[0093] Comparative Example 2

[0094] The difference from Example 1 is only that:

[0095] In the impregnation of step (1), 80 mL of active metal solution with a NiO content of 0.284 g / mL is impregnated into 100 g of polyimide carrier, and finally the amount of Ni introduced into the catalyst accounts for 64.5% of the total Ni in the catalyst, in terms of the mass of the oxides.

[0096] In the impregnation of step (2), an impregnation solution containing 0.312 g / mL of MoO3 and 0.030 g / mL of NiO is prepared to saturate the catalyst intermediate, and finally the final hydrogenation catalyst F is obtained, and its physical and chemical properties are shown in Table 1.

[0097] Comparative Example 3

[0098] The difference from Example 1 is only that:

[0099] The step (2) is prepared in the process of containing silicon, carbon pseudo-boehmite without input metal / polyimide material, but in the extrusion process weighing above-mentioned containing silicon, carbon pseudo-boehmite sample 500g (dry base 80%), metal / polyimide material 100g, 15g sesbania powder mixed and extruded, dried at 120℃ for 4 hours, to obtain intermediate. Finally, the final hydrogenation catalyst G is obtained, and the physicochemical properties are shown in Table 1.

[0100] Example 5

[0101] The catalysts obtained in Examples 1-4 and Comparative Examples 1-3 are respectively used in the residue hydrogenation reaction, the properties of raw materials are shown in Table 2, the evaluation conditions and evaluation results are shown in Table 3.

[0102] Table 1 Physicochemical properties of hydrogenation catalysts

[0103] Catalyst Example 1 Example 2 Example 3 Example 4 Pore volume, mL / g 0.92 0.93 0.88 0.89 Specific surface area, m 2 / g]] 213 210 216 211 Pore size distribution, % Below 8 nm 2.9 3.0 4.0 4.1 15 to 80 nm 11.9 12.2 13.4 15.2 Infrared acid amount, mmol / g 0.701 0.705 0.700 0.623 [C B / C L ]]> 0.077 0.081 0.075 0.069 Mechanical strength, N / mm 24 24 23 23 Composition, wt% MoO3 22.1 21.9 22.0 22.1 NiO 6.1 6.9 6.2 6.1 C 5.3 6.4 5.2 5.5 Si 9.3 9.2 9.4 8.9 N 0.91 1.14 0.87 0.85 Metal dispersion XPS peak intensity ratio, I Mo / I Al ]]> 0.054 0.056 0.052 0.059 XPS peak intensity ratio, I Ni / I Al ]]> 0.032 0.041 0.045 0.039

[0104] Table 1 Physicochemical properties of hydrogenation catalysts (continued)

[0105] Catalyst Comparative Example 1 Comparative Example 2 Comparative Example 3 Pore volume, mL / g 0.67 0.71 0.70 Specific surface area, m 2 / g]] 220 203 214 Pore size distribution, % Below 8 nm 7.2 8.7 6.1 15 to 80 nm 17.1 17.2 16.3 Infrared acid amount, mmol / g 0.603 0.671 0.598 [C B / C L ]]> 0.059 0.043 0.051 Mechanical strength, N / mm 13 12 13 Composition, wt% MoO3 22.1 22.0 22.2 NiO 6.1 6.1 6.0 C 0 5.1 0 Si 10.1 9.2 9.8 N 0 0.84 0.86 Metal dispersion XPS peak intensity ratio, I Mo / I Al ]]> 0.153 0.141 0.092 XPS peak intensity ratio, I Ni / I Al ]]> 0.098 0.096 0.069

[0106] Table 2 Properties of raw oil

[0107] Density (20°C), kg / m 3 ]] 987.2 S, wt% 4.35 N, ppm 2513 CCR, wt% 11.4 Ni, ppm 21.4 V, ppm 70.6

[0108] Table 3 Evaluation conditions and evaluation results of hydrogenation catalysts obtained in each example

[0109] Catalyst Example 1 Example 2 Example 3 Example 4 Evaluation conditions Reaction temperature, °C 385 385 385 385 Hydrogen partial pressure, MPa 14.7 14.7 14.7 14.7 Hydrogen to oil volume ratio 1000 1000 1000 1000 LHSV, h -1 ]] 0.2 (total) 0.2 (total) 0.2 (total) 0.2 (total) Evaluation results S, wt% 0.39 0.38 0.41 0.42 N, ppm 1201 1198 1232 1219 CCR, wt% 4.0 4.3 4.4 4.6 Ni, ppm 4.1 4.2 5.0 5.1 V, ppm 13.1 13.9 13.5 13.1

[0110] Table 3 Evaluation conditions and evaluation results of hydrogenation catalysts obtained in each example (continued)

[0111] Catalyst Comparative Example 1 Comparative Example 2 Comparative Example 3 Evaluation conditions Reaction temperature, °C 385 385 385 Hydrogen partial pressure, MPa 14.7 14.7 14.7 Hydrogen to oil volume ratio 1000 1000 1000 LHSV, h -1 ]]> 0.2 (total) 0.2 (total) 0.2 (total) Evaluation results S, wt% 1.90 1.72 0.53 N, ppm 1673 1732 1302 CCR, wt% 8.2 5.3 6.2 Ni, ppm 12.2 13.7 7.2 V, ppm 18.2 22.1 16.3

[0112] The examples described in the present application are only detailed descriptions of the technical solutions of the present application, but the present application is not limited to the above examples, that is, the present application can be implemented without relying on the steps described in the above examples. In summary, any improvement of the present application made by those skilled in the art, including replacement of the raw materials and additives described in the present application, selection of specific embodiments, etc., all belong to the protection scope and disclosure scope of the present application.

Claims

1. A method for preparing a residue hydrotreating catalyst, wherein, based on the mass of the catalyst, the content of Group VIB metal oxides is 15%~25%, and the content of Group VIII metal oxides is 3%~8%; based on the total mass of Group VIII metal oxides in the catalyst, the content of Group VIII metal oxides in the first active component is 30%~50%, and the content of Group VIII metal oxides in the second active component is 50%~70%. The method for preparing the catalyst includes the following steps: (1) The active metal solution C1 is impregnated onto the polyimide carrier, dried, and calcined to obtain the metal / polyimide material; (2) Prepare a wet filter cake containing silicon and carbon pseudoboehmite, and dry it to obtain silicon and carbon pseudoboehmite; (3) The silicon- and carbon-containing pseudoboehmite obtained in step (2) is shaped and dried to obtain an intermediate; (4) The intermediate obtained in step (3) is mixed with an active metal solution C2 for a second impregnation, dried, and calcined in an oxygen-containing atmosphere to obtain the catalyst; The silicon- and carbon-containing pseudo-boehmite wet filter cake in step (2) is prepared by the following method: (A) Add an aluminum-containing alkaline solution I to the carbonization reactor I, and pass in a mixed gas containing carbon dioxide to carry out the carbonization reaction, while controlling the pH value of the reactants. (B) Add the reactants obtained in step (A) and the mixed solution of aluminum-containing alkaline solution II and water glass in parallel flow to the main reactor to control the pH value of the slurry in the main reactor; (C) Add the slurry obtained in step (B) to carbonization reactor II, and introduce a mixed gas containing carbon dioxide to carry out the carbonization reaction, controlling the pH value of the reactants; (D) Replace the reactants obtained in step (A) of step (B) with the reactants obtained in step (C) and repeat steps (B) and (C); (E) Adjust the pH value of the material obtained in step (D), add the metal / polyimide material obtained in step (1) for adsorption reaction, filter and wash to obtain the silicon- and carbon pseudoboehmite wet filter cake. In step (1), the synthesis of the polyimide carrier includes: (a) Dissolve p-diaminobenzene in N,N-dimethylformamide solution, then add pyromellitic dianhydride, stir, and prepare a viscous solution; (b) Transfer the above solution to a reaction vessel, heat the reaction, cool it, wash it with an organic solvent, dry it, and grind it. (c) The obtained powder sample is calcined under an inert gas atmosphere to obtain the polyimide carrier; In step (A), the pH value of the resulting reactants is 5.5 to 6.5; In step (B), the pH value of the slurry is 11.5~12.5; In step (C), the pH value of the resulting reactants is 7.5~9.5; In step (1), the active metal in the active metal solution C1 is selected from at least one of Group VIII metals; the active component introduced into the catalyst by the active metal solution C1 is the first active component; In step (4), the active metal in the active metal solution C2 is selected from at least one group VIB metal and at least one group VIII metal; the active component introduced into the catalyst by the active metal solution C2 is the second active component.

2. The preparation method according to claim 1, characterized in that, In step (A), the aluminum-containing alkaline solution I is one or both of sodium aluminate solution and potassium aluminate solution, and the concentration of the aluminum-containing alkaline solution I, calculated as Al2O3, is 40~100gAl2O3 / L; and / or, In step (B), the aluminum-containing alkaline solution II is one or both of sodium aluminate solution and potassium aluminate solution, and the concentration of the aluminum-containing alkaline solution II, calculated as Al2O3, is 90~220 gAl2O3 / L; and / or, In step (B), the modulus of the water glass is 2.5 to 3.0, and the concentration of the water glass, calculated as SiO2, is 5 to 95 g SiO2 / L.

3. The preparation method according to claim 2, characterized in that, In step (A), the aluminum-containing alkaline solution I is a sodium aluminate solution, and the concentration of the aluminum-containing alkaline solution I, calculated as Al2O3, is 50~80 g Al2O3 / L; and / or, In step (B), the aluminum-containing alkaline solution II is a sodium aluminate solution, and the concentration of the aluminum-containing alkaline solution II, calculated as Al2O3, is 150~190gAl2O3 / L.

4. The preparation method according to claim 1, characterized in that, In step (A), the volume fraction of carbon dioxide in the carbon dioxide-containing mixed gas is 35%~65%, and the time for introducing the carbon dioxide-containing mixed gas is 10~45 min; and / or, In step (C), the volume fraction of carbon dioxide in the carbon dioxide-containing mixed gas is 35% to 65%, and the time for introducing the carbon dioxide-containing mixed gas is 5 to 25 minutes.

5. The preparation method according to claim 1, characterized in that, In step (B), the reaction time is 20-50 min; and / or, Step (D) is repeated 1 to 4 times; and / or, In step (E), the amount of the metal / polyimide material added is 10% to 40% of the total amount of aluminum-containing alkaline solution II added, based on the mass of alumina.

6. The preparation method according to claim 1, characterized in that, In step (E), the pH value of the material obtained in step (D) is adjusted to 10~10.

5.

7. The preparation method according to claim 1, characterized in that, In step (1), the active metal in the active metal solution C1 is selected from at least one of Group VIII metals, cobalt and nickel; and / or, In step (4), the impregnation is a saturated impregnation; The active metal in the active metal solution C2 is at least one of Group VIB metals, Mo and W, and at least one of Group VIII metals, Co and Ni.

8. The preparation method according to claim 7, characterized in that, The concentration of the active metal solution C1, calculated as active metal oxide, is 0.02~0.4 g / mL; and / or, The concentration of Group VIB metals in the active metal solution C2, calculated as oxides, is 0.05~0.5 g / mL, and the concentration of Group VIII metals, calculated as oxides, is 0.01~0.2 g / mL.

9. The preparation method according to claim 1, characterized in that, In step (1), the calcination temperature is 400~450℃, the atmosphere is inert, and the time is 2~3 hours; and / or, In step (4), the roasting temperature is 600~900℃, the roasting time is 3~5 hours, and the roasting is carried out in an oxygen-containing atmosphere.

10. The residue oil hydrogenation catalyst prepared by any one of the preparation methods described in claims 1-9.

11. The catalyst according to claim 10, characterized in that, The catalyst comprises an active component and a silicon- and carbon-containing alumina component, wherein, based on the mass of the alumina component, the silicon content is 3% to 95% and the carbon content is 2% to 90%.

12. The catalyst according to claim 11, characterized in that, The catalyst comprises an active component and a silicon- and carbon-containing alumina component, wherein, based on the mass of the alumina component, the silicon content is 5% to 20% and the carbon content is 4% to 15%.

13. The catalyst according to claim 11 or 12, characterized in that, The active component includes a first active component and a second active component, wherein the first active component is selected from at least one of Group VIII metals Co and Ni; the second active component is selected from at least one of Group VIB metals and at least one of Group VIII metals, wherein the Group VIB metal in the second active component is at least one of Mo and W, and the Group VIII metal is at least one of Co and Ni.

14. The catalyst according to claim 13, characterized in that, In the catalyst, based on the total mass of Group VIII metal oxides in the catalyst, the content of Group VIII metal oxides in the first active component is 30% to 50%, and the content of Group VIII metal oxides in the second active component is 50% to 70%.

15. The catalyst according to claim 11, characterized in that, The catalyst also contains nitrogen (N), with the N content ranging from 0.8% to 1.3% based on the mass of the catalyst.

16. The catalyst according to claim 11, characterized in that, In the catalyst, the dispersion of the active metal is: I VIB / I Al (×100) is 2~10, I VIII / I Al (×100) is 2~6.

17. The catalyst according to claim 11, characterized in that, The catalyst has a specific surface area of ​​110~235 m². 2 / g, pore volume 0.6~1.4cm 3 / g, with a mechanical strength of 15~28N / mm, the pore volume of pores with a diameter of 15~80nm accounts for 11%~32% of the total pore volume, and the pore volume of pores with a diameter of less than 8nm accounts for less than 5.0% of the total pore volume.

18. The catalyst according to claim 17, characterized in that, The catalyst has a specific surface area of ​​195~220 m². 2 / g, with a mechanical strength of 21~24 N / mm, and the pore volume of pores with a diameter of less than 8nm accounts for 2.0%~4.5% of the total pore volume.

19. The catalyst according to claim 11, characterized in that, The catalyst has an acid content of 0.50~0.95 mmol / g, and the ratio of Brønsted acid to Lewis acid is C. B / C L The value ranges from 0.025 to 0.

095.

20. The catalyst according to claim 19, characterized in that, The catalyst has an acid content of 0.60~0.75 mmol / g, and the ratio of Brønsted acid to Lewis acid is C. B / C L The value ranges from 0.060 to 0.

085.

21. The application of the catalyst according to any one of claims 10-20 in the residual oil hydrotreating process.