Hydrogenation catalyst, process for its preparation and use

Abstract

The application discloses a hydrogenation catalyst and a preparation method and application thereof. The preparation method of the catalyst comprises the following steps: preparing a polyimide material; putting the obtained polyimide material into a gumming 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 the shaped silicon and carbon-containing pseudo-boehmite to obtain an intermediate; mixing the obtained intermediate with a metal solution C to perform saturated impregnation, drying the intermediate, and calcining the intermediate in an inert atmosphere to obtain the hydrogenation catalyst. The catalyst provided by the application is applied to residual oil hydroprocessing, and especially exhibits excellent catalytic performance in the process of removing residual carbon and metal, and also exhibits good catalytic capacity in the process of removing sulfur and nitrogen.

Description

TECHNICAL FIELD

[0001] The present application relates to a hydrogenation catalyst and a preparation method and application thereof. BACKGROUND

[0002] Residue hydroprocessing catalysts are mainly metal supported catalysts, which are mostly supported on alumina and / or silica, and active metal components such as Ni, Mo and Co. In the existing methods, when the active metal loading is large, the metal particles tend to agglomerate or be unevenly distributed. In addition, during the calcination process, the strong interaction between the metal and the support will lead to the formation of metal-oxygen-aluminum bonds, affecting the catalytic efficiency of the catalyst, and ultimately leading to a decrease in the hydrogenation activity of the catalyst. Moreover, it is difficult to synthesize a catalyst with high metal loading, and the introduction of heteroatoms can appropriately adjust the acidity of the support, but the operation during the introduction process is complex, which can easily reduce the pore size of the catalyst, and is not conducive to improving the activity of the residue hydroprocessing catalyst.

[0003] CN1257754A discloses a preparation method of a silica-alumina catalyst support. A silica-alumina precursor is prepared by introducing water glass and aluminum sulfate, and the prepared support has a pore volume of 0.45-0.75 mL / g and an average pore size of 5-10 nm. However, the final synthesized alumina support has a small pore size, which is not suitable for use as a hydroprocessing catalyst for heavy oil or residue with a large molecular weight.

[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 obtain a sol; then the sol is used as a binder, and a macroporous alumina and a microporous alumina are mixed, molded, dried and calcined to obtain an alumina support; then the alumina support is impregnated with an active metal component impregnation solution, and dried and calcined to obtain a hydroprocessing catalyst. This method is complex to operate, the introduction of acid sites will promote the bonding between the active metal and the support, and the use of a large amount of concentrated acid will cause environmental pollution, and the industrial production is relatively dangerous.

[0005] CN105582945A discloses a preparation method of a hydroprocessing catalyst. First, an alumina support is impregnated with a urea aqueous solution, and then a polyol or a monosaccharide aqueous solution is sprayed and impregnated on the alumina support in the order of decreasing concentration, so that the concentration of the polyol and / or monosaccharide forms a gradient distribution from low to high from the outside to the inside of the support, and then an active metal component is loaded. This method requires multiple steps of spraying and impregnation to form a polymeric carbon shell layer, and has a high requirement for the concentration of the solution, 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 organic pore-expanding agent and defoaming agent into a sodium metaaluminate solution, then passing in 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 diameter 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 diameter 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: at a temperature of 15-45℃, passing carbon dioxide with a volume concentration of 20%-50% into a sodium metaaluminate solution with an Al2O3 content of 20-60g / L to perform carbonization, performing slurry separation after the carbonization is completed, adding the filter cake into washing water to mix and perform beating, and then aging at 80-100℃ 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 preparation method and application of a hydrogenation catalyst. The pseudo-boehmite prepared by the present application has concentrated and uniform particle size, and the alumina obtained through calcination has suitable large pore diameter and pore volume. The catalyst provided by the present application has high metal loading and uniform dispersion, high mechanical strength, suitable surface acidity, and is suitable for use in residual oil hydroprocessing.

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

[0010] (1) preparing a 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 obtained in step (3) with a metal solution C to perform saturated impregnation, drying, and calcining in an inert atmosphere to obtain the hydrogenation catalyst;

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

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

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

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

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

[0020] In the method, in step (A), the basic solution containing aluminum I is one or both of sodium meta-aluminate solution or potassium meta-aluminate solution, and preferably sodium meta-aluminate solution; the concentration of the basic solution containing aluminum I is 40-100 g Al2O3 / L, and preferably 50-80 g Al2O3 / L; and the caustic ratio of the basic solution containing aluminum 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 mixed gas containing carbon dioxide is 35%-65%; the pH value at the outlet of the carbonization reactor is controlled by adjusting the flow of the mixed gas, and the pH value at the outlet of the carbonization reactor 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 of the basic solution containing aluminum, 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.

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

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

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

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

[0028] In the method, the number of repetitions of step (D) is 1 to 4.

[0029] In the method, in step (E), the adjustment of the pH value of the material obtained in step (D) has no order restriction with the addition of the polyimide material obtained in step (1).

[0030] In the method, in step (C), the addition amount of the polyimide material is 10% to 40% of the total addition amount of the aluminum-containing alkaline solution II in terms of the mass of aluminum oxide.

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

[0032] In the method, in step (D), the washing can be performed by a conventional washing method in the art, and preferably by using deionized water at 50°C to 80°C.

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

[0034] (a) dissolving p-diaminobenzene in an 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 and washing with an organic solvent, drying, and grinding;

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

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

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

[0045] In the method of the present application, 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. The amount of the extrusion aid added is 1%-6% of the mass of the silicon and carbon-containing pseudo-boehmite.

[0046] In the method of the present application, in step (3), the drying temperature is 80-120℃, and the time is 4-6 h.

[0047] In the method of the present application, in step (4), the impregnation adopts saturation impregnation; the active metal in the active metal solution C is at least one selected from Group VIB metals and at least one selected from Group VIII metals, wherein the Group VIB metal is preferably at least one selected from Mo and W, more preferably Mo, and the Group VIII metal is preferably at least one selected from Co and Ni, more preferably Ni, wherein the concentration of the Group VIB metal in terms of oxide is 0.15-0.40 g / mL, and the concentration of the Group VIII metal in terms of oxide is 0.02-0.09 g / mL.

[0048] In the method of the present application, in step (4), the drying temperature is 80-120℃, the drying time is 2-5 h, the calcination temperature is 600-900℃, and the calcination time is controlled to be 3-5 h, and the calcination is performed in an inert atmosphere (such as N2).

[0049] The second aspect of the present application provides a hydrogenation catalyst prepared by the above method, comprising an active component and an alumina component containing silicon and carbon, wherein the mass content of silicon is 3% to 95%, preferably 5% to 20%, and the mass content of carbon is 2% to 90%, preferably 6% to 20%, and further preferably 7% to 9%, based on the mass of the alumina component.

[0050] In the present application, the active metal in the catalyst is at least one of Group VIB metal and at least one of Group VIII metal, 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.

[0051] In the present application, the catalyst further contains N, and the content of N is 0.8% to 1.5%, based on the mass of the catalyst.

[0052] In the present application, the content of Group VIB metal oxide in the catalyst is 15% to 25%, and the content of Group VIII metal oxide is 1.9% to 6.5%, based on the mass of the catalyst.

[0053] In the present application, the dispersion degree of the active metal in the catalyst is I VIB / I Al (×100) is 2 to 6, and preferably 4 to 5, I VIII / I Al (×100) is 1 to 7.

[0054] In the present application, the specific surface area of the catalyst is 115 to 255 m 2 / g, preferably 195 to 220 m 2 / g, the pore volume is 0.6 to 1.6 cm 3 / g, the mechanical strength is 18 to 28 N / mm, preferably 19 to 25 N / mm, the pore volume of pores with a pore diameter of 15 to 80 nm accounts for 6% to 18% of the total pore volume, and the pore volume of pores with a pore diameter of less than 8 nm accounts for less than 5%, and preferably 1% to 4%, of the total pore volume.

[0055] In the present application, the acid amount of the catalyst is 0.50 to 1.05 mmol / g, and preferably 0.60 to 0.85 mmol / g. The ratio C B / C L of the amount of B acid to the amount of L acid is 0.03 to 0.09, and preferably 0.055 to 0.085.

[0056] The third aspect of the present application provides the use of the above hydrogenation catalyst in a residual oil hydrogenation process.

[0057] In the present application, the residue oil and hydrogen-containing gas are contacted under hydrogenation reaction conditions in the presence of the residue hydrogenation catalyst or the residue hydrogenation catalyst prepared according to the above method.

[0058] In the above residue hydrogenation reaction, the residue material is selected from one of atmospheric residue, vacuum residue and high-temperature coal tar.

[0059] In the above residue hydrogenation reaction, the hydrogen-containing gas is hydrogen or a mixture of hydrogen and other gases, and 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%.

[0060] In the above 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.

[0061] Compared with the prior art, the present application has the following beneficial effects:

[0062] In the preparation method of the catalyst, the high-molecular polymer polyimide contains C, N and O elements, and after calcination, the organic carbon material has a band gap opened to become a semiconductor material. Further, the polyimide material is added in the gelation process by using a one-pot method, which is simple to operate. Since the Si element is contained in the gelation solution, and the preparation method of the present application adopts a carbonization mode of controlling the final pH value in the later stage, the pH value of the main reactor slowly decreases, which 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 fully contacted with the Si element in the gelation solution, so that part of the silicon carbide semiconductor can be formed in the subsequent calcination process. The carbon element will not be removed due to calcination in the inert atmosphere, and the presence of silicon carbide 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. And the retention of more carbon and nitrogen elements in the inert atmosphere is conducive to adjusting the pore size and the surface activity of the carrier. Then, the extrusion molding is performed, and the metal solution is impregnated. Since the metal-semiconductor heterojunction will be formed on the interface between the active phase metal and the polyimide, the heterojunction will accelerate the migration rate of electrons between the active metal and the polyimide, and at the same time, the interaction force between the two will be enhanced, so that the active metal will be more inclined to be loaded on the surface of the polyimide during the loading process, effectively improving the metal dispersion, and the adsorption and bonding action between the active metal and the silicon-containing alumina carrier can be greatly weakened. The synthesized catalyst has higher activity in the residue oil hydrogenation process. Further, the band gap size can be adjusted by adjusting the calcination temperature of the polyimide, so as to adjust the interaction force between the active metal and the polyimide. In the subsequent calcination process, the nitrogen element contained in the polyimide can play a role in adjusting the surface acidity of the catalyst. In addition, the present application adopts the carbonization reaction outside the main reactor, and the low-pH slurry after carbonization is returned to the high-pH solution in the main reactor. Among them, 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. Such a carbonization cycle makes the slurry swing between acidity and alkalinity, which can increase the grain size, concentrate the particle size, and improve the crystallinity of the prepared pseudo-boehmite. 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 process of preparing pseudo-boehmite, and the process is simple and easy to operate.

[0063] The hydrogenation catalyst provided by the present application has high metal loading, uniform dispersion, high mechanical strength, suitable pore distribution and specific surface area, and suitable surface acidity. The catalyst is applied in residue oil hydrogenation treatment and exhibits excellent catalytic performance. DETAILED DESCRIPTION

[0064] In the present application, the nitrogen adsorption-desorption curve of the sample is tested at-196 DEG C 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.

[0065] In the present application, the mechanical strength is tested by using the ZQJ-III intelligent particle strength tester manufactured by the Dalian Zhiqu Tester Factory, and the average mechanical strength of a group of samples with the length of 4-6mm is determined.

[0066] In the present application, the metal dispersion is measured by using the XPS peak intensity ratio of the active metal and aluminum element by XRS (the instrument is Kratos Axis Ultra DLD model).

[0067] In the present application, the infrared acid amount is determined by using the Nicolet 870 Fourier transform infrared spectrometer of the American Nicolet Company.

[0068] The technical scheme and effect of the present application are further illustrated by the following examples, but are not limited to the following examples.

[0069] Example 1

[0070] (1) 100mmol of p-diaminobenzene is dissolved in 60mL of N,N-dimethylformamide solution, and 2.2g of pyromellitic dianhydride is added, and the solution is stirred rapidly for 8h until the solution is viscous. Then the above solution is transferred to a hydrothermal reactor, heated at 180 DEG C for 10h, after cooling, washed with N,N-dimethylformamide solvent for 3 times, dried at 110 DEG C for 4h, and ground for use. The powder sample is calcined under nitrogen protection for 8h, and the calcination temperature is 350 DEG C, to obtain a polyimide carrier;

[0071] (2) Preparation of silicon and carbon-containing pseudo-boehmite

[0072] (A) A sodium metaaluminate mixed solution with a caustic ratio of 1.35 and a concentration of 65g Al2O3 / L is added to the carbonization reactor I, and a mixed gas containing 55% of carbon dioxide and air by volume fraction is introduced from the bottom of the carbonization reactor, and the reaction is carried out for 15min, and the pH value of the carbonization reaction material is controlled to be 6.0;

[0073] (B) The reaction material obtained in step (A) and a mixed solution of water glass with a modulus of 2.8, a concentration of 50g SiO2 / L, and a sodium metaaluminate solution with a concentration of 180g Al2O3 / L and a caustic ratio of 1.25 are added to the main reactor in parallel, and the reaction is carried out for 25min, and the pH value of the slurry in the main reactor is controlled to be 12 by adjusting the flow of the sodium metaaluminate solution;

[0074] (C) adding the slurry obtained in step (B) into carbonization reactor II, introducing a mixed gas containing carbon dioxide and air with a carbon dioxide volume fraction of 55% from the bottom of the carbonization reactor, and reacting for 10 minutes to control the pH of the carbonization reaction material to 8.0;

[0075] (D) replacing the carbonization material obtained in step (A) in step (B) with the reaction material obtained in step (C), and repeating steps (B) and (C) for 3 times;

[0076] (E) adjusting the pH of the material obtained in step (D) to 10, and adding 100 g of the polyimide material obtained in step (1) for adsorption reaction, washing with deionized water at 70°C until neutral, and filtering to obtain a wet filter cake containing silicon and carbon pseudo-boehmite with a solid content of 55%, and drying at 120°C for 6 hours to obtain the silicon and carbon pseudo-boehmite required by the present application;

[0077] (3) mixing 600 g (dry basis 80%) of the silicon and carbon pseudo-boehmite obtained in step (2) with 15 g of sesbania powder, and extruding into a strip, and drying at 120°C for 4 hours to obtain an intermediate;

[0078] (4) preparing an impregnation solution containing MoO3 at 0.280 g / mL and NiO at 0.077 g / mL, and saturating and impregnating the catalyst intermediate obtained in step (3), drying at 120°C for 5 hours after complete impregnation, and calcining at 650°C for 3 hours under a nitrogen atmosphere to obtain the final hydrogenation catalyst A, and the physicochemical properties are shown in Table 1.

[0079] Example 2

[0080] Compared with Example 1, the only difference is that the amount of polyimide material added 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.

[0081] Example 3

[0082] Compared with Example 1, the only difference is that the concentration of SiO2 in the mixed solution in the preparation of pseudo-boehmite is changed to 90 g / L, and the volume fraction of carbon dioxide in the mixed gas of carbon dioxide and air used is 40%, and the final hydrogenation catalyst C is obtained, and the physicochemical properties are shown in Table 1.

[0083] Example 4

[0084] Compared with Example 1, the difference lies in that, in step (2) of the preparation of silicon- and carbon pseudoboehmite, a water glass solution with a modulus of 2.8 and a concentration of 10 g SiO2 / L is added in parallel flow in step (B); in step (4), the product is washed with deionized water at 80°C until neutral and dried at 140°C for 8 hours to obtain the silicon- and carbon pseudoboehmite required by this invention. The final hydrogenation catalyst D is obtained, and its physicochemical properties are shown in Table 1.

[0085] Comparative Example 1

[0086] Compared with Example 1, the only difference is that the support used is activated carbon powder, and the final hydrogenation catalyst E is obtained, the physicochemical properties of which are shown in Table 1.

[0087] Comparative Example 2

[0088] The only difference compared to Example 1 is:

[0089] The preparation process of pseudoboehmite differs. 3000 mL of sodium aluminate solution with a concentration of 65 g Al₂O₃ / L and a caustic ratio of 1.35 was added to a 5.0 L reactor. Simultaneously, 100 g of polyimide material was added to the reactor. Then, a mixture of carbon dioxide and air with a carbon dioxide content of 80% (volume fraction) was introduced. The initial reaction temperature was 25 °C, and the slurry temperature was maintained constant during cooling. The reaction time was controlled at 45 min, allowing the pH of the sodium aluminate solution to drop to 8.8. The slurry was filtered, washed with deionized water at 75 °C, and then dried at 120 °C for 6 hours to obtain the final hydrogenation catalyst F. Its physicochemical properties are shown in Table 1.

[0090] Comparative Example 3

[0091] The only difference compared to Example 1 is:

[0092] In the synthesis of boehmite, no polyimide material was added. During the extrusion process, 500g of the silicon- and carbon-containing boehmite sample (80% dry basis), 100g of polyimide material, and 15g of guar gum powder were weighed, mixed, and extruded. The mixture was then dried at 120℃ for 4 hours to obtain an intermediate. The final hydrogenation catalyst G was obtained, and its physicochemical properties are shown in Table 1.

[0093] Example 5

[0094] The catalysts obtained in Examples 1-4 and Comparative Examples 1-3 were used in the hydrogenation reaction of residue oil, respectively. The properties of the feedstock are shown in Table 2, and the evaluation conditions and results are shown in Table 3.

[0095] Table 1 Physicochemical properties of hydrogenation catalysts

[0096]

[0097]

[0098] Table 1 Physico-chemical properties of hydrogenation catalysts (continued)

[0099] Catalyst Comparative Example 1 Comparative Example 2 Comparative Example 3 Pore volume, mL / g 0.64 0.75 0.73 Specific surface area, m 2 / g]] 219 217 213 Pore size distribution, % 8 nm or less 5.1 6.3 6.2 15 to 80 nm 17.1 19.3 13.9 Infrared acid amount, mmol / g 0.523 0.133 0.521 [C B / C L ]]> 0.043 0.022 0.039 Mechanical strength, N / mm 17 20 19 Composition, wt% MoO3 22.2 22.2 22.0 NiO 6.0 6.1 6.1 C 0 6.3 3.4 Si 10.4 0 9.2 N 0 0.93 0.99 Metal dispersion XPS peak intensity ratio, I Mo / I Al ]]> 0.132 0.162 0.151 XPS peak intensity ratio, I Ni / I Al ]]> 0.081 0.083 0.089

[0100] Table 2 Properties of feedstocks

[0101] 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

[0102] Table 3 Evaluation conditions and results of hydrogenation catalysts obtained in each example

[0103] 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% 0.47 0.43 0.45 0.50 N, ppm 1248 1241 1252 1259 CCR, wt% 3.5 3.6 3.9 3.3 Ni, ppm 3.7 3.6 4.1 4.3 V, ppm 12.9 12.8 12.8 13.1

[0104] Table 3 Evaluation conditions and results of hydrogenation catalysts obtained in each example (continued)

[0105] 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% 1.12 0.92 0.88 N, ppm 1738 1721 1650 CCR, wt% 8.0 7.1 7.9 Ni, ppm 13.3 16.2 11.4 V, ppm 19.4 21.2 19.1

[0106] 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, i.e. the present application can be implemented regardless of the steps described in the above examples. In summary, any improvement of the present application made by a person 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 hydrogenation catalyst, the catalyst having a content of Group VIB metal oxide of 15% to 25% and a content of Group VIII metal oxide of 1.9% to 6.5% by mass of the catalyst; the method comprising the steps of: (1) preparing a polyimide material; (2) preparing a silicon and carbon-containing pseudo-boehmite wet cake, drying the wet cake to obtain a silicon and carbon-containing pseudo-boehmite; (3) forming the silicon and carbon-containing pseudo-boehmite obtained in step (2), drying the formed product to obtain an intermediate; (4) mixing the intermediate obtained in step (3) with an active metal solution C, performing saturated impregnation, drying, and calcining in an inert atmosphere to obtain the hydrogenation catalyst; the silicon and carbon-containing pseudo-boehmite wet cake of step (2) being prepared by the following method: (A) adding an aluminum-containing basic solution I to a carbonization reactor I, introducing a carbon dioxide-containing mixed gas to perform a carbonization reaction, and controlling the pH of the reaction material; (B) adding the reaction material obtained in step (A) and a mixed solution of an aluminum-containing basic solution II and water glass to a main reactor in parallel flow, and controlling the pH of the slurry in the main reactor; (C) adding the slurry obtained in step (B) to a carbonization reactor II, introducing a carbon dioxide-containing mixed gas to perform a carbonization reaction, and controlling the pH of the reaction material; (D) repeating steps (B) and (C) using the reaction material obtained in step (C) to replace the reaction material obtained in step (A) in step (B); (E) adjusting the pH of the material obtained in step (D), adding the polyimide material obtained in step (1) to perform an adsorption reaction, filtering, and washing to obtain the silicon and carbon-containing pseudo-boehmite wet cake; in step (A), the pH of the obtained reaction material is 5.5 to 6.5; in step (B), the pH of the slurry is 11.5 to 12.5; in step (C), the pH of the obtained reaction material is 7.5 to 9.5; in step (1), the synthesis of the polyimide material comprises: (a) dissolving p-diaminobenzene in an N,N-dimethylformamide solution, then adding pyromellitic dianhydride, stirring to obtain a viscous solution; (b) transferring the solution to a reactor, heating and reacting, then cooling, washing with an organic solvent, drying, and grinding; (c) calcining the obtained powder sample under inert gas protection to obtain the polyimide material; in step (4), the active metal in the active metal solution C is selected from at least one of Group VIB metals and at least one of Group VIII metals; in step (A), the aluminum-containing basic solution I is one or both of a sodium metaaluminate solution or a potassium metaaluminate solution, and the concentration of the aluminum-containing basic solution I is 40 to 100 g Al2O3 / L as Al2O3; and / or, in step (B), the aluminum-containing basic solution II is one or both of a sodium metaaluminate solution or a potassium metaaluminate solution, and the concentration of the aluminum-containing basic solution II is 90 to 220 g Al2O3 / L as Al2O3. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ 2. The production method according to claim 1, characterized by, ​ ​ In step (B), the modulus of the water glass is 2.5-3.0, and the concentration of the water glass is 5-95 g SiO2 / L as SiO2.

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

4. The method of claim 1, wherein, In step (A), the volume fraction of carbon dioxide in the mixed gas containing carbon dioxide is 35%-65%, and the time for feeding the mixed gas containing carbon dioxide is 10-45 min; and / or, In step (C), the volume fraction of carbon dioxide in the mixed gas containing carbon dioxide is 35%-65%, and the time for feeding the mixed gas containing carbon dioxide is 5-25 min.

5. The preparation method according to claim 1, characterized in that, In step (B), the reaction time is 20-50 min; and / or, The number of repetitions of step (D) is 1-4; and / or, In step (E), the amount of the polyimide material added is 10%-40% of the total amount of the basic solution II containing aluminum as Al2O3.

6. The method of claim 1, wherein, 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 (4), the impregnation is saturated impregnation; the active metal in the active metal solution C is at least one of Mo and W in Group VIB and at least one of Co and Ni in Group VIII.

8. The method of claim 1, wherein, The concentration of the Group VIB metal in the active metal solution C is 0.15-0.40 g / mL as oxide, and the concentration of the Group VIII metal is 0.02-0.09 g / mL as oxide.

9. The method of claim 1, wherein, In step (4), the temperature of the calcination is 600-900 ℃, and the calcination time is 3-5 hours.

10. The residual hydroprocessing catalyst produced by the process of any of claims 1-9, characterized by, The catalyst comprises an active metal and an alumina component containing silicon and carbon, and the mass content of silicon is 3%-95% and the mass content of carbon is 2%-90% based on the mass of the alumina component.

11. The catalyst of claim 10, characterized in that, The mass content of silicon is 5%-20% and the mass content of carbon is 6%-20% based on the mass of the alumina component in the catalyst.

12. The catalyst of claim 10, wherein The active metal is at least one of Mo and W in Group VIB and at least one of Co and Ni in Group VIII.

13. The catalyst of claim 10, wherein The catalyst contains N, and the content of N is 0.8%-1.5% based on the mass of the catalyst.

14. The catalyst of claim 10, wherein The active metal dispersion degree in the catalyst is: I VIB / I Al (x 100) is 2 to 6, I VIII / I Al (x 100) is 1 to 7.

15. The catalyst of claim 10, wherein The specific surface area of the catalyst is 115 to 255 m 2 / g, the pore volume is 0.6 to 1.6 cm 3 / g, the mechanical strength is 18 to 28 N / mm, the pore volume of the pores having a pore diameter of 15 to 80 nm accounts for 6 to 18% of the total pore volume, and the pore volume of the pores having a pore diameter of 8 nm or less accounts for 5% or less of the total pore volume.

16. The catalyst of claim 15, wherein The specific surface area of the catalyst is 195 to 220 m 2 / g, the mechanical strength is 19 to 25 N / mm, and the pore volume of pores having a pore diameter of 8 nm or less accounts for 1 to 4% of the total pore volume.

17. The catalyst of claim 10, wherein The acid amount of the catalyst is 0.50-1.05 mmol / g; the ratio of the acid amount of B acid to the acid amount of L acid is C B / C L 0.03-0.

09.

18. The catalyst of claim 17, wherein, The acid amount of the catalyst is 0.60-0.85 mmol / g; the ratio of the acid amount of B acid to the acid amount of L acid is C B / C L 0.055-0.

085.

19. The use of the catalyst according to any one of claims 10-18 in a residue hydroprocessing process.

Images