Residue hydroprocessing catalyst, method for preparing the same, 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 a first active metal solution on a porous carbon-nitrogen / SiO2 composite carrier, drying and calcining to obtain a metal / composite carrier material; putting the obtained metal / composite carrier material into a gelatinizing solution, preparing a pseudo-boehmite wet filter cake, drying, and preparing the pseudo-boehmite; shaping the obtained pseudo-boehmite, drying, and obtaining a catalyst precursor; impregnating the obtained catalyst precursor with a second active metal solution, drying, and calcining to obtain the catalyst. The catalyst provided by the application is suitable for residual oil hydrogenation treatment, and especially has excellent catalytic performance in desulfurization and denitrification.

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 easy to produce. In addition, in the calcination process, due to the strong interaction between metal and carrier, metal-oxygen-aluminum bond will be formed, which affects the catalytic efficiency of the catalyst, ultimately leads 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 because of 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 it is more dangerous for industrial production.

[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 of 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℃ to perform carbonization, performing slurry separation after the carbonization is completed, adding the filter cake into washing water to mix and beat up, 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 residue oil hydrogenation catalyst, a preparation method and application thereof. The residue oil hydrogenation catalyst provided by the present application has a high metal loading capacity, uniform dispersion, high mechanical strength, suitable pore distribution and specific surface area, and suitable surface acidity, and is suitable for use in residue oil hydroprocessing.

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

[0010] (1) impregnating a first active metal solution onto a porous carbon-nitrogen / SiO2 composite carrier, drying and calcining to obtain a metal / composite carrier material;

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

[0012] (3) shaping the pseudo-boehmite obtained in step (2), drying to obtain a catalyst precursor;

[0013] (4) impregnating the catalyst precursor prepared in step (3) with a second active metal solution, drying, and calcining to prepare the catalyst;

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

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

[0016] (B) adding the reaction material obtained in step (A) and the aluminum-containing alkaline solution II 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 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 metal / complex carrier material obtained in step (1) to perform adsorption reaction, filtering, and washing to obtain the pseudo-boehmite wet cake.

[0020] In the present application, in step (1), the porous carbon nitride / SiO2 complex carrier comprises:

[0021] (a) dissolving monocyanoamine in silica sol, adding an organic solvent after stirring to form a gel;

[0022] (b) heating and calcining the gel under inert atmosphere to obtain a porous carbon nitride / SiO2 complex carrier, and grinding into powder.

[0023] In the method of the present application, in step (a), the silica sol concentration is 30% to 55% in terms of SiO2, and preferably 40% to 50%.

[0024] In the method of the present application, in step (a), the mass ratio of the amount of monocyanoamine added to the silica sol is 0.5 to 1.5, and preferably 0.6 to 1.2.

[0025] In the method of the present application, in step (a), the organic solvent is selected from one of ethanol or ethylene glycol, and preferably ethanol, and the mass ratio of the amount of the organic solvent added to the silica sol is 0.5 to 1.5.

[0026] In the method, in step (b), the calcination temperature is 250-650 DEG C, preferably 300-450 DEG C, and the time is 2-15 h, and the inert atmosphere is selected from at least one of Ar, He, N2.

[0027] In the method, in step (1), the active metal in the first active metal solution is selected from at least one of group VIII metals cobalt and nickel, preferably nickel; the loading is 30%-50% of the total active metal oxide mass of group VIII in the catalyst; and the concentration of the active metal oxide in the first active metal solution is 0.02-0.40 g / mL.

[0028] In the method, in step (1), the drying temperature is 100-120 DEG C, and the time is 2-5 h; the calcination temperature is 400-450 DEG C, and the time is 2-3 h under the protection of an inert atmosphere, and the inert atmosphere is selected from at least one of Ar, He, N2.

[0029] In the method, in step (A), the aluminum-containing alkaline solution I is one or both of sodium metaaluminate solution and potassium metaaluminate solution, preferably sodium metaaluminate solution; the concentration of the aluminum-containing alkaline solution I is 40-100 g Al2O3 / L, preferably 50-80 g Al2O3 / L; and the caustic ratio of the aluminum-containing alkaline solution I is 1.15-1.45, preferably 1.20-1.40.

[0030] 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 feeding the carbon dioxide-containing mixed gas is 10-45 min, and the pH value of the obtained reaction material is 5.5-6.5.

[0031] In the method, in step (B), the pH value of the slurry in the main reactor is controlled by adjusting the flow of the aluminum-containing alkaline solution, and the pH value of the slurry is 11.5-12.5.

[0032] In the method, in step (B), the aluminum-containing alkaline solution II is one or both of sodium metaaluminate solution and potassium metaaluminate solution, preferably sodium metaaluminate solution, and the concentration of the aluminum-containing alkaline solution II is 90-220 g Al2O3 / L, preferably 150-190 g Al2O3 / L.

[0033] In the method, in step (B), the reaction time is 20-50 min.

[0034] 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 min, and the pH value of the obtained reaction material is 7.5 to 9.5.

[0035] In the method, the carbonization reactor I and the carbonization reactor II can be the same reactor.

[0036] In the method, the number of repetitions of step (D) is 1 to 4.

[0037] In the method, in step (E), the adjustment of the pH value of the material obtained in step (D) and the addition of the metal / complex carrier material obtained in step (1) are not limited in sequence.

[0038] In the method, in step (E), the addition amount of the metal / complex carrier material is 5% to 45% of the total addition amount of the aluminum-containing alkaline solution II in terms of aluminum oxide.

[0039] In the method, in step (E), the adjustment of the pH value of the material obtained in step (D) is 10 to 10.5.

[0040] In the method, in step (D), the washing can be performed by a conventional washing method in the art, and deionized water at 50°C to 80°C is preferably used for washing.

[0041] In the method, in step (2), the drying temperature is 60 to 150°C, and the drying time is 4 to 10 h.

[0042] In the method, in step (3), an extrusion aid can be added during the forming process, and the extrusion aid can be pearl millet powder. The addition amount of the extrusion aid is 1% to 6% of the mass of the pseudo-boehmite.

[0043] In the method, in step (3), the drying temperature is 80 to 120°C, and the time is 4 to 6 h.

[0044] In the method, in step (4), the impregnation is saturated impregnation. The active metal in the second active metal solution 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, more preferably Mo, and the group VIII metal is preferably at least one of Co and Ni, more preferably Ni; wherein the concentration of the group VIB metal in the second active metal solution 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.

[0045] In the method, the amount of the Group VIII metal introduced into the catalyst in step (4) accounts for 50% to 70% of the total mass of the Group VIII metal oxides in the catalyst.

[0046] In the method, in step (4), the content of the Group VIB metal oxides in the catalyst is 10% to 30% based on the mass of the catalyst, and the content of the Group VIII metal oxides is 2% to 15%.

[0047] In the method, in step (4), the drying temperature is 80 to 120°C, and the drying time is 2 to 5 hours, and after drying, the catalyst is calcined at a calcination temperature of 600 to 900°C for 3 to 5 hours.

[0048] The second aspect of the present application provides a residue hydroprocessing catalyst prepared by the method of the first aspect.

[0049] In the present application, the active metal in the catalyst is at least one of the Group VIB metal and at least one of the 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.

[0050] In the present application, the content of the Group VIB metal oxides in the catalyst is 10% to 30% based on the mass of the catalyst, and the content of the Group VIII metal oxides is 2% to 15%.

[0051] In the present application, the content of the Group VIB metal oxides in the catalyst is 10% to 30% based on the mass of the catalyst, and the content of the Group VIII metal oxides is 2% to 15%.

[0052] In the present application, the catalyst further contains N, and the content of N in the form of an element is 0.5% to 1.2% based on the mass of the catalyst.

[0053] In the present application, the catalyst further contains SiC, and the content of SiC is 6% to 50%, and preferably 12% to 18% based on the mass of the catalyst.

[0054] In the present application, the active metal dispersion degree I VIB / I Al (×100) is 2.5 to 8.0, and preferably 5.0 to 6.0, I VIII / I Al (×100) is 1.0 to 7.0, and preferably 3.0 to 5.0.

[0055] In the present application, the specific surface area of the catalyst is 130 to 210 m 2 / g, and preferably 160 to 190 m2 / cm, and the pore volume is 0.6-1.4 cm 3 / cm, preferably 0.8-1.1 cm 3 / cm, the mechanical strength is 18-28 N / mm, preferably 19-24 N / mm, the pore volume of the pores with a pore size of 15-80 nm accounts for 5.5%-19% of the total pore volume, preferably 7%-13%, and the pore volume of the pores with a pore size of less than 8 nm accounts for 6% or less of the total pore volume, preferably 2%-5%.

[0056] In the present application, the acid amount of the catalyst is 0.6-1.2 mmol / g, preferably 0.75-1.0 mmol / g. The ratio of the acid amount of B acid to the acid amount of L acid is C B / cm L , preferably 0.071-0.090.

[0057] The third aspect of the present application provides the use of the above-mentioned residue oil hydrogenation catalyst in a residue oil hydrogenation process.

[0058] In the present application, the 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 prepared according to the above-mentioned method.

[0059] 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.

[0060] In the above-mentioned residue oil hydrogenation reaction, the hydrogen-containing gas is hydrogen gas or a mixture of hydrogen gas and other gases, and the volume content of hydrogen gas in the mixture is generally not less than 80%, preferably not less than 85%, and more preferably not less than 95%.

[0061] In the above-mentioned residue oil hydrogenation process, the operating conditions of the residue oil 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.

[0062] Compared with the prior art, the present application has the following beneficial effects:

[0063] In the preparation method of the residue oil hydrogenation catalyst, on the one hand, monocyanoamine is subjected to a thermal polymerization reaction in silica sol to form a nitrogen-carbon composite carrier containing silicon dioxide. Since the nitrogen-carbon carrier has a certain band gap, and the band gap size can be adjusted by adjusting the calcination temperature, a metal-semiconductor heterojunction can be formed during the loading of the Group VIII metal, thereby strengthening the interaction between the metal and the nitrogen-carbon carrier, improving the metal dispersion, and increasing the metal loading. Moreover, the electronic transfer efficiency between the active metal and the alumina can be greatly weakened, and the adsorption and bonding between the two can be weakened. The synthesized catalyst has higher activity in the residue oil hydrogenation process. Further, the metal / composite carrier material is added in the gelation process by one-pot method. The operation is simple. Since the preparation method of the present application adopts the control end-point pH value carbonization method in the later stage, the pH value of the main reaction kettle slowly decreases, which provides time for the metastable state of the pseudo-boehmite to be converted to the stable state, and at the same time, it ensures that the silicon and carbon elements in the gelation solution are fully contacted. Part of the silicon carbide semiconductor can be formed in the subsequent calcination process, and the carbon element will not be removed due to the oxygen calcination. The presence of silicon carbide also plays a role in transferring electrons and promoting metal dispersion. On the other hand, a large amount of silicon dioxide balls contained in the nitrogen-carbon carrier will not be completely converted into silicon carbide. After the secondary impregnation, the silicon dioxide balls enter the alumina carrier during the calcination in the air atmosphere. The silicon element not only plays a pore expanding role, but also can adjust the surface acidity of the alumina carrier to form a silicon-containing hydrogenation catalyst. This synthesis method is efficient and controllable, and can provide a higher activity for the hydrogenation catalyst. In addition, the present application adopts the carbonization reaction outside the main reaction kettle, and the low-pH slurry after carbonization is returned to the high-pH solution in the main reaction kettle. Among them, the incomplete or defective crystal grains grown after carbonization are dissolved in the high-pH solution, while the complete crystal grains grow as the crystal nucleus for preparing 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 increase 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 method for preparing pseudo-boehmite, and the process is simple and easy to operate.

[0064] 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. When applied to residue oil hydrogenation treatment, it exhibits excellent catalytic performance in desulfurization and denitrification, and also has good activity in removing residual carbon and metals. DETAILED DESCRIPTION

[0065] 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.

[0066] In the present application, the mechanical strength is tested by using the ZQJ-III intelligent particle strength tester made by the Dalian Zhiqu Testing Machine Factory, and the average mechanical strength of a group of samples with the length of 4-6mm is determined.

[0067] 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).

[0068] In the present application, the infrared acid amount is determined by using the Nicolet 870 Fourier transform infrared spectrometer of the American Nicolet Company.

[0069] The technical scheme and effect of the present application are further illustrated by the following examples, but are not limited to the following examples.

[0070] Example 1

[0071] (1) 10g of cyanamide is dissolved in 12.5g of silica sol with the concentration of 40%, and then 12mL of anhydrous ethanol is added under vigorous stirring to form a gel. The gel is transferred to a crucible, heated to 400 DEG C in a tube furnace, kept at constant temperature for 6h, and protected by nitrogen to obtain a sample which is ground into powder, i.e. a porous carbon nitride / SiO2 composite carrier;

[0072] 80mL of active metal solution with the NiO content of 0.135g / mL is impregnated into 100g of the porous carbon nitride / SiO2 composite carrier, and dried at 110 DEG C for 4h, and then calcined at 430 DEG C for 3h under the protection of nitrogen atmosphere to obtain a metal / composite carrier 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;

[0073] (2) Preparation of pseudo-boehmite

[0074] (A) A sodium metaaluminate mixed solution with the caustic ratio of 1.35 and the concentration of 65g Al2O3 / L is added into 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;

[0075] (B) adding the mixed solution of the reaction material obtained in step (A) and sodium metaaluminate solution with a concentration of 180 g Al203 / L and a caustic ratio of 1.25 into the main reactor in parallel flow, and reacting for 25 min, wherein 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;

[0076] (C) adding the slurry obtained in step (B) into the carbonization reactor II, and introducing a mixed gas containing 55% of carbon dioxide by volume and air from the bottom of the carbonization reactor, and reacting for 10 min, wherein the pH value of the carbonization reaction material is controlled to be 8.0;

[0077] (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;

[0078] (E) adjusting the pH value of the material obtained in step (D) to be 10, and adding 100 g of the metal / composite carrier material obtained in step (1) for adsorption reaction, and washing with deionized water at a temperature of 70°C until neutral, and obtaining a silicon and carbon-containing pseudo-boehmite wet filter cake with a solid content of 58% after filtration, and drying at 120°C for 6 hours to obtain the pseudo-boehmite required by the present application;

[0079] (3) mixing 600 g (dry basis 80%) of the pseudo-boehmite sample obtained in step (2) and 15 g of sesbania powder, and extruding into a strip, and drying at 120°C for 4 hours to obtain a catalyst precursor;

[0080] (4) preparing an impregnation solution containing MoO3 of 0.309 g / mL and NiO of 0.058 g / mL, and saturating and impregnating the catalyst intermediate obtained in step (3), and drying at 120°C for 5 hours after complete impregnation, and calcining at 650°C for 3 hours to obtain the final hydrogenation catalyst A, and the physicochemical properties of which are shown in Table 1.

[0081] Example 2

[0082] Compared with Example 1, the only difference is that the amount of the metal / composite carrier material added is changed to 200 g, and the final hydrogenation catalyst B is obtained, and the physicochemical properties of which are shown in Table 1.

[0083] Example 3

[0084] 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, and the solution in step (4) is a MoO3 and NiO solution, in which the concentration of MoO3 is changed to 0.312 g / mL and the concentration of NiO is 0.045 g / mL, and the calcination temperature after impregnation is changed to 450°C, to obtain a final hydrogenation catalyst C (see Table 1 for the physical and chemical properties), in which the amount of Ni introduced into the catalyst, in terms of the mass of the oxide, accounts for 46.9% of the total Ni in the catalyst.

[0085] Example 4

[0086] The difference from Example 1 is only that the amount of metal / composite support material added during the preparation of the pseudoboehmite is changed to 50 g, and the reaction time in step (B) is changed to 45 min, and the number of repetitions in step (D) is changed to 2, to obtain a final hydrogenation catalyst D, the physical and chemical properties of which are shown in Table 1.

[0087] Comparative Example 1

[0088] The difference from Example 1 is only that the support used is activated carbon powder, to obtain a final hydrogenation catalyst E, the physical and chemical properties of which are shown in Table 1.

[0089] Comparative Example 2

[0090] The difference from Example 1 is only that:

[0091] In step (1) of impregnation, 80 mL of an active metal solution with a NiO content of 0.284 g / mL is impregnated into 100 g of a porous carbon nitride / SiO2 composite support, and finally the amount of Ni introduced into the catalyst, in terms of the mass of the oxide, accounts for 64.5% of the total Ni in the catalyst.

[0092] In step (4) of impregnation, an impregnation solution containing MoO3 at 0.312 g / mL and NiO at 0.030 g / mL is used to saturate the catalyst intermediate, and finally a final hydrogenation catalyst F is obtained, the physical and chemical properties of which are shown in Table 1.

[0093] Comparative Example 3

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

[0095] No metal / composite support material is added during the synthesis of the pseudoboehmite, and 500 g (dry basis 80%) of the above-mentioned pseudoboehmite sample and 100 g of metal / composite support material and 15 g of sesbania powder are weighed out during the extrusion process, mixed and extruded, and dried at 120°C for 4 hours to obtain an intermediate. Finally, a final hydrogenation catalyst G is obtained, the physical and chemical properties of which are shown in Table 1.

[0096] Example 5

[0097] The catalysts obtained in Examples 1-4 and Comparative Examples 1-3 were used in the residue hydroprocessing reaction, the feedstock properties are shown in Table 2, the evaluation conditions and results are shown in Table 3.

[0098] Table 1 Physical and chemical properties of the hydrogenation catalysts

[0099]

[0100]

[0101] Table 1 Physical and chemical properties of the hydrogenation catalysts (continued)

[0102] Catalyst Comparative Example 1 Comparative Example 2 Comparative Example 3 Pore volume, mL / g 0.74 0.79 0.82 Specific surface area, m 2 / g]] 203 212 207 Pore size distribution, % 8 nm or less 7.1 8.6 8.5 15 to 80 nm 18.2 15.1 14.0 Infrared acid amount, mmol / g 0.427 0.591 0.529 [C B / C L ]]> 0.032 0.063 0.054 Mechanical strength, N / mm 17 14 17 Composition, wt% MoO3 20.8 20.1 20.5 NiO 6.6 6.1 6.4 N 0 0.87 0.80 SiO2 0 9.7 9.5 SiC 1.2 13.0 2.3 Metal dispersion XPS peak intensity ratio, I Mo / I Al ]]> 0.113 0.093 0.072 XPS peak intensity ratio, I Ni / I Al ]]> 0.087 0.085 0.063

[0103] Table 2 Properties of the feedstock oil

[0104] 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

[0105] Table 3 Evaluation conditions and results of the hydrogenation catalysts obtained in each example

[0106] 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% 0.35 0.37 0.37 0.41 N, ppm 1193 1198 1204 1221 CCR, wt% 4.7 4.7 5.0 5.1 Ni, ppm 4.4 4.5 4.7 5.0 V, ppm 13.9 14.1 14.2 14.5

[0107] Table 3 Evaluation conditions and results of the hydrogenation catalysts obtained in each example (continued)

[0108]

[0109]

[0110] 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 without relying on the steps described in the above examples. In summary, any improvement of the present application made by a person skilled in the art, including the replacement of the raw materials and additives described in the present application, the selection of the specific embodiments, etc., all belong to the protection scope and disclosure scope of the present application.

Claims

1. A method for preparing a residue hydroprocessing catalyst, the catalyst comprising 10-30% of Group VIB metal oxide, 2-15% of Group VIII metal oxide and 4-25% of silicon oxide, based on the mass of the catalyst; the method comprising the following steps: (1) impregnating a first active metal solution into a porous carbon nitride / SiO2 composite carrier, drying and calcining to obtain a metal / composite carrier material; (2) preparing a pseudo-boehmite wet cake, drying to obtain pseudo-boehmite; (3) shaping the pseudo-boehmite obtained in step (2), drying to obtain a catalyst precursor; (4) impregnating the catalyst precursor obtained in step (3) with a second active metal solution, drying and calcining to obtain the catalyst; the pseudo-boehmite wet cake in step (2) is prepared by the following method: (A) adding an aluminum-containing alkaline solution I into a carbonation reactor I, introducing a carbon dioxide-containing mixed gas to perform carbonation reaction, and controlling the pH value of the reaction material; (B) adding the reaction material obtained in step (A) and an aluminum-containing alkaline solution II into a main reactor in parallel flow, and controlling the pH value of the slurry in the main reactor; (C) adding the slurry obtained in step (B) into a carbonation reactor II, introducing a carbon dioxide-containing mixed gas to perform carbonation reaction, and controlling the pH value of the reaction material; (D) replacing the reaction material obtained in step (A) in step (B) with the reaction material obtained in step (C), repeating steps (B) and (C); (E) adjusting the pH value of the material obtained in step (D), adding the metal / composite carrier material obtained in step (1) to perform adsorption reaction, filtering and washing to obtain the pseudo-boehmite wet cake; in step (A), the pH value of the obtained reaction material is 5.5-6.5; in step (B), the pH value of the slurry is 11.5-12.5; in step (C), the pH value of the obtained reaction material is 7.5-9.5; in step (1), the porous carbon nitride / SiO2 composite carrier comprises: (a) dissolving monocyanamide in silica sol, adding an organic solvent after stirring to form a gel; (b) calcining the gel under inert atmosphere to obtain a porous carbon nitride / SiO2 composite carrier, and grinding into powder; in step (1), the active metal in the first active metal solution is selected from at least one of Group VIII metals, and the loading amount is 30-50% of the total active metal oxide in the catalyst; the active metal in the second active metal solution is selected from at least one of Group VIB metals and at least one of Group VIII metals; in step (A), the aluminum-containing alkaline solution I is one or both of sodium metaaluminate solution or potassium metaaluminate solution, and the concentration of the aluminum-containing alkaline solution I is 40-100 g Al2O3 / L based on Al2O3; and / or, ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ 2. The production method according to claim 1, characterized by, ​ In step (B), the aluminum-containing basic solution II is one or both of sodium aluminate solution or potassium aluminate solution, and the concentration of the aluminum-containing basic solution II is 90-220 g Al2O3 / L as Al2O3.

3. The preparation method according to claim 2, characterized in that, In step (A), the aluminum-containing basic solution I is sodium aluminate solution, and the concentration of the aluminum-containing basic solution I is 50-80 g Al2O3 / L as Al2O3; and / or, In step (B), the aluminum-containing basic solution II is sodium aluminate solution, and the concentration of the aluminum-containing basic solution II 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 carbon dioxide-containing mixed gas is 35%-65%, and the time for feeding 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%-65%, and the time for feeding the carbon dioxide-containing mixed gas 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 times; and / or, In step (E), the amount of the metal / complex carrier material added is 5%-45% of the total amount of the aluminum-containing basic solution II 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 (1), the active metal in the first active metal solution is at least one selected from the group consisting of cobalt and nickel of Group VIII; and / or, In step (4), the impregnation is saturation impregnation, and the active metal in the second active metal solution is at least one selected from the group consisting of Mo and W of Group VIB and at least one selected from the group consisting of Co and Ni of Group VIII.

8. The preparation method according to claim 7, characterized in that, The concentration of the active metal in the first active metal solution is 0.02-0.40 g / mL as the oxide of the active metal; and / or, The concentration of the Group VIB metal in the second active metal solution is 0.05-0.5 g / mL as the oxide of the Group VIB metal, and the concentration of the Group VIII metal is 0.01-0.2 g / mL as the oxide of the Group VIII metal.

9. The method of claim 1, wherein, In step (1), the temperature of the calcination is 400-450 ℃, the atmosphere is inert atmosphere, and the time is 2-3 hours; and / or, In step (4), the temperature of the calcination is 600-900 ℃, and the time of the calcination is 3-5 hours.

10. The residue hydroprocessing catalyst prepared by the preparation method of any one of claims 1-9.

11. The catalyst of claim 10, wherein In the catalyst, the active metal is at least one selected from the group consisting of Mo and W of Group VIB and at least one selected from the group consisting of Co and Ni of Group VIII.

12. Catalyst according to claim 10 or 11, characterized in that The catalyst contains N, and the content of N as the element is 0.5%-1.2% based on the mass of the catalyst; and / or, The catalyst contains SiC, and the content of SiC is 6%-50% based on the mass of the catalyst.

13. The catalyst of claim 12, wherein, The content of SiC is 12%-18% 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 2.5 to 8.0, I VIII / I Al (x 100) is 1.0 to 7.

0.

15. The catalyst of claim 10, wherein The specific surface area of the catalyst is 130 to 210 m 2 / g, the pore volume is 0.6 to 1.4 cm 3 / g, the mechanical strength is 18 to 28 N / mm, the pore volume of the pores with a pore diameter of 15 to 80 nm accounts for 5.5% to 19% of the total pore volume, and the pore volume of the pores with a pore diameter of 8 nm or less accounts for 6% or less of the total pore volume.

16. The catalyst of claim 15, wherein The specific surface area of the catalyst is 160 to 190 m 2 / g, the pore volume is 0.8 to 1.1 cm 3 / g, the mechanical strength is 19 to 24 N / mm, the pore volume of the pores having a pore diameter of 15 to 80 nm accounts for 7 to 13% of the total pore volume, and the pore volume of the pores having a pore diameter of 8 nm or less accounts for 2 to 5% of the total pore volume.

17. The catalyst of claim 10, wherein The acid amount of the catalyst is 0.6-1.2 mmol / g, the ratio of the B acid amount to the L acid amount C is 0.04-0.

095. B / C L 0.04-0.

095.

18. The catalyst of claim 17, wherein, The acid amount of the catalyst is 0.75-1.0 mmol / g, the ratio of the acid amount of B acid to the acid amount of L acid is C B / C L 0.07-0.

09.

19. Use of a catalyst according to any one of claims 10 to 18 in a residue hydroprocessing process.

Images