A hydrodecarbon residue catalyst, its preparation method and application

Abstract

The application discloses a hydroresid catalyst, a preparation method and application thereof. The catalyst comprises a carrier and an active metal component; the carrier comprises kaolin and alumina; the content of the kaolin is 6-25% and the content of the alumina is 50-80% based on the weight of the carrier; the active metal component comprises Mo and group VIII metal elements; the Mo comprises +5 valence Mo; the group VIII metal elements exist in the catalyst in the form of metal phosphide. The hydroresid catalyst is used in a hydroresid process of residual oil, is beneficial to the hydrogenation saturation and hydrogenolysis reaction of polycyclic and condensed ring aromatic hydrocarbons of the raw oil, has good hydroresid performance, and can further remove nitrogen-containing compounds and has good stability.

Description

Technical Field

[0001] This invention belongs to the field of preparation of hydrodecarbonization catalysts, specifically relating to a hydrodecarbonization catalyst, its preparation method, and its application. Background Technology

[0002] The overall trend in global oil resource development is the continuous depletion of conventional crude oil, with increasingly deteriorated and heavier properties. Meanwhile, market demand for light oil products is growing, and environmental regulations are becoming increasingly stringent. The combination of fixed-bed hydrotreating technology and catalytic cracking (RFCC) of residue oil is a core technology for large-scale refineries to improve economic efficiency. It primarily addresses the issues of high levels of metals, residual carbon, sulfur, and nitrogen in RFCC feedstock, thereby reducing catalyst consumption in FCC units, improving product distribution, increasing liquid product yield, and improving product quality. Therefore, residue hydrotreating technology is receiving increasing attention from refiners worldwide.

[0003] Residue oil contains a large amount of iron, nickel, vanadium, sodium, calcium, as well as sulfur, nitrogen, and residual carbon. The main function of a fixed-bed hydrotreating unit for residue oil is to effectively remove these undesirable elements from the feedstock, while simultaneously performing appropriate hydroconversion to improve the chemical properties of the heavy feedstock oil and provide high-quality feedstock for downstream FCC units. Based on their different functions, the catalyst system for fixed-bed hydrotreating of residue oil is mainly divided into protective agents, demetallizing agents, desulfurizing agents, and residual carbon removal catalysts. The residual carbon removal catalyst in residue oil hydrotreating is located at the downstream end of the catalyst system and mainly undergoes desulfurization, denitrification, and residual carbon hydroconversion reactions. This type of catalyst should focus more on the conversion capacity of residual carbon, i.e., reducing the impact of carbon deposits on catalyst activity loss. The residue oil hydrotreating reaction is a diffusion-controlled reaction. Larger pore sizes facilitate the diffusion and mass transfer of residue oil molecules within the catalyst particles, allowing them to diffuse into the interior of the catalyst particles for reaction, and enabling more active sites to contact and react with the residue oil molecules. Therefore, larger pore sizes in fixed-bed hydrotreating catalysts for residual carbon removal also help improve catalyst utilization and impurity removal performance.

[0004] CN117000260A discloses a hydrocracking catalyst and its preparation method. The catalyst comprises a catalyst body, a sub-outer layer, and a macroporous alumina layer. The catalyst body includes an alumina support and active components molybdenum and nickel. The active metals in the catalyst are non-uniformly distributed. The outermost layer of the catalyst does not contain active metals and is a layer of macroporous alumina. The sub-outer layer contains less active metals and has relatively large pores. During the preparation of the catalyst body, a microemulsion containing active metals is impregnated. The catalyst has poor acidity, insufficient to promote the hydrocracking and ring-opening / isomerization reactions of macromolecules. The decarbonization performance of the catalyst still needs further improvement.

[0005] CN103785397A discloses a hydrogenation decarbonization catalyst and its preparation method. The catalyst uses alumina as a support and Mo and Ni as active components. The preparation method includes the following steps: (1) After neutralization reaction between an acidic aluminum salt aqueous solution and an alkali metal aluminate aqueous solution, an alkaline precipitant or an alkaline aluminate aqueous solution is introduced to adjust the pH of the slurry for aging; (2) After aging in step (1), the material is filtered, washed, and dried, and then aluminum ammonium carbonate is added for molding; (3) The molded material is loaded with active components, dried, and calcined to obtain the hydrogenation decarbonization catalyst. The catalyst exhibits strong acidity at its macropores, resulting in a vigorous hydrogenation reaction. The generated carbon deposits and metal deposits easily clog the pores and cover the hydrogenation active sites. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a hydrodecarbonization catalyst, its preparation method, and its application. This hydrodecarbonization catalyst, used in the hydrodecarbonization process of residual oil, facilitates the hydrogenation saturation and hydrolysis reactions of polycyclic aromatic hydrocarbons (PAHs) in the feedstock oil. It not only exhibits excellent hydrodecarbonization performance but also further removes nitrogen-containing compounds and possesses good stability.

[0007] The first aspect of this invention provides a hydrocracking catalyst, comprising a support and an active metal component. The support comprises kaolin and alumina; based on the weight of the support, the kaolin content is 6%–25%, and the alumina content is 50%–80%; the active metal component comprises Mo and a Group VIII metal element; the Mo comprises +5 valence Mo; the Group VIII metal element exists in the catalyst in the form of a metal phosphide.

[0008] According to the present invention, based on the weight of the catalyst, the mass content of the support is 74% to 83%, the content of Group VIII metals as oxides is 2% to 6%, and the content of molybdenum as oxides is 15% to 24%.

[0009] According to the present invention, the carrier further contains gallium, and the gallium content, calculated as gallium oxide, is 2.0% to 5.0% based on the weight of the carrier.

[0010] According to the present invention, the catalyst has the following properties: a specific surface area of ​​160–270 m². 2 / g, pore volume is 0.3-1.2mL / g, average pore size is 10-18nm. Total acid content is 0.3-0.7mmol / g, and the ratio of B acid content to L acid content is 0.1-0.6.

[0011] According to the present invention, the catalyst has a pore size distribution in which the pore volume of pores with a diameter <10 nm accounts for 5% to 12% of the total pore volume, the pore volume of pores with a diameter of 10 to 20 nm accounts for 60% to 68% of the total pore volume, and the pore volume of pores with a diameter >20 nm accounts for 20% to 35% of the total pore volume.

[0012] According to the present invention, the active metal component includes Mo and a Group VIII metal element; the Mo includes +5 valence Mo; the Group VIII metal element exists in the catalyst in the form of a metal phosphide.

[0013] According to the present invention, the catalyst further includes +4 valent Mo and +6 valent Mo.

[0014] According to the present invention, in the catalyst, +5 valence Mo accounts for more than 50% of the total Mo atomically, preferably 55% to 80%. As a non-limiting example, +5 valence Mo accounts for any value of 65%, 68%, 70%, 72%, 75%, or 78% of the total Mo atomically.

[0015] According to the present invention, in the catalyst, the sum of +4 valence Mo and +6 valence Mo accounts for 20% to 45% of the total Mo atoms. More preferably, in the catalyst, +4 valence Mo accounts for 10% to 43% of the total Mo atoms; and +6 valence Mo accounts for 2% to 10% of the total Mo atoms. As a non-limiting example, +4 valence Mo accounts for any value of 15%, 20%, 22%, 25%, 32%, 35%, 38%, or 40% of the total Mo atoms; and +6 valence Mo accounts for any value of 4%, 6%, 8%, or 9% of the total Mo atoms.

[0016] According to the present invention, in the catalyst, +5 valence Mo is preferably molybdenum pentachloride; +4 valence Mo is preferably molybdenum disulfide; and +6 valence Mo is preferably molybdenum oxide.

[0017] According to the present invention, the group VIII metal element is selected from one or more of Fe, Co, and Ni, preferably at least one of Co and Ni, and more preferably Ni.

[0018] A second aspect of the present invention provides a method for preparing the above-mentioned hydrodecarbonization catalyst, comprising:

[0019] (1) A first impregnation solution is obtained by mixing molybdenum source, sulfur source and water, and then impregnated on a support. After drying, catalyst intermediate I is obtained.

[0020] (2) React the catalyst intermediate I described in step (1) with chlorine gas to obtain catalyst intermediate II;

[0021] (3) The catalyst intermediate II described in step (2) is impregnated with a second impregnation solution containing nickel and phosphorus sources, and then cured, dried and calcined to obtain the catalyst.

[0022] According to the present invention, in step (1), the method for preparing the carrier includes:

[0023] (11) Acidic aluminum salt aqueous solution, alkaline aluminum salt aqueous solution and kaolin suspension containing surfactant are reacted in a single flow to obtain slurry I;

[0024] (12) Pass an alkaline solution into the slurry I from step (11) to carry out a secondary reaction to obtain slurry II;

[0025] (13) The slurry II obtained in step (12) is subjected to hydrothermal treatment with gallium nitrate solution, washed and dried to obtain gallium-containing macroporous aluminum silicon material;

[0026] (14) Gallium-containing macroporous silicon-aluminum material is mixed with extrusion aid and adhesive, kneaded and shaped, dried and calcined to obtain catalyst support.

[0027] According to the present invention, in the method for preparing the carrier, the surfactant in step (11) is one or more of long-chain fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, fatty acid polyoxyethylene esters, polyoxyethylene alkylamines, polyoxyethylene alkylolamides, and polyethers, and the amount of the surfactant is 0.3% to 3.0% of the mass of kaolin, preferably 0.5% to 2.5%.

[0028] According to the present invention, in the method for preparing the carrier, the reaction in step (11) is controlled at a pH value of 1.2 to 1.8, and the pH value is adjusted by adding at least one of hydrochloric acid, nitric acid or sulfuric acid.

[0029] According to the present invention, in the method for preparing the carrier, the acidic aluminum salt in step (11) is at least one of aluminum sulfate, aluminum chloride, or aluminum nitrate, and the concentration of the acidic aluminum salt solution, calculated as Al2O3, is 20–100 g / 100 mL. The alkaline aluminum salt is at least one of sodium aluminate or potassium aluminate, and the concentration of the alkaline aluminum salt solution, calculated as Al2O3, is 20–100 g / 100 mL. The concentration of kaolin in the surfactant-containing kaolin suspension is 0.5–5 g / 100 mL. The volume ratio of the surfactant-containing kaolin suspension, the acidic aluminum salt solution, and the alkaline aluminum salt solution is 1:1–5:1–3. The co-current reaction time in step (11) is 60–180 min, the reaction temperature is 60–90 °C, and the reaction is preferably carried out under stirring conditions, with a stirring rate of 100–500 rad / min, preferably 150–450 rad / min.

[0030] According to the present invention, in the method for preparing the carrier, the alkaline solution in step (12) is a solution of at least one of sodium hydroxide or sodium carbonate. The concentration of the alkaline solution is 50-70 g / 100 mL, the reaction time of the secondary reaction is 60-120 min, the reaction temperature is 120-180 °C, the reaction is preferably carried out under stirring conditions, the stirring rate is 100-500 rad / min, preferably 250-500 rad / min, and the pH value of the secondary reaction is controlled at 8.5-9.7.

[0031] According to the present invention, in the method for preparing the carrier, the concentration of the gallium nitrate solution in step (13) is 0.3 to 2.5 mol / L. The mass ratio of the slurry II obtained in step (12) to the gallium nitrate solution is 3:1 to 7:1, calculated based on Al2O3 and Ga2O3.

[0032] According to the present invention, in the method for preparing the carrier, in step (13), the hydrothermal treatment temperature is 200-500°C, the pressure is 10-20 MPa, and the time is 2-4 hours. The washing can be carried out using conventional washing methods in the art, preferably using deionized water, and more preferably at 50-90°C. The drying conditions are 120-160°C, and the drying time is 3-6 hours.

[0033] According to the present invention, in the preparation method of the catalyst support, the preparation process of the catalyst support in step (14) involves mixing an extrusion aid, an adhesive, and a gallium-containing macroporous silicon-aluminum material into a plastic body and then molding it. The molding can be carried out using conventional molding methods, such as extrusion molding, sheet molding, etc., preferably extrusion molding, followed by drying and calcination. The drying temperature is 110-160°C, and the drying time is 2-8 hours; the calcination temperature is 600-750°C, and the calcination time is 6-10 hours.

[0034] According to the present invention, in the method for preparing the carrier, the extrusion aid in step (14) is guar gum powder, and its dosage is 1% to 5% of the carrier mass. The adhesive is one or more of nitric acid, formic acid, acetic acid, citric acid, methylcellulose, and polyethylene glycol, and its dosage is 0.5% to 3% of the gallium-containing macroporous silicon-aluminum material.

[0035] According to the present invention, in the method for preparing the catalyst, the molybdenum source in step (1) is selected from at least one of ammonium dimolybdate, ammonium tetramolybdate dihydrate, and ammonium heptamolybdate tetrahydrate; the sulfur source is selected from at least one of thiourea, ammonium sulfide, thioacetamide, and sodium thiosulfate; the mass ratio of the molybdenum source to the sulfur source is 3-5:2-4. In the first impregnation solution, the mass content of the molybdenum source is 25wt%-45wt%.

[0036] According to the present invention, in the method for preparing the catalyst, the impregnation in step (1) can be carried out by spray impregnation, and the impregnation can be carried out by saturated impregnation or supersaturated impregnation. The drying conditions are drying at 100-140°C for 4-8 hours.

[0037] According to the present invention, in the method for preparing the catalyst, in step (2), the purity of the chlorine gas is 96% or higher by volume fraction. The flow rate of the chlorine gas is 2.7 to 6.8 mL / (min·g catalyst intermediate I); and / or, the reaction conditions are as follows: the reaction temperature is 300 to 400 °C, and the reaction time is 40 to 90 min.

[0038] According to the present invention, in the method for preparing the catalyst, the nickel source in step (3) is a soluble salt, such as at least one of nitrates, monohydrogen phosphates, and dihydrogen phosphates; the phosphorus source is selected from at least one of ammonium phosphates, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, and phytic acid. In the second impregnation solution, the molar ratio of the nickel source (based on metal element) to the phosphorus source (based on phosphorus element) is 0.3 to 3:1. In the second impregnation solution, the mass content of the nickel source is 40 wt% to 60 wt%.

[0039] According to the present invention, in the preparation method of the catalyst, the impregnation in step (3) can be carried out by spray impregnation, and the impregnation can be carried out by saturated impregnation or supersaturated impregnation.

[0040] According to the present invention, in the method for preparing the catalyst, the conditioning in step (3) involves placing the impregnated sample under sealed conditions at 10–30°C for 6–12 hours. The conditioning pressure is not particularly limited and can be autogenous pressure. And / or, the drying conditions are drying at 100–160°C for 1–8 hours. The calcination conditions are calcination at 480–550°C for 4–8 hours. The drying atmosphere is an oxygen-containing atmosphere. The calcination atmosphere is selected from any one of a nitrogen atmosphere, an inert gas atmosphere, a hydrogen / nitrogen atmosphere, and a hydrogen / inert gas atmosphere, wherein the hydrogen gas fraction in the hydrogen / nitrogen atmosphere and the hydrogen / inert gas atmosphere is 5%–50%.

[0041] The third aspect of the present invention provides the application of the above-described hydrodecarbonization catalyst or the residue hydrodecarbonization catalyst prepared by the above-described preparation method in the hydrotreating of residue oil.

[0042] According to the present invention, the application conditions are: reaction temperature of 350–480°C; reaction pressure of 9–16 MPa; and liquid hourly space velocity of 0.5–2.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is 450:1 to 1200:1. The reaction pressure is the total pressure.

[0043] According to the present invention, the catalyst needs to be sulfided before application. The sulfidation process is as follows: the catalyst is contacted with a sulfidation liquid and hydrogen to undergo sulfidation. The sulfidation liquid includes a solvent and a sulfur-containing solute; the sulfur-containing solute has a mass content of 4.0 wt% to 15.0 wt% in the sulfidation liquid; the sulfur-containing solute is a sulfur-containing compound with a solubility of more than 10 wt% in the solvent at room temperature, and which decomposes with hydrogen to produce H2S under high temperature conditions. The sulfur-containing solute includes at least one of carbon disulfide, dimethyl sulfide, dimethyl disulfide (DMDS), n-butyl mercaptan, etc. The solvent is straight-run diesel oil with a nitrogen content of not more than 200 μg / g. The purity of the hydrogen is not less than 90 vol%.

[0044] According to the present invention, the vulcanization conditions can be conventional vulcanization conditions. Preferably, the vulcanization conditions are as follows: the vulcanization process includes low-temperature vulcanization and high-temperature vulcanization. Low-temperature vulcanization stage: heating to 150–230°C and holding at that temperature for 3–8 hours; High-temperature vulcanization stage: heating to 260–310°C and holding at that temperature for 3–8 hours. The heating rate to the low-temperature vulcanization stage is 8–12.0°C / h. The heating rate to the high-temperature vulcanization stage is 5–12.0°C / h, the flow rate of the vulcanizing liquid is 15–30 mL / (h·g catalyst), the hydrogen pressure is 7.0–16.0 MPa, and the hydrogen flow rate is 80–130 mL / (min·g catalyst).

[0045] Compared with the prior art, the present invention has the following advantages:

[0046] 1. The catalyst of the present invention comprises a support and an active metal component; the support comprises kaolin and alumina; based on the weight of the support, the content of kaolin is 6%–25%, and the content of alumina is 50%–80%; the active metal component comprises Mo and Group VIII metal elements; the Mo comprises +5 valence Mo; the Group VIII metal elements exist in the catalyst in the form of metal phosphides.

[0047] In the catalyst of this invention, +5-valent molybdenum is more easily sulfided into +4-valent molybdenum disulfide during the sulfidation process. This accelerates the rate of molybdenum disulfide formation, leading to a greater likelihood of forming Ni-Mo-S(II) and Brim active sites with a MoS2 framework and metallic nickel on the outer surface. The catalyst also forms a suitable amount of transition metal phosphides, compounds formed by phosphorus atoms inserting into the metal lattice, exhibiting noble metal-like properties. Due to the large size of phosphorus atoms, after bonding with the transition metal, octahedral coordination structures are more easily formed around the phosphorus atoms, placing them at the central position. This results in a structure closer to spherical than the layered structure of sulfides, exposing more active sites during the catalytic reaction and making it easier for large molecular reactants to approach the active sites on the catalyst surface. The combined action of the support and active metal components in this hydrodecarbonization catalyst is beneficial for the hydrogenation saturation and hydrogenolysis reactions of polycyclic and fused-ring aromatic hydrocarbons in feedstock oils. It not only has excellent hydrodecarbonization performance but also further removes nitrogen-containing compounds and exhibits good stability.

[0048] 2. In the catalyst preparation process of the present invention, the support is first impregnated with an impregnation solution containing a molybdenum source and a sulfur source to obtain intermediate I, which is then reacted with chlorine gas to obtain intermediate II. Finally, intermediate II is impregnated with a nickel-phosphorus impregnation solution to prepare the catalyst. This process is beneficial for the hydrodecarbonization catalyst to have a suitable pore structure, acid content, and acid distribution. Through the comprehensive coordination of each step, the catalyst support and the active metal work together to significantly improve the catalytic performance of the catalyst.

[0049] 3. In the method of the present invention, acidic aluminum salt aqueous solution, alkaline aluminum salt aqueous solution and kaolin suspension containing surfactant are co-flowed to form a gel. The acidified active silicon is adsorbed on the aluminum hydroxide colloid, providing crystal nuclei for subsequent reactions and helping to form new silicon-aluminum structures. At the same time, the surfactant forms hydrogen bonds with the hydroxyl groups of the aluminum hydroxide hydrosol, which can prevent particles from adhering and agglomerating with each other, so that the gel particles are oriented to form ordered crystal precipitates or colloidal particles with crystalline structures. During the secondary reaction, the incomplete small crystals are redissolved and recrystallized or adsorbed onto other crystals, which promotes the increase of the crystal size of the prepared silicon-aluminum material, reduces the formation of amorphous silicon-aluminum, and is conducive to the formation of silicon-aluminum materials with large pore volume and large pore size.

[0050] 4. In the method of the present invention, the sol particles with complete crystal form in slurry II and gallium nitrate solution generate a large number of particles with complete crystal form under high temperature, high pressure and high pH value to form gallium-containing silicon-aluminum material precipitate, thereby making the final material with high crystal purity and concentrated pore size distribution. The presence of silicon and gallium improves the corresponding catalyst's resistance to carbon deposition and sintering, and increases the service life of the catalyst. Detailed Implementation

[0051] The technical solutions and effects of the present invention will be further illustrated by the following embodiments, but the following embodiments do not constitute a limitation on the method of the present invention.

[0052] In this invention, unless otherwise specified, % refers to mass fraction.

[0053] In this invention, the specific surface area, pore volume, and pore distribution are measured using an ASAP2420 fully automated physical adsorption instrument from Micron Instruments, Inc.

[0054] In this invention, the XPS operating conditions are as follows: light source: MgK Alpha, energy step: 0.05 eV, scan range: 220–240 eV (molybdenum), 850–880 eV (nickel), 280–300 eV (carbon). When analyzing the valence state of molybdenum, the binding energy is determined as follows: +6 valence molybdenum species at 232–233 eV, +5 valence molybdenum species at 230–232 eV, and +4 valence molybdenum species at 228–230 eV. The proportions of +6, +5, and +4 valence molybdenum in the total Mo can be calculated using the peak areas of these three peaks.

[0055] In this invention, the catalyst composition was determined using spectrophotometry. The testing instrument was a Lambda 365 UV spectrophotometer.

[0056] In this invention, the total amount of infrared acid, the amount of L acid, and the amount of B acid are determined by infrared spectroscopy, and the instrument used is a Nicot Fourier transform infrared spectrometer-6700 from the United States.

[0057] In this invention, HDCCR stands for hydrodecarbonization; HDN stands for hydrodenitrogenation.

[0058] Example 1

[0059] (1) Preparation of the carrier:

[0060] 2.0 L of purified water was added to the reactor and heated to 60 °C. The stirring rate was 200 rad / min. The flow rates of 20 g / 100 mL aluminum sulfate solution, 15 g / 100 mL sodium aluminate solution, and 3.5 g / 100 mL kaolin suspension (nonylphenol polyoxyethylene ether-10 was used at 1.2% of the kaolin mass) were continuously added to the reactor at 20 mL / min, 15 mL / min, and 10 mL / min, respectively. During the reaction, hydrochloric acid was added to maintain the pH at 1.4. The reaction time was 70 min. After the reaction was complete, the temperature was raised to 120℃, and the stirring rate was adjusted to 300 rad / min. A sodium carbonate solution with a concentration of 55 g / 100 mL was introduced into the reactor for a secondary reaction. The pH of the reaction was adjusted to 9, and the reaction time was 90 min. After the reaction was complete, 0.92 L of a gallium nitrate solution with a concentration of 1.5 mol / L was added. The hydrothermal treatment was carried out at a temperature of 250℃, a pressure of 15 MPa, and a time of 2 hours. The slurry after the reaction was washed with hot water at 90℃ until neutral, and dried at 120℃ for 3 hours to obtain gallium-containing silicon-aluminum material. 448 g of gallium-containing silicon-aluminum material was weighed and mixed with 9 g of guar gum powder, 4 g of nitric acid, 3 g of citric acid, and 292 g of water. After kneading and molding, the mixture was dried at 110℃ for 3 hours and calcined at 650℃ for 8 hours to obtain catalyst support A-1 (gallium content of 3.6%).

[0061] Catalyst preparation:

[0062] A first impregnation solution was prepared by mixing 61.9 g of ammonium heptamolybdate tetrahydrate, 47.8 g of ammonium sulfide, and water. The molybdenum source in the first impregnation solution contained 29 wt%. The first impregnation solution was then applied to support A-1. The impregnation was saturated. After drying at 100°C for 6 hours in air, catalyst intermediate I was obtained.

[0063] (2) Catalyst intermediate I was reacted with chlorine gas to obtain catalyst intermediate II. The purity of the chlorine gas was 98 v%. The flow rate of the chlorine gas was 3.4 mL / (min·g catalyst intermediate I). The reaction conditions were as follows: reaction temperature was 400℃, and reaction time was 90 min.

[0064] (3) The catalyst intermediate II described in step (2) is impregnated with a second impregnation solution containing nickel and phosphorus sources (40.4 g of nickel nitrate hexahydrate and 9.2 g of diammonium hydrogen phosphate dissolved in water, wherein the mass content of nickel source in the second impregnation solution is 58 wt%). The impregnation is a saturated impregnation. After being cured at 25°C for 10 h, dried at 110°C in air for 6 h, and calcined at 510°C in nitrogen for 6 h, the catalyst C1 is obtained.

[0065] The catalyst composition, properties, and pore distribution are shown in Table 1. Group VIII metals exist in the catalyst as metal phosphides. The Mo includes +5, +6, and +4 valence Mo, i.e., Mo exists as molybdenum pentachloride, molybdenum disulfide, and molybdenum oxide. +5 valence Mo accounts for 78.9% of the total Mo atoms, +4 valence Mo accounts for 13.2%, and +6 valence Mo accounts for 7.9%.

[0066] Example 2

[0067] (1) Preparation of the carrier:

[0068] 2.5L of purified water was added to the reactor and heated to 70℃. The stirring rate was 300 rad / min. The flow rates of aluminum sulfate solution (35g / 100mL), sodium aluminate solution (40g / 100mL), and kaolin suspension (5g / 100mL, with dodecyl fatty alcohol polyoxyethylene ether-11 accounting for 1.4% of the kaolin mass) were continuously added to the reactor at 15mL / min, 20mL / min, and 15mL / min, respectively. During the reaction, hydrochloric acid was added to control the pH at 1.3. The reaction time was 90 min. After the reaction was complete, the temperature was raised to 140℃, and the stirring rate was adjusted to 400 rad / min. A 60 g / 100 mL sodium hydroxide solution was introduced into the reactor for a secondary reaction. The pH was adjusted to 8.8, and the reaction time was 70 min. After the reaction was complete, 1.25 L of a 1.0 mol / L gallium nitrate solution was added. The hydrothermal treatment was carried out at 300℃ and 18 MPa for 3 hours. The slurry after the reaction was washed with hot water at 70℃ until neutral, and then dried at 140℃ for 4 hours to obtain gallium-containing silicon-aluminum material. 604 g of the gallium-containing silicon-aluminum material was weighed and mixed with 12 g of guar gum powder, 6 g of nitric acid, 4 g of citric acid, and 304 g of water. After kneading and molding, the mixture was dried at 120℃ for 4 hours and calcined at 700℃ for 6 hours to obtain catalyst support B-1 (gallium content of 2.8%).

[0069] Catalyst preparation:

[0070] A first impregnation solution was prepared by mixing 59.4 g of ammonium heptamolybdate tetrahydrate, 37.1 g of thiourea, and water. The molybdenum source in the first impregnation solution contained 36 wt%. The first impregnation solution was then applied to support B-1. The impregnation was saturated. After drying at 120°C for 4 hours in air, catalyst intermediate I was obtained.

[0071] (2) Catalyst intermediate I was reacted with chlorine gas to obtain catalyst intermediate II. The purity of the chlorine gas was 97 v%. The flow rate of the chlorine gas was 4.8 mL / (min·g catalyst intermediate I). The reaction conditions were as follows: reaction temperature was 400℃, and reaction time was 65 min.

[0072] (3) The catalyst intermediate II described in step (2) was impregnated with a second impregnation solution containing nickel and phosphorus sources (37.4 g of nickel nitrate hexahydrate and 10.3 g of disodium hydrogen phosphate dissolved in water, wherein the nickel source content in the second impregnation solution was 53 wt%). The impregnation was saturated. After being cured at 23°C for 12 h, dried at 120°C in air for 5 h, and calcined at 495°C in nitrogen for 6 h, the catalyst C2 was obtained.

[0073] The catalyst composition, properties, and pore distribution are shown in Table 1. Group VIII metals exist in the catalyst as metal phosphides. The Mo includes +5, +6, and +4 valence Mo, i.e., Mo exists as molybdenum pentachloride, molybdenum disulfide, and molybdenum oxide. +5 valence Mo accounts for 76.5% of the total Mo atoms, +4 valence Mo accounts for 17.5%, and +6 valence Mo accounts for 6.0%.

[0074] Example 3

[0075] (1) Preparation of the carrier:

[0076] 3L of purified water was added to the reactor and heated to 80℃. The stirring speed was 350 rad / min. The flow rates of 55 g / 100 mL aluminum sulfate solution, 50 g / 100 mL sodium aluminate solution, and 4 g / 100 mL kaolin suspension (dodecylalkylphenol polyoxyethylene ether-10 was used at 1.1% of the kaolin mass) were controlled at 30 mL / min, 35 mL / min, and 25 mL / min, respectively, and were continuously added to the reactor. During the reaction, hydrochloric acid was added to control the pH at 1.7, and the reaction time was 120 min. After the reaction was complete, the temperature was raised to 160℃, and the stirring rate was adjusted to 500 rad / min. A sodium hydroxide solution with a concentration of 55 g / 100 mL was introduced into the reactor for a secondary reaction. The pH of the reaction was adjusted to 9.0, and the reaction time was 100 min. After the reaction was complete, 1.12 L of a gallium nitrate solution with a concentration of 2.2 mol / L was added. The hydrothermal treatment was carried out at a temperature of 400℃, a pressure of 16 MPa, and a time of 4 hours. The slurry after the reaction was washed with hot water at 90℃ until neutral, and dried at 130℃ for 5 hours to obtain gallium-containing silicon-aluminum material. 756 g of the gallium-containing silicon-aluminum material was weighed and mixed with 15 g of guar gum powder, 7 g of nitric acid, 5 g of citric acid, and 562 g of water. After kneading and molding, the mixture was dried at 130℃ for 5 hours and calcined at 750℃ for 7 hours to obtain catalyst support C-1 (gallium content of 2.6%).

[0077] Catalyst preparation:

[0078] A first impregnation solution was prepared by mixing 59.9 g of ammonium heptamolybdate tetrahydrate, 51.4 g of sodium thiosulfate, and water. The molybdenum source in the first impregnation solution contained 41 wt%. The first impregnation solution was then applied to support C-1. The impregnation was saturated. After drying at 130°C for 5 hours in air, catalyst intermediate I was obtained.

[0079] (2) Catalyst intermediate I was reacted with chlorine gas to obtain catalyst intermediate II. The purity of the chlorine gas was 98 v%. The flow rate of the chlorine gas was 5.3 mL / (min·g catalyst intermediate I). The reaction conditions were as follows: reaction temperature was 350℃, and reaction time was 60 min.

[0080] (3) The catalyst intermediate II described in step (2) was impregnated with a second impregnation solution containing nickel and phosphorus sources (40g of nickel nitrate hexahydrate and 7.3g of diammonium hydrogen phosphate dissolved in water, wherein the mass content of nickel source in the second impregnation solution was 57wt%). The impregnation was saturated impregnation. After being cured at 23°C for 12h, dried at 120°C in air for 6h, and calcined at 500°C in nitrogen for 7h, the catalyst C3 was obtained.

[0081] The catalyst composition, properties, and pore distribution are shown in Table 1. Group VIII metals exist in the catalyst as metal phosphides. The Mo includes +5, +6, and +4 valence Mo, i.e., Mo exists as molybdenum pentachloride, molybdenum disulfide, and molybdenum oxide. +5 valence Mo accounts for 76.6% of the total Mo atoms, +4 valence Mo accounts for 16.1%, and +6 valence Mo accounts for 7.3%.

[0082] Example 4

[0083] (1) Preparation of the carrier:

[0084] 2.5L of purified water was added to the reactor and heated to 90℃. The stirring rate was 250 rad / min. The flow rates of 45g / 100mL aluminum sulfate solution, 40g / 100mL sodium aluminate solution, and 4.5g / 100mL kaolin suspension (dodecylalkylphenol polyoxyethylene ether-10 was used at 2% of the kaolin mass) were controlled at 35mL / min, 30mL / min, and 20mL / min, respectively, and were continuously added to the reactor. During the reaction, hydrochloric acid was added to control the pH to 1.2, and the reaction time was 100min. After the reaction was complete, the temperature was raised to 180℃, and the stirring rate was adjusted to 400 rad / min. A sodium bicarbonate solution with a concentration of 60 g / 100 mL was introduced into the reactor for a secondary reaction. The pH of the reaction was adjusted to 9.5, and the reaction time was 120 min. After the reaction was complete, 1.17 L of a gallium nitrate solution with a concentration of 1.5 mol / L was added. The hydrothermal treatment was carried out at a temperature of 500℃, a pressure of 11 MPa, and a time of 3 hours. The slurry after the reaction was washed with hot water at 80℃ until neutral, and dried at 140℃ for 4 hours to obtain gallium-containing silicon-aluminum material. 632 g of gallium-containing silicon-aluminum material was weighed and mixed with 14 g of guar gum powder, 6 g of nitric acid, 4.5 g of citric acid, and 478 g of water. After kneading and molding, the mixture was dried at 140℃ for 4 hours and calcined at 700℃ for 6 hours to obtain catalyst support D-1 (gallium content of 3.7%).

[0085] Catalyst preparation:

[0086] A first impregnation solution was prepared by mixing 56.4 g of ammonium heptamolybdate tetrahydrate, 42.3 g of thiourea, and water. The molybdenum source in the first impregnation solution contained 40 wt%. The first impregnation solution was then applied to support D-1. The impregnation was saturated. After drying at 130°C for 5 hours in air, catalyst intermediate I was obtained.

[0087] (2) Catalyst intermediate I was reacted with chlorine gas to obtain catalyst intermediate II. The purity of the chlorine gas was 99 v% by volume. The flow rate of the chlorine gas was 3.9 mL / (min·g catalyst intermediate I). The reaction conditions were as follows: reaction temperature was 300℃, and reaction time was 80 min.

[0088] (3) The catalyst intermediate II described in step (2) was impregnated with a second impregnation solution containing nickel and phosphorus sources (38.9 g of nickel nitrate hexahydrate and 11.7 g of diammonium hydrogen phosphate dissolved in water, wherein the nickel source content in the second impregnation solution was 56 wt%). The impregnation was saturated. After being cured at 23°C for 12 h, dried at 120°C in air for 6 h, and calcined at 500°C in nitrogen for 7 h, the catalyst C4 was obtained.

[0089] The catalyst composition, properties, and pore distribution are shown in Table 1. Group VIII metals exist in the catalyst as metal phosphides. The Mo includes +5, +6, and +4 valence Mo, i.e., Mo exists as molybdenum pentachloride, molybdenum disulfide, and molybdenum oxide. +5 valence Mo accounts for 78.7% of the total Mo atoms, +4 valence Mo accounts for 15.2%, and +6 valence Mo accounts for 6.1%.

[0090] Comparative Example 1

[0091] Compared to Example 1, no secondary reaction was performed during the preparation of the carrier. Other steps were the same as in Example 1.

[0092] The carrier preparation process is as follows:

[0093] 2.0L of purified water was added to the reactor and heated to 60℃. The stirring rate was 200 rad / min. The flow rates of 20 g / 100 mL aluminum sulfate solution, 15 g / 100 mL sodium aluminate solution, and 3.5 g / 100 mL kaolin suspension (nonylphenol polyoxyethylene ether-10 was used at 1.2% of the kaolin mass) were controlled at 20 mL / min, 15 mL / min, and 10 mL / min, respectively, and were continuously added to the reactor. During the reaction, hydrochloric acid was added to control the reaction pH to 1.4. The reaction time was 70 min. After the reaction was completed, 0.92 L of 1.5 mol / L gallium nitrate solution was added. The hydrothermal treatment temperature was 250℃, the pressure was 15 MPa, and the time was 2 hours. The slurry after the reaction was washed with hot water at 90℃ until neutral and dried at 120℃ for 3 hours to obtain gallium-containing silicon-aluminum material. 448g of gallium-containing silicon-aluminum material was weighed and mixed with 9g of guar gum powder, 4g of nitric acid, 3g of citric acid and 292g of water. After kneading and molding, the mixture was dried at 110℃ for 3 hours and calcined at 650℃ for 8 hours to obtain catalyst support DA.

[0094] A comparative hydrogenation catalyst, DCA-1, was prepared. The composition, properties, and pore distribution of the catalyst are shown in Table 1.

[0095] Comparative Example 2

[0096] Compared to Example 1, in the preparation of the carrier, no acid was added to adjust the pH value during the first reaction. Other steps were the same as in Example 1.

[0097] The carrier preparation process is as follows:

[0098] 2.0 L of purified water was added to the reactor and heated to 60 °C. The stirring rate was 200 rad / min. The flow rates of 20 g / 100 mL aluminum sulfate solution, 15 g / 100 mL sodium aluminate solution, and 3.5 g / 100 mL kaolin suspension (nonylphenol polyoxyethylene ether-10 was used at 1.2% of the kaolin mass) were controlled at 20 mL / min, 15 mL / min, and 10 mL / min, respectively, and were continuously added to the reactor. The reaction time was 70 min. After the reaction was completed, the temperature was adjusted. The temperature was raised to 120℃, and the stirring rate was adjusted to 300 rad / min. A sodium carbonate solution with a concentration of 55 g / 100 mL was introduced into the reactor for a secondary reaction. The pH of the reaction was adjusted to 9, and the reaction time was 90 min. After the reaction was completed, 0.92 L of a gallium nitrate solution with a concentration of 1.5 mol / L was added. The hydrothermal treatment was carried out at a temperature of 250℃ and a pressure of 15 MPa for 2 hours. The slurry after the reaction was washed with hot water at 90℃ until neutral, and dried at 120℃ for 3 hours to obtain gallium-containing silicon-aluminum material. 448 g of gallium-containing silicon-aluminum material was weighed and mixed with 9 g of guar gum powder, 4 g of nitric acid, 3 g of citric acid, and 292 g of water. After kneading and molding, the mixture was dried at 110℃ for 3 hours and calcined at 650℃ for 8 hours to obtain the catalyst support DB.

[0099] A comparative hydrogenation catalyst, DCA-2, was prepared. The composition, properties, and pore distribution of the catalyst are shown in Table 1.

[0100] Comparative Example 3

[0101] The active metals in this catalyst include molybdenum oxide and nickel phosphide.

[0102] Compared with Example 1, in the catalyst preparation method, air is used to replace chlorine in step (2) of Example 1, that is, catalyst intermediate I reacts with air. Other steps are the same as in Example 1.

[0103] The comparative hydrogenation catalyst DCA-3 was prepared.

[0104] The catalyst composition, properties, and pore distribution are shown in Table 1. The Mo is in the +6 and +4 valence states, and does not contain +5 valence Mo. That is, Mo exists in the form of molybdenum disulfide and molybdenum oxide. +4 valence Mo accounts for 14.6% of the total Mo atoms, and +6 valence Mo accounts for 85.4% of the total Mo atoms.

[0105] Comparative Example 4

[0106] The active metals in this catalyst include molybdenum oxide and nickel oxide.

[0107] Compared to Example 1, in step (2), air is used instead of chlorine in Example 1, that is, catalyst intermediate I reacts with air. In step (3), no phosphorus source is added to the second impregnation solution. Other steps are the same as in Example 1.

[0108] The comparative hydrogenation catalyst DCA-4 was prepared.

[0109] The catalyst composition, properties, and pore distribution are shown in Table 1. The Mo is in the +6 and +4 valence states, and does not contain +5 valence Mo. That is, Mo exists in the form of molybdenum disulfide and molybdenum oxide. +4 valence Mo accounts for 14.4% of the total Mo atoms, and +6 valence Mo accounts for 85.6% of the total Mo atoms.

[0110] Application examples

[0111] The catalysts obtained in the examples and comparative examples were evaluated using the feed oils listed in Table 2. The properties of the feed oils and reaction conditions are shown in Table 2, and the evaluation results are shown in Table 3.

[0112] The catalyst was sulfided before application. The sulfidation conditions were as follows: the sulfidation solution was straight-run diesel fuel containing 8.0 wt% DMDS; the flow rate of the sulfidation solution was 20.0 mL / (h·g catalyst); the hydrogen pressure was 8.5 MPa; and the hydrogen flow rate was 100.0 mL / (min·g catalyst). The low-temperature sulfidation stage started at 25°C with a heating rate of 10.0°C / h, reaching 160°C and then holding at that temperature for 6.0 h. The high-temperature sulfidation stage started at 160°C with a heating rate of 8.0°C / h, reaching 310°C and then holding at that temperature for 4.0 h, at which point sulfidation was complete.

[0113] Table 1. Composition and properties of catalysts in the examples and comparative examples.

[0114]

[0115]

[0116] Table 2. Properties of feedstock oil and reaction conditions

[0117] properties of crude oil <![CDATA[Density (20°C) / kg·m -3 > 999.4 S / wt% 2.6 <![CDATA[Ni+V / μg·g -1 ]]> 92 N / wt% 0.68 Reaction conditions Reaction temperature / °C 360 Reaction pressure / MPa 10.8 <![CDATA[Volumetric space velocity / h -1 > 0.55 Hydrogen-to-oil volume ratio 900

[0118] Table 3. Activity evaluation results of each catalyst example.

[0119]

[0120] The specific embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A hydrocracking catalyst, comprising a support and an active metal component; the support comprising kaolin and alumina; the kaolin content being 6%–25% and the alumina content being 50%–80% based on the weight of the support; the active metal component comprising Mo and a Group VIII metal element; the Mo comprising +5 valence Mo; the Group VIII metal element existing in the catalyst in the form of a metal phosphide; The carrier also contains gallium; Mo also includes +4 valence Mo and +6 valence Mo; +5 valence Mo accounts for 55% to 80% of the total Mo atoms; +4 valence Mo and +6 valence Mo together account for 20% to 45% of the total Mo atoms. In the catalyst, +5 valence Mo is molybdenum pentachloride; +4 valence Mo is molybdenum disulfide; and +6 valence Mo is molybdenum oxide. The catalyst has the following properties: specific surface area of ​​160~270 m². 2 / g, pore volume is 0.3~1.2mL / g, average pore size is 10~18nm; total acid content is 0.3~0.7mmol / g, and the ratio of B acid content to L acid content is 0.1~0.6; in, The total acid content, L acid content, and Brønsted acid content were determined by infrared spectroscopy. The catalyst has a pore size distribution in which pores with a diameter <10 nm account for 5% to 12% of the total pore volume, pores with a diameter of 10 to 20 nm account for 60% to 68% of the total pore volume, and pores with a diameter >20 nm account for 20% to 35% of the total pore volume.

2. The catalyst according to claim 1, characterized in that, Based on the weight of the catalyst, the mass content of the support is 74% to 83%, the content of Group VIII metals as oxides is 2% to 6%, and the content of molybdenum as oxides is 15% to 24%.

3. The catalyst according to claim 1, characterized in that, Based on the weight of the carrier, the gallium content, expressed as gallium oxide, is 2.0% to 5.0%.

4. The catalyst according to claim 1, characterized in that, In the catalyst, +4 valence Mo accounts for 10% to 43% of the total Mo atoms; +6 valence Mo accounts for 2% to 10% of the total Mo atoms.

5. A method for preparing the catalyst according to any one of claims 1 to 4, comprising: (1) A first impregnation solution is obtained by mixing molybdenum source, sulfur source and water, and then impregnated on a support. After drying, catalyst intermediate I is obtained. (2) React the catalyst intermediate I described in step (1) with chlorine gas to obtain catalyst intermediate II; (3) The group VIII metal is selected from nickel. The catalyst intermediate II described in step (2) is impregnated with a second impregnation solution containing nickel source and phosphorus source, and then cured, dried and calcined to obtain the catalyst.

6. The method according to claim 5, characterized in that, The method for preparing the carrier includes: (11) Acidic aluminum salt aqueous solution, alkaline aluminum salt aqueous solution and kaolin suspension containing surfactant are reacted in a single flow to obtain slurry I; (12) Pass an alkaline solution into the slurry I from step (11) to carry out a secondary reaction to obtain slurry II; (13) The slurry II obtained in step (12) is subjected to hydrothermal treatment with gallium nitrate solution, washed and dried to obtain gallium-containing macroporous aluminum silicon material; (14) Gallium-containing macroporous silicon-aluminum material is mixed with extrusion aid and adhesive, kneaded and shaped, dried and calcined to obtain catalyst support.

7. The method according to claim 6, characterized in that, In step (11), the surfactant is a polyether.

8. The method according to claim 6, characterized in that, In step (11), the surfactant is one or more of the following: long-chain fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, fatty acid polyoxyethylene esters, polyoxyethylene alkylamines, and polyoxyethylene alkylolamides; the amount of surfactant used is 0.3% to 3.0% of the mass of kaolin. And / or, in step (11), the reaction is controlled at a pH of 1.2 to 1.8, and the pH is adjusted by adding at least one of hydrochloric acid, nitric acid or sulfuric acid; And / or, in step (11), the acidic aluminum salt is at least one of aluminum sulfate, aluminum chloride or aluminum nitrate, and the concentration of the acidic aluminum salt aqueous solution, calculated as Al2O3, is 20~100g / 100mL. And / or, in step (11), the alkaline aluminum salt is at least one of sodium aluminate or potassium aluminate, and the concentration of the alkaline aluminum salt aqueous solution, calculated as Al2O3, is 20~100g / 100mL. And / or, in step (11), the concentration of kaolin in the surfactant-containing kaolin suspension is 0.5~5g / 100mL; And / or, in step (11), the ratio of the volume rates of the addition of the surfactant-containing kaolin suspension, the acidic aluminum salt aqueous solution and the alkaline aluminum salt aqueous solution is 1:1~5:1~3; And / or, in step (11), the reaction time is 60~180 min and the reaction temperature is 60~90℃.

9. The method according to claim 8, characterized in that, In step (11), the amount of surfactant used is 0.5% to 2.5% of the mass of kaolin; And / or, in step (11), the reaction is carried out under stirring conditions, wherein the stirring rate is 100 to 500 rad / min.

10. The method according to claim 9, characterized in that, In step (11), the stirring rate is 150 to 450 rad / min.

11. The method according to claim 6, characterized in that, In step (12), the alkaline solution is a solution of at least one of sodium hydroxide or sodium carbonate; And / or, in step (12), the concentration of the alkaline solution is 50~70g / 100mL; And / or, in step (12), the reaction time of the secondary reaction is 60~120 min, the reaction temperature is 120~180℃, and the pH value of the secondary reaction is controlled at 8.5~9.

7.

12. The method according to claim 11, characterized in that, In step (12), the reaction is carried out under stirring conditions, and the stirring rate is 100 to 500 rad / min.

13. The method according to claim 12, characterized in that, In step (12), the stirring rate is 250 to 500 rad / min.

14. The method according to claim 6, characterized in that, In step (13), the concentration of the gallium nitrate solution is 0.3~2.5 mol / L; And / or, the mass ratio of slurry II obtained in step (12) to gallium nitrate solution is 3:1 to 7:1, calculated based on Al2O3 and Ga2O3; And / or, the hydrothermal treatment temperature is 200~500℃, the pressure is 10~20MPa, and the time is 2~4 hours.

15. The method according to claim 5, characterized in that, In step (1), the molybdenum source is selected from at least one of ammonium dimolybdate, ammonium tetramolybdate dihydrate, and ammonium heptamolybdate tetrahydrate; And / or, the sulfur source is selected from at least one of thiourea, ammonium sulfide, thioacetamide and sodium thiosulfate; And / or, the mass ratio of the molybdenum source to the sulfur source is 3~5:2~4.

16. The method according to claim 5, characterized in that, In step (2), the purity of the chlorine gas is 96% or higher by volume fraction; the flow rate of the chlorine gas is 2.7~6.8 mL / (min·g catalyst intermediate I); and / or, the reaction conditions are as follows: the reaction temperature is 300~400℃ and the reaction time is 40~90 min.

17. The method according to claim 5, characterized in that, In step (3), the molar ratio of nickel source (calculated as metal element) to phosphorus source (calculated as phosphorus element) in the second impregnation solution is 0.3~3:

1.

18. The use of the catalyst according to any one of claims 1 to 4 in the hydrotreating of residual oil.

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