Hydrogenation catalyst and method for producing the same

Abstract

The application discloses a hydrogenation catalyst and a production method thereof. The production method of the catalyst comprises the following steps: adding alcohol, polar metal seeds, a solution I of active metal containing a modifier and an aluminum alcohol solution I into a first reaction kettle in parallel flow to hydrolyze and gel, so as to obtain a generated liquid I; the generated liquid I is introduced into a settling tank to perform settling separation, so as to obtain an upper alcohol part and a lower alcohol-containing sol I; the sol I is introduced into a second reaction kettle, and a solution II of active metal containing a modifier and an aluminum alcohol solution II are added in parallel flow to continuously perform hydrolysis and gelation, so as to obtain a generated liquid II; the generated liquid II is introduced into an aging kettle to perform an aging reaction; the aged material is dried and calcined, so as to obtain the hydrogenation catalyst. The hydrogenation catalyst is distributed in a gradient increasing mode from inside to outside in the particles, and the modifier, the active metal and the pore structure are distributed in a gradient increasing mode, so that the hydrogenation catalyst can be used as a hydrogenation catalyst for poor raw materials.

Description

Technical Field

[0001] This invention relates to the field of catalyst preparation, and in particular to a method for the continuous production of hydrogenation catalysts using the aluminum alkoxide process. Background Technology

[0002] Alumina is widely used as a support material for hydrotreating catalysts. However, the interaction between the active metal on the surface of pure alumina and the support is relatively strong, easily forming inactive species (such as nickel-aluminum spinel), and it is not easy to completely sulfide to form an active phase with high hydrotreating activity. How to weaken the strong interaction between the metal and the support has become the key to the preparation of highly active hydrotreating catalysts. To improve the activity and stability of hydrotreating catalysts, it is often necessary to modify the alumina support, such as by adding additives like silicon, phosphorus, fluorine, boron, zirconium, titanium, and magnesium. These modifications aim to: 1) adjust the acidity of the alumina; 2) alter the interaction between the active component and the alumina; and 3) improve the thermal stability of the alumina.

[0003] Coprecipitation is a typical method for preparing aluminum hydroxide. However, during coprecipitation, the initial Al(OH)3 crystal nuclei have many hydroxyl groups (and water molecules bound to them), resulting in a complex structure, low molecular polarity, and extremely low solubility. Consequently, the aggregation rate is much greater than the directional rate, easily forming amorphous gel-like precipitates with low crystallinity, incomplete crystal forms, and undesirable pore structures. Correspondingly, catalysts prepared using the coprecipitation method also suffer from the same problems.

[0004] CN101491768A discloses a method for preparing a silicon- and zirconium-containing hydrogenation catalyst. The method involves neutralizing an acidic aluminum salt solution with ammonia water prepared in a specific ratio to form a gel, followed by aging after a period of reaction. Then, an acidic silicon salt solution is added, and after aging for a period of time, a zirconium-containing solution is added, followed by further aging. The mixture is then washed, filtered, and dried to obtain the desired silicon- and zirconium-containing alumina dry gel, which is then used to prepare the desired hydrogenation catalyst. In this catalyst, the promoters are uniformly distributed, and the catalyst pore structure shows no gradient change.

[0005] In the existing technology, although there are different methods to control the grain size and thus prepare hydrogenation catalysts with different pore structures and properties, how to prepare large-pore hydrogenation catalysts with high specific surface area and concentrated particle size distribution, and with active metals and modifiers in gradient distribution inside the catalyst particles and gradient distribution of catalyst pore structure, is also an important topic that has been continuously studied in this field. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a hydrogenation catalyst and its production method, particularly a method for the continuous production of hydrogenation catalysts from aluminum alkoxides. The hydrogenation catalyst of this invention features large and concentrated particle size, high specific surface area, large pore volume, large pore size, high crystallinity, and a gradient distribution of modifiers, active metals, and pore structure from the inside out within the catalyst particles. It can be used as a hydrogenation catalyst for low-quality raw materials.

[0007] The first aspect of this invention provides a method for producing a hydrogenation catalyst, comprising:

[0008] (1) Alcohol, polar metal seed crystals, active metal solution I containing modifier and aluminum alkoxide solution I are added in parallel to the first reaction vessel for hydrolysis into gel to obtain product liquid I;

[0009] (2) The generated liquid I enters a settling tank for settling and separation to obtain an upper layer of alcohol and a lower layer of alcohol-containing sol I;

[0010] (3) The sol I is added to the second reaction vessel, and solution II containing the modifier of the active metal and solution II of aluminum alkoxide are added to continue hydrolysis into sol to obtain liquid II;

[0011] (4) The generated liquid II enters the aging vessel for aging reaction;

[0012] (5) The aged material obtained in step (4) is dried and calcined to obtain the hydrogenation catalyst.

[0013] The production method of the hydrogenation catalyst of the present invention is preferably carried out in a continuous manner. Multiple sedimentation tanks used in step (2) and multiple aging tanks used in step (4) can be set up and switched during continuous production.

[0014] In the method of this invention, when using continuous production of hydrogenation catalyst, preferably, in step (1), the first reactor is operated by overflowing the generated liquid I out of the first reactor. When the first reactor is started, preferably, an alcohol and polar metal seed crystals are first added as a base liquid, and then a solution I of active metal containing modifier and an aluminum alkoxide solution I are added in parallel for hydrolysis into a gel until the generated liquid I begins to be discharged from the first reactor. The amount of alcohol added to the base liquid is 1 / 5 to 1 / 2 of the actual effective volume of the first reactor; based on the total mass of the aluminum alkoxide solution (calculated as Al2O3), the hydrogenation active metal (calculated as oxide), and the modifier (calculated as element) in the first reactor when the generated liquid I begins to be discharged from the first reactor, the amount of polar metal salt seed crystals added is 0.1% to 2.0%, preferably 0.5% to 2.0%.

[0015] In the method of this invention, when using continuous production of the hydrogenation catalyst, preferably, in step (3), the second reactor is operated by overflow to discharge the product liquid II from the second reactor. When the second reactor is started, preferably, alcohol is first added as a base liquid, and then a solution II of an active metal containing a modifier and an aluminum alkoxide solution II are added to hydrolyze into a gel until the product liquid II begins to be discharged from the second reactor. The amount of alcohol added as the base liquid is 1 / 7 to 1 / 2 of the actual effective volume of the second reactor, preferably 1 / 4 to 1 / 2.

[0016] In the method of this invention, the alcohol mentioned in step (1) is selected from at least one of organic monohydric alcohols and organic polyhydric alcohols, wherein the molecular structural formula of the organic monohydric alcohol is C n H 2n+2 O (n≥2, preferably n=2~12), can be at least one of ethanol, isopropanol, n-propanol, n-hexanol, n-heptanol, etc.; wherein the molecular structural formula of the polyol is C n H 2n+2-x (OH) x (n≥2, preferably n=2~12, x≥3), and can be at least one of the following polyols: ethylene glycol, diethylene glycol, propylene glycol glycerol, butanediol, pentaerythritol, glycerol, trimethylolethane, xylitol, sorbitol, etc.

[0017] In the method of the present invention, the polar metal seed crystal is selected from at least one of metal halide compounds and metal sulfides, preferably selected from one or more of AgCl, ZnS, CuS or HgS.

[0018] In the method of this invention, the operating conditions of the first reaction vessel in step (1) are as follows: temperature is -15 to 15°C, preferably 0 to 15°C; pressure is 1 to 10 MPa, preferably 4 to 10 MPa. The pressure atmosphere can be one or more of air, nitrogen, or inert gases. The reaction time is 10 to 180 minutes, preferably 10 to 60 minutes (when continuous production is used, the reaction time is the residence time of the active metal solution I containing the modifier and the aluminum alkoxide solution I entering the first reaction vessel). The hydrolysis gelation reaction is preferably carried out under stirring conditions, and the stirring rate is 50 to 200 rad / min, preferably 100 to 200 rad / min.

[0019] In the method of this invention, the aluminum alkoxide mentioned in step (1) can be selected from at least one of monohydric aluminum alkoxide and organic polyhydric aluminum alkoxide, wherein the molecular structural formula of the monohydric alcohol in the organic monohydric aluminum alkoxide is C n H 2n+2 O (n≥2, preferably n=2~12), can be at least one of ethanol, isopropanol, n-propanol, n-hexanol, n-heptanol, etc.; wherein the molecular structural formula of the polyol in the organic polyol aluminum is C n H2n+2-x (OH) x (n≥2, preferably n=2~12, x≥3), and can be at least one of the following polyols: ethylene glycol, diethylene glycol, propylene glycol glycerol, butanediol, pentaerythritol, glycerol, trimethylolethane, xylitol, sorbitol, etc. The aluminum alkoxide solution is mainly a mixed solution of aluminum alkoxide and its corresponding alcohol, and its concentration is 10~100g / 100mL based on Al2O3.

[0020] In the method of the present invention, the flow rate ratio of the active metal solution I containing the modifier to the aluminum alkoxide solution I in step (1) is 1:2 to 1:100.

[0021] In the method of this invention, the modifier in step (1) is at least one of fluorine, boron, phosphorus, and silicon. In the solution I containing the modifier, the concentration of the modifier, calculated as an element, accounts for 1.0 wt% to 2.0 wt% of the total mass of the aluminum alkoxide solution I (calculated as Al2O3) and the active metal (calculated as oxide). For example, the source of the modifier may be ammonium fluoride or sodium fluoride for fluorine, boron may be boric acid, sodium borate, or ammonium borate for boron, phosphoric acid or sodium phosphate for phosphorus, and silicic acid or sodium silicate for silicon.

[0022] In the method of this invention, the components introduced into the hydrogenation catalyst by the active metal solution I containing the modifier and the aluminum alkoxide solution I include alumina, a hydrogenation active metal, and a modifier, namely, first alumina, first hydrogenation active metal, and first modifier. The components introduced into the modified hydrogenation catalyst by the active metal solution II containing the modifier and the aluminum alkoxide solution II include alumina, a hydrogenation active metal, and a modifier, namely, second alumina, second hydrogenation active metal, and second modifier. The active metal is selected from at least one metal from Group VIB and Group VIII. Group VIB metals are preferably at least one from Mo and W, and Group VIII metals are preferably at least one from Ni and Co. The first hydrogenation active metal and the second hydrogenation active metal can be the same or different. The mass ratio of first alumina to second alumina is 1:25 to 12:1. The mass ratio of the first hydrogenation active metal and the second hydrogenation active metal, based on oxides, is 1:15 to 10:1. The mass ratio of the first modifier and the second modifier, based on elemental composition, is 1:6 to 6:1. Preferably, the first hydrogenation active metal is selected from the first group VIB metal and the first group VIII metal, and the second hydrogenation active metal is selected from the second group VIB metal and the second group VIII metal. More preferably, the mass ratio of the first group VIB metal to the second group VIB metal, based on oxides, is 1:5 to 5:1, and the mass ratio of the first group VIII metal to the second group VIII metal, based on oxides, is 1:5 to 5:1.

[0023] In the method of this invention, step (1) involves a first hydrogenation active metal source, for example, a molybdenum source such as molybdenum oxide, ammonium molybdate, or molybdic acid; a tungsten source such as sodium tungstate, ammonium metatungstate, or tungstic acid; a nickel source such as nickel nitrate, nickel chloride, or basic nickel carbonate; and a cobalt source such as cobalt nitrate, cobalt chloride, or basic cobalt carbonate. The concentration of the active metal solution I containing the modifier, calculated as oxides, is 5–50 g / 100 mL, preferably 10–30 g / 100 mL. The concentration of the modifier, calculated as an element, accounts for 1.0 wt%–2.0 wt% of the total mass of the aluminum alkoxide solution I (calculated as Al2O3) and the active metal (calculated as oxides).

[0024] In the method of the present invention, alcohol and polar metal seed crystals are added in parallel to the first reaction vessel. The alcohol addition rate is the ratio of the sum of the addition rates of the active metal solution I containing the modifier and the aluminum alkoxide solution I based on their volumes to 0.1:1 to 10:1, preferably 0.2:1 to 5:1. The polar metal seed crystal addition rate is 1% to 10% of the sum of the total mass addition rates of the active metal solution I containing the modifier (based on oxides), the aluminum alkoxide solution I (based on Al2O3), and the modifier (based on elemental form), preferably 1% to 5%.

[0025] In the method of this invention, the sol I obtained in step (2) has a pore volume of 0.9-1.1 mL / g and a specific surface area of ​​200-250 m² after being calcined at 500-800℃ for 1-5 hours. 2 / g, average pore size ≥90nm, preferably 90~120nm.

[0026] In the method of the present invention, the operating conditions of the settling tank in step (2) are as follows: the temperature is -15 to 15°C, preferably 0 to 15°C, and the pressure is 1 to 10 MPa, preferably 4 to 10 MPa.

[0027] In the method of the present invention, after sedimentation in step (2), a portion of the alcohol obtained in the upper layer can be recycled back to the first reaction vessel for continued use.

[0028] In the method of the present invention, the operating conditions of the second reactor in step (3) are as follows: the temperature is 200-350℃, preferably 200-300℃, and preferably, the reaction temperature of the second reactor is at least 150℃ higher than that of the first reactor; the pressure is 10-20MPa, preferably 12-20MPa, and more preferably 12-18MPa. Preferably, the operating pressure of the second reactor is at least 5MPa higher than that of the first reactor. The hydrolysis gelation reaction conditions in step (3) are as follows: the reaction time is 50-120 minutes, preferably 65-100 minutes (when continuous production is used, the reaction time is the residence time of the active metal solution II containing the modifier and the aluminum alkoxide solution II entering the second reactor). The hydrolysis gelation reaction is preferably carried out under stirring conditions, the stirring rate is 200-350 rad / min, preferably 250-350 rad / min, and the stirring rate of the second reactor is at least 50 rad / min higher than that of the first reactor.

[0029] In the method of this invention, the aluminum alkoxide mentioned in step (3) is selected from at least one of organic monohydric aluminum alkoxides and organic polyhydric aluminum alkoxides, wherein the molecular structural formula of the monohydric alcohol in the organic monohydric aluminum alkoxide is C n H 2n+2 O (n≥2, preferably n=2~12), can be at least one of ethanol, isopropanol, n-propanol, n-hexanol, n-heptanol, etc.; wherein the molecular structural formula of the polyol in the organic polyol aluminum is C n H 2n+2-x (OH) x (n≥2, preferably n=2~12, x≥3), and can be at least one of the following polyols: ethylene glycol, diethylene glycol, propylene glycol glycerol, butanediol, pentaerythritol, glycerol, trimethylolethane, xylitol, sorbitol, etc. The aluminum alkoxide solution is mainly a mixed solution of aluminum alkoxide and its corresponding alcohol, and its concentration is 10~100g / 100mL based on Al2O3.

[0030] In the method of the present invention, the flow rate ratio of the active metal solution II containing the modifier to the aluminum alkoxide solution II in step (3) is 1:1 to 1:10, preferably 1:2 to 1:10.

[0031] In the method of the present invention, the modifier in step (3) is at least one of fluorine, boron, phosphorus, and silicon. In the solution II containing the modifier, the concentration of the modifier, calculated as an element, accounts for 2.5 wt% to 3.5 wt% of the total mass of the aluminum alkoxide solution II (calculated as Al2O3) and the active metal (calculated as oxide). For example, the source of the modifier is ammonium fluoride or sodium fluoride for fluorine, boron source is boric acid, sodium borate, or ammonium borate for boron, phosphoric acid or sodium phosphate for phosphorus, and silicon source is silicic acid or sodium silicate.

[0032] In the method of this invention, the second hydrogenation active metal source in step (3) is, for example, molybdenum source is molybdenum oxide, ammonium molybdate, or molybdic acid; tungsten source is sodium tungstate, ammonium metatungstate, or tungstic acid; nickel source is one or more of nickel nitrate, nickel chloride, and basic nickel carbonate; and cobalt source is one or more of cobalt nitrate, cobalt chloride, and basic cobalt carbonate. The concentration of the active metal solution II containing the modifier, calculated as oxides, is 50-100 g / 100 mL, preferably 60-100 g / 100 mL. The concentration of the modifier, calculated as an element, accounts for 2.5 wt% to 3.5 wt% of the total mass of the aluminum alkoxide solution II (calculated as Al2O3) and the active metal (calculated as oxides).

[0033] In the method of the present invention, the concentration of aluminum alkoxide solution II in step (3) is at least 2 g / 100 ml lower than the concentration of aluminum alkoxide solution I in step (1), preferably 2 to 20 g / 100 ml.

[0034] In the method of the present invention, the concentration of the active metal solution II containing the modifier in step (3) is at least 20 g / 100 mL higher than the concentration of the active metal solution I containing the modifier in step (1), preferably 20 to 90 g / 100 mL.

[0035] In the method of the present invention, the aging reaction conditions in step (4) are as follows: the temperature is 300-400℃, and the temperature of the aging vessel is at least 20℃ higher than that of the second reaction vessel; the pressure is 15-20MPa, and the pressure of the aging vessel is at least 2MPa higher than that of the second reaction vessel; the aging time is 100-360min, preferably 150-250min; the aging is carried out under stirring conditions, and the stirring speed is preferably 350-450rad / min, and the stirring speed of the aging reaction vessel is at least 50rad / min higher than that of the second reaction vessel.

[0036] In the method of this invention, the drying temperature in step (5) is 100–450°C, preferably 150–400°C, and the drying time is 1–10 hours. The drying method can be flash drying, cyclone drying, oven drying, spray drying, etc. The calcination temperature is 300–800°C, preferably 350–550°C, and the calcination time is 2–5 hours, preferably 2–4 hours. The calcination atmosphere is one or more of air, nitrogen, or water vapor.

[0037] A second aspect of the present invention provides a hydrogenation catalyst produced by the above-described production method.

[0038] The hydrogenation catalyst of this invention comprises alumina, a hydrogenation active metal, and a modifier. The hydrogenation catalyst is in the form of spherical particles, including a non-central region and a central region. The concentration of the hydrogenation active metal in the central region is 15-40 percentage points lower than that in the non-central region. The concentration of the modifier in the central region is 0.5-2.5 percentage points lower than that in the non-central region. The pore volume of the hydrogenation catalyst is at least 0.5 mL / g higher than that in the central region, preferably 0.6-1.1 mL / g. The radial thickness ratio of the central region to the non-central region of the hydrogenation catalyst particle is 1:2 to 2:1.

[0039] In the hydrogenation catalyst of the present invention, in the central region of the modified hydrogenation catalyst particles, the concentration of the hydrogenation active metal, calculated as oxide, is 4 wt% to 50 wt%, preferably 4 wt% to 20 wt%, and the concentration of the modifier, calculated as elemental, is 1.0 wt% to 2.0 wt%; in the non-central region of the modified hydrogenation catalyst, the concentration of the hydrogenation active metal, calculated as oxide, is 20 wt% to 90 wt%, preferably 25 wt% to 40 wt%, and the concentration of the modifier, calculated as elemental, is 2.5 wt% to 3.5 wt%.

[0040] In the hydrogenation catalyst of the present invention, the hydrogenation active metal is selected from at least one of Group VIB and Group VIII metals, the Group VIB metal is selected from at least one of Mo and W, the Group VIII metal is selected from at least one of Ni and Co, and the modifier is selected from at least one of fluorine, boron, phosphorus, and silicon.

[0041] In the hydrogenation catalyst of the present invention, preferably, the modifier is selected from at least two of fluorine, boron, phosphorus, and silicon, wherein the content of any one modifier accounts for 10% to 60% of the total mass of the modifier. Preferably, the modifier is selected from fluorine-boron, silicon-phosphorus, boron-phosphorus, fluorine-boron-phosphorus, or fluorine-boron-phosphorus-silicon.

[0042] In the hydrogenation catalyst of this invention, based on the mass of the catalyst, the mass content of the hydrogenation active metal (calculated as oxide) is 10% to 80%, the mass content of alumina is 18% to 89%, and the mass content of the modifier (calculated as element) is 0.5% to 3.0%.

[0043] In the hydrogenation catalyst of the present invention, preferably, based on the mass of the catalyst, the mass content of Group VIB metals as oxides is 5% to 45%, the mass content of Group VIII metals as oxides is 2% to 15%, the mass content of alumina is 20% to 80%, and the mass content of modifier as elemental is 0.5% to 3.0%.

[0044] The hydrogenation catalyst of this invention has the following properties: pore volume of 1.5–2.0 mL / g; specific surface area of ​​300–350 m² / g. 2 / g, average pore size ≥150nm, preferably 160–200nm; the properties of the central region of the hydrogenation catalyst are as follows: pore volume 0.9–1.0mL / g, specific surface area 200–250m² / g. 2 / g, average pore size ≥90nm, preferably 90~120nm.

[0045] The specific surface area of ​​the hydrogenation catalyst of this invention is at least 50 m² higher than that of the central region of the hydrogenation catalyst. 2 / g, preferably 50-150m 2 / g; the average pore size of the hydrogenation catalyst is at least 40 nm higher than the average pore size of the central region of the hydrogenation catalyst, preferably 50–90 nm.

[0046] In the hydrogenation catalyst of the present invention, the particle size distribution of the catalyst is as follows: particles with a diameter less than 300 μm account for 1.0% to 2.5%, particles with a diameter of 300 to 350 μm account for 2.0% to 2.5%, and particles with a diameter of 350 to 500 μm, excluding 350 μm, account for 95.0% to 97.0%.

[0047] The third aspect of the present invention provides the application of the above-mentioned hydrogenation catalyst in the hydrogenation of inferior heavy oil, preferably in the hydrogenation of heavy inferior feedstock with high asphaltenes content.

[0048] Compared with the prior art, the present invention has the following beneficial effects:

[0049] 1. In the production method of the hydrogenation catalyst provided by this invention, an alcohol immiscible with water is first used as the reaction medium, and a polar metal salt is used as a seed crystal. A hydrolysis reaction is carried out under high pressure and low reaction temperature. On the one hand, the sol-gel particles generated by hydrolysis, due to the hydrophilic hydroxyl groups on their surface, do not adhere to each other in the water-immiscible alcohol. Under the action of the polar seed crystal, utilizing their small molecular size, high polarity, and large orientation rate, they easily form crystalline precipitates or colloidal particles with crystalline structures. On the other hand, the higher pressure and lower temperature reduce the Brownian motion of sol-gel molecules or ions, reducing the aggregation of particles into clusters due to continuous collisions, thereby effectively controlling... In sol I, the crystals are suitable and complete. The concentrations of metal solution and modifier used in this stage are relatively low, which can prepare sol-gel particles with low metal and modifier concentrations, complete crystal form, and suitable specific surface area, pore size, and pore volume. Then, under high temperature, high pressure, and higher metal and modifier concentrations, the sol-gel particles with complete crystal form are subjected to accelerated Brownian motion, and hydrolysis is carried out again in the alcohol substrate using the complete crystal form sol-gel as seed crystals. This results in particles with more complete crystal structure, larger specific surface area, pore size, and pore volume. Finally, aging is continued under high temperature and high pressure conditions, resulting in a hydrogenation catalyst with large surface area, large pore volume, concentrated particle size distribution, and high crystallinity.

[0050] 2. The hydrogenation catalyst provided by this invention has the characteristics of large surface area, large pore volume, highly concentrated particle size distribution, gradient distribution of modifier, active metal and pore structure from the inside to the outside, and high crystallinity. It is particularly suitable as a hydrogenation catalyst for use as a hydrogenation refining agent for heavy and inferior raw materials such as residue oil, wax oil, coal liquefaction oil and coal tar.

[0051] 3. In the catalyst provided by this invention, the gradient increasing distribution of modifier, active metal and pore structure from the inside to the outside systematically optimizes the activity distribution of the catalyst particles prepared therefrom. This allows large molecules that are difficult to react to react first on the outer surface of the catalyst and generate smaller molecules that are easier to react. Then the smaller molecules enter the interior to carry out further reactions, so that the reactants undergo reasonable graded reactions from the outside to the inside, which is beneficial to optimizing the hydrogenation activity of the catalyst and improving the overall utilization rate of the catalyst. Attached Figure Description

[0052] Figure 1 This is a scanning electron microscope (SEM) image of the hydrogenation catalyst particles obtained in Example 1 of the present invention. Detailed Implementation

[0053] The preparation method of the hydrogenation catalyst of the present invention will be described in more detail below through specific embodiments. These embodiments are merely illustrative examples of specific implementation methods of the present invention and do not constitute a limitation on the scope of protection of the present invention.

[0054] In this invention, terms such as "first" and "second" are used to distinguish two different elements or parts, such as a first reaction vessel and a second reaction vessel, and are not used to define a specific position or relative relationship. Alternatively, "first" and "second" are used to distinguish two different steps in which substances are introduced, such as first alumina and second alumina, first hydrogenation active metal and second hydrogenation active metal, first modifier and second modifier, and are not used to define their specific composition. In other words, in some embodiments, the terms "first" and "second" can be used interchangeably.

[0055] In this invention, the specific surface area, pore volume, and pore size are determined by low-temperature liquid nitrogen adsorption method; the particle size distribution is determined by laser particle size analyzer.

[0056] In this invention, the concentrations of hydrogenation active metals and modifiers on the catalyst particles were measured using a field emission scanning electron microscope (SEM). The electron gun type was a cold field emission gun, the accelerating voltage was 0.1 kW to 30 kW, the resolution was 1.0 nm (secondary electrons), 3.0 nm (backscattered electrons), and the magnification was 25 to 1,000,000. During the test, 5 to 10 points were taken in both the central and non-central regions, and the average values ​​were calculated to obtain the concentrations of hydrogenation active metals and modifiers in the corresponding regions.

[0057] In this invention, based on the relationship that the total pore volume and specific surface area of ​​a sample are equal to the sum of its parts, if the overall specific surface area and pore volume are larger than those of the central region, then the surface area and pore volume of the non-central region will be larger than those of the central region. The central region and the non-central region of the catalyst particle are two regions formed radially in proportion to the thickness, with the center of the particle as the starting point. The region containing the center is the central region, and the other region is the non-central region.

[0058] In the embodiments and comparative examples of the present invention, the Mo-Ni acidic active metal solution is a mixed solution of Mo-Ni, prepared using molybdenum oxide, basic nickel carbonate and phosphoric acid, wherein the mass ratio of MoO3 to NiO is 4:1, and the concentration of the Mo-Ni acidic active metal solution is calculated as MoO3 and NiO; the Mo-Ni alkaline active metal solution is a mixed solution of Mo-Ni-NH3, prepared using ammonium molybdate, nickel nitrate and ammonia, wherein the mass ratio of MoO3 to NiO is 4:1, and the concentration of the Mo-Ni alkaline active metal solution is calculated as MoO3 and NiO.

[0059] In the embodiments and comparative examples of the present invention, the obtained sol I was calcined at 500°C for 3 hours before testing.

[0060] Example 1

[0061] Add 2L of n-hexanol as the reaction medium to the 10L first reactor I, add 1.6g of AgCl, adjust the pressure of the first reactor I to 5MPa, the temperature to 5℃, the atmosphere to air, and the stirring speed to 100rad / min. After the mixture is stirred evenly, open the metal solution inlet and aluminum alkoxide solution inlet at the top of the first reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 23 g / 100 mL based on metal oxide, with added ammonium fluoride, and fluorine accounting for 1.2 wt% of the oxide mass in the solution) and the aluminum glycolate solution (aluminum glycolate solution concentration is 50 g / 100 mL based on Al2O3) to be 5 mL / min and 25 mL / min, respectively. After the hydrolysis reaction has been carried out for 20 min, open the overflow control valve at the bottom to allow the generated liquid I to flow into the settling tank II. At the same time, add n-hexanol (AgCl) to the first reactor I at rates of 33 mL / min and 0.15 g / min, respectively. After the volume of the generated liquid in the settling tank II reaches 1 / 2, switch to the settling tank III and separate the ethylene glycol and sol I in the settling tank II. The n-hexanol can be recycled back to the first reactor I. The properties of sol IA are shown in Table 1.

[0062] Add 2.5 L of ethylene glycol and the separated sol IA to the second reactor IV. Adjust the pressure of the second reactor to 15 MPa, the temperature to 200 °C, and the stirring rate to 200 rad / min. Open the Mo-Ni metal solution inlet and the aluminum alkoxide solution inlet at the top of the second reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 100 g / 100 mL based on metal oxides, with added ammonium fluoride, fluorine accounting for 2.7 wt% of the oxides in the solution) and the aluminum hexoxide solution (aluminum hexoxide solution concentration is 47 g / 100 mL based on Al2O3) to 3.5 mL / min and 20 mL / min, respectively. After the hydrolysis reaction for 100 min, the product liquid II is discharged from the second reactor.

[0063] The generated liquid II was introduced into an aging vessel. The pressure of the aging vessel was adjusted to 17 MPa, the temperature to 300℃, and the stirring rate to 350 rad / min. After aging for 150 min, it was filtered, dried at 150℃ for 4 h, and calcined at 400℃ for 3 h in air atmosphere to obtain alumina A. Its properties are shown in Table 2.

[0064] Example 2

[0065] Add 2.5L of n-butanol as the reaction medium to the 10L first reactor I, add 3.6g of ZnS, adjust the pressure of the first reactor I to 7MPa, the temperature to 10℃, the atmosphere to nitrogen, and the stirring speed to 200rad / min. After the mixture is stirred evenly, open the Mo-Ni metal solution inlet and the aluminum butoxide solution inlet at the top of the first reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 30 g / 100 mL based on metal oxide, with added phosphoric acid, phosphorus accounting for 1.5 wt% of the oxide mass in the solution) and the aluminum isopropoxide solution (aluminum isopropoxide solution concentration is 45 g / 100 mL based on Al2O3) to 2 mL / min and 30 mL / min, respectively. After the hydrolysis reaction is completed for 40 min, open the overflow control valve at the bottom to allow the generated liquid I to flow into the settling tank II. At the same time, add n-butanol and ZnS to the first reactor I at rates of 40 mL / min and 0.2 g / min, respectively. After the volume of the generated liquid in the settling tank II reaches 1 / 2, switch to the settling tank III and separate the n-butanol and sol I in the settling tank II. The isopropanol can be recycled back to the first reactor I. The properties of sol IB are shown in Table 1.

[0066] Add 2.5 L of isopropanol and the separated sol IB to the second reactor IV. Adjust the pressure of the second reactor to 12 MPa, the temperature to 250 °C, and the stirring rate to 250 rad / min. Open the Mo-Ni metal solution inlet and the aluminum alkoxide solution inlet at the top of the second reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 95 g / 100 mL based on metal oxide, with added phosphoric acid and silicic acid, phosphorus and silicon accounting for 3.0 wt% of the oxide mass in the solution) and the aluminum butoxide solution (aluminum isopropoxide solution concentration is 30 g / 100 mL based on Al2O3) to 4 mL / min and 22 mL / min, respectively. After the hydrolysis reaction for 90 min, the product liquid II is discharged from the second reactor.

[0067] The generated liquid II was introduced into an aging vessel. The pressure of the aging vessel was adjusted to 19 MPa, the temperature to 310 °C, and the stirring rate to 300 rad / min. After aging for 200 min, it was filtered, dried at 180 °C for 3 h, and calcined at 450 °C for 4 h in air atmosphere to obtain alumina B. Its properties are shown in Table 2.

[0068] Example 3

[0069] Add 5L of n-pentanol as the reaction medium to the 10L first reactor I, add 13g of CuS, adjust the pressure of the first reactor I to 8MPa, the temperature to 15℃, the atmosphere to air, and the stirring speed to 150rad / min. After the mixture is stirred evenly, open the Mo-Ni metal solution inlet and the aluminum pentoxide solution inlet at the top of the first reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 28 g / 100 mL based on metal oxide, with added boric acid and phosphoric acid, boron and phosphorus accounting for 1.5 wt% of the oxide mass in the solution) and the aluminum diethylene glycol solution (aluminum diethylene glycol solution concentration is 38 g / 100 mL based on Al2O3) to 3.5 mL / min and 50 mL / min, respectively. After the hydrolysis reaction is carried out for 30 min, open the overflow control valve at the bottom to allow the generated liquid I to flow into the settling tank II. At the same time, add n-pentanol and CuS to the first reactor I at rates of 70 mL / min and 0.9 g / min, respectively. After the volume of the generated liquid in the settling tank II reaches 1 / 2, switch to the settling tank III and separate the n-pentanol sol I in the settling tank II. The n-pentanol can be recycled back to the first reactor I. The properties of the sol I are shown in Table 1.

[0070] Add 5 L of n-pentanol and the separated sol IC to the second reactor IV. Adjust the pressure of the second reactor to 16 MPa, the temperature to 220 °C, and the stirring rate to 300 rad / min. Open the Mo-Ni metal solution inlet and the aluminum alkoxide solution inlet at the top of the second reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 100 g / 100 mL based on metal oxide, with added sodium fluoride, and fluorine accounting for 2.8 wt% of the oxide mass in the solution) and the aluminum alkoxide solution (aluminum alkoxide solution concentration is 20 g / 100 mL based on Al2O3) to 5 mL / min and 40 mL / min, respectively. After the hydrolysis reaction for 65 min, the product liquid II is discharged from the second reactor.

[0071] The generated liquid II was introduced into an aging vessel. The pressure of the aging vessel was adjusted to 20 MPa, the temperature to 320 °C, and the stirring rate to 350 rad / min. After aging for 180 min, it was filtered, dried at 200 °C for 3 h, and calcined at 500 °C for 4 h in air atmosphere to obtain alumina C. Its properties are shown in Table 2.

[0072] Example 4

[0073] Add 4L of n-hexanol as the reaction medium to the 10L first reactor I, add 7g of HgS, adjust the pressure of the first reactor I to 9MPa, the temperature to 5℃, the atmosphere to air, and the stirring speed to 160rad / min. After the mixture is stirred evenly, open the Mo-Ni metal solution inlet and the aluminum hexoxide solution inlet at the top of the first reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 28 g / 100 mL based on metal oxide, with added boric acid and phosphoric acid, boron and phosphorus accounting for 1.3 wt% of the oxide mass in the solution) and the aluminum hexoxide solution (aluminum hexoxide solution concentration is 90 g / 100 mL based on Al2O3) to 8 mL / min and 20 mL / min, respectively. After the hydrolysis reaction is carried out for 50 min, open the overflow control valve at the bottom to allow the generated liquid I to flow into the settling tank II. At the same time, add hexanol and HgS to the first reactor I at rates of 50 mL / min and 1.2 g / min, respectively. After the volume of the generated liquid in the settling tank II reaches 1 / 2, switch to the settling tank III and separate the hexanol and sol I in the settling tank II. The hexanol can be recycled back to the first reactor I. The properties of sol ID are shown in Table 1.

[0074] Add 5 L of n-hexanol and the separated sol ID to the second reactor IV. Adjust the pressure of the second reactor to 15 MPa, the temperature to 250 °C, and the stirring rate to 350 rad / min. Open the Mo-Ni metal solution inlet and the aluminum alkoxide solution inlet at the top of the second reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 67 g / 100 mL based on metal oxides, with added sodium fluoride, sodium silicate, ammonium borate, and sodium phosphate, and fluorine, silicon, boron, and phosphorus accounting for 3.0 wt% of the oxide mass in the solution) and the aluminum alkoxide solution (aluminum alkoxide solution concentration is 70 g / 100 mL based on Al2O3) to 6.5 mL / min and 15 mL / min, respectively. After the hydrolysis reaction for 80 min, the product liquid II is discharged from the second reactor.

[0075] The generated liquid II was introduced into an aging vessel. The pressure of the aging vessel was adjusted to 19 MPa, the temperature to 350 °C, and the stirring rate to 400 rad / min. After aging for 250 min, it was filtered, dried at 150 °C for 4 h, and calcined at 450 °C for 5 h in air atmosphere to obtain alumina D. Its properties are shown in Table 2.

[0076] Example 5

[0077] Add 5L of n-butanol as the reaction medium to the 10L first reactor I, add 13g of HgS, adjust the pressure of the first reactor I to 4MPa, the temperature to 15℃, the atmosphere to nitrogen, and the stirring speed to 140rad / min. After the mixture is stirred evenly, open the Mo-Ni metal solution inlet and the aluminum butoxide solution inlet at the top of the first reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 25 g / 100 mL based on metal oxide, with added boric acid and phosphoric acid, boron and phosphorus accounting for 1.4 wt% of the oxide mass in the solution) and the aluminum butoxide solution (aluminum butoxide solution concentration is 70 g / 100 mL based on Al2O3) to 9 mL / min and 35 mL / min, respectively. After the hydrolysis reaction has been carried out for 60 min, open the overflow control valve at the bottom to allow the generated liquid I to flow into the settling tank II. At the same time, add n-butanol and HgS to the first reactor I at rates of 76 mL / min and 2.0 g / min, respectively. After the volume of the generated liquid in the settling tank II reaches 1 / 2, switch to the settling tank III and separate the n-butanol and sol I in the settling tank II. The n-butanol can be recycled back to the first reactor I. The properties of the sol IE are shown in Table 1.

[0078] Add 5 L of n-butanol and the separated sol IE to the second reactor IV. Adjust the pressure of the second reactor to 14 MPa, the temperature to 270 °C, and the stirring rate to 260 rad / min. Open the Mo-Ni metal solution inlet and the aluminum alkoxide solution inlet at the top of the second reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 67 g / 100 mL based on metal oxides, with added boric acid and phosphoric acid, boron and phosphorus accounting for 2.9 wt% of the oxide mass in the solution) and the aluminum alkoxide solution (aluminum alkoxide solution concentration is 55 g / 100 mL based on Al2O3) to 8 mL / min and 20 mL / min, respectively. After the hydrolysis reaction for 72 min, the product liquid II is discharged from the second reactor.

[0079] The generated liquid II was introduced into an aging vessel. The pressure of the aging vessel was adjusted to 18 MPa, the temperature to 340℃, and the stirring rate to 320 rad / min. After aging for 160 min, it was filtered, dried at 120℃ for 5 h, and calcined at 550℃ for 3.5 h in air atmosphere to obtain alumina E. Its properties are shown in Table 2.

[0080] Comparative Example 1

[0081] Add 5L of n-butanol as the reaction medium to the 10L first reactor I, add 13g of HgS, adjust the pressure of the first reactor I to 4MPa, the temperature to 15℃, the atmosphere to nitrogen, and the stirring speed to 140rad / min. After the mixture is stirred evenly, open the Mo-Ni metal solution inlet and the aluminum butoxide solution inlet at the top of the first reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 25 g / 100 mL based on metal oxide, with added boric acid and phosphoric acid, boron and phosphorus accounting for 1.4 wt% of the oxide mass in the solution) and the aluminum butoxide solution (aluminum butoxide solution concentration is 70 g / 100 mL based on Al2O3) to 9 mL / min and 35 mL / min, respectively. After the hydrolysis reaction has been carried out for 60 min, open the overflow control valve at the bottom to allow the generated liquid I to flow into the settling tank II. At the same time, add n-butanol and HgS to the first reactor I at rates of 76 mL / min and 2.0 g / min, respectively. After the volume of the generated liquid in the settling tank II reaches 1 / 2, switch to the settling tank III and separate the n-butanol and sol I in the settling tank II. The n-butanol can be recycled back to the first reactor I. The properties of the sol IF are shown in Table 1.

[0082] Add 5 L of n-butanol and the separated sol IF to the second reactor IV. Adjust the pressure of the second reactor to 4 MPa, the temperature to 15 °C, and the stirring rate to 260 rad / min. Open the Mo-Ni metal solution inlet and the aluminum alkoxide solution inlet at the top of the second reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 67 g / 100 mL based on metal oxides, with added boric acid and phosphoric acid, boron and phosphorus accounting for 2.9 wt% of the oxide mass in the solution) and the aluminum alkoxide solution (aluminum alkoxide solution concentration is 55 g / 100 mL based on Al2O3) to 8 mL / min and 20 mL / min, respectively. After the hydrolysis reaction for 72 min, the product liquid II is discharged from the second reactor.

[0083] The generated liquid II was introduced into an aging vessel. The pressure of the aging vessel was adjusted to 4 MPa, the temperature to 15 °C, and the stirring rate to 320 rad / min. After aging for 160 min, it was filtered, dried at 120 °C for 5 h, and calcined at 550 °C for 3.5 h in air atmosphere to obtain alumina F. Its properties are shown in Table 2.

[0084] Comparative Example 2

[0085] Add 5L of pure water as the reaction medium to the 10L first reactor I, add 13g of HgS, adjust the pressure of the first reactor I to 4MPa, the temperature to 15℃, the atmosphere to nitrogen, and the stirring speed to 140rad / min. After the mixture is stirred evenly, open the Mo-Ni metal solution inlet and the aluminum butoxide solution inlet at the top of the first reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 25 g / 100 mL based on metal oxide, with added boric acid and phosphoric acid, boron and phosphorus accounting for 1.4 wt% of the oxide mass in the solution) and the aluminum butoxide solution (aluminum butoxide solution concentration is 70 g / 100 mL based on Al2O3) to 9 mL / min and 35 mL / min, respectively. After the hydrolysis reaction has been carried out for 60 min, open the overflow control valve at the bottom to allow the generated liquid I to flow into the settling tank II. At the same time, add pure feed water and HgS to the first reactor I at rates of 76 mL / min and 2.0 g / min, respectively. When the volume of the generated liquid in the settling tank II reaches 1 / 2, switch to the settling tank III and separate the n-butanol and sol I in the settling tank II. The n-butanol can be recycled back to the first reactor I. The properties of sol IG are shown in Table 1.

[0086] Add 5L of pure feed water and separated sol IG to the second reactor IV. Adjust the pressure of the second reactor to 14MPa, the temperature to 270℃, and the stirring rate to 260rad / min. Open the Mo-Ni metal solution inlet and the aluminum alkoxide solution inlet at the top of the second reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 67g / 100mL based on metal oxide, with added boric acid and phosphoric acid, boron and phosphorus accounting for 2.9wt% of the oxide mass in the solution) and the aluminum butoxide solution (aluminum butoxide solution concentration is 55g / 100mL based on Al2O3) to 8mL / min and 20mL / min, respectively. After the hydrolysis reaction for 72min, the product liquid II is discharged from the second reactor.

[0087] The generated liquid II was introduced into an aging vessel. The pressure of the aging vessel was adjusted to 18 MPa, the temperature to 340℃, and the stirring rate to 320 rad / min. After aging for 160 min, it was filtered, dried at 120℃ for 5 h, and calcined at 550℃ for 3.5 h in air atmosphere to obtain alumina G. Its properties are shown in Table 2.

[0088] Comparative Example 3

[0089] Add 5L of n-butanol as the reaction medium to the 10L first reactor I, adjust the pressure of the first reactor I to 4MPa, the temperature to 15℃, the atmosphere to nitrogen, and the stirring speed to 140rad / min. After the mixture is stirred evenly, open the Mo-Ni metal solution inlet and the aluminum butoxide solution inlet at the top of the first reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 25 g / 100 mL based on metal oxide, with added boric acid and phosphoric acid, boron and phosphorus accounting for 1.4 wt% of the oxide mass in the solution) and the aluminum butoxide solution (aluminum butoxide solution concentration is 70 g / 100 mL based on Al2O3) to 9 mL / min and 35 mL / min, respectively. After the hydrolysis reaction has been carried out for 60 min, open the overflow control valve at the bottom to allow the generated liquid I to flow into the settling tank II. At the same time, add n-butanol to the first reactor I at rates of 76 mL / min and 2.0 g / min, respectively. After the volume of the generated liquid in the settling tank II reaches 1 / 2, switch to the settling tank III and separate the n-butanol and sol I in the settling tank II. The n-butanol can be recycled back to the first reactor I. The properties of sol IH are shown in Table 1.

[0090] Add 5 L of n-butanol and the separated sol IH to the second reactor IV. Adjust the pressure of the second reactor to 14 MPa, the temperature to 270 °C, and the stirring rate to 260 rad / min. Open the Mo-Ni metal solution inlet and the aluminum alkoxide solution inlet at the top of the second reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 67 g / 100 mL based on metal oxides, with added boric acid and phosphoric acid, boron and phosphorus accounting for 2.9 wt% of the oxide mass in the solution) and the aluminum alkoxide solution (aluminum alkoxide solution concentration is 55 g / 100 mL based on Al2O3) to 8 mL / min and 20 mL / min, respectively. After the hydrolysis reaction for 72 min, the product liquid II is discharged from the second reactor.

[0091] The generated liquid II was introduced into an aging vessel. The pressure of the aging vessel was adjusted to 18 MPa, the temperature to 340℃, and the stirring rate to 320 rad / min. After aging for 160 min, it was filtered, dried at 120℃ for 5 h, and calcined at 550℃ for 3.5 h in air atmosphere to obtain alumina H. Its properties are shown in Table 2.

[0092] Comparative Example 4

[0093] Add 5L of n-butanol as the reaction medium to the 10L first reactor I, add 13g of HgS, adjust the pressure of the first reactor I to 4MPa, the temperature to 15℃, the atmosphere to nitrogen, and the stirring speed to 140rad / min. After the mixture is stirred evenly, open the Mo-Ni metal solution inlet and the aluminum butoxide solution inlet at the top of the first reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 25 g / 100 mL based on metal oxide, with added boric acid and phosphoric acid, boron and phosphorus accounting for 1.4 wt% of the oxide mass in the solution) and the aluminum butoxide solution (aluminum butoxide solution concentration is 70 g / 100 mL based on Al2O3) to 9 mL / min and 35 mL / min, respectively. After the hydrolysis reaction has been carried out for 60 min, open the overflow control valve at the bottom to allow the generated liquid I to flow into the settling tank II. At the same time, add n-butanol and HgS to the first reactor I at rates of 76 mL / min and 2.0 g / min, respectively. After the volume of the generated liquid in the settling tank II reaches 1 / 2, switch to the settling tank III and separate the n-butanol and sol I in the settling tank II. The n-butanol can be recycled back to the first reactor I. The properties of sol II are shown in Table 1.

[0094] Add 5 L of n-butanol and the separated sol II to the second reactor IV. Adjust the pressure of the second reactor to 14 MPa, the temperature to 270 °C, and the stirring rate to 260 rad / min. Open the Mo-Ni metal solution inlet and the aluminum alkoxide solution inlet at the top of the second reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 67 g / 100 mL based on metal oxides, with added boric acid and phosphoric acid, boron and phosphorus accounting for 2.9 wt% of the oxides in the solution) and the aluminum alkoxide solution (aluminum alkoxide solution concentration is 55 g / 100 mL based on Al2O3) to 8 mL / min and 20 mL / min, respectively. After the hydrolysis reaction for 72 min, the product liquid II is discharged from the second reactor.

[0095] The generated liquid II was introduced into an aging vessel. The pressure of the aging vessel was adjusted to 18 MPa, the temperature to 340℃, and the stirring rate to 320 rad / min. After aging for 160 min, it was filtered, dried at 120℃ for 5 h, and calcined at 550℃ for 3.5 h in air atmosphere to obtain alumina I. Its properties are shown in Table 2.

[0096] Comparative Example 5

[0097] Add 5L of n-butanol as the reaction medium to the 10L first reactor I, add 13g of HgS, adjust the pressure of the first reactor I to 4MPa, the temperature to 15℃, the atmosphere to nitrogen, and the stirring speed to 140rad / min. After the mixture is stirred evenly, open the Mo-Ni metal solution inlet and the aluminum butoxide solution inlet at the top of the first reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 67 g / 100 mL based on metal oxides, with added boric acid and phosphoric acid, boron and phosphorus accounting for 1.4 wt% of the oxide mass in the solution) and the aluminum butoxide solution (aluminum butoxide solution concentration is 70 g / 100 mL based on Al2O3) to 9 mL / min and 35 mL / min, respectively. After the hydrolysis reaction has been carried out for 60 min, open the overflow control valve at the bottom to allow the generated liquid I to flow into the settling tank II. At the same time, add n-butanol and HgS to the first reactor I at rates of 76 mL / min and 2.0 g / min, respectively. After the volume of the generated liquid in the settling tank II reaches 1 / 2, switch to the settling tank III and separate the n-butanol and sol I in the settling tank II. The n-butanol can be recycled back to the first reactor I. The properties of sol I are shown in Table 1.

[0098] Add 5 L of n-butanol and the separated sol IJ to the second reactor IV. Adjust the pressure of the second reactor to 14 MPa, the temperature to 270 °C, and the stirring rate to 260 rad / min. Open the Mo-Ni metal solution inlet and the aluminum alkoxide solution inlet at the top of the second reactor. Control the flow rates of the Mo-Ni metal solution (metal solution concentration is 67 g / 100 mL based on metal oxides, with added boric acid and phosphoric acid, boron and phosphorus accounting for 1.3 wt% of the oxide mass in the solution) and the aluminum alkoxide solution (aluminum alkoxide solution concentration is 55 g / 100 mL based on Al2O3) to 8 mL / min and 20 mL / min, respectively. After the hydrolysis reaction for 72 min, the product liquid II is discharged from the second reactor.

[0099] The generated liquid II was introduced into an aging vessel. The pressure of the aging vessel was adjusted to 18 MPa, the temperature to 340℃, and the stirring rate to 320 rad / min. After aging for 160 min, it was filtered, dried at 120℃ for 5 h, and calcined at 550℃ for 3.5 h in air atmosphere to obtain alumina J. Its properties are shown in Table 2.

[0100] Table 1 Properties of Sol I obtained from Examples and Comparative Examples

[0101] Sol I number A B C D E <![CDATA[Specific surface area, m 2 / g]]> 215 232 200 229 231 Pore ​​volume, mL / g 0.90 0.95 1.00 0.98 0.99 Average pore size, nm 120 100 110 115 118

[0102] Table 1 Properties of Sol I obtained from the Examples and Comparative Examples (continued)

[0103] Sol I number F G H I J <![CDATA[Specific surface area, m 2 / g]]> 158 132 169 230 225 Pore ​​volume, mL / g 0.56 0.45 0.50 0.90 0.95 Average pore size, nm 75 60 80 92 91

[0104] Table 2. Composition and properties of hydrogenation catalysts obtained in the examples and comparative examples.

[0105]

[0106]

[0107] Table 2. Composition and properties of hydrogenation catalysts obtained in the examples and comparative examples (continued)

[0108]

[0109]

[0110] Example 6

[0111] This example is a comparative activity test of the catalysts prepared in Examples 1-5 and Comparative Examples 1-5 on a 100mL fixed-bed small-scale hydrogenation unit. The activity comparison results are the results after 2000 hours of operation, and the feed method is top feed. The properties of the feed oil are shown in Table 3; the evaluation conditions are shown in Table 4; with the activity of catalyst F in Comparative Example 1 as 100, the catalyst evaluation results are shown in Table 5.

[0112] Table 3 Properties of Feed Oil

[0113] crude oil Inferior residual oil <![CDATA[Density (20 °C), g·cm -3 > 0.98 Residual carbon, wt% 20.3 S, wt% 4.6 <![CDATA[Ni+V,μg·g -1 ]]> 234.8

[0114] Table 4 Evaluation Process Conditions

[0115] Reaction temperature, °C 410 Partial pressure of hydrogen in reaction, MPa 15 <![CDATA[Liquid hourly space velocity, h -1 > 0.2 Hydrogen-to-oil volume ratio 1200

[0116] Table 5 Evaluation results of the catalysts obtained in each example and comparative example.

[0117] Catalyst number A B C D E Relative desulfurization rate, % 110 112 113 115 114 Relative demetallization rate, % 115 116 116 118 114 Relative carbon removal rate, % 110 111 110 110 113

[0118] Table 5 Evaluation results of the catalysts obtained in each example and comparative example (continued)

[0119] Catalyst number F G H I J Relative desulfurization rate, % 100 101 102 103 105 Relative demetallization rate, % 100 102 100 102 103 Relative carbon removal rate, % 100 100 100 102 102

[0120] As can be seen from Tables 2 and 5, the catalyst provided by the present invention has a large specific surface area, large pore volume, and concentrated grain distribution. The active metal, modifier and pore structure in the catalyst are distributed in a gradient from the inside to the outside along the particle size, and it has high hydrogenation activity, making it very suitable for use as a catalyst for the hydrogenation treatment of heavy and inferior raw materials.

[0121] The embodiments described above are merely detailed descriptions of the technical solutions of the present invention, but the present invention is not limited to the above embodiments, that is, the present invention does not depend on the steps described in the above embodiments to be implemented. In summary, any improvements made to the present invention by those skilled in the art, including the substitution of the raw materials and additives described in the present invention, the selection of specific implementation methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for producing a hydrogenation catalyst, characterized in that, The hydrogenation catalyst comprises alumina, a hydrogenation active metal, and a modifier. The hydrogenation catalyst is in the form of spherical particles, including a non-central region and a central region. The concentration of the hydrogenation active metal in the central region is 15-40 percentage points lower than that in the non-central region. The concentration of the modifier in the central region is 0.5-2.5 percentage points lower than that in the non-central region. The pore volume of the hydrogenation catalyst is at least 0.5 mL / g higher than that of the central region. The radial thickness ratio of the central region to the non-central region of the hydrogenation catalyst particle is 1:2 to 2:

1. The preparation method of the hydrogenation catalyst includes: (1) Add alcohol, polar metal seed crystals, solution I of active metal containing modifier and aluminum alkoxide solution I in parallel flow to the first reaction vessel for hydrolysis into gel to obtain product liquid I; (2) The generated liquid I enters a settling tank for settling and separation to obtain an upper layer of alcohol and a lower layer of alcohol-containing sol I; (3) The sol I is added to the second reaction vessel, and a solution II of active metal containing modifier and an aluminum alkoxide solution II are added to continue hydrolysis into sol to obtain liquid II; (4) The generated liquid II enters the aging tank for aging reaction; (5) The aged material obtained in step (4) is dried and calcined to obtain the hydrogenation catalyst; The polar metal seed crystals mentioned in step (1) are selected from one or more of AgCl, ZnS, CuS or HgS; The operating conditions of the first reactor in step (1) are as follows: temperature is -15~15℃, pressure is 1~10MPa; The operating conditions of the second reactor in step (3) are as follows: temperature is 200~350℃, pressure is 10~20MPa; In step (4), the aging reaction conditions are: temperature of 300~400℃, pressure of 15~20MPa, and aging time of 100~360min.

2. The production method according to claim 1, characterized in that, The preparation method is carried out in a continuous manner.

3. The production method according to claim 2, characterized in that, Multiple sedimentation tanks used in step (2) and multiple aging tanks used in step (4) are provided for switching purposes; in step (1), the first reactor adopts an overflow method to discharge the generated liquid I from the first reactor, and in step (3), the second reactor adopts an overflow method to discharge the generated liquid II from the second reactor.

4. The production method according to claim 2, characterized in that, When preparing the hydrogenation catalyst using a continuous process, when the first reactor is started, an alcohol and polar metal seed crystals are first added as a base liquid. Then, a solution I containing a modifier of the active metal and a solution I of aluminum alkoxide are added in parallel to hydrolyze into a gel until the product liquid I begins to be discharged from the first reactor. The amount of alcohol added to the base liquid is 1 / 5 to 1 / 2 of the actual effective volume of the first reactor. When the product liquid I is discharged from the first reactor, the total mass of the aluminum alkoxide solution (calculated as Al2O3), the hydrogenation active metal (calculated as oxide), and the modifier (calculated as element) in the first reactor is used as the basis. The amount of polar metal seed crystals added accounts for 0.1% to 2.0%.

5. The production method according to claim 4, characterized in that, The total mass of the aluminum alkoxide solution in the first reactor (calculated as Al2O3), the hydrogenated active metal (calculated as oxide), and the modifier (calculated as element) is used as the basis, and the amount of polar metal seed crystals added is 0.5% to 2.0%.

6. The production method according to claim 2, characterized in that, When preparing the modified hydrogenation catalyst using a continuous process, when the second reactor is started, alcohol is first added as the base liquid, and then a solution II of the active metal containing the modifier and an aluminum alkoxide solution II are added to hydrolyze into a gel until the generated liquid II begins to be discharged from the second reactor; wherein, the amount of alcohol added is 1 / 7 to 1 / 2 of the actual effective volume of the second reactor.

7. The production method according to claim 6, characterized in that, The amount of alcohol added is 1 / 4 to 1 / 2 of the actual effective volume of the second reactor.

8. The production method according to claim 1, characterized in that, The alcohol mentioned in step (1) is selected from at least one of organic monohydric alcohols and organic polyhydric alcohols.

9. The production method according to claim 1, characterized in that, The operating conditions of the first reactor in step (1) are as follows: temperature 0~15℃, pressure 4~10MPa; and / or, The operating conditions of the settling tank in step (2) are as follows: temperature -15~15℃, pressure 1~10MPa; and / or, The operating conditions of the second reactor in step (3) are as follows: temperature 200~300℃, pressure 12~20MPa; and / or, In step (4), the aging time is 150~250 min.

10. The production method according to claim 9, characterized in that, The operating conditions of the settling tank in step (2) are as follows: temperature is 0~15℃ and pressure is 4~10MPa.

11. The production method according to claim 1, characterized in that, The hydrolysis-gelation reaction time in step (1) is 10-180 minutes; the hydrolysis-gelation reaction is carried out under stirring conditions, and the stirring rate is 50-200 rad / min; and / or, In step (3), the hydrolysis gelation reaction conditions are as follows: the reaction time is 50-120 minutes, the hydrolysis gelation reaction is carried out under stirring conditions, and the stirring rate is 200-350 rad / min; and / or, In step (4), the aging is carried out under stirring conditions, with a stirring speed of 350~450 r / min.

12. The production method according to claim 11, characterized in that, The hydrolysis-gelation reaction time in step (1) is 10-60 minutes; the stirring rate of the hydrolysis-gelation reaction is 100-200 rad / min; and / or, In step (3), the reaction conditions for hydrolysis into gel are as follows: the reaction time is 65~100 minutes, and the stirring rate of the hydrolysis into gel reaction is 250~350 rad / min.

13. The production method according to claim 1, characterized in that, In step (1) or step (3), the aluminum alkoxide is selected from at least one of organic monohydric aluminum alkoxide and organic polyhydric aluminum alkoxide, and the concentration of the aluminum alkoxide solution, calculated as Al2O3, is 10~100g / 100mL; and / or, The concentration of aluminum alkoxide solution II in step (3) should be at least 2 g / 100 mL lower than the concentration of aluminum alkoxide solution I in step (1).

14. The production method according to claim 13, characterized in that, The concentration of aluminum alkoxide solution II in step (3) should be 2-20 g / 100 mL lower than the concentration of aluminum alkoxide solution I in step (1).

15. The production method according to claim 1, characterized in that, In step (1), the flow rate ratio of the active metal solution I containing the modifier to the aluminum alkoxide solution I is 1:2 to 1:100; and / or, The flow rate ratio of the active metal solution II containing the modifier to the aluminum alkoxide solution II in step (3) is 1:1 to 1:

10.

16. The production method according to claim 15, characterized in that, The flow rate ratio of the active metal solution II containing the modifier to the aluminum alkoxide solution II in step (3) is 1:2 to 1:

10.

17. The production method according to claim 1, characterized in that, An alcohol and polar metal seed crystals are added concurrently to the first reactor. The alcohol addition rate is 0.1:1 to 10:1, which is the sum of the addition rates of the active metal solution I containing the modifier and the aluminum alkoxide solution I, based on their volumes. The polar metal seed crystal addition rate is 1% to 10% of the sum of the total mass addition rates of the active metal solution I containing the modifier (based on oxides), the aluminum alkoxide solution I (based on Al2O3), and the modifier (based on elemental form).

18. The production method according to claim 17, characterized in that, The addition rate of alcohol is the ratio of the sum of the addition rates of the active metal solution I containing the modifier and the aluminum alkoxide solution I, based on their volumes, to 0.2:1 to 5:

1. The addition rate of polar metal seed crystals is 1% to 5% of the sum of the total mass addition rates of the active metal solution I containing the modifier (based on oxides), the aluminum alkoxide solution I (based on Al2O3), and the modifier (based on elemental form).

19. The production method according to claim 1, characterized in that, The components introduced into the hydrogenation catalyst by the active metal solution I containing the modifier and the aluminum alkoxide solution I include alumina, hydrogenation active metal, and modifier, namely, first alumina, first hydrogenation active metal, and first modifier. The components introduced into the modified hydrogenation catalyst by the active metal solution II containing the modifier and the aluminum alkoxide solution II include alumina, hydrogenation active metal, and modifier, namely, second alumina, second hydrogenation active metal, and second modifier. The mass ratio of first alumina to second alumina is 1:25 to 12:1, the mass ratio of first hydrogenation active metal to second hydrogenation active metal as oxides is 1:15 to 10:1, and the mass ratio of first modifier to second modifier as elemental is 1:6 to 6:

1.

20. The production method according to claim 1, characterized in that, In step (1), the concentration of the active metal solution I containing the modifier, calculated as oxides, is 5~50 g / 100 mL; the concentration of the modifier, calculated as an element, accounts for 1.0 wt%~2.0 wt% of the total mass of the aluminum alkoxide solution I (calculated as Al2O3) and the active metal (calculated as oxides); and / or, In step (3), the concentration of the active metal solution II containing the modifier, calculated as oxides, is 50-100 g / 100 mL; the concentration of the modifier, calculated as an element, accounts for 2.5 wt%-3.5 wt% of the total mass of the aluminum alkoxide solution II (calculated as Al2O3) and the active metal (calculated as oxides); and / or, The concentration of the active metal solution II containing the modifier in step (3) must be at least 20 g / 100 mL higher than the concentration of the active metal solution I containing the modifier in step (1).

21. The production method according to claim 20, characterized in that, The concentration of the active metal solution I containing the modifier in step (1) is 10~30g / 100mL, calculated as oxides; The concentration of the active metal solution II containing the modifier in step (3) is 20-90 g / 100 mL higher than the concentration of the active metal solution I containing the modifier in step (1); and / or, The concentration of the active metal solution II containing the modifier in step (3) is 60~100g / 100mL, calculated as oxides.

22. The production method according to claim 1, characterized in that, The properties of the sol I obtained in step (2) after calcination at 500~800℃ for 1~5h are as follows: pore volume is 0.9~1.1mL / g, and specific surface area is 200~250 m². 2 / g, average pore size ≥90nm.

23. The production method according to claim 22, characterized in that, The average pore size of the sol I obtained in step (2) after calcination at 500~800℃ for 1~5h is 90~120nm.

24. A hydrogenation catalyst produced according to any one of claims 1-23.

25. The hydrogenation catalyst according to claim 24, characterized in that, The pore volume of the hydrogenation catalyst is at least 0.6 to 1.1 mL / g higher than the pore volume of the central region of the hydrogenation catalyst.

26. The hydrogenation catalyst according to claim 24, characterized in that, In the hydrogenation catalyst, in the central region of the modified hydrogenation catalyst particles, the concentration of the hydrogenation active metal, calculated as oxide, is 4 wt% to 50 wt%, and the concentration of the modifier, calculated as element, is 1.0 wt% to 2.0 wt%; in the non-central region of the modified hydrogenation catalyst, the concentration of the hydrogenation active metal, calculated as oxide, is 20 wt% to 90 wt%, and the concentration of the modifier, calculated as element, is 2.5 wt% to 3.5 wt%.

27. The hydrogenation catalyst according to claim 26, characterized in that, In the central region of the modified hydrogenation catalyst particles, the concentration of the hydrogenation active metal, calculated as oxide, is 4 wt% to 20 wt%; in the non-central region of the modified hydrogenation catalyst, the concentration of the hydrogenation active metal, calculated as oxide, is 25 wt% to 40 wt%.

28. The hydrogenation catalyst according to claim 24, characterized in that, The hydrogenation active metal is selected from at least one of Group VIB and Group VIII metals, the Group VIB metal is selected from at least one of Mo and W, the Group VIII metal is selected from at least one of Ni and Co, and the modifier is selected from at least one of fluorine, boron, phosphorus, and silicon.

29. The hydrogenation catalyst according to claim 28, characterized in that, The modifier is selected from at least two of fluorine, boron, phosphorus and silicon, and the content of any one of the modifiers accounts for 10% to 60% of the total mass of the modifier.

30. The hydrogenation catalyst according to claim 29, characterized in that, The modifier is selected from fluorine-boron, silicon-phosphorus, boron-phosphorus, fluorine-boron-phosphorus, or fluorine-boron-phosphorus-silicon.

31. The hydrogenation catalyst according to claim 24, characterized in that, Based on the mass of the catalyst, the hydrogenation active metal, calculated as oxide, has a mass content of 10% to 80%, the alumina has a mass content of 18% to 89%, and the modifier has a mass content of 0.5% to 3.0% based on the mass of the element.

32. The hydrogenation catalyst according to claim 24, characterized in that, The hydrogenation catalyst has the following properties: pore volume of 1.5~2.0 mL / g; specific surface area of ​​300~350 m² / g. 2 / g, average pore size ≥150nm; the properties of the central region of the hydrogenation catalyst are as follows: pore volume 0.9~1.0mL / g, specific surface area 200~250 m² / g. 2 / g, average pore size ≥90nm.

33. The hydrogenation catalyst according to claim 32, characterized in that, The average pore size of the hydrogenation catalyst is 160~200nm; the average pore size of the central region of the hydrogenation catalyst is 90~120nm.

34. The hydrogenation catalyst according to claim 24, characterized in that, The particle size distribution of the hydrogenation catalyst is as follows: particles with a diameter less than 300 μm account for 1.0% to 2.5%, particles with a diameter of 300 to 350 μm account for 2.0% to 2.5%, and particles with a diameter of 350 to 500 μm, excluding 350 μm, account for 95.0% to 97.0%.

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