Preparation method of bulk hydrotreating catalyst

Abstract

The present invention discloses a method for preparing a bulk hydrorefining catalyst, comprising: (1) gelling and aging a sodium hydroxide solution, a sodium molybdate solution and a solution containing Ni and Si to obtain a first slurry; (2) adding a solution containing Ni and a quaternary ammonium salt compound, a sodium tungstate solution, a sodium carbonate and / or sodium bicarbonate aqueous solution, and the first slurry to a mixture of an oily liquid and water in parallel, and performing a three-stage decreasing pH gelling reaction for n consecutive times, and adding a 1 / n soluble aluminum salt solution at the end of each first-stage pH reaction to generate a second slurry; (3) aging the second slurry, separating, drying, and molding; (4) desalting, washing, drying, and calcining the molded product to obtain a bulk hydrorefining catalyst. The metal oxide particles in the catalyst prepared by the method of the present invention are small and evenly distributed, and the pore volume and pore size of the catalyst are large. The catalyst is applied to the hydroprocessing process of distillate oil and has high hydrodesulfurization and denitrogenation reaction performance.

Description

Technical Field

[0001] The present invention relates to a method for preparing a hydrorefining catalyst, in particular to a method for preparing a bulk phase hydrorefining catalyst. Background Art

[0002] Bulk hydrogenation catalysts are currently the catalysts with the highest hydrogenation activity centers. Bulk catalysts prepared by existing methods have smaller pore volumes and pore sizes, resulting in reactions on the catalyst surface that is inaccessible to reactant molecules. At the same time, the smaller pore volume and specific surface area cause the high content of active metals in the bulk catalyst to accumulate excessively on the catalyst surface, reducing the generation of active phases, lowering the activity of the catalyst, and also affecting the utilization rate of the active metals in the catalyst, thereby increasing the cost of using the catalyst.

[0003] The existing co-precipitation method mostly uses ammonia water as a precipitant and nitrogen-containing soluble salts as raw materials. The distribution of hydrogenation active metals and the interaction between different hydrogenation active metals are improved by changing the precipitation method and gelation conditions. However, it does not solve the problems of small pore volume and specific surface area of ​​bulk catalysts, small pore size of catalysts (pore size distribution is mainly concentrated below 8nm), large metal oxide particles in catalysts, and "ammonia nitrogen" and NO in catalyst preparation. X There are many problems such as pollution and high cost. Especially when using cheaper sodium-containing raw materials, the gel-forming materials are loose and difficult to shape, and the catalyst has many small pores.

[0004] CN106179474B discloses a high-activity bulk hydroprocessing catalyst and a preparation method thereof. A two-step method of positive addition and parallel flow is adopted to prepare a precipitate containing W, Ni and Mo, and a microporous and mesoporous composite molecular sieve is added. The catalyst has a high surface active metal content, a more uniform active metal dispersion, good coordination between active metals, and a high active metal utilization rate. At the same time, the catalyst has a reasonable pore structure, high mechanical strength, and high hydrodesulfurization and hydrodenitrogenation activity. The catalyst prepared by this method contains a molecular sieve, and a strong acidity can improve the ultra-deep desulfurization activity of the catalyst, but a cracking reaction occurs, which reduces the yield of the diesel product.

[0005] CN102451706A discloses a method for preparing a hydrogenation catalyst composition, which comprises using a sodium aluminate solution, a mixed solution containing Ni and W component salts, and CO 2The gas reacts in parallel to generate a precipitate. CN110038581A discloses a method for preparing a hydrorefining catalyst. The hydrorefining catalyst is prepared by two-step precipitation, using sodium tungstate alkaline solution and sodium molybdate alkaline solution as precipitants. Both methods use a large amount of sodium ion-containing salt as raw material for precipitation reaction, but the precipitate generated by this method contains a certain amount of sodium ions, the metal oxide particles are relatively large, and the residual sodium ions lead to poor adhesion of the material. The residual sodium ions also make the pore volume and specific surface area of ​​the catalyst small.

[0006] CN106513006A discloses a method for preparing a bulk phase hydrorefining catalyst, which comprises: pre-dispersing a Ni-containing compound with deionized water under an ultrasonic environment, then adding a Mo-containing compound to form a Ni-Mo fine grain structure, then adding a W-containing compound and a complexing agent for hydrothermal reaction, and then kneading and extruding the obtained active component powder with aluminum hydroxide dry glue, drying and calcining to obtain a catalyst. The catalyst prepared by the method of the present invention has uniform dispersion between different active phase grains, W source is embedded in the Ni-Mo skeleton structure, Ni-W active phase is easily wrapped by Ni-Mo active phase at the microscopic level, and is not an oxide core-shell structure at the macroscopic level, the pore volume is small, the effective active phase is not much, the metal oxide particles are large, and the removal efficiency of complex sulfur-containing compounds with high nitrogen content is limited. Summary of the invention

[0007] In view of the shortcomings of the prior art, the present invention provides a method for preparing a bulk hydrorefining catalyst. The metal oxide particles in the catalyst prepared by the method of the present invention are small and evenly distributed, the pore volume and pore diameter of the catalyst are large, the preparation cost is low, the preparation process is clean and pollution-free, and it is applied to the hydroprocessing process of distillate oil and has high hydrodesulfurization and denitrogenation reaction performance.

[0008] The preparation method of the bulk hydrotreating catalyst of the present invention comprises the following contents:

[0009] (1) a sodium hydroxide solution, a sodium molybdate solution and a solution containing Ni and Si are subjected to a gelling reaction, and then aged to obtain a first slurry containing Ni, Si and Mo;

[0010] (2) adding a solution containing Ni and a quaternary ammonium salt compound, a sodium tungstate solution, an aqueous solution of sodium carbonate and / or sodium bicarbonate, and a first slurry to a mixture of an oily liquid and water in parallel, and performing a three-stage decreasing pH gelation reaction for n consecutive times, and adding 1 / n soluble aluminum salt solution at the end of each first-stage pH reaction to generate a second slurry;

[0011] The specific process of each three-stage decreasing pH value reaction is as follows: the reaction temperature is 60-98°C, preferably 65-92°C; in the first stage, the pH value is 11.0-13.5, the reaction time is 0.05-0.5 hours, and 1 / n Al-containing solution is added after the first stage reaction is completed; in the second stage, the pH value is adjusted to 8.5-10.5, and the reaction time is 0.05-0.5 hours; in the third stage, the pH value is adjusted to 5.5-8.3, and the reaction time is 0.05-0.5 hours; wherein n is an integer of 2-8;

[0012] (3) aging the second slurry, separating the solid from the liquid after aging, and drying and molding the solid phase to obtain a molded product;

[0013] (4) The formed product is desalted, washed, dried and calcined to obtain a bulk hydrogenation refining catalyst.

[0014] In the method of the present invention, the weight concentration of the sodium hydroxide solution in step (1) is 5% to 30%, and those skilled in the art can determine the amount according to actual needs. 3 The weight concentration is 5 to 110 g / L, preferably 10 to 100 g / L.

[0015] In the method of the present invention, in the solution containing Ni and Si in step (1), the weight concentration of Ni in terms of NiO is 5 to 120 g / L, preferably 10 to 110 g / L, and the weight concentration of Si in terms of SiO 2 The weight concentration is 2-80 g / L, preferably 4-70 g / L; when preparing a solution containing Ni and Si, the nickel source used is one or more of nickel sulfate, nickel nitrate or nickel chloride, and the silicon source is one or more of water glass, silica sol or sodium silicate.

[0016] In the method of the present invention, the gelling reaction conditions of step (1) are: reaction temperature is 30-90°C, preferably 40-85°C, pH value is controlled to be 7.0-11.0, preferably 7.2-10.0, and gelling time is 0.2-2.5 hours, preferably 0.3-2.0 hours.

[0017] In the method of the present invention, the aging conditions in step (1) are as follows: the aging temperature is 60-90°C, preferably 65-85°C, the pH value during aging is controlled to be 7.0-11.0, preferably 7.2-10.5, and the aging time is 0.3-2.5 hours, preferably 0.5-2.0 hours.

[0018] In the method of the present invention, in step (1), the weight of the introduced Ni accounts for 30% to 80%, preferably 35% to 78%, of the total Ni weight in the hydrotreating catalyst obtained in step (4), and the remaining Ni in the catalyst is introduced through step (2).

[0019] In the method of the present invention, in the Ni-containing solution of step (2), the weight concentration of Ni in terms of NiO is 5 to 110 g / L, preferably 10 to 100 g / L. When preparing the Ni-containing solution, the nickel source generally used may be one or more of nickel sulfate, nickel nitrate, and nickel chloride; in the sodium tungstate solution, W is in terms of WO 3 The weight concentration is 4 to 140 g / L, preferably 6 to 120 g / L;

[0020] In the method of the present invention, the quaternary ammonium salt compound in step (2) is one or more of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, tetrabutylammonium hydroxide, hexadecyltrimethylammonium bromide or dodecyltrimethylammonium chloride; and the molar ratio of the added amount of the quaternary ammonium salt compound to W in the sodium tungstate solution is 0.1-1.8, preferably 0.2-1.5.

[0021] In the method of the present invention, the soluble aluminum salt in step (2) is one or more of aluminum nitrate, aluminum sulfate, aluminum chloride, etc., and the Al in the soluble aluminum salt solution is Al 2 O 3 The weight concentration is 3-100 g / L, preferably 5-90 g / L, and is divided into n equal parts by volume, wherein n is an integer of 2-8.

[0022] In the method of the present invention, the weight concentration of the sodium carbonate and / or sodium bicarbonate aqueous solution in step (2) is 5% to 40%, and those skilled in the art can determine the dosage according to actual needs.

[0023] In the method of the present invention, the volume ratio of the water added in step (2) to the first slurry is 0.1:1 to 3:1.

[0024] In the method of the present invention, the oily liquid in step (2) is unsaturated higher fatty acid glyceride (vegetable oil), preferably one or more of peanut oil, rapeseed oil, cottonseed oil, sunflower seed oil, soybean oil, corn oil, tea oil or olive oil. The volume ratio of the oily liquid to water is 1:60 to 1:4, preferably 1:40 to 1:6.

[0025] In the method of the present invention, the aging conditions in step (3) are as follows: aging temperature is 40 to 90° C., aging time is 1 to 5 hours, and pH value is 7.0 to 11.0. The aging is generally carried out under stirring conditions.

[0026] In the method of the present invention, the aging conditions described in step (3) are preferably carried out as follows: the first step is normal pressure aging: the aging temperature is 30-90°C, preferably 40-80°C, the aging time is 1-6 hours, preferably 1.2-5 hours, and the pH value is 6.5-10.0, preferably 7.0-9.0; the second step is high pressure aging: the temperature is 100-195°C, preferably 100-190°C, the time is 0.1-3.5 hours, preferably 0.3-2.8 hours, the pressure is not less than 10 MPa, preferably 10-15 MPa, and the pH value is 10.0-13.0, preferably 10.0-12.5.

[0027] The mild conditions in the above-mentioned aging process are more conducive to the formation of uniform particle size. During the aging process in a closed environment, the material phase structure has generated a regular body in the first step of aging. In a closed environment, under the action of higher temperature and pressure, the microscopic morphology of the material changes, and the material phase changes from a regular body to an irregular body formed by irregular flake accumulation. This structural change causes the sodium ions inside the phase to transfer to the surface of the phase, which is more conducive to the next step of desalination treatment, and is also conducive to increasing the specific surface area of ​​the bulk catalyst, improving the pore structure, exposing more active metals to the catalyst surface, and generating more hydrogenation active centers on the catalyst surface.

[0028] In the method of the present invention, the solid-liquid separation in step (3) is generally carried out by filtration, centrifugation or the like.

[0029] In the method of the present invention, the drying temperature in step (3) is 50 to 140° C., and the drying time is 0.5 to 24 hours.

[0030] In the method of the present invention, the molding process described in step (3) is well known in the field of catalyst preparation. During the extrusion molding process, an extrusion aid and a peptizing agent are generally added. The extrusion aid can be one or more of sesbania powder, carbon black, graphite powder or cellulose, etc. The peptizing agent is generally an acid solution containing one or more of hydrochloric acid, sulfuric acid, acetic acid, etc. The amount of the extrusion aid accounts for 1wt% to 10wt% of the total material dry basis. The catalyst of the present invention can be prepared into the shape of flakes, spheres, cylindrical strips and special-shaped strips (three-leaf clover, four-leaf clover) as needed.

[0031] In the method of the present invention, the desalination treatment process described in step (4) is: first curing is performed, and then washing can be performed to remove the salt precipitated on the surface of the molded object. The curing conditions are a temperature of 5 to 100° C., preferably a temperature of 10 to 90° C., and a time of 10 to 100 hours, preferably 24 to 90 hours.

[0032] In the method of the present invention, the desalination treatment described in step (4) is preferably carried out in the following manner: in the first stage, the temperature is 60 to 90° C., and the curing time is 5 to 60 hours, preferably 8 to 55 hours, so that the hydrated sodium ions are precipitated and vacancies are retained; in the second stage, the temperature is 10 to 30° C., and the time is 1 to 48 hours, preferably 2 to 42 hours, so that the vacancies are retained and shrunk, so that the pore volume of the catalyst is increased and the catalyst has good mechanical strength, and then the precipitated salt is washed away. The washing process can use a solvent with good solubility for sodium salts, such as water and ethanol.

[0033] In the method of the present invention, the washing, drying and roasting in step (4) can be carried out under conventional conditions in the art. The drying conditions are as follows: drying at 40-150°C for 1-48 hours, preferably drying at 50-120°C for 4-36 hours. The roasting conditions are as follows: roasting at 350-650°C for 1-24 hours, preferably roasting at 400-600°C for 2-12 hours. Washing is generally carried out with deionized water or ethanol solution until neutral.

[0034] The bulk hydrorefining catalyst of the present invention is a composite amorphous oxide particle with a core-shell structure, wherein the core phase is an amorphous composite oxide containing molybdenum, nickel and silicon, and the shell phase is an amorphous composite oxide containing tungsten, nickel and aluminum; the catalyst of the present invention can be in the form of flakes, spheres, cylindrical bars and shaped bars (three-leaf clover, four-leaf clover) as required, preferably cylindrical bars and shaped bars (three-leaf clover, four-leaf clover). The average particle size of the catalyst particles is 8-13nm. Preferably, the particle size distribution of the catalyst particles is as follows: the number of particles with a particle size less than 7nm accounts for 2%-15% of the total number of particles, the number of particles with a particle size of 7nm-13nm accounts for 66%-88% of the total number of particles, and the number of particles with a particle size greater than 13nm accounts for 3%-21% of the total number of particles.

[0035] In the catalyst of the present invention, based on the mass of the core-shell structured composite oxide particles, the core phase accounts for 20% to 90%, preferably 25% to 88%, and the shell phase accounts for 10% to 80%, preferably 12% to 75%.

[0036] In the catalyst of the present invention, the molar ratio of molybdenum to nickel atoms in the core phase is 1:28 to 12:1, preferably 1:22 to 10:1, and the content of silicon is expressed as SiO 2 It accounts for 2% to 38% of the mass of the hydrotreating catalyst, preferably 4% to 36%.

[0037] In the catalyst of the present invention, the molar ratio of tungsten to nickel atoms in the shell phase is 1:22-8:1, preferably 1:20-5:1, and the content of aluminum is expressed as Al 2 O 3 It accounts for 5% to 36% of the mass of the hydrotreating catalyst, preferably 7% to 34%.

[0038] In the catalyst of the present invention, the mass of NiO in the core phase accounts for 30% to 80% of the total mass of NiO in the hydrorefining catalyst, and the mass of NiO in the shell phase accounts for 20% to 70% of the total mass of NiO in the hydrorefining catalyst.

[0039] The Na in the catalyst of the present invention 2 The O content is less than 0.12%, preferably less than 0.1%.

[0040] In the catalyst of the present invention, the properties of the hydrotreating catalyst are as follows: the specific surface area is 180~700m 2 / g, pore volume is 0.30~0.90mL / g. The pore size distribution of the bulk hydrorefining catalyst of the present invention is as follows: the pore volume occupied by pores with a diameter of less than 4nm accounts for 1%~10% of the total pore volume, the pore volume occupied by pores with a diameter of 4~10nm accounts for 12%~40% of the total pore volume, the pore volume occupied by pores with a diameter of 10~15nm accounts for 22%~56% of the total pore volume, and the pore volume of pores with a diameter of more than 15nm accounts for 18%~45% of the total pore volume; the preferred pore size distribution is as follows: the pore volume occupied by pores with a diameter of less than 4nm accounts for 2%~8% of the total pore volume, the pore volume occupied by pores with a diameter of 4~10nm accounts for 14%~36% of the total pore volume, the pore volume occupied by pores with a diameter of 10~15nm accounts for 24%~54% of the total pore volume, and the pore volume of pores with a diameter of more than 15nm accounts for 20%~42% of the total pore volume.

[0041] The bulk phase hydrorefining catalyst of the present invention is used in the diesel hydrorefining reaction. The diesel hydrorefining reaction conditions are as follows: the reaction temperature is 330-400°C, the reaction pressure is 2.5-12MPa, the hydrogen-oil volume ratio is 250:1-1200:1, and the liquid hourly volume space velocity is 0.3-5.0h -1 .

[0042] Compared with the prior art, the present invention has the following advantages:

[0043] 1. In the method of the present invention, molybdenum-nickel-silicon aged slurry is first prepared, and then added to a reactor containing water, greasy liquid and quaternary ammonium salt compounds in parallel with a nickel-aluminum mixed solution, a sodium tungstate solution and a precipitant to form a gel, so that tungsten and nickel are uniformly and orderly precipitated on molybdenum-nickel grains, thereby forming tungsten-nickel coated molybdenum-nickel nanoparticles with uniform particle size and good dispersion. In the gel process, a three-level decreasing pH value reaction method is used for n times continuously, which improves the dispersibility of active metals in the catalyst shell phase, well controls the growth of the shell phase, and the particle shape is regular, and the generated particle size is also more uniform. The addition of quaternary ammonium salt compounds makes the pores at the core-shell junction of the composite oxide particles unobstructed, and the oxide pore size in the shell phase is increased, which is conducive to the smooth passage of macromolecular reactants. The hydrofining catalyst prepared in this way is suitable for the hydrofining reaction of heavy distillate oil (such as diesel), especially conducive to deep hydrodesulfurization and denitrification, and can also avoid reducing the diesel yield.

[0044] 2. The present invention adopts a clean method to prepare a low-cost catalyst. The inventor retains the sodium salt in the material during the molding process, and then desalts the molded material to remove the precipitated sodium salt. In this process, due to the occupation of the sodium salt during the molding process, the vacancies after sodium removal are more conducive to the formation of the catalyst pore structure, the pore distribution moves toward the macropore direction, the pore volume and pore diameter of the catalyst increase, and the diffusion performance of the catalyst is improved, which solves the problem that the catalyst pore volume is small and difficult to mold when the prior art uses clean raw materials to prepare bulk catalysts. In the catalyst preparation process, washing is only required during the desalting process, which reduces the number of washing times in the conventional catalyst preparation process and reduces the amount of water. Through the comprehensive control of the preparation steps and preparation conditions, the core-shell composite oxide structure obtained by the present invention is more conducive to the desalting of the material.

[0045] 3. The hydrofining catalyst of the present invention improves the distribution state of active metals at the nano level, that is, it is mainly composed of composite oxide particles containing molybdenum, nickel and silicon coated with composite oxide containing tungsten, nickel and aluminum. This coating structure is different from the structure at the macro level (such as millimeter level). The structure of the catalytic material is controlled at the micro level, so that the overall performance of the catalyst can be broken through, the hydrodesulfurization performance of the catalyst is improved, and a certain amount of acid centers are formed at the junction of the core-shell structure of the catalyst, so that the catalyst can eliminate steric hindrance while performing hydrodesulfurization reaction, and reduce the occurrence of side reactions such as excessive cracking, so that when the sulfur and nitrogen-containing distillate oil raw materials (especially the distillate oil raw materials containing sulfur and nitrogen that are difficult to remove) contact with the hydrofining catalyst of the present invention, the desulfurization and denitrification activities are significantly improved, and at the same time, the cracking reaction of the diesel fraction is reduced, and the diesel yield is avoided. In addition, the catalyst of the present invention can reduce the content of active metals while ensuring the desulfurization and denitrification activities, thereby reducing the preparation cost of the catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 This is the TEM image of catalyst D obtained in Example 2. DETAILED DESCRIPTION

[0047] In the present invention, the specific surface area and pore volume are measured by low temperature liquid nitrogen adsorption method, and the mechanical strength is measured by lateral pressure method. The specific surface area, pore volume and pore size distribution are measured by ASAP-2405 BET nitrogen adsorption instrument; the crushing strength of the catalyst is measured by ZQJ-2 intelligent particle strength testing machine.

[0048] In the present invention, in the core-shell composite oxide particles, the metal content in the composite oxide in the core and the shell and the thickness of the shell are measured by TEM transmission electron microscope (Japan JSM-2100). Among them, the method for determining the metal content in the composite oxide in the core and the shell is as follows: the core-shell composite oxide particles are uniformly mixed with liquid epoxy resin, and then an appropriate amount of curing agent is added, and the mixture is heated and cured after being stirred evenly to form solid particles. The solid particles are cut into thin slices with a thickness of 5-20nm by an ultrathin slicer, and the obtained slices are placed in a transmission electron microscope for observation to find a core-shell structure (cross section) with a clear interface. The diameter of the electron beam is adjusted by a condenser so that its diameter basically covers the outline of the entire core-shell structure, and the energy spectrum EDS spectrum is collected to record the intensity of the main energy peak, which corresponds to the actual content of each element in the known feed and the energy peak intensity of each element. The electron beam diameter is adjusted so that it is smaller than or close to the core or shell size, and the metal content in the composite oxide in the core and the shell at this time is calculated according to the energy peak intensity corresponding to the element, compared with the peak intensity under full coverage and the corresponding actual value. In the core-shell structure, the shell thickness is identified and measured from the transmission electron microscope image, and the ratio of the shell thickness to the total core-shell thickness is the average value obtained by measuring 40 to 100 core-shell particles. In the present invention, wt% is the mass fraction and v% is the volume fraction.

[0049] Example 1

[0050] Add nickel chloride and dilute water glass solution into a dissolving tank 1 filled with deionized water to prepare a solution containing Ni and Si. The concentration of Ni in the Ni and Si solution is 28 g / L in terms of NiO and 28 g / L in terms of SiO. 2 The weight concentration is 36g / L. Nickel chloride and tetrabutylammonium hydroxide are added to the dissolution tank 2 filled with deionized water to prepare a solution containing Ni and tetrabutylammonium hydroxide. The weight concentration of Ni in the solution containing Ni and tetrabutylammonium hydroxide is 24g / L in terms of NiO, and the molar ratio of tetrabutylammonium hydroxide to W in the sodium tungstate solution is 0.8. Aluminum chloride solution is added to the dissolution tank 3 filled with deionized water to prepare a solution containing Al. The Al in the solution containing Al is Al. 2 O 3The weight concentration is 36 g / L, and the solution is divided into 5 equal parts by volume. The mass ratio of Ni in the solution containing Ni and Si used in the reaction of this embodiment to Ni in the solution containing Ni and tetrabutylammonium hydroxide used is 14:12. The solution containing Ni and Si is placed in the reaction tank 1, and the sodium hydroxide solution (weight concentration is 12%) and the sodium molybdate solution (Mo is in the form of MoO 3 The weight concentration of the reaction mixture is 36g / L) and is dropped into the reaction tank 1 for the first gelation reaction. The gelation temperature is maintained at 62°C. At the end of the reaction, the pH value is controlled at 7.8 and the gelation time is controlled at 1.2 hours. After the reaction is completed, aging is performed at 78°C and the aging pH value is controlled at 7.5 for 1.8 hours to obtain the first slurry. First, 800mL of deionized water and 70mL of rapeseed oil are added to the reaction tank 2. Then, a 12wt% sodium carbonate solution, the first slurry, a solution containing Ni and tetrabutylammonium hydroxide, and a sodium tungstate solution (W in WO 3 The weight concentration of the measured solution is 40g / L) and then added to the reaction tank 2 for the second gelling reaction. The gelling temperature is maintained at 60°C. The reaction pH is first controlled to 12.8. After the reaction time is 0.2 hours, 1 equal portion of the Al-containing solution is added and the pH is controlled to 9.7. After the reaction time is 0.2 hours, the pH is then controlled to 7.4. The reaction time is 0.2 hours. The above operation process is repeated 5 times to end the second gelling reaction and start aging. The aging temperature is 78°C, the pH is controlled to 8.0, and the aging time is 2.5 hours to obtain the second slurry. The aged slurry is filtered, the filter cake is dried at 100°C for 7 hours, rolled, and extruded into a clover shape. The formed strips are cured at a temperature of 70°C for 50 hours, then the temperature is reduced to 20°C, and the curing is continued for 30 hours. Wash with deionized water at room temperature until neutral. The wet strips are then dried at 100°C for 12.0 hours, and the dried material is calcined at 500°C for 4 hours to obtain catalyst A. The composition and main properties of the catalyst are shown in Table 1.

[0051] Example 2

[0052] The nickel chloride and the dilute water glass solution are added to the dissolution tank 1 filled with deionized water respectively, and the solution containing Ni and Si, wherein the weight concentration of Ni in terms of NiO is 50 g / L, and the weight concentration of SiO 2 The weight concentration is 50g / L. Nickel chloride and hexadecyltrimethylammonium bromide are added to the dissolution tank 2 filled with deionized water to prepare a solution containing Ni and hexadecyltrimethylammonium bromide. The weight concentration of Ni in the solution containing Ni and hexadecyltrimethylammonium bromide is 20g / L in terms of NiO, and the molar ratio of hexadecyltrimethylammonium bromide to W in the sodium tungstate solution is 0.9. Aluminum chloride solution is added to the dissolution tank 3 filled with deionized water to prepare a solution containing Al. The Al-containing solution contains Al in the form of Al. 2 O3 The weight concentration of the solution is 20 g / L, and the solution is divided into 4 equal parts by volume. The mass ratio of Ni in the solution containing Ni and Si used in the reaction of this embodiment to Ni in the solution containing Ni and hexadecyltrimethylammonium bromide used is 5:2. The solution containing Ni and Si is placed in a reaction tank 1, and a sodium hydroxide solution (weight concentration of 12%) and a sodium molybdate solution (Mo in the form of MoO 3 The weight concentration of the solution is 40g / L) and then dropped into the reaction tank 1 for the first gelation reaction. The gelation temperature is maintained at 55°C. At the end of the reaction, the pH value is controlled at 8.4 and the gelation time is controlled at 1.3 hours. After the reaction, aging is performed at 82°C and the pH value is controlled at 8.0 for 1.7 hours to obtain the first slurry. First, 800mL of deionized water and 70mL of corn oil are added to the reaction tank 2, and then a 13wt% sodium carbonate solution, the first slurry, a solution containing Ni and hexadecyltrimethylammonium bromide, and a sodium tungstate solution (W in WO 3 The weight concentration of the measured solution is 20g / L) and then added to the reaction tank 2 for the second gelling reaction. The gelling temperature is maintained at 66°C. The reaction pH is first controlled to 13.3. After the reaction time is 0.2 hours, 1 equal portion of the Al-containing solution is added and the pH is controlled to 9.8. After the reaction time is 0.10 hours, the pH is then controlled to 6.8. The reaction time is 0.15 hours. The above operation process is repeated 4 times to end the second gelling reaction and start aging. The aging temperature is 80°C, the pH is controlled to 8.4, and the aging time is 3.2 hours to obtain the second slurry. The aged slurry is filtered, and the filter cake is dried for the first time, dried at 80°C for 13 hours, rolled, and extruded into a clover shape. The formed strips are cured at a temperature of 73°C for 46 hours, then the temperature is reduced to 25°C and the curing is continued for 26 hours. Wash with deionized water at room temperature until neutral. The wet strips were then dried at 90°C for 9.0 hours, and the dried material was calcined at 540°C for 6 hours to obtain Catalyst B. The composition and main properties of the catalyst are shown in Table 1.

[0053] Example 3

[0054] Add nickel chloride and dilute water glass solution into a dissolving tank 1 filled with deionized water to prepare a solution containing Ni and Si. The weight concentration of Ni in the Ni and Si solution is 32 g / L in terms of NiO and 32 g / L in terms of SiO. 2 The weight concentration is 32g / L. Nickel chloride and tetrapropylammonium bromide are added to the dissolution tank 2 filled with deionized water to prepare a solution containing Ni and tetrapropylammonium bromide. The weight concentration of Ni in the solution containing Ni and tetrapropylammonium bromide is 16g / L in terms of NiO, and the molar ratio of tetrapropylammonium bromide to W in the sodium tungstate solution is 1.1. Aluminum chloride solution is added to the dissolution tank 3 filled with deionized water to prepare a solution containing Al. The Al in the solution containing Al is Al.2 O 3 The weight concentration is 42 g / L, and the solution is divided into 5 equal parts by volume. The mass ratio of Ni in the solution containing Ni and Si used in the reaction of this embodiment to Ni in the solution containing Ni and tetrapropylammonium bromide used is 2:1. The solution containing Ni and Si is placed in a reaction tank 1, and a sodium hydroxide solution (weight concentration of 14%) and a sodium molybdate solution (Mo in the form of MoO 3 The weight concentration of the solution is 42g / L) and is dropped into the reaction tank 1 for the first gelation reaction. The gelation temperature is maintained at 55°C. The pH value is controlled at 7.9 at the end of the reaction. The gelation time is controlled at 1.1 hours. After the reaction is completed, aging is performed. The aging temperature is 75°C, the aging pH value is controlled at 8.1, and the aging is performed for 1.5 hours to obtain the first slurry. First, 1000mL of deionized water and 90mL of peanut oil are added to the reaction tank 2, and then a 13wt% sodium carbonate solution, the first slurry, a solution containing Ni and tetrapropylammonium bromide, and a sodium tungstate solution (W is WO 3 The weight concentration of the measured solution is 36g / L) and then added to the reaction tank 2 for the second gelling reaction. The gelling temperature is maintained at 55°C. The reaction pH is first controlled to 12.5. After the reaction time is 0.1 hour, 1 equal portion of the Al-containing solution is added and the pH is controlled to 8.9. After the reaction time is 0.1 hour, the pH is then controlled to 7.2. The reaction time is 0.1 hour. The above operation process is repeated 5 times to end the second gelling reaction. The aging temperature is 78°C and the aging pH is controlled to 8.6. After aging for 2.6 hours, the precipitate slurry continues to be aged under high pressure. The pressure is 12.9MPa, the aging temperature is 170°C, the aging time is 1.4 hours, and the aging pH is 12.0 to obtain the second slurry. The aged slurry is filtered, the filter cake is dried at 100°C for 8 hours, rolled, and extruded into a clover shape. The formed strips are cured for 66 hours at a temperature of 50°C. Wash with deionized water at room temperature until neutral. The wet strips were then dried at 90°C for 12.0 hours, and the dried material was calcined at 520°C for 5 hours to obtain Catalyst C. The composition and main properties of the catalyst are shown in Table 1.

[0055] Example 4

[0056] Add nickel chloride and dilute water glass solution into a dissolving tank 1 filled with deionized water to prepare a solution containing Ni and Si. The concentration of Ni in the Ni and Si solution is 20 g / L in terms of NiO and 20 g / L in terms of SiO. 2The weight concentration is 26 g / L. Nickel chloride and tetraethylammonium hydroxide are added to the dissolution tank 2 filled with deionized water to prepare a solution containing Ni and tetrapropylammonium bromide. The weight concentration of Ni in the solution containing Ni and tetrapropylammonium bromide is 20 g / L in terms of NiO, and the molar ratio of tetrapropylammonium bromide to W in the sodium tungstate solution is 1.2. Aluminum chloride solution is added to the dissolution tank 3 filled with deionized water to prepare a solution containing Al. The Al-containing solution contains Al in the form of Al. 2 O 3 The weight concentration is 48 g / L, and the solution is divided into 6 equal parts by volume. The mass ratio of Ni in the Ni-containing solution used in the reaction of this embodiment to Ni in the Ni-containing solution used is 1:1. The Ni-containing solution is placed in a reaction tank 1, and a sodium hydroxide solution (weight concentration of 12%) and a sodium molybdate solution (Mo in the form of MoO 3 The weight concentration of the solution is 34g / L) and is dropped into the reaction tank 1 for the first gelation reaction. The gelation temperature is maintained at 70°C. At the end of the reaction, the pH value is controlled at 7.9 and the gelation time is controlled at 1.2 hours. After the reaction is completed, aging is performed. The aging temperature is 77°C and the aging pH value is controlled at 8.3. The aging is performed for 1.6 hours to obtain the first slurry. First, 800mL of deionized water and 80mL of sunflower oil are added to the reaction tank 2. Then, a 12wt% sodium carbonate solution, the first slurry, a solution containing Ni and tetrapropylammonium bromide, and a sodium tungstate solution (W is WO 3 The weight concentration of the measured solution is 52g / L) and then added to the reaction tank 2 for the second gelling reaction. The gelling temperature is maintained at 68°C. The reaction pH is first controlled to 12.3. After the reaction time is 0.1 hour, 1 equal portion of the Al-containing solution is added and the pH is controlled to 9.9. After the reaction time is 0.1 hour, the pH is then controlled to 7.3. The reaction time is 0.2 hour. The above operation process is repeated 6 times to end the second gelling reaction. The aging temperature is 85°C, the aging pH is controlled to 8.2, and the aging is performed for 3.4 hours. Then, the precipitate slurry is further aged under high pressure. The pressure is 12.4MPa, the aging temperature is 176°C, the aging time is 1.5 hours, and the aging pH is 11.5. The second slurry is obtained. The aged slurry is filtered, the filter cake is dried at 75°C for 11 hours, rolled, and extruded into a clover shape. The formed strips are cured at a temperature of 75°C for 44 hours, then the temperature is reduced to 15°C, and the curing is continued for 33 hours. The wet strips were washed with deionized water at room temperature until neutral. The wet strips were then dried at 90°C for 9.0 hours and the dried material was calcined at 530°C for 4 hours to obtain catalyst D. The catalyst composition and main properties are shown in Table 1.

[0057] Example 5

[0058] Similar to Example 1, a solution containing Ni, Al and tetrabutylammonium hydroxide was first prepared, and the aluminum-containing solution was added all at once in the second gelling reaction to prepare Catalyst E.

[0059] Comparative Example 1

[0060] The reference agent F having the same catalyst composition as that of Example 1 was prepared, and the specific process was as follows:

[0061] According to the catalyst composition of Example 1, nickel chloride, aluminum chloride and water glass were dissolved in deionized water to prepare a mixed solution, wherein the weight concentration of Ni in terms of NiO was 52 g / L, and the weight concentration of Al in terms of Al 2 O 3 The weight concentration is 36g / L, SiO 2 The weight concentration is 36g / L. 500mL of deionized water is added to the reaction tank, and a 10wt% NaOH solution, a sodium molybdate solution (Mo in the form of MoO 3 The weight concentration is 36g / L), sodium tungstate solution (W is WO 3 The weight concentration of the measured solution is 40g / L) and the mixed solution are added to the reaction tank for gelation. The gelation temperature is maintained at 62°C. The pH value is controlled at 7.8 at the end. The gelation time is controlled at 1.2 hours to generate a slurry containing nickel and tungsten precipitates. Then the aging is carried out. The aging time is 2.0 hours, the aging temperature is 78°C, and the pH value is controlled at 7.5 during aging. After the aging, the reaction slurry is filtered, the filter cake is dried at 100°C for 7 hours, rolled, and extruded into strips. The molded product is washed with deionized water at room temperature, and no molded product is obtained after washing. The powder is dried at 100°C for 12 hours and calcined at 500°C for 4 hours to obtain catalyst F. The composition and main properties of the catalyst are shown in Table 1.

[0062] Comparative Example 2

[0063] According to the method disclosed in CN102049295A, a reference agent G having a catalyst composition similar to that of Example 1 was prepared. The specific process is as follows:

[0064] After adding 1000mL of deionized water to the dissolving tank, nickel chloride, ammonium metatungstate, and aluminum chloride solution were added in sequence, and stirred evenly to form a mixed solution. The weight concentration of Ni in terms of NiO is 52g / L, and the weight concentration of W in terms of WO 3 The weight concentration is 40g / L, Al is expressed as Al 2 O 3The weight concentration is 54g / L. Take 160g of ammonium bicarbonate to prepare an aqueous solution with a molar concentration of 2.5mol / L. Then the mixed solution, ammonium bicarbonate aqueous solution, and precipitant 10% ammonia water are added to a reaction tank filled with deionized water to form a gel. The pH value of the gel is 7.8 and the gel temperature is 62°C. After the gel is completed, add a slurry containing SAPO-11 molecular sieve and age for 2 hours at an aging temperature of 78°C. The pH value is controlled at 7.5 during aging. After aging, filter, add 600mL of deionized water and 36 grams of molybdenum trioxide to the filter cake, beat and stir evenly, filter, and dry the obtained filter cake at 100°C for 7 hours, then extrude into strips, wash with deionized water until neutral, dry the wet strips at 100°C for 12 hours, and calcine at 500°C for 4 hours to obtain the final catalyst G. The composition and main properties are shown in Table 1.

[0065] The SAPO-11 molecular sieve used in the comparative example is the one used in CN102049295A, which can be synthesized by conventional methods, such as hydrothermal crystallization method, and has the following properties: SiO 2 / Al 2 O 3 The molar ratio is 0.85, the infrared acid content is 0.9mmol / g, the pore volume is 0.24mL / g, and the specific surface area is 250m 2 / g, particle size is 450nm and crystallinity is 85%.

[0066] Comparative Example 3

[0067] Reference agent H was prepared according to the preparation method of Example 1 (no grease was added to the gelling tank during the second step of gelling) and the catalyst composition.

[0068] Add nickel chloride and dilute water glass solution into a dissolving tank 1 filled with deionized water to prepare a solution containing Ni and Si. The concentration of Ni in the Ni and Si solution is 28 g / L in terms of NiO and 28 g / L in terms of SiO. 2 The weight concentration is 36g / L. Nickel chloride and tetrabutylammonium hydroxide are added to the dissolution tank 2 filled with deionized water to prepare a solution containing Ni and tetrabutylammonium hydroxide. The weight concentration of Ni in the solution containing Ni and tetrabutylammonium hydroxide is 24g / L in terms of NiO, and the molar ratio of tetrabutylammonium hydroxide to W in the sodium tungstate solution is 0.8. Aluminum chloride solution is added to the dissolution tank 3 filled with deionized water to prepare a solution containing Al. The Al in the solution containing Al is Al. 2 O 3 The weight concentration is 36 g / L, and the solution is divided into 5 equal parts by volume. The mass ratio of Ni in the Ni-containing solution used in the reaction of this embodiment to Ni in the Ni-containing solution used is 14:12. The Ni-containing solution is placed in a reaction tank 1, and a sodium hydroxide solution (weight concentration of 12%) and a sodium molybdate solution (Mo in the form of MoO 3The weight concentration of the reaction mixture is 36 g / L) and is dropped into the reaction tank 1 for the first gelation reaction. The gelation temperature is maintained at 62°C. At the end of the reaction, the pH value is controlled at 7.8 and the gelation time is controlled at 1.2 hours. After the reaction is completed, aging is performed at 78°C and the aging pH value is controlled at 7.5 for 1.8 hours to obtain the first slurry. First, 800 mL of deionized water is added to the reaction tank 2. Then, a 12 wt% sodium carbonate solution, the first slurry, a solution containing Ni and tetrabutylammonium hydroxide, and a sodium tungstate solution (W in WO 3 The weight concentration of the measured solution is 40g / L) and then added to the reaction tank 2 for the second gelling reaction. The gelling temperature is maintained at 60℃. The reaction pH is first controlled to 12.8. After the reaction time is 0.2 hours, 1 equal portion of the Al-containing solution is added and the pH is controlled to 9.7. After the reaction time is 0.2 hours, the pH is then controlled to 7.4. The reaction time is 0.2 hours. The above operation process is repeated 5 times to end the second gelling reaction and start aging. The aging temperature is 78℃, the pH is controlled to 8.0, and the aging time is 2.5 hours to obtain the second slurry. The aged slurry is filtered, the filter cake is dried at 100℃ for 7 hours, rolled, and extruded into a clover shape. The formed strips are cured at a temperature of 70℃ for 50 hours, then the temperature is reduced to 20℃, and the curing is continued for 30 hours. Wash with deionized water at room temperature until neutral. The wet strips are then dried at 100℃ for 12.0 hours, and the dried material is calcined at 500℃ for 4 hours to obtain catalyst H. The composition and main properties of the catalyst are shown in Table 1.

[0069] Comparative Example 4

[0070] Reference agent I was prepared according to the preparation method of Example 1 (no silicon was added when preparing mixed solution A).

[0071] The nickel chloride and aluminum chloride solutions are added to the dissolving tank 1 filled with deionized water to prepare a solution containing Ni and Al. The weight concentration of Ni in the solution containing Ni and Al is 28 g / L in terms of NiO and 28 g / L in terms of Al. 2 O 3 The weight concentration of nickel chloride and tetrabutylammonium hydroxide is 36g / L. Nickel chloride and tetrabutylammonium hydroxide are added to the dissolution tank 2 filled with deionized water to prepare a solution containing Ni and tetrabutylammonium hydroxide. The weight concentration of Ni in the solution containing Ni and tetrabutylammonium hydroxide is 24g / L as NiO, and the molar ratio of tetrabutylammonium hydroxide to W in the sodium tungstate solution is 0.8. Aluminum chloride solution is added to the dissolution tank 3 filled with deionized water to prepare a solution containing Al. The Al in the solution containing Al is Al. 2 O 3The weight concentration is 36 g / L, and the solution is divided into 5 equal parts by volume. The mass ratio of Ni in the Ni-containing solution used in the reaction of this embodiment to Ni in the Ni-containing solution used is 14:12. The Ni-containing solution is placed in a reaction tank 1, and a sodium hydroxide solution (weight concentration of 12%) and a sodium molybdate solution (Mo in the form of MoO 3 The weight concentration of the reaction mixture is 36g / L) and is dropped into the reaction tank 1 for the first gelation reaction. The gelation temperature is maintained at 62°C. At the end of the reaction, the pH value is controlled at 7.8 and the gelation time is controlled at 1.2 hours. After the reaction is completed, aging is performed at 78°C and the aging pH value is controlled at 7.5 for 1.8 hours to obtain the first slurry. First, 800mL of deionized water and 70mL of rapeseed oil are added to the reaction tank 2. Then, a 12wt% sodium carbonate solution, the first slurry, a solution containing Ni and tetrabutylammonium hydroxide, and a sodium tungstate solution (W in WO 3 The weight concentration of the measured solution is 40g / L) and then added to the reaction tank 2 for the second gelling reaction. The gelling temperature is maintained at 60°C. The reaction pH is first controlled to 12.8. After the reaction time is 0.2 hours, 1 equal portion of the Al-containing solution is added and the pH is controlled to 9.7. After the reaction time is 0.2 hours, the pH is then controlled to 7.4. The reaction time is 0.2 hours. The above operation process is repeated 5 times to end the second gelling reaction and start aging. The aging temperature is 78°C, the pH is controlled to 8.0, and the aging time is 2.5 hours to obtain the second slurry. The aged slurry is filtered, the filter cake is dried at 100°C for 7 hours, rolled, and extruded into a clover shape. The formed strips are cured at a temperature of 70°C for 50 hours, then the temperature is reduced to 20°C, and the curing is continued for 30 hours. Wash with deionized water at room temperature until neutral. The wet strips are then dried at 100°C for 12.0 hours, and the dried material is calcined at 500°C for 4 hours to obtain catalyst I. The composition and main properties of the catalyst are shown in Table 1.

[0072] Comparative Example 5

[0073] Catalyst J was prepared according to the method of Example 1 and the component content ratio of Catalyst A in Table 1. The formed strips were not subjected to desalination treatment.

[0074] Add nickel chloride and dilute water glass solution into a dissolving tank 1 filled with deionized water to prepare a solution containing Ni and Si. The concentration of Ni in the Ni and Si solution is 28 g / L in terms of NiO and 28 g / L in terms of SiO. 2The weight concentration is 36g / L. Nickel chloride and tetrabutylammonium hydroxide are added to the dissolution tank 2 filled with deionized water to prepare a solution containing Ni and tetrabutylammonium hydroxide. The weight concentration of Ni in the solution containing Ni and tetrabutylammonium hydroxide is 24g / L in terms of NiO, and the molar ratio of tetrabutylammonium hydroxide to W in the sodium tungstate solution is 0.8. Aluminum chloride solution is added to the dissolution tank 3 filled with deionized water to prepare a solution containing Al. The Al in the solution containing Al is Al. 2 O 3 The weight concentration is 36 g / L, and the solution is divided into 5 equal parts by volume. The mass ratio of Ni in the Ni-containing solution used in the reaction of this embodiment to Ni in the Ni-containing solution used is 14:12. The Ni-containing solution is placed in a reaction tank 1, and a sodium hydroxide solution (weight concentration of 12%) and a sodium molybdate solution (Mo in the form of MoO 3 The weight concentration of the reaction mixture is 36g / L) and is dropped into the reaction tank 1 for the first gelation reaction. The gelation temperature is maintained at 62°C. At the end of the reaction, the pH value is controlled at 7.8 and the gelation time is controlled at 1.2 hours. After the reaction is completed, aging is performed at 78°C and the aging pH value is controlled at 7.5 for 1.8 hours to obtain the first slurry. First, 800mL of deionized water and 70mL of rapeseed oil are added to the reaction tank 2. Then, a 12wt% sodium carbonate solution, the first slurry, a solution containing Ni and tetrabutylammonium hydroxide, and a sodium tungstate solution (W in WO 3 The weight concentration of the measured solution is 40g / L) and then added to the reaction tank 2 for the second gelling reaction. The gelling temperature is maintained at 60°C. The reaction pH is first controlled to 12.8. After the reaction time is 0.2 hours, 1 equal portion of the Al-containing solution is added and the pH is controlled to 9.7. After the reaction time is 0.2 hours, the pH is then controlled to 7.4 for 0.2 hours. The above operation process is repeated 5 times to end the second gelling reaction and start aging. The aging temperature is 78°C, the pH is controlled to 8.0, and the aging time is 2.5 hours to obtain the second slurry. The aged slurry is filtered, the filter cake is dried at 100°C for 7 hours, rolled, and extruded into a clover shape. Wash with deionized water at room temperature, and no molded product is obtained after washing. The powder is calcined at 500°C for 4 hours to obtain catalyst J. The catalyst composition and main properties are shown in Table 1.

[0075] Comparative Example 6

[0076] According to the preparation method disclosed in CN106513006A, a reference agent K having a composition similar to that of the catalyst in Example 1 of the present invention was prepared. The specific process is as follows:

[0077] Nickel carbonate and 300 ml of deionized water were uniformly mixed and added to a 1L high-pressure ultrasonic reactor. The ultrasonic frequency was set to 60 KHz, and the mixture was heated to 80°C. After being kept at this temperature for 1 hour, the ultrasonic frequency was reduced to 20 KHz, the system temperature was increased to 120°C, ammonium molybdate and 3 g of polyvinyl pyrrolidone were added, and then 10 ml of 25 wt% ammonia water was added dropwise to the system. After being kept at this temperature for 2 hours, the ultrasound was turned off, stirring was turned on, and the speed was 300 rpm. Ammonium metatungstate was added, and then citric acid was added until the pH of the system was 4.2. After being kept at this temperature for 2 hours, the heating was turned off, and the slurry was collected after the system was cooled to room temperature. The slurry was spray dried, and the inlet temperature and outlet temperature were controlled at about 200°C and 100°C, respectively. The obtained dry powder was roasted at 330°C in a muffle furnace for 3 hours to obtain the active component powder. The active component powder was mixed with aluminum hydroxide dry gel, and then a 10% dilute nitric acid aqueous solution was added for kneading and extrusion to obtain a strip. The strip was dried at 110°C for 10 hours and calcined in a muffle furnace at 400°C for 5 hours to obtain a reference agent K. The catalyst composition and main properties are shown in Table 1.

[0078] Comparative Example 7

[0079] According to the preparation method disclosed in CN1951558A, reference agent L was prepared as follows:

[0080] Add deionized water to the dissolving tank, add nickel chloride, ammonium metatungstate and aluminum chloride to dissolve, and prepare acidic working solution A. The weight concentration of Ni in solution A is 74.8 g / L in terms of NiO, and the weight concentration of W in terms of WO 3 The weight concentration is 48.6 g / L, Al is expressed as Al 2 O 3 The weight concentration of the solution is 44g / L, and the pH value of solution A is 1.8. 350mL of deionized water was added to the reaction tank, and the temperature was raised to 62°C. Under stirring, solution A and 10wt% ammonia water were added to the reaction tank in parallel to form gel, the gelling temperature was 62°C, the gelling time was 1 hour, and the pH value of the slurry during the gelling process was 8.5. After the gelling was completed, it was aged for 2 hours, the aging temperature was 75°C, and the pH value was controlled at 7.6 during aging. Then filter, add 600mL of deionized water and 32.6g of molybdenum trioxide to the filter cake, beat and stir evenly, filter, dry the filter cake at 120°C for 8 hours, roll, and extrude into a cylindrical shape. Wash with deionized water at room temperature until neutral. Then the wet strips were dried at 80°C for 10 hours and calcined at 500°C for 4 hours to obtain catalyst L. The composition and main properties of the catalyst are shown in Table 1.

[0081] Example 5

[0082] This example is an activity evaluation experiment of the catalyst of the present invention, and is compared with the catalyst of the comparative example. From the physicochemical properties of the catalyst in Table 1, it can be seen that when the raw materials contain more sodium raw materials during the preparation process, the catalysts A, B, C, E of the present invention and the comparative catalysts G, H, I, K, L (the comparative catalysts F and J are washed into powders without activity evaluation) are used respectively during washing. A comparative evaluation test is carried out on a 200mL small hydrogenation device, and mixed diesel (the weight ratio of straight-run diesel, coking diesel, and catalytic diesel is 28:20:52) is used as the test raw material. The process conditions for the evaluation of catalyst activity are: hydrogen partial pressure of 6.4MPa, reaction temperature of 365°C, liquid hourly volume space velocity of 2.0h -1 , the volume ratio of hydrogen to oil is 500:1, and the main properties of the raw materials are shown in Table 4. The results of catalyst activity evaluation are shown in Table 5. The types of sulfides in the hydrorefined oil were detected by gas chromatography-atomic emission spectrometry detector (GC-AED), and the results are shown in Table 6.

[0083] It can be seen from Table 1 that when the catalyst of the present invention uses a relatively high sodium-containing raw material in the preparation process, the catalyst has good crushing strength after desalting and washing after molding, while without desalting, the molded catalyst strips become powder after washing.

[0084] It can be seen from the evaluation results that compared with the comparative example catalyst, the catalyst of the present invention shows high hydrodesulfurization activity when removing difficult-to-treat 4,6-DMDBT macromolecular sulfides, and has excellent ultra-deep hydrodesulfurization activity. At the same time, the diesel product has a good yield. When the activity evaluation reaction space velocity is increased, the catalyst of the present invention still has excellent ultra-deep desulfurization activity by increasing the reaction temperature. Compared with the evaluation results of the comparative example catalyst, the catalyst of the present invention effectively reduces the influence of thermodynamic equilibrium on the high-temperature hydrogenation pathway and has good temperature adaptability. The hydrorefining catalyst of the present invention has a large pore volume and specific surface area, and the pore distribution is mainly concentrated above 10nm. The catalyst of the present invention is used for processing light distillate oil, especially for processing inferior diesel fractions, and has excellent ultra-deep hydrodesulfurization and denitrification performance.

[0085] Table 1 Composition and properties of catalysts prepared in Examples and Comparative Examples

[0086] Catalyst No. A B C D E NiO, wt% 26 35 24 20 26 <![CDATA[WO 3 ,wt%]]> 20 10 18 26 20 <![CDATA[MoO 3 ,wt%]]> 18 20 21 17 18 <![CDATA[SiO 2 ,wt%]]> 18 25 16 13 18 <![CDATA[Al 2 O 3 ,wt%]]> 18 10 21 24 18 <![CDATA[Na 2 O,%]]> 0.072 0.070 0.078 0.061 0.075 <![CDATA[Specific surface area, m 2 / g]]> 301 308 298 314 287 Pore ​​volume, mL / g 0.421 0.434 0.418 0.446 0.392 Pore ​​distribution <4nm 5.32 5.21 5.42 4.87 6.38 4nm~10nm 21.56 21.31 22.02 20.75 25.68 10nm~15nm 41.36 41.65 41.15 42.26 39.13 >15nm 31.76 31.83 31.41 32.12 28.81 Mechanical strength, N / mm 19.4 19.2 19.5 19.1 19.3

[0087] Table 1 (Continued) Composition and properties of catalysts prepared in Examples and Comparative Examples

[0088] Catalyst No. F G H I J K L NiO, wt% 26 26 26 26 26 26 37.4 <![CDATA[WO 3 ,wt%]]> 20 20 20 20 20 20 24.3 <![CDATA[MoO 3 ,wt%]]> 18 18 18 18 18 18 16.3 <![CDATA[SiO 2 ,wt%]]> 18 4 18 - 18 - - <![CDATA[Al 2 O 3 ,wt%]]> 18 28 18 36 18 36 22 <![CDATA[P 2 O 5 ,wt%]]> - 4 - - - - - <![CDATA[Na 2 O,%]]> 0.34 0.14 0.092 0.074 0.51 0.13 0.13 <![CDATA[Specific surface area, m 2 / g]]> 142 199 272 296 251 283 174 Pore ​​volume, mL / g 0.232 0.252 0.372 0.414 0.345 0.385 0.301 Pore ​​distribution <4nm 62.81 22.82 13.34 5.41 14.82 38.21 46.87 4nm~10nm 30.52 71.44 34.54 21.67 42.15 48.61 40.72 10nm~15nm 4.37 4.50 35.42 41.04 28.24 7.28 8.26 >15nm 2.30 1.24 16.70 31.88 14.79 5.90 4.15 Mechanical strength, N / mm - 17.6 18.4 19.3 - 13.6 19.1

[0089] Table 2 Composition of composite oxides in the core and shell of the catalyst (based on catalyst mass)

[0090] Catalyst No. A B C D E H I J Based on the catalyst mass, the composite oxide composition in the core NiO, wt% 14 25 16 10 14 10 14 14 <![CDATA[MoO 3 ,wt%]]> 18 20 21 17 18 11 18 18 <![CDATA[SiO 2 ,wt]]> 18 25 16 13 18 12 - 18 <![CDATA[WO 3 ,wt%]]> - - - - - 7 - - <![CDATA[Al 2 O 3 ,wt%]]> - - - - - 6 18 - Based on the catalyst mass, the composite oxide composition in the shell NiO, wt% 12 10 8 10 12 16 12 12 <![CDATA[WO 3 ,wt%]]> 20 10 18 26 20 13 20 20 <![CDATA[Al 2 O 3 ,wt%]]> 18 10 21 24 18 12 18 18 <![CDATA[MoO 3 ,wt%]]> - - - - 7 - - <![CDATA[SiO 2 ,wt%]]> - - - - 6 - -

[0091] Table 3 Average particle size and particle size distribution of the catalyst core-shell composite oxide particles obtained in each example

[0092] Catalyst No. A B C D E F G Average particle size of core-shell composite oxide particles, nm 9.2 9.3 8.8 9.0 12.8 33.6 23.8 Particle size distribution of core-shell composite oxide particles, % Particle size less than 7nm 6.22 6.31 5.04 5.11 7.43 3.32 4.05 Particle size is 7nm-13nm 83.42 83.22 84.33 84.92 76.31 21.22 28.19 Particle size greater than 13nm 10.36 10.47 10.63 10.97 16.26 77.46 67.76

[0093] Table 3 (Continued) Average particle size and particle size distribution of the catalyst core-shell composite oxide particles obtained in each example

[0094] Catalyst No. H I J K L Average particle size of core-shell composite oxide particles, nm 37.1 9.3 12.1 22.4 19.4 Particle size distribution of core-shell composite oxide particles, % Particle size less than 7nm 5.66 6.32 7.25 8.93 8.42 Particle size is 7nm-13nm 23.72 83.58 77.13 43.46 33.62 Particle size greater than 13nm 70.62 10.10 15.62 47.61 57.96

[0095] Table 4 Main properties of crude oil

[0096] project Analyze the results <![CDATA[Density (20 °C), g / cm 3 > 0.8897 Distillation range, ℃ 175-379 S, µg / g 13100 N, µg / g 922

[0097] Table 5 Catalyst activity evaluation results

[0098] Catalyst No. A B C E G H I K L <![CDATA[Generated oil density (20 °C), g / cm 3 > 0.8632 0.8628 0.8634 0.8643 0.8656 0.8704 0.8644 0.8732 0.8707 S, µg / g 7.3 7.1 7.6 15.6 38.2 139.1 28.2 236.8 118.8 N, µg / g 2.7 2.5 2.9 6.5 16.4 61.2 8.6 112.8 62. 2 Diesel yield, % 99.2 99.2 99.1 99.1 86.6 98.8 99.1 98.3 98.9

[0099] Table 6 Content of different sulfides in hydrorefined oil

[0100] Catalyst No. A B C E G H I K L Sulfur content in hydrorefined oil, µg / g 7.3 7.1 7.6 15.6 38.2 139.1 28.2 236.8 118.8 <![CDATA[C 1 -DBT,µg / g]]> 0 0 0 0 3.2 10.3 2.6 22.1 9.1 4- MDBT, µg / g 1.6 1.6 1.7 3.9 8.1 29.1 5.8 52.2 25.4 6-MDBT, µg / g 2.2 2.1 2.2 4.8 9.6 33.4 6.2 60.2 26.3 4,6-DMDBT, µg / g 3.5 3.4 3.7 6.9 17.3 66.3 13.6 102.3 58.0

Claims

1. A method for preparing a bulk hydrotreating catalyst, characterized in that It includes the following: (1) a sodium hydroxide solution, a sodium molybdate solution and a solution containing Ni and Si are subjected to a gelling reaction, and then aged to obtain a first slurry containing Ni, Si and Mo; (2) adding a solution containing Ni and a quaternary ammonium salt compound, a sodium tungstate solution, a sodium carbonate and / or sodium bicarbonate aqueous solution, and a first slurry to a mixture of an oily liquid and water in parallel, and performing a three-stage decreasing pH gelation reaction for n consecutive times, and adding a 1 / n soluble aluminum salt solution at the end of each first-stage pH reaction to generate a second slurry; the oily liquid is an unsaturated higher fatty acid glyceride; The specific process of each three-stage decreasing pH value reaction is as follows: in the first stage, the pH value is 11.0-13.5, the reaction time is 0.05-0.5 hours, and 1 / n Al-containing solution is added after the first stage reaction; in the second stage, the pH value is adjusted to 8.5-10.5, and the reaction time is 0.05-0.5 hours; in the third stage, the pH value is adjusted to 5.5-8.3, and the reaction time is 0.05-0.5 hours; wherein n is an integer of 2-8; and the reaction temperature is 60-98°C; (3) aging the second slurry, separating the solid from the liquid after aging, and drying and molding the solid phase to obtain a molded product; (4) The formed product is desalted, washed, dried and calcined to obtain a bulk hydrogenation refining catalyst.

2. The method according to claim 1, characterized in that: The weight concentration of the sodium hydroxide solution in step (1) is 5% to 30%; in the sodium molybdate solution in step (1), the weight concentration of Mo calculated as MoO3 is 5 to 110 g / L; in the Ni and Si-containing solution in step (1), the weight concentration of Ni calculated as NiO is 5 to 120 g / L, and the weight concentration of Si calculated as SiO2 is 2 to 80 g / L.

3. The method according to claim 1, characterized in that: The gelling reaction conditions of step (1) are as follows: reaction temperature is 30-90° C., pH value is controlled at 7.0-11.0, and gelling time is 0.2-2.5 hours.

4. The method according to claim 1, characterized in that: The aging conditions of step (1) are as follows: the aging temperature is 60-90° C., the pH value is controlled at 7.0-11.0 during aging, and the aging time is 0.3-2.5 hours.

5. The method according to claim 1, characterized in that: In step (1), the weight of the introduced Ni accounts for 30% to 80% of the total Ni weight in the hydrotreating catalyst obtained in step (4), and the remaining Ni in the catalyst is introduced through step (2).

6. The method according to claim 1, characterized in that: In the solution containing Ni and quaternary ammonium salt compounds in step (2), the weight concentration of Ni calculated as NiO is 5-110 g / L; in the sodium tungstate solution, the weight concentration of W calculated as WO3 is 4-140 g / L.

7. The method according to claim 1, characterized in that: The quaternary ammonium salt compound in step (2) is one or more of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, tetrabutylammonium hydroxide, hexadecyltrimethylammonium bromide or dodecyltrimethylammonium chloride; and the molar ratio of the added amount of the quaternary ammonium salt compound to W in the sodium tungstate solution is 0.1-1.

8.

8. The method according to claim 1, characterized in that: The soluble aluminum salt described in step (2) is one or more of aluminum nitrate, aluminum sulfate, and aluminum chloride. The weight concentration of Al in the soluble aluminum salt solution as Al2O3 is 3-100 g / L, and the solution is divided into n equal parts by volume, wherein n is an integer of 2-8.

9. The method according to claim 1, characterized in that: The weight concentration of the sodium carbonate and / or sodium bicarbonate aqueous solution in step (2) is 5% to 40%.

10. The method according to claim 1, characterized in that: The volume ratio of the water added in step (2) to the first slurry is 0.1:1 to 3:

1.

11. The method according to claim 1, characterized in that: The unsaturated higher fatty acid glyceride described in step (2) is one or more of peanut oil, rapeseed oil, cottonseed oil, sunflower seed oil, soybean oil, corn oil, tea oil or olive oil; the volume ratio of the unsaturated higher fatty acid glyceride to water is 1:60~1:

4.

12. The method according to claim 1, characterized in that: The aging conditions described in step (3) are as follows: aging temperature is 40 to 90° C., aging time is 1 to 5 hours, and pH value is 7.0 to 11.

0.

13. The method according to claim 1, characterized in that: The aging conditions in step (3) are as follows: the first step is normal pressure aging: the aging temperature is 30-90°C, the aging time is 1-6 hours, and the pH value is 6.5-10.0; the second step is high pressure aging: the temperature is 100-195°C, the time is 0.1-3.5 hours, the pressure is not less than 10 MPa, and the pH value is 10.0-13.

0.

14. The method according to claim 1, characterized in that: The desalination process described in step (4) is: first curing, then washing to remove the salt precipitated on the surface of the molded product, the curing conditions are a temperature of 5 to 100° C. and a time of 10 to 100 hours.

15. The method according to claim 1, characterized in that: The desalination treatment in step (4) is carried out as follows: the first stage is carried out at a temperature of 60 to 90°C for curing for 5 to 60 hours; the second stage is carried out at a temperature of 10 to 30°C for 1 to 48 hours, and then the precipitated salt is removed by washing.

16. A bulk hydrotreating catalyst prepared according to any one of claims 1 to 15, characterized in that: The bulk hydrotreating catalyst comprises composite amorphous oxide particles with a core-shell structure, wherein the core phase is an amorphous composite oxide containing molybdenum, nickel and silicon, and the shell phase is an amorphous composite oxide containing tungsten, nickel and aluminum; the average particle size of the catalyst particles is 8-13 nm; the particle size distribution of the catalyst particles is as follows: the number of particles with a particle size less than 7 nm accounts for 2%-15% of the total number of particles, the number of particles with a particle size of 7 nm-13 nm accounts for 66%-88% of the total number of particles, and the number of particles with a particle size greater than 13 nm accounts for 3%-21% of the total number of particles; the Na2O content in the catalyst is less than 0.078%.

17. The bulk hydrotreating catalyst according to claim 16, characterized in that: Based on the mass of the core-shell structured composite amorphous oxide particles, the core phase is 20% to 90%, and the shell phase is 10% to 80%.

18. The bulk hydrotreating catalyst according to claim 16, characterized in that: The atomic molar ratio of molybdenum to nickel in the core phase is 1:28 to 12:1, and the silicon content in terms of SiO2 accounts for 2% to 38% of the mass of the hydrotreating catalyst.

19. The bulk hydrotreating catalyst according to claim 16, characterized in that: The atomic molar ratio of tungsten to nickel in the shell phase is 1:22 to 8:1, and the aluminum content, calculated as Al2O3, accounts for 5% to 36% of the mass of the hydrotreating catalyst.

20. The bulk hydrotreating catalyst according to claim 16, characterized in that: The mass of NiO in the core phase accounts for 30% to 80% of the total mass of NiO in the hydrotreating catalyst, and the mass of NiO in the shell phase accounts for 20% to 70% of the total mass of NiO in the hydrotreating catalyst.

21. The bulk hydrotreating catalyst according to claim 16, characterized in that: The properties of the hydrotreating catalyst are as follows: Specific surface area is 180~700m 2 / g, and the pore volume is 0.30~0.90mL / g; the pore size distribution of the catalyst is as follows: the pore volume occupied by pores with a diameter of less than 4nm accounts for 1%~10% of the total pore volume, the pore volume occupied by pores with a diameter of 4~10nm accounts for 12%~40% of the total pore volume, the pore volume occupied by pores with a diameter of 10~15nm accounts for 22%~56% of the total pore volume, and the pore volume with a diameter of more than 15nm accounts for 18%~45% of the total pore volume.

22. Use of a bulk hydrotreating catalyst prepared according to any one of claims 1 to 15 in a diesel hydrotreating reaction, characterized in that: The conditions for diesel hydrofining reaction are as follows: reaction temperature is 330~400℃, reaction pressure is 2.5~12MPa, hydrogen-oil volume ratio is 250:1~1200:1, liquid hourly volume space velocity is 0.3~5.0h -1 .

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