CN107774277B - Method for preparing hydrotreating catalyst - Google Patents

Method for preparing hydrotreating catalyst Download PDF

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CN107774277B
CN107774277B CN201610735853.9A CN201610735853A CN107774277B CN 107774277 B CN107774277 B CN 107774277B CN 201610735853 A CN201610735853 A CN 201610735853A CN 107774277 B CN107774277 B CN 107774277B
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oxide precursor
preparing
slurry
salt
precursor slurry
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CN107774277A (en
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刘东香
王海涛
徐学军
冯小萍
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a method for preparing a hydrotreating catalyst. The method comprises the following steps: preparing oxide precursor slurry A of Al; preparing oxide precursor slurry B of Mo and Ni and/or Co; preparing W, Ni oxide precursor slurry C; preparing oxide precursor slurry D of Ni; and mixing the slurry A, the slurry B, the slurry C and the slurry D, aging, filtering, drying, forming, washing, drying and roasting to obtain the hydrotreating catalyst. The hydrotreating catalyst prepared by the method can optimize the reaction path from raw materials to products in the hydrodesulfurization process, particularly in the ultra-deep hydrodesulfurization process, reduce hydrogen consumption and more economically realize the ultra-deep hydrodesulfurization of diesel oil. The catalyst prepared by the method is suitable for the diesel hydrodesulfurization process.

Description

Method for preparing hydrotreating catalyst
Technical Field
The invention relates to a preparation method of a hydrotreating catalyst, in particular to a preparation method of an ultra-deep hydrodesulfurization catalyst.
Background
The tendency of crude oil to be highly sulfurized due to the deterioration and heaviness of crude oil is increasing. Low sulfur crude oil is reported to account for only 17wt% of the world today, with high sulfur crude oils with sulfur > 2wt% being as high as about 58 wt%.
SO (sulfur, nitrogen, aromatic hydrocarbon) and the like in diesel oil discharged in the combustion processx、NOxThe environmental pollution and the serious harm to the health of residents can be caused by acid rain, photochemical smog, carcinogens and the like which can be caused by CH, soot and the like, and the requirements on the specifications of the vehicle diesel are more and more strict based on that governments pay more and more attention to the cleanness of the atmosphere. The future clean diesel oil specification is developing towards the direction of no-sulfuration, low aromatic hydrocarbon, low density and high cetane number.
The diesel oil hydrofining raw material is mostly one or more of straight firewood, coke firewood, catalytic firewood and the like. In recent years, refineries process a large amount of high-sulfur crude oil in middle east and other areas, so that the sulfur content in straight-run diesel oil is greatly increased, the ratio of catalytic cracking blending residual oil and wax oil is increased, some high-boiling-point macromolecular sulfides, nitrides, polycyclic aromatic hydrocarbons and the like in catalytic diesel oil are aggregated, the reaction performance of the actual diesel oil hydrofining raw material is further reduced, and the processing difficulty is greatly increased.
The main three types of sulfides in diesel oil are alkyl thiophene, alkyl benzothiophene and alkyl dibenzothiophene, the difficulty of desulfurizing is that thiophene < benzothiophene < dibenzothiophene, and the hydrodesulfurization reaction activity of 4-MDBT and 4,6-DMDBT with substituent at β position is lowest, when all the sulfides with high reaction activity and non-substituent dibenzothiophene are removed, the diesel oil containing 350 mug/g of sulfur can be produced, but the dibenzothiophene sulfides with poor reaction activity, larger molecules and substituent at 4 or 4,6 position must be removed to produce clean diesel oil containing less than 50 mug/g, even less than 10 mug/g.
Macromolecular basic nitride, polycyclic aromatic hydrocarbon and the like in the raw oil have similarities with the structures of 4,6-DMDBT sulfides, and the reaction mechanism has similarities, namely the aromatic ring is firstly subjected to hydrogenation saturation and then subjected to the next reaction. These types of compounds interact in a similar manner with the catalyst surface, competing for adsorption, and retarding their hydrogenation reactions. Especially, macromolecule basic nitride in raw oil is easier to adsorb on the surface of catalyst than sulfur-containing compound and arene, and its existence inhibits hydrodesulfurization reaction, especially affects hydrodesulfurization of difficult-to-remove 4, 6-DMDBT.
Many studies have shown that hydrodesulfurization of 4-MDBT and 4,6-DMDBT is mainly realized by a first hydrogenation and then desulfurization path on different catalysts, and the hydrodesulfurization of DBT is mainly based on a direct desulfurization path, but the ratio of hydrogenolysis desulfurization and hydrodesulfurization on different active metal component catalysts such as Co-Mo, Ni-W and the like is different, especially DBT sulfide with higher reaction activity.
Although the hydrogenation catalyst with high total amount of active metals can provide more hydrogenation active centers, can convert nitrides, polycyclic aromatic hydrocarbons and the like more quickly and more in the hydrodesulfurization process, and can reduce the influence on the hydrodesulfurization of 4-MDBT and 4,6-DMDBT sulfides to a certain extent, how to more economically and more easily realize the production of ultra-low sulfur clean diesel oil is still an important subject of research in the field.
CN101722007A discloses a hydrogenationCatalyst compositions and methods for their preparation. The catalyst is prepared by co-current co-precipitation of an acidic solution containing nickel and a solution containing tungsten to obtain NixWyOzCompounding, pulping, adding MoO3The final catalyst is obtained through molding and activation, the loading of the active metal is not limited, and more total active metal can be provided. Although the W-Ni-Mo hydrogenation catalyst obtained by the method has good hydrogenation performance, in the diesel oil hydrodesulfurization process, part of sulfides with high reaction activity and unsubstituted dibenzothiophene sulfides can be desulfurized through a hydrogenation path, so that hydrogen is excessively consumed, and the processing cost is increased.
CN101089132A discloses a hydrodesulfurization catalyst of W-Mo-Ni-Co four active metal components, which adopts W-Mo-Ni-Co-P active components with specific compositions, but the active components are loaded on a carrier in a saturated Co-immersion mode, so that the loading capacity of the active metals is limited, more total active metals cannot be provided, and the method cannot well control the matching mode of different active metals, so that the aim of producing ultra-low sulfur diesel oil by deep hydrodesulfurization cannot be achieved.
CN201210442629.2 discloses a W-Mo-Ni-Co multi-metal combined hydrodesulfurization catalyst, which is prepared by preparing a W, Ni composite oxide precursor by adopting a coprecipitation method, forming the precursor into a catalyst intermediate, and then loading active metals Co and Mo by utilizing a specific impregnation method to obtain the multi-metal combined hydrodesulfurization catalyst with high total amount of active metals. The catalyst improves the hydrogenation performance and the hydrogenolysis performance of the catalyst by utilizing the cooperation of a W-Ni active phase and a Co-Mo active phase, two reaction paths are required to be further optimized, and the purpose of more economically carrying out ultra-deep hydrodesulfurization on diesel oil is realized.
Disclosure of Invention
In view of the deficiencies of the prior art, the present invention provides a process for preparing a hydroprocessing catalyst. The hydrotreating catalyst prepared by the method can optimize the reaction path from raw materials to products in the hydrodesulfurization process, particularly in the ultra-deep hydrodesulfurization process, reduce hydrogen consumption and more economically realize the ultra-deep hydrodesulfurization of diesel oil.
The preparation method of the hydrotreating catalyst of the invention comprises the following steps:
(1) preparing oxide precursor slurry A of Al;
(2) preparing oxide precursor slurry B of Mo and Ni and/or Co;
(3) preparing W, Ni oxide precursor slurry C;
(4) preparing an oxide slurry D of Ni;
(5) mixing the slurry obtained in the steps (1), (2), (3) and (4), aging, filtering and drying;
(6) and (5) forming, washing, drying and roasting the material obtained in the step (5) to obtain the hydrotreating catalyst.
In the preparation method of the hydrotreating catalyst of the present invention, the slurry a of the oxide precursor of Al (i.e., aluminum hydroxide) prepared in step (1) can be prepared by a conventional method such as neutralization precipitation, aluminum alkoxide hydrolysis, etc., and the oxide precursor of Al is preferably pseudo-boehmite.
In the method for producing a hydrotreating catalyst of the present invention, in the step (2) and/or the step (3), 1/20 to 1/10 by volume of the Al oxide precursor slurry a produced in the step (1) is preferably introduced.
In the preparation method of the hydrotreating catalyst, the oxide precursor slurry B of Mo and Ni and/or Co prepared in the step (2) adopts a precipitation method, namely nickel salt and/or cobalt salt is prepared into an acidic solution B1, molybdenum salt is prepared into an alkaline solution B2, the acidic solution B1 and the alkaline solution B2 are gelatinized, the reaction temperature is 65-90 ℃, and the pH value is 4-6. Wherein the molar ratio of Mo to Ni and/or Co is 1: 1.0 to 1.2.
In the preparation method of the hydrotreating catalyst, the oxide precursor slurry C prepared in the step (3) is prepared into W, Ni by a precipitation method, namely nickel salt is prepared into an acidic solution C1, tungsten salt is prepared into an alkaline solution C2, the acidic solution C1 and the alkaline solution C2 are gelatinized, the reaction temperature is 65-85 ℃, and the pH value is 4-6; wherein the molar ratio of W to Ni is 1: 1.0 to 1.2.
Step (2) introducing the molybdenum amountMoO3Metering and step (3) amount of tungsten introduced WO3The calculated molar ratio is 1: 10-10: 1, preferably 1: 6-6: 1.
in the preparation method of the hydrotreating catalyst, ammonium carbonate salt and/or alkali metal carbonate salt, such as one or more of ammonium carbonate, ammonium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, is/are added in the gelling process in the step (2) and/or the step (3). When ammonium carbonate salt and/or alkali metal carbonate salt is added in the step (2), the addition amount is CO2The molar ratio of Mo to Mo is 0.05-1.0, preferably 0.08-0.80. When ammonium carbonate salt and/or alkali metal carbonate salt is added in the step (3), the addition amount is CO2The molar ratio of W to W is 0.05 to 1.0, preferably 0.08 to 0.80.
Preparing Ni oxide precursor slurry D in the step (4) by adopting a precipitation method, namely preparing nickel salt into an acidic solution D1, neutralizing the acidic solution D1 with an alkaline precipitator to form gel, wherein the reaction temperature is 40-65 ℃, and the pH value is 7-9; the alkaline precipitating agent may be one or more of ammonia, sodium hydroxide, potassium hydroxide, etc., and ammonia gas is preferred. The ratio of the addition amount of Ni in the step (4) to the total mole number of W and Mo in the hydrotreating catalyst is 1: 8-1, preferably 1: 5-1.
In the step (5), the slurries obtained in the steps (1), (2), (3) and (4) are mixed, the pH value is controlled to be 7-9, the temperature of the slurry is 65-90 ℃, and the mixture is stirred for 10-30 minutes; the aging conditions in the step (5) are as follows: the pH value is 7-9, the aging temperature is 70-90 ℃, and the aging time is 0.5-3.0 hours.
The forming in step (6) can adopt a conventional forming method, such as extrusion forming and the like. The catalyst can be made into tablet, sphere, cylindrical strip and special-shaped strip (such as clover and clover) according to the requirement, preferably cylindrical strip and special-shaped strip. In the forming process, a proper amount of forming aids, such as extrusion aids and the like, can be added. The washing can be carried out by pure water washing at normal temperature, and the drying and roasting can be carried out by conventional drying and roasting modes. Wherein the drying and roasting conditions are as follows: drying at 50-120 ℃ for 2.0-6.0 hours, and calcining at 450-600 ℃ for 3.0-6.0 hours.
In the method for producing a hydrotreating catalyst of the present invention, a catalyst auxiliary may be added as needed in at least one of the steps (1), (2), (3), (4) (5), and (6) according to the catalyst. The auxiliary agent generally comprises one or more of Si, P, F, B, Zr, Ti and the like, and Si and/or P are preferred. The method for adding the auxiliary agent adopts the conventional method in the field. The addition amount of the auxiliary agent is less than 25 percent of the weight of the hydrotreating catalyst calculated by oxide, and is preferably 1 to 15 percent.
In the hydrotreating catalyst prepared by the method of the invention, the total weight content of the hydrogenation active metal W, Mo and Ni and/or Co calculated by oxides is 40-90%, preferably 50-80%, and the content of alumina is 10-60%, preferably 20-50%, based on the weight of the hydrotreating catalyst.
The hydrotreating catalyst of the present invention preferably contains a promoter P, based on the weight of the hydrotreating catalyst, P2O5The content is 5.0% or less, preferably 0.3% to 5.0%, and more preferably 0.5% to 3.0%.
The hydrotreating catalyst of the invention further preferably contains an auxiliary agent Si, based on the weight of the hydrotreating catalyst, SiO2The content is 10.0% or less, preferably 2.0% to 8.0%.
The properties of the hydroprocessing catalyst of the invention are as follows: the pore volume is 0.20-0.65 mL/g, the specific surface area is 180-400 m2/g。
In the preparation method of the hydrotreating catalyst, by controlling the precipitation form of the hydrogenation active metal, namely molybdenum and tungsten are mainly precipitated in the form of nickel tungstate, nickel molybdate and/or cobalt molybdate, ammonium carbonate and/or alkali metal salt is added in the precipitation process, and the carbonate can slowly and uniformly release carbon dioxide in a weak acid reaction environment, prevent the growth of nickel tungstate, nickel molybdate and cobalt molybdate precipitate particles, enrich the pore structure of the nickel tungstate, nickel molybdate and cobalt molybdate precipitate particles, and increase the specific surface area of the nickel molybdate, nickel molybdate and cobalt molybdate precipitate particles; and the other part of nickel is precipitated in the form of hydroxide, and ammonia gas is preferably used as a precipitator, so that the nickel hydroxide is generated by reaction with the nickel, the particle growth is blocked, and the pore structure and the specific surface area are improved. The preparation method of the invention can better match hydrogenation active metals, so that the catalyst has richer pore structures and active surfaces, and can optimize a hydrodesulfurization reaction path, so that sulfides with high reaction activity and dibenzothiophene sulfides without substituents can realize desulfurization through hydrogenolysis paths, and the hydrodesulfurization activity of the 4-MDBT and the 4,6-DMDBT sulfides can be better exerted, therefore, the adoption of the hydrotreating catalyst not only reduces the consumption of hydrogen in the diesel hydrodesulfurization process, but also can improve the hydrodesulfurization activity, thereby realizing more economic diesel ultra-deep hydrodesulfurization.
The hydrotreating agent is suitable for the diesel hydrodesulfurization process, and is particularly suitable for the diesel ultra-deep hydrodesulfurization process.
Detailed Description
The preparation method of the hydrotreating catalyst provided by the invention specifically comprises the following steps:
(1) preparation of oxide precursor slurry A of Al
The method preferably adopts a neutralization precipitation method, namely, an aluminum salt solution and ammonia water are subjected to neutralization precipitation in a parallel flow manner to obtain the pseudo-boehmite slurry, wherein the gelling temperature is 65-85 ℃, and the gelling pH value is 8-10. The aluminum salt can be one or more of aluminum chloride, aluminum nitrate, aluminum sulfate and the like. The concentration of ammonia can be in any feasible proportion, preferably from 15% to 25% by weight. The assistant can be introduced into the aluminum salt solution according to the requirement of the catalyst, the assistant is preferably P and/or Si, the phosphorus source can be one or more of phosphoric acid, phosphorous acid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and the like, and the silicon source can be one or more of water glass, silica sol and the like.
(2) Preparation of oxide precursor slurry B of Mo and Ni and/or Co
Preparing nickel salt and/or cobalt salt into acidic solution B1, preparing molybdenum salt into alkaline solution B2, and gelatinizing acidic solution B1 and alkaline solution B2, wherein ammonium carbonate salt and/or alkali metal carbonate salt can be added into alkaline solution B2 and introduced into a reaction system, or can be prepared into solution alone and introduced into the reaction system, and gelatinizing can be carried out by adopting a parallel-flow gelatinizing method or a dropwise adding methodA gelling method, preferably a method of adding the alkaline solution B2 dropwise into the acidic solution B1 to carry out gelling; the gelling conditions are as follows: the reaction temperature is 65-90 ℃, and the pH value is 4-6; and (3) introducing 1/20-1/10 of the volume A of the Al oxide precursor slurry prepared in the step (1) in the gelling process in the step (2). In the step (2), the cobalt salt is one or more of cobalt nitrate and cobalt chloride, the nickel salt is one or more of nickel nitrate and nickel chloride, the molybdenum salt is ammonium molybdate, the ammonium carbonate salt is one or more of ammonium carbonate and ammonium bicarbonate, the alkali metal carbonate salt is one or more of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, and preferably the ammonium carbonate salt. In the acidic solution B1, the concentration of cobalt salt is 3.5-15.0 g/L calculated by CoO, and the concentration of nickel salt is 5-25 g/L calculated by NiO. In the alkaline solution B2, the molybdenum salt is MoO3The concentration is 15-50 g/L.
(3) Preparation of W, Ni oxide precursor slurry C
Preparing nickel salt into an acidic solution C1, preparing tungsten salt into an alkaline solution C2, and gelatinizing the acidic solution C1 and the alkaline solution C2, wherein ammonium carbonate salt and/or alkali carbonate salt can be added into the alkaline solution C2 to be introduced into a reaction system, or can be independently prepared into a solution to be introduced into the reaction system, and the gelatinizing can be carried out by adopting a parallel-flow gelatinizing method or a dropwise gelatinizing method, preferably a method of dropwise adding the alkaline solution C2 into the acidic solution C1 to carry out gelatinizing; the gelling conditions are as follows: the reaction temperature is 65-85 ℃, and the pH value is 4-6; and (3) introducing 1/20-1/10 of the volume A of the Al oxide precursor slurry prepared in the step (1) in the gelling process in the step (3). In the step (3), the tungsten salt can be one or more of ammonium metatungstate, sodium tungstate and the like, the ammonium carbonate salt can be one or more of ammonium carbonate and ammonium bicarbonate, the alkali metal carbonate salt can be one or more of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, and the ammonium carbonate salt is preferably selected. The nickel salt can be one or more of nickel sulfate, nickel nitrate, nickel chloride, basic nickel carbonate, nickel oxalate and the like. In the acidic solution C1, the concentration of nickel salt in NiO is 15-45 g/L. In the alkaline solution C2, the tungsten salt is replaced by WO3The concentration is 35-65 g/L.
(4) Preparation of Ni oxide precursor slurry D
Taking ammonia gas as a precipitator for example, the process is as follows: preparing nickel salt into an acidic solution D1, adding a certain amount of water into a reaction tank, heating to 40-65 ℃, dropwise adding the nickel salt into the water, introducing ammonia gas, controlling the flow rate of the nickel salt and the ammonia gas to enable the pH value to be within 7-9, reacting for 30-40 minutes, and controlling the concentration of the nickel salt in NiO to be 15-45 g/L in the acidic solution D1.
(5) Mixing the slurry obtained in the steps (1), (2), (3) and (4), heating to 65-90 ℃, controlling the pH value to be 7-9, stirring for 10-30 minutes, then aging, filtering and drying; wherein the aging conditions are as follows: the pH value is 7-9, the aging temperature is 70-90 ℃, and the aging time is 0.5-3.0 hours.
(6) And (5) forming, washing, drying and roasting the material obtained in the step (5) to obtain the hydrotreating catalyst. Wherein the drying and roasting conditions are as follows: drying at 50-120 ℃ for 2.0-6.0 hours, and calcining at 450-600 ℃ for 3.0-6.0 hours.
In the method of the present invention, the pH value of the slurry in steps (1), (2), (3), (4) and (5) can be adjusted by using acid or alkali, the acid can be one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, etc., and the alkali can be one or more of sodium hydroxide, potassium hydroxide, ammonia water, etc.
The embodiments and effects of the present invention are further illustrated by the following specific examples. In the present invention, wt% is a mass fraction. In the method, the pore volume and the specific surface area of the catalyst are measured by adopting a low-temperature liquid nitrogen adsorption method.
Example 1
(1) Preparation of oxide precursor slurry A of Al
Adding 600mL of purified water and 59g of aluminum nitrate into a container, and stirring to dissolve the purified water and the aluminum nitrate to obtain an aluminum salt solution; 2000mL of 20wt% aqueous ammonia solution was prepared in a container; adding 500mL of purified water into a gelling tank, heating to 75 ℃, adding an aluminum salt solution and a 20wt% ammonia water solution into a reaction tank in a cocurrent manner under the condition of continuous stirring to gel, controlling the reaction temperature to be about 75 ℃, controlling the pH of the slurry to be 8.5 +/-0.2, and controlling the reaction time to be about 60min to obtain Al oxide precursor slurry A;
(2) preparation of oxide precursor slurry B of Mo, Ni and Co
Adding 600mL of purified water, 16.8g of ammonium paramolybdate and 2.4g of ammonium bicarbonate into a container, heating to 75 ℃, and stirring to dissolve the ammonium paramolybdate and the ammonium hydrogencarbonate to obtain an alkaline solution B2; adding 1000mL of purified water, 6.8g of nickel nitrate and 11.7g of cobalt nitrate into a gelling tank, stirring to dissolve the purified water to obtain an acidic solution B1, adding 170mL of Al oxide precursor slurry prepared in the step (1) into the acidic solution B1, uniformly stirring, heating to 75 ℃, slowly adding an alkaline solution B2 into the gelling tank under continuous stirring, adjusting the pH value of the slurry to 5 +/-0.2 by using ammonia water, keeping the pH value at 75 ℃, and reacting for about 30min to obtain oxide precursor slurry B of Mo, Ni and Co;
(3) preparation of W, Ni oxide precursor slurry C
Adding 1000mL of water, 41.1g of sodium tungstate and 3.4g of ammonium bicarbonate into a container, and stirring to dissolve the sodium tungstate and the ammonium bicarbonate to obtain an alkaline solution C2; adding 1000mL of purified water and 25.6g of nickel nitrate into a gelling tank, stirring to dissolve the purified water and the nickel nitrate to obtain an acidic solution C1, adding 170mL of Al oxide precursor slurry prepared in the step (1) into the acidic solution C1, uniformly stirring, heating to 75 ℃, slowly adding an alkaline solution C2 into the gelling tank under continuous stirring, adjusting the pH value of the slurry to 5 +/-0.2 by using ammonia water, keeping the pH value at 75 ℃, and reacting for about 30min to obtain W, Ni oxide precursor slurry C;
(4) preparation of Ni oxide precursor slurry D
Adding 600mL of purified water into a container, adding 23.8g of nickel nitrate, stirring to dissolve the nickel nitrate to obtain an acidic solution D1, adding 500mL of purified water into a gelling tank, heating to 50 ℃, dropwise adding the acidic solution D1 into the gelling tank, introducing ammonia gas, controlling the flow rate of the acidic solution and the ammonia gas to keep the pH value of the slurry at 6.8 +/-0.2, keeping the reaction temperature at about 50 ℃, and completing gelling within 30 minutes to obtain Ni oxide precursor slurry D;
(5) mixing the residual slurry in the step (1), the slurry in the step (2), the slurry in the step (3) and the slurry in the step (4), controlling the pH value of the slurry to be 7.5 +/-0.2, stirring for 20 minutes, heating to about 75 ℃, controlling the pH value to be 7.5 +/-0.2, aging for 1 hour, filtering and drying;
(6) and (3) forming and washing the material obtained in the step (5), drying at 90 ℃ for 3.0 hours, and roasting at 500 ℃ for 4.0 hours to obtain the hydrotreating catalyst A.
Example 2
The preparation method of the catalyst B of the invention is the same as that of the example 1, except that 19.8g of ammonium paramolybdate and 2.8g of ammonium bicarbonate are added into the alkaline solution B2 when the oxide precursor slurry B of Mo, Ni and Co is prepared in the step (2); adding 8.4g of nickel nitrate and 13.4g of cobalt nitrate into the acidic solution B1; when preparing W, Ni oxide precursor slurry C in step (3), adding 23.8g of nickel nitrate into an acidic solution C1, and adding 38.2g of sodium tungstate and 3.0g of ammonium bicarbonate into an alkaline solution C2; step (4) in the preparation of Ni oxide precursor slurry D, 20.1g of nickel nitrate was added to the acidic solution D1, and the procedure was otherwise as in example 1, to obtain catalyst B of the present invention.
Example 3
The preparation method of the catalyst C of the invention is the same as that of the example 1, except that when the oxide precursor slurry B of Mo, Ni and Co is prepared in the step (2), 15.3g of ammonium paramolybdate and 0.8g of ammonium bicarbonate are added into the alkaline solution B2; adding 8.4g of nickel nitrate and 8.4g of cobalt nitrate into the acidic solution B1; when preparing W, Ni oxide precursor slurry C in step (3), adding 27.4g of nickel nitrate into an acidic solution C1, and adding 44.1g of sodium tungstate and 1.2g of ammonium bicarbonate into an alkaline solution C2; step (4) in the preparation of Ni oxide precursor slurry D, 23.8g of nickel nitrate was added to the acidic solution D1, and the procedure was otherwise as in example 1, to obtain catalyst C according to the present invention.
Example 4
The preparation method of the catalyst D of the invention is the same as that of the example 1, except that when the oxide precursor slurry B of Mo, Ni and Co is prepared in the step (2), 26.6g of ammonium paramolybdate and 3.2g of ammonium bicarbonate are added into the alkaline solution B2; adding 17.7g of nickel nitrate and 12.6g of cobalt nitrate into the acidic solution B1; when preparing W, Ni oxide precursor slurry C in step (3), adding 20g of nickel nitrate into acidic solution C1, and adding 32.3g of sodium tungstate and 2.1g of ammonium bicarbonate into alkaline solution C2; step (4) in the preparation of Ni oxide precursor slurry D, 12.2g of nickel nitrate was added to the acidic solution D1, and the procedure was otherwise as in example 1 to obtain catalyst D of the present invention.
Example 5
The preparation method of the catalyst E of the invention is the same as that of the example 1, except that when the oxide precursor slurry B of Mo, Ni and Co is prepared in the step (2), 23g of ammonium paramolybdate and 4.4g of ammonium bicarbonate are added into the alkaline solution B2; adding 12.6g of nickel nitrate and 12.6g of cobalt nitrate into the acidic solution B1; when preparing W, Ni oxide precursor slurry C in step (3), adding 9.7g of nickel nitrate into an acidic solution C1, and adding 38.2g of sodium tungstate and 4.2g of ammonium bicarbonate into an alkaline solution C2; step (4) in the preparation of Ni oxide precursor slurry D, 20g of nickel nitrate was added to the acidic solution D1, and the same procedure as in example 1 was repeated, thereby obtaining catalyst E of the present invention.
Comparative example 1
500mL of purified water and 35 g of nickel chloride were added to the dissolution tank 1 to prepare an acidic solution A. 500mL of purified water, 52g of sodium tungstate and 82g of sodium metaaluminate are added into the dissolving tank 2, stirred and dissolved, and an alkaline solution B is prepared. 350mL of purified water was added to the reaction tank, and the temperature was raised to 60 ℃. Under the condition of stirring, adding the solution A and the solution B into a reaction tank in a cocurrent manner for gelling, wherein the gelling temperature is 60 ℃, the gelling time is 0.5 hour, the pH value of slurry in the gelling process is 8.0, and aging is carried out for 1 hour after gelling is finished. Then, filtration was carried out, 800mL of purified water and 17.1g of molybdenum trioxide were added to the filter cake, the mixture was beaten and stirred uniformly, filtration was carried out, the filter cake was dried at 80 ℃ for 5 hours, then, strip-forming was carried out, washing was carried out 3 times with purified water, drying was carried out at 120 ℃ for 5 hours, and calcination was carried out at 500 ℃ for 4 hours, to obtain catalyst F of comparative example.
Comparative example 2
500mL of purified water was put into a vessel A, and 43g of ammonium metatungstate, 39.5g of nickel chloride and 2.5g of ammonium dihydrogen phosphate were added thereto and stirred uniformly.
300mL of purified water was added to a vessel B, and 53g of aluminum chloride was added thereto and dissolved with stirring.
In a vessel C, the concentration is adjusted to SiO2100mL of 3.1wt% dilute water glass solution.
Adding the aluminum chloride solution in the container B into the container A under the stirring state, dripping the dilute water glass solution in the container C into the container A under the stirring state, and adjusting the total volume of the solution to 1000mL by using pure water to obtain the aluminum chloride solution containing metals W, Ni and Al2O3、P2O5、SiO2Salt solution of precursor.
And (2) carrying out cocurrent flow on the prepared salt solution and 15wt% of ammonia water solution to form gel, controlling the gelling temperature to be 50 ℃, controlling the pH value of slurry to be 8.2 +/-0.2, completing gelling within 1h, aging the slurry for 3h, filtering the slurry after aging, drying an obtained filter cake in an oven at 70 ℃, carrying out rolling and strip extrusion molding, extruding strips by using a phi 2.0 clover orifice plate, washing after molding, drying for 8 h in the oven at 110 ℃, and roasting and activating for 3h at 500 ℃ to obtain the catalyst precursor strip containing the active metal W, Ni.
24g of citric acid, 33g of basic cobalt carbonate and 75.5g of ammonium molybdate are prepared into 300mL of impregnation liquid with 20wt% ammonia water concentration, and the impregnation liquid is sealed and stored for later use.
The catalyst precursor strip containing W, Ni was placed in a converter and spray-soaked with 75mL of the impregnation solution prepared above, after the spray-soaking was completed, the material was taken out and dried in an oven at 110 ℃ for 8 hours, and calcined and activated at 500 ℃ in a high-temperature furnace for 3 hours to obtain catalyst G of this comparative example.
TABLE 1 catalyst compositions and physicochemical Properties of the inventive and comparative examples
Catalyst numbering WO3，wt% MoO3，wt% CoO，wt% NiO，wt% Al2O3，wt% Specific surface area, m2/g Pore volume, mL/g
A 32.5 14.5 4.9 23.1 Balance of 241 0.281
B 30.4 17.5 5.5 21.7 Balance of 238 0.277
C 34.6 13.1 3.5 24.2 Balance of 225 0.251
D 25.7 23.2 5.4 20.6 Balance of 231 0.268
E 30.2 19.9 5.1 23.0 Balance of 234 0.283
F 36.0 18.0 - 21.0 Balance of 174 0.211
G 30.5 17.6 5.4 21.6 Balance of 216 0.173
Example 6
Based on 2wt% of DBT-containing model compoundThe toluene solution is taken as a raw material, and the hydrogen pressure is 2.0MPa, the volume ratio of hydrogen to oil is 200: 1, volume space velocity of 3h-1And the hydrodesulfurization performance of the catalyst and the comparative catalyst is evaluated on a micro reaction device at the reaction temperature of 320 ℃. The evaluation results are shown in Table 2.
TABLE 2 comparative data on the relative hydrodesulfurization activities of the catalysts of the present invention and the comparative examples
Catalyst numbering A B C D E F G
Relative desulfurization activity of% 163 165 157 162 168 100 128
Example 7
Respectively taking toluene solution containing DBT, 4-MDBT and 4,6-DMDBT three model compounds with the concentration of 2wt% as raw materials, and carrying out hydrogenation reaction under the conditions that the hydrogen pressure is 2.0MPa, the hydrogen-oil volume ratio is 200: 1, volume space velocity of 3h-1The catalysts of the invention and the comparative examples were evaluated for hydrogenation and hydrogenolysis desulfurization performance on a micro-reactor at a reaction temperature of 320 ℃.
The reaction was carried out on a miniature reaction apparatus and quantitative analysis and identification of the reaction products were carried out by using a Varian3800 type capillary gas chromatograph and a Finnigan SSQ710X type quadrupole mass spectrometer.
If r represents the ratio of the hydrogenation reaction rate to the hydrogenolysis reaction rate of the model compound and DBT is taken as the model compound, r is expressed by the molar ratio of the content of cyclohexylbenzene to biphenyl in the DBT product; when 4-MDBT is taken as a model compound, r is expressed by the molar ratio of the content of cyclohexylbenzene to biphenyl; when 4,6-DMDBT was used as a model compound, r was represented by the molar ratio of the contents of 1-methyl-3- (3-methylcyclohexylbenzene) to 3, 3-dimethylbiphenyl, and the results are shown in Table 3.
Table 3 representative hydrogenation to hydrogenolysis product ratios for the inventive and comparative catalysts
Catalyst numbering B F G
r(DBT) 0.26 0.97 0.29
r (4-MDBT) 1.47 2.71 1.50
r(4,6-DMDBT) 4.65 5.25 4.73
The data in Table 3 show that the hydrogenolysis performance of the catalyst of the invention is better than that of the catalyst of the comparative example, and especially the hydrogenolysis desulfurization performance of the catalyst can be greatly improved for DBT sulfides with higher reaction activity.

Claims (22)

1. A method of preparing a hydroprocessing catalyst, comprising:
(1) preparing oxide precursor slurry A of Al;
(2) preparing oxide precursor slurry B of Mo and Ni and/or Co;
(3) preparing W, Ni oxide precursor slurry C;
(4) preparing oxide precursor slurry D of Ni;
(5) mixing the slurry obtained in the steps (1), (2), (3) and (4), aging, filtering and drying;
(6) forming, washing, drying and roasting the material obtained in the step (5) to obtain a hydrotreating catalyst;
preparing oxide precursor slurry B of Mo and Ni and/or Co in the step (2) by adopting a precipitation method, namely preparing nickel salt and/or cobalt salt into an acidic solution B1, preparing molybdenum salt into an alkaline solution B2, and gelatinizing the acidic solution B1 and the alkaline solution B2 to obtain the oxide precursor slurry B;
preparing W, Ni oxide precursor slurry C by precipitation method, namely preparing nickel salt into acid solution C1, preparing tungsten salt into alkaline solution C2, and gelatinizing acid solution C1 and alkaline solution C2;
in the step (2) and/or the step (3), ammonium carbonate and/or alkali metal carbonate are/is added in the gelling process;
and (4) preparing Ni oxide precursor slurry D by adopting a precipitation method, namely preparing nickel salt into an acidic solution D1, and neutralizing the acidic solution D1 with alkaline precipitator ammonia gas to form gel.
2. The method of claim 1, wherein: the Al oxide precursor in the step (1) is pseudo-boehmite.
3. The production method according to claim 1 or 2, characterized in that: the preparation method of the Al oxide precursor slurry A in the step (1) comprises the following steps: and (3) carrying out neutralization and precipitation by using aluminum salt solution and ammonia water in parallel flow to obtain slurry A, wherein the gelling temperature is 65-85 ℃, and the gelling pH value is 8-10.
4. The method of claim 1, wherein: the reaction conditions of the precipitation method for preparing the oxide precursor slurry B of Mo and Ni and/or Co in the step (2) are as follows: the reaction temperature is 65-90 ℃, the pH value is 4-6, and the molar ratio of Mo to Ni and/or Co is 1: 1.0 to 1.2.
5. The method of claim 1, wherein: the reaction conditions of the precipitation method for preparing W, Ni oxide precursor slurry C in step (3) are as follows: the reaction temperature is 65-85 ℃, the pH value is 4-6, and the molar ratio of W to Ni is 1: 1.0 to 1.2.
6. The method of claim 1, wherein: and (3) introducing 1/20-1/10 of the volume of the Al oxide precursor slurry A prepared in the step (1) in the step (2) and/or the step (3), wherein the volume of the Al oxide precursor slurry A accounts for the volume of the Al oxide precursor slurry A prepared in the step (1).
7. The production method according to claim 1, 4 or 5, characterized in that: adding ammonium carbonate salt and/or carbonic acid in the step (2)Alkali metal salts, when added in amounts of CO2The molar ratio of the carbon dioxide to Mo is 0.05-1.0, and when the ammonium carbonate salt and/or the alkali carbonate salt are/is added in the step (3), the addition amount is CO2The molar ratio of W to W is 0.05-1.0.
8. The production method according to claim 1, 4 or 5, characterized in that: when ammonium carbonate salt and/or alkali metal carbonate salt is added in the step (2), the addition amount is CO2The molar ratio of the carbon dioxide to Mo is 0.08-0.80, and when the ammonium carbonate salt and/or the alkali metal carbonate salt are/is added in the step (3), the addition amount is CO2The molar ratio of W to W is 0.08-0.80.
9. The method of claim 1, wherein: the ammonium carbonate salt and/or the alkali metal carbonate salt is selected from one or more of ammonium carbonate, ammonium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.
10. The production method according to claim 1, 4 or 5, characterized in that: step (2) introducing MoO as molybdenum3Metering and step (3) amount of tungsten introduced WO3The calculated molar ratio is 1: 10-10: 1.
11. the production method according to claim 1, 4 or 5, characterized in that: step (2) introducing MoO as molybdenum3Metering and step (3) amount of tungsten introduced WO3The calculated molar ratio is 1: 6-6: 1.
12. the production method according to claim 1, 4 or 5, characterized in that: the reaction conditions of the precipitation method for preparing the Ni oxide precursor slurry D in the step (4) are as follows: the reaction temperature is 40-65 ℃, and the pH value is 7-9; the ratio of the addition amount of Ni to the total mole number of W and Mo in the hydrotreating catalyst in the step (4) is 1: 8-1.
13. The production method according to claim 1, 4 or 5, characterized in that: the ratio of the addition amount of Ni to the total mole number of W and Mo in the hydrotreating catalyst in the step (4) is 1: 5-1.
14. The method of claim 1, wherein: and (5) when the slurry obtained in the steps (1), (2), (3) and (4) is mixed, controlling the pH value to be 7-9, controlling the temperature of the slurry to be 65-90 ℃, and stirring for 10-30 minutes.
15. The method of claim 1, wherein: aging in the step (5) under the following conditions: the pH value is 7-9, the aging temperature is 70-90 ℃, and the aging time is 0.5-3.0 hours.
16. The method of claim 1, wherein: the drying and baking conditions in step (6) are as follows: drying at 50-120 ℃ for 2.0-6.0 hours, and calcining at 450-600 ℃ for 3.0-6.0 hours.
17. The method of claim 1, wherein: introducing a catalyst auxiliary agent into at least one of the steps (1), (2), (3), (4), (5) and (6), wherein the auxiliary agent comprises one or more of Si, P, F, B, Zr and Ti, and the addition of the auxiliary agent accounts for less than 25 percent of the weight of the hydrotreating catalyst in terms of oxide.
18. The method of claim 17, wherein: the auxiliary agent is Si and/or P.
19. The method of claim 17, wherein: the addition amount of the auxiliary agent is 1-15% of the weight of the hydrotreating catalyst calculated by oxide.
20. The method of claim 1, wherein: in the hydrotreating catalyst, the total weight content of the hydrogenation active metal W, Mo and Ni and/or Co calculated by oxides is 50-80 percent and the content of alumina is 20-50 percent on the basis of the weight of the hydrotreating catalyst.
21. The method of claim 1, 17 or 20, wherein: the hydrotreating catalyst contains an auxiliary agent P, and the weight of the hydrotreating catalyst is taken as the reference, and the auxiliary agent P is P2O5The content is 5.0% or less.
22. The method of claim 1, 17 or 20, wherein: the hydrotreating catalyst contains an auxiliary agent Si, and takes the weight of the hydrotreating catalyst as a reference and takes SiO2The content is below 10.0%.
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