CN114433117A - Preparation method of heavy diesel oil fraction hydrofining catalyst - Google Patents

Preparation method of heavy diesel oil fraction hydrofining catalyst Download PDF

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CN114433117A
CN114433117A CN202011116861.8A CN202011116861A CN114433117A CN 114433117 A CN114433117 A CN 114433117A CN 202011116861 A CN202011116861 A CN 202011116861A CN 114433117 A CN114433117 A CN 114433117A
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catalyst
pore volume
acid
aging
hours
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CN114433117B (en
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徐学军
王海涛
王继锋
李娟�
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian 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
    • B01J23/70—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
    • 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
    • B01J35/615—
    • B01J35/633—
    • B01J35/695—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a preparation method of a hydrofining catalyst for heavy diesel oil fractions. The method comprises the following steps: (1) carrying out parallel flow gelling reaction on a mixed solution containing Ni, Al, organic acid and organic alcohol, a sodium tungstate solution and a precipitator, and filtering the slurry I to obtain a filter cake; (2) mixing the filter cake obtained in the step (1) with a mixed solution containing Ni and Al to obtain a solid-liquid mixture, adding the solid-liquid mixture, a sodium molybdate solution and a precipitator into a reaction tank in a concurrent flow manner for gelling reaction, aging the slurry II, and carrying out solid-liquid separation, drying and molding after aging; (3) and desalting the molded product, washing, drying and roasting to obtain the hydrofining catalyst. The catalyst prepared by the method has low cost, clean and pollution-free preparation process, large pore volume and pore diameter, high hydrodesulfurization and hydrodenitrogenation reaction performance and is particularly suitable for ultra-deep hydrodesulfurization and denitrogenation reactions of heavy diesel oil fractions.

Description

Preparation method of heavy diesel oil fraction hydrofining catalyst
Technical Field
The invention relates to a preparation method of a hydrofining catalyst for heavy diesel oil fractions.
Background
With the stricter and stricter diesel oil product indexes around the world, oil refining enterprises must achieve ultra-deep hydrodesulfurization of diesel oil by increasing the reaction severity, so that the production cost of the enterprises is increased, and the production profits of the enterprises are reduced. In order to meet the index requirements of diesel products without increasing the oil refining cost, oil refining enterprises adopt high-activity hydrogenation catalysts to achieve the effect of ultra-deep hydrodesulfurization of diesel. The traditional supported diesel hydrofining catalyst is difficult to meet the requirements of oil refining enterprises for producing new standard products due to the limitation of metal loading, and the non-supported catalyst with high hydrogenation activity can realize the deep hydrodesulfurization of diesel by adopting a traditional hydrogenation device under a milder condition.
Particularly, in recent years, in order to improve the market competitiveness of the catalyst and meet the increasingly strict requirements of environmental protection laws and regulations, the catalyst is urgently needed to be prepared by using raw materials with relatively low price, and the nitrogen-free raw materials are used in the preparation process of the catalyst, so that ammonia nitrogen and NO are solved from the sourceXThe pollution problem and the preparation cost of the catalyst are reduced. The impregnation method and the kneading method for preparing the catalyst have the disadvantages of high preparation cost and high wastewater treatment cost due to the fact that the sodium-containing raw material with relatively low price cannot be used. The coprecipitation method can use sodium-containing raw materials with relatively low price to prepare the catalyst, thereby greatly reducing the preparation cost of the catalyst and the cost of wastewater treatment. However, the introduction of a large amount of sodium ions makes the sodium ions in the catalyst difficult to remove, only the sodium ions on the surface of the catalyst can be removed, the large amount of sodium ions still exist in the precipitated material, the residual sodium ions cause poor cohesiveness of the material, and the sodium ions which are not removed are not beneficial to the formation of a pore channel structure of the catalyst, so that the pore volume and the pore diameter of the catalyst are smaller.
In the ultra-deep desulfurization stage (mainly removing sulfur-containing compounds with substituents such as 4, 6-dimethyldibenzothiophene and the like), the reaction rate is greatly reduced due to the steric hindrance effect of methyl adjacent to a sulfur atom and the obvious inhibition effect of nitride on the hydrodesulfurization reaction. In the face of the two limits of ultra-deep desulfurization reaction, the development of high-activity hydrogenation catalysts is required, the bulk phase catalyst is the catalyst with the highest hydrogenation activity center at present, the limit of metal content is eliminated, the catalyst is mainly prepared by a coprecipitation method, and active metals are exposed on the surface of the catalyst to provide reaction activity centers for reactant molecules. The bulk phase catalyst prepared by the existing method has smaller pore volume and pore diameter, and macromolecular sulfides and nitrides can not smoothly enter a pore channel to carry out hydrodenitrogenation and desulfurization reactions. Meanwhile, the small pore volume and the small specific surface area can cause excessive accumulation of high-content active metal on the surface of the bulk catalyst, reduce the generation of active phases, reduce the activity of the catalyst, influence the utilization rate of the active metal of the catalyst and improve the use cost of the catalyst.
CN1951561A discloses a method for preparing a hydrogenation catalyst by coprecipitation, US 6,162,350, CN1339985A disclose a mixed metal catalyst composition, CN101153228A discloses a multi-metal bulk catalyst for ultra-deep hydrodesulfurization of diesel oil, CN110975911A discloses a bulk phase catalyst and a preparation method thereof, and a hydrogenation catalyst containing the bulk phase catalyst, wherein the catalysts in the patents are all prepared by coprecipitation method, and have small specific surface area, pore volume and pore diameter.
CN102049265A discloses a bulk phase hydrogenation catalyst, ammonium bicarbonate is added in the coprecipitation process, the bulk phase hydrogenation catalyst disclosed in CN102451703A is added in the coprecipitation process, carbon dioxide is added to generate carbonate or bicarbonate, the above-mentioned methods are all that the pore volume and specific surface area of the catalyst are changed under the impact action of gas by utilizing a certain amount of gas released in the roasting process. Both methods use external force impact to increase the surface of the bulk catalyst and improve pore distribution, but their effect is limited.
CN106179380A discloses a bulk phase hydrofining catalyst and a preparation method thereof. The method comprises the steps of preparing a nickel-aluminum mixed precipitate by a positive addition method, preparing a tungsten, molybdenum and aluminum mixed precipitate by a cocurrent flow precipitation method, mixing the nickel and aluminum mixed precipitate, aging and filtering to obtain a metal mixture, carrying out steam treatment on the metal mixture under proper conditions, adding urea, drying, forming and roasting the material after the hydrothermal treatment to obtain the catalyst. The bulk phase catalyst obtained by the method is easy to excessively accumulate the surfactant metal, thereby influencing the formation of the pore structure of the bulk phase catalyst and reducing the pore volume and the specific surface area of the catalyst.
CN101733120A discloses a multi-metal bulk catalyst with a layered structure, and CN106268850A discloses a hydrofinishing multi-metal bulk catalyst for ultra-deep desulfurization and denitrification and a preparation method thereof, wherein the catalysts comprise transition metals and cheap metals, and the cost of the bulk catalyst is reduced. However, since there is a certain interaction between the inexpensive metal component and the active metal component, the space for increasing the activity is limited. CN201811411697.6 discloses a multi-metal non-supported hydrorefining catalyst, a preparation method and application thereof, wherein a soluble salt solution containing at least one + 3-valent metal and an alkaline precipitator solution are reacted and aged to obtain a colloid A containing + 3-valent metal; adding soluble salts of at least one VIII group metal and at least one IVB group metal into the colloid A to be dissolved into a solution, then adding an alkaline precipitator solution to carry out precipitation reaction, filtering and washing a product to obtain a catalyst precursor B, dissolving two soluble salts of VIB group metals into water to prepare a solution, adding the solution into the catalyst precursor B to carry out ion exchange reaction, and filtering, washing, drying and roasting the product to obtain the multi-metal non-supported hydrofining catalyst. The method introduces cheap + 3-valent metal, changes the IVB group metal introduction method, can effectively weaken strong interaction between the cheap + 3-valent metal and active metal, but does not increase the pore volume and specific surface area and improve the pore distribution.
CN101172261A discloses a preparation method of a catalyst composition. The sodium metaaluminate solution and the salt mixed solution containing Ni and W components are adopted for parallel flow reaction to generate a precipitate. CN110038581A discloses a method for preparing a hydrofining catalyst. The hydrorefining catalyst is prepared by two-step precipitation, wherein sodium tungstate alkaline solution and sodium molybdate alkaline solution are respectively used as precipitating agents for precipitation, the two methods both adopt sodium ion-containing salt as the precipitating agent, but the precipitate generated by the method contains a certain amount of sodium ions, the residual sodium ions cause poor cohesiveness of materials, and the residual sodium ions also cause small pore volume and small specific surface area of the catalyst.
The existing coprecipitation method is mainly characterized in that ammonia water is used as a precipitator and soluble salt containing nitrogen is used as a raw material, the precipitation mode and the gelling condition are changed to improve the distribution of hydrogenation active metals and the interaction relation among different hydrogenation active metals, but the problems of small pore volume and specific surface area of a bulk phase catalyst, small pore diameter of the catalyst (the pore diameter distribution is mainly concentrated below 8 nm), pollution in catalyst preparation, high preparation cost and the like are not solved. Especially, when a cheap sodium-containing raw material is adopted, the colloid forming material is loose and is difficult to form, and the catalyst has more pores.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a hydrofining catalyst for heavy diesel oil fractions. The catalyst prepared by the method has low cost, clean and pollution-free preparation process, large pore volume and pore diameter, high hydrodesulfurization and hydrodenitrogenation reaction performance and is particularly suitable for ultra-deep hydrodesulfurization and denitrogenation reactions of heavy diesel oil fractions.
The preparation method of the heavy diesel oil fraction hydrofining catalyst comprises the following steps:
(1) preparing nickel, tungsten and aluminum containing precipitates: carrying out parallel flow gelling reaction on a mixed solution containing Ni, Al, organic acid and organic alcohol, a sodium tungstate solution and a precipitator, and filtering the slurry I to obtain a filter cake;
(2) preparing a molded product: mixing the filter cake obtained in the step (1) with a mixed solution containing Ni and Al to obtain a solid-liquid mixture, adding the solid-liquid mixture, a sodium molybdate solution and a precipitator into a reaction tank in a concurrent flow manner for gelling reaction, aging the slurry II, and carrying out solid-liquid separation, drying and molding after aging;
(3) and desalting the molded product, washing, drying and roasting to obtain the hydrofining catalyst.
The Ni and Al components in the step (1) are soluble metal salts of the components, preferably metal salts without nitrogen elements; for example, the nickel salt can be one or more of nickel sulfate, nickel chloride and the like; the aluminum salt may be one or more of aluminum chloride, aluminum sulfate, and the like.
The mixed solution containing Ni, Al, organic acid and organic alcohol in the step (1), wherein the mass concentration of Ni in NiO is 3-80 g/L, preferably 5-70 g/L, and Al in Al2O3The mass concentration is 2-70 g/L, preferably 3-60 g/L.
The mol ratio of the organic acid to the organic alcohol in the step (1) is 0.1: 1-1: 0.1, preferably 0.2: 1-1: 0.2; the molar ratio of the total moles of the organic acid and the organic alcohol to the Ni is 0.2: 1-2: 1, preferably 0.3: 1-1.7: 1.
in the method of the present invention, the weight of the Ni introduced in step (1) is 20 to 80%, preferably 30 to 70%, of the weight of Ni in the bulk hydrofining catalyst.
In the method of the invention, the weight of the Al introduced in the step (1) accounts for 30-80%, preferably 35-75% of the weight of the Al in the bulk phase hydrofining catalyst.
The organic acid in the step (1) is selected from one or more carboxylic acids with carbon number of C2-C8, is further selected from one or more of malic acid, citric acid, isocitric acid, tartaric acid, oxalic acid, succinic acid, salicylic acid, lactic acid, beta-hydroxybutyric acid, maleic acid, glutaric acid, adipic acid, benzoic acid or malonic acid, and is preferably selected from one or more of malic acid, citric acid, tartaric acid, oxalic acid, succinic acid, salicylic acid or maleic acid.
The organic alcohol in the step (1) is selected from one or more of C2-C5 fatty alcohol and C2-C10 dihydric alcohol; further selected from one or more of ethanol, isopropanol, butanol, pentanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, diethylene methyl glycol, diethylene ethyl glycol, diethylene allyl glycol, and diethylene butyl glycol; more preferably one or more of ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, diethylene glycol, or diethylene butyl glycol.
The precipitant in step (1) and step (2) may be an aqueous solution of a basic compound without nitrogen element, the basic compound may be one or more of sodium hydroxide, sodium bicarbonate or sodium carbonate, and the concentration and the amount of the precipitant solution may be adjusted according to the actual preparation requirement.
In the sodium tungstate solution in the step (1), W is WO3The mass concentration is 5-100 g/L, preferably 10-90 g/L.
The gelling reaction conditions in the step (1) are as follows: the gelling temperature is 30-100 ℃, the gelling time is 0.5-5.0 hours, preferably 0.5-3.0 hours, and the pH value is controlled to be 7.0-10.0.
In the mixed solution containing Ni and Al in the step (2), the mass concentration of Ni in NiO is 3-90 g/L, preferably 5-80 g/L, and Al in Al2O3The mass concentration is 1-60 g/L, preferably 3-50 g/L.
In the sodium molybdate solution in the step (2), Mo is MoO3The mass concentration is 2-60 g/L, preferably 3-50 g/L.
The gelling reaction conditions in the step (2) are as follows: the gelling temperature is 30-100 ℃, the gelling time is 0.5-5.0 hours, preferably 0.5-3.0 hours, and the pH value is 10.0-12.0.
In the method of the invention, the aging conditions in the step (2) are as follows: the aging temperature is 30-90 ℃, the aging time is 1-5 hours, and the pH value is 7.0-10.0. The aging is generally carried out under stirring.
In the method of the present invention, the aging conditions in the step (2) are preferably performed as follows, and the first step is atmospheric aging: the aging temperature is 30-90 ℃, preferably 40-80 ℃, 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; and (2) second-step high-pressure aging: the temperature is 100-195 ℃, preferably 100-190 ℃, the time is 0.1-4.0 hours, preferably 0.3-3.0 hours, the pressure is not less than 10MPa, preferably 10-15 MPa, and the pH value is 10.0-13.0. The mild conditions in the first-step aging process are more favorable for generating uniform particle size, the material phase structure in the first-step aging process generates a regular body in the aging process in a closed environment, the microscopic form of the material is changed under the action of higher temperature and pressure in the closed environment, the material phase is converted from the regular body to an irregular body formed by irregular sheet accumulation, and the change of the structure enables sodium ions in the material phase to be transferred to the surface of the material phase, so that the next-step desalting treatment is more favorable, the specific surface area of a bulk phase catalyst is increased, the pore structure is improved, more active metals are exposed on the surface of the catalyst, and more hydrogenation active centers are generated on the surface of the catalyst.
And (3) drying at 50-140 ℃ for 0.5-24 hours.
The forming process in the step (2) is well known in the field of catalyst preparation, an extrusion aid and a peptizing agent are generally added in the extrusion forming process, the extrusion aid can be one or more of sesbania powder, carbon black, graphite powder or cellulose, the peptizing agent is one or more acid solutions containing hydrochloric acid, sulfuric acid, acetic acid and the like, and the amount of the extrusion aid accounts for 1wt% -10 wt% of the total dry material basis.
In the method of the present invention, the desalting treatment process in step (3): curing is carried out firstly, and then salt precipitated on the surface of the formed object can be removed by washing, wherein the curing condition is that the temperature is 5-100 ℃, preferably 10-95 ℃, and the time is 10-100 hours, preferably 24-90 hours.
In the method of the present invention, the desalting treatment in step (3) is preferably performed as follows: in the first stage, the temperature is 60-90 ℃, the curing is carried out for 5-60 hours, preferably 8-55 hours, so that hydrated sodium ions are separated out and vacancies are reserved; and in the second stage, the temperature is 10-30 ℃, the time is 1-48 hours, preferably 2-42 hours, vacancy retention and shrinkage are promoted, the pore volume of the catalyst is increased, the catalyst has good mechanical strength, then the precipitated salt is removed by washing, and solvents with good dissolving capacity for sodium salts, such as water, ethanol and the like, can be adopted in the washing process.
In the method of the present invention, the drying and baking in step (3) may be performed under conventional conditions in the art, such as drying at 50-200 ℃ for 1-48 hours, and baking at 450-600 ℃ for 0.5-24 hours, preferably 1-8 hours.
The catalyst can be prepared into shapes of sheet, sphere, cylinder strip, special-shaped strip (clover and clover) and the like according to requirements.
The hydrofining catalyst provided by the invention is a bulk hydrofining catalyst, and comprises a hydrogenation active metal component WO3NiO and MoO3And alumina, wherein the total content of Ni, W and Mo in terms of oxides is 50-95%, preferably 55-85%, and the content of alumina is 5-50%, preferably 15-50%, based on the weight of the oxidation state hydrofining catalyst.
In the hydrofining catalyst of the invention, the molar ratio of W/Mo is 1: 5-27: 1, preferably 1: 3-24: 1, the molar ratio of Ni/(Mo + W) is 1: 12-18: 1, preferably 1: 10-16: 1; na in catalyst2The O content is less than 0.12%, preferably less than 0.10%.
The specific surface area of the hydrofining catalyst is 180-500 m2The pore volume is 0.20-0.80 mL/g.
The pore size distribution of the hydrorefining catalyst of the invention is as follows: the pore volume of pores with the diameter of less than 4nm accounts for 1-10% of the total pore volume, the pore volume of pores with the diameter of 4-10 nm accounts for 18-48% of the total pore volume, the pore volume of pores with the diameter of 10-15 nm accounts for 24-54% of the total pore volume, and the pore volume of pores with the diameter of more than 15nm accounts for 15-38% of the total pore volume; preferred pore size distributions are as follows: the pore volume of pores with the diameter of less than 4nm accounts for 2-8% of the total pore volume, the pore volume of pores with the diameter of 4-10 nm accounts for 20-46% of the total pore volume, the pore volume of pores with the diameter of 10-15 nm accounts for 26-52% of the total pore volume, and the pore volume of pores with the diameter of more than 15nm accounts for 18-36% of the total pore volume.
The relation among the active metal content, the pore volume, the specific surface area and the pore distribution of the hydrofining catalyst is as follows: when the active metal is 50-70%, the specific surface area is 300-500 m2The pore volume is 0.43-0.80 mL/g, the pore volume with the diameter of more than 10nm accounts for more than 57 percent of the total pore volume, and the specific surface area is 180-300 m when the active metal accounts for 70-95 percent2A pore volume of 0.20 to 0.43mL/g,the pore volume with the diameter of more than 10nm accounts for more than 48 percent of the total pore volume.
The hydrofining catalyst has larger pore volume and specific surface area, is mainly distributed over 10nm, has higher hydrodesulfurization and hydrodenitrogenation reaction performances, and is particularly suitable for application in ultra-deep hydrodesulfurization and denitrogenation reactions of heavy diesel oil fractions.
According to the invention, through controlling the components of the precipitation slurry in the steps (1) and (2), the particle size obtained in the precipitation process is appropriate, the generated pore distribution is better controlled, and the active metal can be dispersed more uniformly. The catalyst is prepared from clean raw materials (soluble sodium salt) with relatively low price, and precipitates after gelling contain a large amount of sodium ions, so that the catalyst has small pore volume and is difficult to form due to the existence of the large amount of sodium ions. The inventor firstly retains sodium salt in the material in the forming process, and then carries out desalination treatment on the formed material to remove the precipitated sodium salt, in the process, due to the occupying effect of the sodium salt in the forming process, vacancy is more beneficial to the formation of a catalyst pore channel structure after sodium removal, pore distribution moves towards the direction of a large pore, the pore volume and the pore diameter of the catalyst are increased, the diffusion performance of the catalyst is improved, and the problems that the pore volume of the catalyst is smaller and the forming is difficult when clean raw materials are adopted to prepare a bulk phase catalyst in the prior art are solved. Meanwhile, the catalyst has the advantages of more active centers, uniform dispersion, high utilization rate and good mechanical strength, and greatly improves the desulfurization and denitrification capabilities when the bulk phase catalyst is used for processing heavy diesel distillate oil. The catalyst preparation process only needs to be carried out in the desalting treatment process, so that the times in the conventional catalyst preparation process are reduced, and the water consumption is reduced.
The application of the hydrofining catalyst in the ultra-deep hydrodesulfurization and denitrification reaction of the heavy diesel oil fraction has the following general reaction conditions: the temperature is 340-400 ℃, the hydrogen pressure is 3.0-10.0 MPa, and the liquid hourly space velocity is 0.3-4.0 h-1And the hydrogen-oil ratio is 300: 1-1000: 1.
Detailed Description
In the present invention, the specific surface area and the pore volume are measured by a low-temperature liquid nitrogen adsorption method, and the mechanical strength is measured by a side pressure method. In the present invention, wt% is a mass fraction and v% is a volume fraction.
Example 1
(1) An aqueous solution containing nickel chloride, aluminum chloride, citric acid and butanol (the mass concentration of Ni is 16g/L calculated by NiO, and Al is Al2O3The mass concentration is 12g/L, the mole ratio of citric acid to butanol is 0.8, the mole ratio of the total mole number of organic auxiliary agents to Ni is 1.0), 12wt% sodium hydroxide solution and sodium tungstate solution (W is WO)3The mass concentration is measured to be 40 g/L) and added into a gelling tank with a certain amount of water to carry out gelling reaction, the gelling temperature is 60 ℃, the pH value is 7.8, the gelling time is 1 hour, precipitate slurry I is obtained after gelling, and filter cake is obtained after the slurry I is filtered;
(2) the filter cake obtained in the step (1) and an aqueous solution containing Ni and Al (the mass concentration of Ni in NiO is 10g/L, and Al in Al2O3The calculated mass concentration is 10 g/L) are evenly mixed to obtain a solid-liquid mixture, and the solid-liquid mixture and a sodium molybdate solution (Mo is MoO)3Measured mass concentration of 12 g/L) and 12wt% of sodium hydroxide solution are added into a reaction tank in parallel for gelling reaction, the gelling temperature is 60 ℃, the pH value is 10.8, the gelling time is 1 hour, slurry II is obtained, aging is carried out, the aging temperature is 75 ℃, the pH value is 8.0, after aging is 2 hours, the slurry is filtered, a filter cake is dried for 10 hours at 80 ℃, and rolling and strip extrusion molding are carried out, so as to obtain a molded object;
(3) curing the formed product at 85 ℃ for 45 hours, cooling to 24 ℃, and continuing curing for 34 hours. Washing with deionized water for 3 times, drying the wet strip at 80 deg.C for 10 hr, and calcining at 500 deg.C for 4 hr to obtain catalyst A, whose composition and properties are shown in Table 1.
Example 2
(1) An aqueous solution containing nickel chloride, aluminum chloride, maleic acid and ethanol (the mass concentration of Ni in NiO is 14g/L, and Al in Al2O3The mass concentration is 8g/L, the mole ratio of maleic acid and ethanol is 1.8, the mole ratio of the total mole number of maleic acid and ethanol and Ni is 1.1), 12wt% sodium hydroxide solution and sodium tungstate solution (W is WO3Mass concentration of 44 g/L) and adding glue with a certain amount of waterCarrying out gelling reaction in a tank, wherein the gelling temperature is 55 ℃, the pH value is 8.3, the gelling time is 0.9 hour, precipitate slurry I is obtained after gelling is finished, and a filter cake is obtained after the slurry I is filtered;
(2) the filter cake obtained in the step (1) and an aqueous solution containing Ni and Al (the mass concentration of Ni is 16g/L in terms of NiO, and Al is Al2O3The measured mass concentration is 8 g/L) are evenly mixed to obtain a solid-liquid mixture, and the solid-liquid mixture and a sodium molybdate solution (Mo is MoO)3The measured mass concentration is 10 g/L) and 10wt% of sodium hydroxide solution are added into a reaction tank in a concurrent flow manner for gelling reaction, the gelling temperature is 58 ℃, the pH value is 11.7, the gelling time is 1.1 hour, slurry II is obtained, aging is carried out, the aging temperature is 72 ℃, the pH value is 7.5, after aging is carried out for 2.2 hours, the slurry is filtered, a filter cake is dried for 10 hours at 90 ℃, and rolling, strip extrusion and forming are carried out, so that a formed object is obtained;
(3) curing the formed product at 75 ℃ for 49 hours, cooling to 28 ℃, and continuing curing for 30 hours. Washing with deionized water for 2 times, drying wet strips at 85 deg.C for 13 hr, and calcining at 540 deg.C for 5 hr to obtain catalyst B, whose composition and properties are shown in Table 1.
Example 3
(1) Mixing aqueous solution containing nickel sulfate, aluminum chloride solution, tartaric acid and propylene glycol (mass concentration of Ni is 18g/L calculated as NiO, and Al is Al2O3The mass concentration is 12g/L, the molar ratio of tartaric acid to propylene glycol is 1.8, the total number of moles of organic auxiliary agent added to the molar ratio of Ni in the mixed solution is 0.9), 10wt% of sodium hydroxide solution and sodium tungstate solution (W is WO)3The measured mass concentration is 38 g/L) and added into a gelling tank with a certain amount of water to carry out gelling reaction, the gelling temperature is 65 ℃, the pH value is 7.6, the gelling time is 0.8 hour, precipitate slurry I is obtained after gelling is finished, and a filter cake is obtained after the slurry I is filtered;
(2) the filter cake obtained in the step (1) and an aqueous solution containing Ni and Al (the mass concentration of Ni in NiO is 14g/L, and Al in Al2O3The calculated mass concentration is 9 g/L) are evenly mixed to obtain a solid-liquid mixture, and the solid-liquid mixture and a sodium molybdate solution (Mo is MoO)3Calculated mass concentration of 9 g/L) and 8wt% of hydrogen hydroxideAdding sodium solution into a reaction tank in a concurrent flow manner for gelling reaction, wherein the gelling temperature is 65 ℃, the pH value is 11.0, and the gelling time is 1.3 hours to obtain slurry II, aging the slurry II at the aging temperature of 78 ℃ and the pH value of 7.6 for 1.6 hours, then continuing aging the precipitate slurry under high pressure at the pressure of 12MPa, the aging temperature of 150 ℃, the aging time of 1.8 hours and the pH value of 12.4, filtering the slurry after aging, drying a filter cake at 70 ℃ for 12 hours, rolling and extruding the filter cake to form a formed product;
(3) and curing the formed product at 70 ℃ for 48 hours, cooling to 20 ℃, and continuing curing for 32 hours. Washing with deionized water for 2 times, drying the wet strip at 70 deg.C for 14 hr, and calcining at 550 deg.C for 4 hr to obtain catalyst C, the composition and properties of which are shown in Table 1.
Example 4
(1) Mixing an aqueous solution containing nickel chloride, aluminum sulfate solution, succinic acid and propylene glycol (mass concentration of Ni in NiO is 12g/L, and Al in Al2O3The mass concentration is 19g/L, the molar ratio of succinic acid to propylene glycol is 2.5, the total number of moles of organic auxiliary agent added to the molar ratio of Ni in the mixed solution is 1.3), 8wt% sodium hydroxide solution and sodium tungstate solution (W is WO)3The mass concentration is 28 g/L) and added into a gelling tank with a certain amount of water to carry out gelling reaction, the gelling temperature is 70 ℃, the pH value is 8.3, the gelling time is 1.2 hours, precipitate slurry I is obtained after gelling, and filter cake is obtained after the slurry I is filtered;
(2) the filter cake obtained in the step (1) and an aqueous solution containing Ni and Al (the mass concentration of Ni in NiO is 10g/L, and Al in Al2O3The calculated mass concentration is 20 g/L) are evenly mixed to obtain a solid-liquid mixture, and the solid-liquid mixture and a sodium molybdate solution (Mo is MoO)311 g/L) and 15wt% of sodium carbonate solution are added into a reaction tank in parallel for gelling reaction, the gelling temperature is 55 ℃, the pH value is 10.2, the gelling time is 1.3 hours, slurry II is obtained, aging is carried out, the aging temperature is 78 ℃, the pH value is 8.0, after 2.1 hours of aging, the precipitate slurry is continuously aged under high pressure, the pressure is 12.5MPa, the aging temperature is 180 ℃, the aging time is 2.0 hours, the pH value is 12.2, and the precipitate slurry is aged and cementedFiltering the slurry, drying the filter cake at 100 ℃ for 8 hours, rolling and extruding to form a formed product;
(3) and curing the formed product at 85 ℃ for 46 hours, cooling to 15 ℃, and continuing curing for 29 hours. Washing with deionized water for 2 times, drying the wet strip at 100 deg.C for 7 hr, and calcining at 510 deg.C for 5 hr to obtain catalyst D, the composition and properties of which are shown in Table 1.
Example 5
(1) Mixing aqueous solution containing nickel chloride, aluminum chloride solution, citric acid and ethanol (mass concentration of Ni in NiO is 22g/L, and Al in Al2O3The mass concentration is 7g/L, the mole ratio of citric acid to ethanol is 1.8, the mole ratio of the total mole number of organic auxiliary agents to Ni is 1.3), 10wt% sodium hydroxide solution and sodium tungstate solution (W is WO)3The mass concentration is 32 g/L) and added into a gelling tank with a certain amount of water to carry out gelling reaction, the gelling temperature is 70 ℃, the pH value is 7.9, the gelling time is 0.9 hour, precipitate slurry I is obtained after gelling, and filter cake is obtained after the slurry I is filtered;
(2) the filter cake obtained in the step (1) and an aqueous solution containing Ni and Al (the mass concentration of Ni is 18g/L in terms of NiO, and Al is Al2O3The calculated mass concentration is 7 g/L) are evenly mixed to obtain a solid-liquid mixture, and the solid-liquid mixture and a sodium molybdate solution (Mo is MoO)3Measured mass concentration of 14 g/L) and 12wt% of sodium hydroxide solution are added into a reaction tank in parallel for gelling reaction, the gelling temperature is 55 ℃, the pH value is 11.6, the gelling time is 1.3 hours, slurry II is obtained, aging is carried out, the aging temperature is 75 ℃, the pH value is 8.0, after aging is carried out for 2.6 hours, the slurry is filtered, a filter cake is dried for 11 hours at 85 ℃, and rolling, strip extrusion and forming are carried out, so that a formed product is obtained;
(3) the shaped product was cured at 65 ℃ for 68 hours, washed with deionized water 2 times, the wet strip was dried at 80 ℃ for 10 hours, and calcined at 560 ℃ for 3.5 hours to give the final catalyst E, the composition, main properties and pore distribution of which are shown in table 1.
Example 6
(1) Mixing nickel chloride, aluminum chloride solution, tartaric acid and ethanol (mass concentration of Ni in NiO is 16g/L, and Al in Al)2O39g/L in mass concentration, 1.8 in molar ratio of tartaric acid to ethanol, 1.1 in molar ratio of total number of moles of organic auxiliary to Ni, 12wt% sodium carbonate solution and sodium tungstate solution (W in WO)3The mass concentration is 34 g/L) and added into a gelling tank with a certain amount of water to carry out gelling reaction, the gelling temperature is 50 ℃, the pH value is 7.7, the gelling time is 0.9 hour, precipitate slurry I is obtained after gelling, and filter cake is obtained after the slurry I is filtered;
(2) the filter cake obtained in the step (1) and an aqueous solution containing Ni and Al (the mass concentration of Ni in NiO is 20g/L, and Al in Al2O3The calculated mass concentration is 11 g/L) are evenly mixed to obtain a solid-liquid mixture, and the solid-liquid mixture and a sodium molybdate solution (Mo is MoO)3The measured mass concentration is 10 g/L) and 8wt% of sodium carbonate solution are added into a reaction tank in parallel to carry out gelling reaction, the gelling temperature is 50 ℃, the pH value is 11.2, the gelling time is 1.3 hours, slurry II is obtained and is aged, the aging temperature is 75 ℃, the pH value is 7.6, after 2.1 hours of aging, the precipitate slurry is continuously aged under high pressure, the pressure is 10.8MPa, the aging temperature is 160 ℃, the aging time is 2.0 hours, the pH value is 11.2, after aging, slurry filtration is carried out, a filter cake is dried for 11 hours at 85 ℃, and rolling and strip extrusion molding are carried out, so as to obtain a molded object;
(3) the shaped article was cured at 80 ℃ for 77 hours, washed with deionized water 2 times, the wet strip was dried at 80 ℃ for 10 hours, and calcined at 550 ℃ for 5 hours to give the final catalyst E, the composition, main properties and pore distribution of which are shown in table 1.
Comparative example 1
According to the method disclosed in CN101172261 and in example 1, the catalyst composition is unchanged, and the catalyst G is prepared by the following specific processes: respectively adding nickel chloride and ammonium metatungstate into a dissolving tank 1 filled with deionized water, dissolving to prepare an acidic working solution A, wherein the mass concentration of Ni in the solution is 26g/L calculated by NiO, and W is calculated by WO3The mass concentration is 40g/L, sodium metaaluminate is added into a dissolving tank 2 filled with deionized water to prepare an alkaline working solution B, and Al in the solution is Al2O3The mass concentration is 22 g/L. Deionized water was added to the reaction tank and the temperature was raised to 60 ℃. Under stirringUnder the condition of (1), the solution A and the solution B are added into a reaction tank in a cocurrent manner to form the gel, the gelling temperature is 60 ℃, the gelling time is 1 hour, and the pH value of the slurry in the gelling process is 7.6. Aging for 2 hours after the gelling is finished. Then filtering, adding 600ml of purified water and 12G of molybdenum trioxide into the filter cake, pulping, uniformly stirring, filtering, drying the filter cake at 80 ℃ for 10 hours, extruding into strips, forming, washing with purified water for 3 times, drying wet strips at 80 ℃ for 10 hours, and roasting at 500 ℃ for 4 hours to obtain the final catalyst G, wherein the composition and the main properties are shown in Table 1.
Comparative example 2
Reference catalyst H was prepared according to the procedure of example 1, with the compositional proportions of catalyst A in Table 1, and the formed strands were not desalted.
(1) An aqueous solution containing nickel chloride, aluminum chloride, citric acid and butanol (the mass concentration of Ni is 16g/L calculated by NiO, and Al is Al2O3The mass concentration is 12g/L, the mole ratio of citric acid to butanol is 0.8, the mole ratio of the total mole number of organic auxiliary agents to Ni is 1.0), 12wt% sodium hydroxide solution and sodium tungstate solution (W is WO)3The mass concentration is measured to be 40 g/L) and added into a gelling tank with a certain amount of water to carry out gelling reaction, the gelling temperature is 60 ℃, the pH value is 7.8, the gelling time is 1 hour, precipitate slurry I is obtained after gelling, and filter cake is obtained after the slurry I is filtered;
(2) the filter cake obtained in the step (1) and an aqueous solution containing Ni and Al (the mass concentration of Ni in NiO is 10g/L, and Al in Al2O3The calculated mass concentration is 10 g/L) are evenly mixed to obtain a solid-liquid mixture, and the solid-liquid mixture and a sodium molybdate solution (Mo is MoO)3Calculated mass concentration of 12 g/L) and 12wt% of sodium hydroxide solution are added into a reaction tank in parallel for gelling reaction, the gelling temperature is 60 ℃, the pH value is 10.8, the gelling time is 1 hour, slurry II is obtained, aging is carried out, the aging temperature is 75 ℃, the pH value is 8.0, after aging is 2 hours, the slurry is filtered, a filter cake is dried for 10 hours at 80 ℃, and a formed product is not obtained after rolling, strip extrusion and washing. (ii) a
(3) The powder was calcined at 500 ℃ for 4 hours to give the final catalyst H, the composition, the main properties and the pore distribution of which are shown in Table 1.
Comparative example 3
The same reference agent as the catalyst of example 1 was prepared according to the catalyst preparation method disclosed in CN 106179380A. Adding aluminum chloride and nickel chloride solution into the dissolving tank 1 to prepare working solution A, wherein the mass concentration of Ni in the mixed solution A is 26g/L in terms of NiO, and Al in terms of Al2O3The mass concentration is 12 g/L. Adding aluminum chloride, ammonium metatungstate and ammonium molybdate into the dissolving tank 2 to prepare a working solution B, and mixing W in the solution B with WO3The mass concentration is 40g/L, Mo is MoO3The mass concentration is 12g/L, Al is Al2O3The mass concentration is 10 g/L. Adding 10wt% ammonia water into the solution A under stirring, keeping the gelling temperature at 60 ℃, controlling the pH value at 7.6 after finishing gelling, and controlling the gelling time at 60 minutes to generate nickel-aluminum-containing precipitate slurry I. Adding 500mL of deionized water into a reaction tank, adding 10wt% ammonia water and the solution B into the reaction tank in a cocurrent manner, keeping the gelling temperature at 60 ℃, controlling the pH value to be 7.6 in the cocurrent gelling reaction process, and controlling the gelling time to be 1.0 hour to generate precipitate slurry II containing tungsten, molybdenum and aluminum. Mixing the two types of slurry containing the precipitate, aging for 2.0 hours at 72 ℃, controlling the pH value at 7.8 after aging, then filtering, and carrying out hydrothermal treatment on a filter cake under the water vapor containing urea, wherein the hydrothermal treatment conditions are as follows: the mol ratio of the total amount of the urea and the active metal atoms is 3:1, the temperature is 230 ℃, the pressure is 3.5MPa, the processing time is 4 hours, the materials after the hydro-thermal treatment are dried for 10 hours at the temperature of 80 ℃, rolled and extruded into strips for forming. Washed 5 times with deionized water at room temperature. The wet strands were then dried at 80 ℃ for 10 hours and calcined at 500 ℃ for 4 hours to give catalyst I. The catalyst composition and the main properties are shown in table 1.
Comparative example 4
Reference J, having the same composition as the catalyst of example 1, was prepared according to the catalyst preparation method disclosed in CN 201810037402.7.
Respectively adding nickel chloride and aluminum chloride into a dissolving tank 1 filled with deionized water to prepare an acid solution A, wherein the mass concentration of Ni in the acid solution A is 26g/L calculated by NiO, and Al is Al2O3 The mass concentration is 12 g/L. Are respectively provided withAdding ammonium metatungstate and aluminum chloride into a dissolving tank 2 filled with deionized water to prepare a mixed solution B, wherein W in the solution B is WO3The mass concentration is 20g/L, Al is Al2O3The mass concentration is 10 g/L. Adding deionized water into a reaction tank, and adding WO serving as mass concentration3And adding the sodium tungstate alkaline solution and the acidic solution A with the mass concentration of 20g/L into a reaction tank in a concurrent flow manner, keeping the gelling temperature at 60 ℃, controlling the pH value at 7.6 in the concurrent flow gelling reaction process, and controlling the gelling time at 60 minutes to generate precipitate slurry I containing nickel, tungsten and aluminum. And ageing the obtained precipitate slurry I under stirring, wherein the stirring speed is 220 rpm, the ageing temperature is 75 ℃, the ageing pH value is controlled at 7.0, and the ageing time is 0.8 hour. After the aging is finished, Mo is treated by MoO3Adding an alkaline solution of sodium molybdate with the mass concentration of 12g/L and an acidic solution B into the slurry I in a concurrent flow manner, keeping the gelling temperature at 60 ℃, controlling the pH value at 7.8 in the concurrent flow gelling reaction process, controlling the gelling time at 2.0 hours to obtain a nickel, tungsten, molybdenum and aluminum precipitate slurry II, aging the precipitate slurry II under the stirring condition, controlling the stirring speed at 370 revolutions per minute, the aging temperature at 75 ℃, controlling the pH value at 8.2 and the aging time at 3.0 hours, filtering the aged slurry, drying a filter cake at 8 ℃ for 10 hours, rolling, extruding and forming. Washed 5 times with deionized water at room temperature. The wet strands were then dried at 80 ℃ for 10 hours and calcined at 500 ℃ for 4 hours to give catalyst J. The catalyst composition and properties are shown in table 1.
Example 7
This example is an evaluation experiment of the activity of the catalyst of the present invention and is compared with a comparative catalyst. A comparative evaluation test is carried out on a 200mL small hydrogenation device by adopting the catalyst A, B, D, E of the invention and the comparative catalyst G, I, J, catalytic diesel oil with high nitrogen content and high desulfurization difficulty is adopted as a test raw material, and the main properties of the raw material are shown in Table 2. Catalyst activity evaluation process conditions: the hydrogen partial pressure is 6.4MPa, the reaction temperature is 360 ℃, and the liquid hourly space velocity is 2.0h-1The hydrogen-oil volume ratio was 500:1, and the evaluation results are shown in Table 3. The types of nitrides in the hydrorefined oil were measured by a gas chromatography-atomic emission spectrometry detector (GC-AED), and the results are shown in table 4.
As can be seen from Table 1, the catalyst prepared by using clean raw materials containing sodium salt has the advantages of less sodium oxide content, increased pore volume and specific surface area, and obviously increased macropores with the size of more than 10nm compared with the catalyst of the comparative example, as can be seen from Table 2, the nitrogen content of the raw oil used for catalyst activity evaluation is high, which also increases the difficulty of ultra-deep hydrodesulfurization of the raw oil. As can be seen from tables 3-4, the catalyst provided by the invention has excellent hydrodenitrogenation activity when used for treating heavy diesel oil fractions, effectively eliminates the inhibition effect of nitrides on hydrodesulfurization reaction, and greatly improves deep hydrodesulfurization activity. The catalyst of the invention is used for processing and treating diesel oil fractions, and particularly has excellent ultra-deep hydrodesulfurization and denitrification performances when being used for treating heavy diesel oil fractions.
TABLE 1 compositions and Properties of catalysts prepared in examples and comparative examples
Figure DEST_PATH_IMAGE002
TABLE 1 (subsequent) catalyst compositions and Properties prepared in examples and comparative examples
Figure DEST_PATH_IMAGE004
TABLE 2 Primary Properties of the base oils
Figure DEST_PATH_IMAGE006
TABLE 3 evaluation results of catalyst Activity
Figure DEST_PATH_IMAGE008
TABLE 3 (continuous) evaluation results of catalyst Activity
Figure DEST_PATH_IMAGE010
TABLE 4 content of different nitrides in hydrorefined oils
Figure DEST_PATH_IMAGE012
Table 4 (continuation)
Catalyst numbering G I J
Nitrogen content in hydrofined oil, mug/g 97.2 85.4 24.5
1-MCB，µg/g 29.5 26.3 10.3
1，8-DMCB，µg/g 46.7 41.7 8.2
1，4，8-TMCB，µg/g 21.0 17.4 6.0
Note: the main nitrogen-containing compounds difficult to remove by hydrogenation and denitrification are Carbazole (CB), 1-methylcarbazole (1-MCB), 1, 8-dimethylcarbazole (1, 8-DMCB), 1, 4, 8-trimethylcarbazole (1, 4, 8-TMCB) and the like which have larger molecules and steric hindrance.

Claims (22)

1. A preparation method of a heavy diesel oil fraction hydrofining catalyst is characterized by comprising the following steps: (1) preparing nickel, tungsten and aluminum containing precipitates: carrying out parallel flow gelling reaction on a mixed solution containing Ni, Al, organic acid and organic alcohol, a sodium tungstate solution and a precipitator, and filtering the slurry I to obtain a filter cake; (2) preparing a molded product: mixing the filter cake obtained in the step (1) with a mixed solution containing Ni and Al to obtain a solid-liquid mixture, adding the solid-liquid mixture, a sodium molybdate solution and a precipitator into a reaction tank in a concurrent flow manner for gelling reaction, aging the slurry II, and carrying out solid-liquid separation, drying and molding after aging; (3) and desalting the molded product, washing, drying and roasting to obtain the hydrofining catalyst.
2. The method of claim 1, wherein: in the mixed solution containing Ni, Al, organic acid and organic alcohol in the step (1), the mass concentration of Ni in NiO is 3-80 g/L, and Al in Al2O3The mass concentration is 2-70 g/L.
3. The method of claim 1, wherein: the mol ratio of the organic acid to the organic alcohol in the step (1) is 0.1: 1-1: 0.1; the molar ratio of the total moles of the organic acid and the organic alcohol to the Ni is 0.2: 1-2: 1.
4. the method of claim 1, wherein: the weight of the introduced Ni in the step (1) accounts for 20-80% of the weight of Ni in the catalyst; the weight of the introduced Al in the step (1) accounts for 30-80% of the weight of Al in the catalyst.
5. The method of claim 1, wherein: the organic acid in the step (1) is selected from one or more of carboxylic acids with carbon number of C2-C8, and is further selected from one or more of malic acid, citric acid, isocitric acid, tartaric acid, oxalic acid, succinic acid, salicylic acid, lactic acid, beta-hydroxybutyric acid, maleic acid, glutaric acid, adipic acid, benzoic acid or malonic acid.
6. The method of claim 1, wherein: the organic alcohol in the step (1) is selected from one or more of C2-C5 fatty alcohol and C2-C10 dihydric alcohol; further comprises one or more selected from ethanol, isopropanol, butanol, pentanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, diethylene methyl glycol, diethylene ethyl glycol, diethylene allyl glycol, and diethylene butyl glycol.
7. The method of claim 1, wherein: in the sodium tungstate solution in the step (1), W is WO3The mass concentration is 5-100 g/L.
8. The method of claim 1, wherein: the precipitant in the step (1) and the step (2) is an alkaline compound aqueous solution without nitrogen element, and the alkaline compound is one or more of sodium hydroxide, sodium bicarbonate or sodium carbonate.
9. The method of claim 1, wherein: the gelling reaction conditions in the step (1) are as follows: the gelling temperature is 30-100 ℃, the gelling time is 0.5-5.0 hours, and the pH value is controlled to be 7.0-10.0.
10. The method of claim 1, wherein: in the mixed solution containing Ni and Al in the step (2), the mass concentration of Ni in NiO is 3-90 g/L, and Al in Al2O3The mass concentration is 1-60 g/meter.
11. The method of claim 1, wherein: in the sodium molybdate solution in the step (2), Mo is MoO3The mass concentration is 2-60 g/L.
12. The method of claim 1, wherein: the gelling reaction conditions in the step (2) are as follows: the gelling temperature is 30-100 ℃, the gelling time is 0.5-5.0 hours, and the pH value is 10.0-12.0.
13. The method of claim 1, wherein: the aging condition of the step (2): the aging temperature is 30-90 ℃, the aging time is 1-5 hours, and the pH value is 7.0-10.0.
14. The method of claim 1, wherein: the aging condition of the step (2) is carried out according to the following mode, wherein the first step is normal pressure aging: the aging temperature is 30-90 ℃, preferably 40-80 ℃, the aging time is 1-6 hours, and the pH value is 6.5-10.0; and (2) second-step high-pressure aging: the temperature is 100-195 ℃, the time is 0.1-4.0 hours, the pressure is not less than 10MPa, preferably 10-15 MPa, and the pH value is 10.0-13.0.
15. The method of claim 1, wherein: the desalting treatment process in the step (3): curing is carried out firstly, and then salt precipitated on the surface of the formed object can be removed by washing, wherein the curing condition is that the temperature is 5-100 ℃ and the time is 10-100 hours.
16. The method of claim 1, wherein: the desalting treatment in the step (3) is carried out as follows: in the first stage, the temperature is 60-90 ℃, and the curing is carried out for 5-60 hours; the temperature of the second stage is 10-30 ℃, and the time is 1-48 hours; then, the precipitated salt was removed by washing.
17. A catalyst prepared according to any one of claims 1 to 16, wherein: the specific surface area of the hydrofining catalyst is 180-500 m2The pore volume is 0.20-0.80 mL/g; the pore size distribution is as follows: the pore volume of pores with the diameter of less than 4nm accounts for 1-10% of the total pore volume, the pore volume of pores with the diameter of 4-10 nm accounts for 18-48% of the total pore volume, the pore volume of pores with the diameter of 10-15 nm accounts for 24-54% of the total pore volume, and the pore volume of pores with the diameter of more than 15nm accounts for 15-38% of the total pore volume; the preferred pore size distribution is as follows: the pore volume of pores with the diameter of less than 4nm accounts for 2-8% of the total pore volume, the pore volume of pores with the diameter of 4-10 nm accounts for 20-46% of the total pore volume, the pore volume of pores with the diameter of 10-15 nm accounts for 26-52% of the total pore volume, and the pore volume of pores with the diameter of more than 15nm accounts for 18-36% of the total pore volume.
18. The catalyst of claim 17, wherein: the hydrofining catalyst is bulk hydrofining catalyst and comprises a hydrogenation active metal component WO3NiO and MoO3And alumina, wherein the total content of Ni, W and Mo in terms of oxides is 50-95% and the content of alumina is 5-50% based on the weight of the oxidation-state hydrofining catalyst.
19. The catalyst of claim 17, wherein: the relation among the active metal content, the pore volume, the specific surface area and the pore distribution of the hydrofining catalyst is as follows: when the active metal is 50-70%, the specific surface area is 300-500 m2The pore volume is 0.43-0.80 mL/g, the pore volume with the diameter of more than 10nm accounts for more than 57 percent of the total pore volume, and the specific surface area is 180-300 m when the active metal accounts for 70-95 percent2The pore volume is 0.20-0.43 mL/g, and the pore volume with the diameter of more than 10nm accounts for more than 48 percent of the total pore volume.
20. The catalyst of claim 17, wherein: the molar ratio of W/Mo is 1: 5-27: 1, the molar ratio of Ni/(Mo + W) is 1: 12-18: 1.
21. according to claimThe catalyst of claim 17, characterized in that: na in catalyst2The O content is less than 0.12%, preferably less than 0.10%.
22. The use of the catalyst prepared by the method according to any one of claims 1 to 16 in ultra-deep hydrodesulfurization and denitrification reactions of heavy diesel oil fractions under the following reaction conditions: the temperature is 340-400 ℃, the hydrogen pressure is 3.0-10.0 MPa, and the liquid hourly space velocity is 0.3-4.0 h-1And the hydrogen-oil ratio is 300: 1-1000: 1.
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