CN114433117B - Preparation method of heavy diesel fraction hydrofining catalyst - Google Patents

Preparation method of heavy diesel fraction hydrofining catalyst Download PDF

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CN114433117B
CN114433117B CN202011116861.8A CN202011116861A CN114433117B CN 114433117 B CN114433117 B CN 114433117B CN 202011116861 A CN202011116861 A CN 202011116861A CN 114433117 B CN114433117 B CN 114433117B
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catalyst
pore volume
acid
hours
aging
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CN114433117A (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 heavy diesel fraction hydrofining catalyst. The method comprises the following steps: (1) Mixing a mixed solution containing Ni, al, organic acid and organic alcohol, a sodium tungstate solution and a precipitator, performing parallel flow gelling reaction, and filtering 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 parallel flow for gelling reaction, ageing slurry II, and carrying out solid-liquid separation, drying and forming after ageing; (3) 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, larger pore volume and pore diameter, higher hydrodesulfurization and hydrodenitrogenation reaction performance, and is particularly suitable for being applied to ultra-deep hydrodesulfurization and denitrification reactions of heavy diesel oil fractions.

Description

Preparation method of heavy diesel fraction hydrofining catalyst
Technical Field
The invention relates to a preparation method of a heavy diesel fraction hydrofining catalyst.
Background
With the increasingly strict index of diesel products in all parts of the world, oil refining enterprises tend to achieve ultra-deep hydrodesulfurization of diesel by increasing the severity of the reaction, so that the production cost of the enterprises is increased, and the production profits of the enterprises are reduced. In order to not increase the oil refining cost and meet the index requirement of diesel products, 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 requirement of oil refining enterprises for producing new standard products due to the limitation of metal loading, and the unsupported catalyst with high hydrogenation activity can realize deep hydrodesulfurization of diesel by adopting a traditional hydrogenation device under a mild condition.
In particular, in recent years, in order to improve the market competitiveness of the catalyst and meet the requirements of increasingly strict environmental regulations, there is an urgent need to prepare the catalyst by using raw materials with relatively low price, and to use raw materials without nitrogen in the preparation process of the catalyst, so as to solve the problems of ammonia nitrogen and NO from the source X The pollution problem of the catalyst is reduced. The catalyst prepared by the impregnation method and the kneading method has high preparation cost and high wastewater treatment cost due to the fact that the catalyst cannot be used by sodium-containing raw materials with relatively low price. And the coprecipitation method can be used for preparing sodium-containing raw materials with relatively low price, so that the preparation cost of the catalyst and the wastewater treatment cost are greatly reduced. However, due to the introduction of a large amount of sodium ions, the sodium ions in the catalyst are difficult to remove, only the sodium ions on the surface of the catalyst can be removed, a 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 the 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 substituent groups such as 4, 6-dimethyldibenzothiophene, and the like), the reaction rate is greatly reduced because of the steric hindrance effect generated by methyl closely adjacent to sulfur atoms and the obvious inhibition effect of nitride on the hydrodesulfurization reaction. In the face of the limitations of the two ultra-deep desulfurization reactions, the development of a hydrogenation catalyst with high activity is required, the bulk phase catalyst is the catalyst with the highest hydrogenation activity center at present, the limitation of metal content is eliminated, the catalyst is mainly prepared by adopting a coprecipitation method, and active metals are exposed on the surface of the catalyst to provide the reaction activity center for reactant molecules. The bulk phase catalyst prepared by the prior method has smaller pore volume and smaller pore diameter, and macromolecular sulfides and nitrides can not smoothly enter the pore canal to perform hydrodenitrogenation and desulfurization reactions. Meanwhile, the small pore volume and specific surface area can cause the excessive accumulation of high-content active metal in the bulk phase catalyst on the surface of the catalyst, thereby reducing the generation of an active phase, lowering the activity of the catalyst, affecting the utilization rate of the active metal of the catalyst and improving the use cost of the catalyst.
CN1951561a discloses a method for preparing a hydrogenation catalyst by adopting coprecipitation, US 6,162,350 and 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 catalyst, a preparation method thereof and a hydrogenation catalyst comprising the bulk catalyst, wherein the catalysts in the above patents are all prepared by adopting the coprecipitation method, and the specific surface area, pore volume and pore diameter are smaller.
CN102049265A discloses a bulk hydrogenation catalyst, ammonium bicarbonate is added in the coprecipitation process, carbon dioxide is added in the coprecipitation process to generate carbonate or bicarbonate, and the method utilizes a certain amount of gas discharged in the roasting process, and the pore volume and specific surface area of the catalyst are changed under the impact of the gas. Both methods employ external impact to increase the surface of the bulk catalyst and improve pore distribution, but their effect is limited.
CN106179380a discloses a bulk hydrofining catalyst and a method for preparing the same. The method adopts a forward method to prepare nickel-aluminum mixed precipitate, adopts a parallel flow precipitation method to prepare tungsten, molybdenum and aluminum mixed precipitate, mixes the two, ages and filters the mixed precipitate to obtain a metal mixture, carries out steam treatment under proper conditions, adds urea, and carries out drying, molding and roasting on the material after the hydrothermal treatment to obtain the catalyst. The phase active metal in the bulk catalyst obtained by the method is easy to excessively accumulate, so that the formation of a pore structure of the bulk catalyst is affected, and the pore volume and the specific surface area of the catalyst are reduced.
CN101733120a discloses a multi-metal bulk catalyst with a layered structure, CN106268850a discloses a hydrofined multi-metal bulk catalyst for ultra-deep desulfurization and denitrification, and a preparation method thereof, wherein the catalysts comprise transition metal and cheap metal, and the cost of the bulk catalyst is reduced. But the activity enhancement space is limited due to some interaction between the inexpensive metal component and the active metal component. CN201811411697.6 discloses a multi-metal non-supported hydrofining catalyst, its preparation method and application, which comprises reacting and aging a soluble salt solution containing at least one +3 valent metal and an alkaline precipitant solution to obtain colloid a containing +3 valent metal; dissolving at least one soluble salt of VIII group metal and at least one soluble salt of IVB group metal into colloid A to form a solution, then adding an alkaline precipitant solution to perform precipitation reaction, filtering and washing a product to obtain a catalyst precursor B, dissolving soluble salts of two VIB group metals into water to prepare a solution, adding the catalyst precursor B to perform ion exchange reaction, filtering, washing, drying and roasting the product to obtain the multi-metal non-supported hydrofining catalyst. The method introduces cheap +3 metal, changes the IVB metal introduction method, and can effectively weaken the strong interaction between the cheap +3 metal and the active metal, but does not increase the pore volume and the specific surface area and improve the pore distribution.
CN101172261a discloses a process for preparing a catalyst composition. Sodium metaaluminate solution and mixed solution containing Ni and W components and salt are adopted to react in parallel to generate precipitate. CN110038581a discloses a process for preparing hydrofining catalysts. The hydrofining catalyst is prepared by adopting two steps of precipitation, and sodium tungstate alkaline solution and sodium molybdate alkaline solution are respectively used as precipitants for precipitation, and both the two methods adopt sodium ion-containing salt as the precipitants, but the precipitate generated by the method contains a certain amount of sodium ions, the residual sodium ions cause poor adhesiveness of materials, and the residual sodium ions also cause small pore volume and small specific surface area of the catalyst.
The existing coprecipitation method mostly adopts ammonia water as a precipitant and soluble salt containing nitrogen as raw materials, and improves the interaction relationship between the distribution of hydrogenation active metals and different hydrogenation active metals by changing a precipitation mode and an adhesive tape forming piece, but the problems of small pore volume and specific surface area of a bulk catalyst, small pore diameter of the catalyst (the pore diameter distribution is mainly concentrated below 8 nm), high preparation cost of the catalyst and the like are not solved. Especially when cheaper sodium-containing raw materials are adopted, the gel forming materials are loose and 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 heavy diesel fraction hydrofining catalyst. The catalyst prepared by the method has low cost, clean and pollution-free preparation process, larger pore volume and pore diameter, higher hydrodesulfurization and hydrodenitrogenation reaction performance, and is particularly suitable for being applied to ultra-deep hydrodesulfurization and denitrification reactions of heavy diesel oil fractions.
The preparation method of the heavy diesel fraction hydrofining catalyst comprises the following steps:
(1) Preparing a precipitate containing nickel, tungsten and aluminum: mixing a mixed solution containing Ni, al, organic acid and organic alcohol, a sodium tungstate solution and a precipitator, performing parallel flow gelling reaction, and filtering slurry I to obtain a filter cake;
(2) Preparing a formed 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 parallel flow for gelling reaction, ageing slurry II, and carrying out solid-liquid separation, drying and forming after ageing;
(3) 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) has the mass concentration of Ni calculated by NiO of 3-80 g/L, preferably 5-70 g/L, and Al calculated by Al 2 O 3 The mass concentration is 2-70 g/L, preferably 3-60 g/L.
The molar ratio of the organic acid to the organic alcohol in the step (1) is 0.1:1 to 1:0.1, preferably 0.2:1 to 1:0.2; the molar ratio of the total mole number of the organic acid and the organic alcohol to Ni is 0.2: 1-2: 1, preferably 0.3:1 to 1.7:1.
in the method of the present invention, the weight of Ni introduced in step (1) is 20 to 80% of the weight of Ni in the bulk hydrofining catalyst, preferably 30 to 70%.
In the method of the present invention, the weight of Al introduced in step (1) is 30 to 80% of the weight of Al in the bulk hydrofining catalyst, preferably 35 to 75%.
The organic acid in the step (1) is one or more selected from carboxylic acids with carbon number of C2-C8, and is further one or more selected from 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, preferably one or more selected from 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 with carbon number; further selected from one or more of ethanol, isopropanol, butanol, amyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, diethylene methyl glycol, diethylene ethyl glycol, diethylene propyl glycol, and diethylene butyl glycol; more preferably one or more of ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tributyl glycol, tetraethylene glycol, diethylene ethyl glycol or diethylene butyl glycol.
The precipitants in the step (1) and the step (2) can be alkaline compound aqueous solutions without nitrogen elements, the alkaline compound can be one or more of sodium hydroxide, sodium bicarbonate or sodium carbonate, and the concentration and the dosage of the precipitant solution can be adjusted according to the actual preparation requirement.
In the sodium tungstate solution in the step (1), W is WO 3 The mass concentration is 5-100 g/L, preferably 10-90 g/L.
The gelling reaction conditions described in step (1): the gel forming temperature is 30-100 ℃, the gel forming 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 terms of NiO is 3-90 g/L, preferably 5-80 g/L, and Al in terms of Al 2 O 3 The mass concentration is 1-60 g/L, preferably 3-50 g/L.
In the sodium molybdate solution in the step (2), mo is MoO 3 The mass concentration is 2-60 g/L, preferably 3-50 g/L.
The gelling reaction conditions described in step (2): the gel forming temperature is 30-100 ℃, the gel forming 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 described in step (2) are: 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 process of the present invention, the aging conditions described in step (2) are preferably carried out as follows, the first step of atmospheric aging: the aging temperature is 30-90 ℃, preferably 40-80 ℃, the aging time is 1-6 hours, preferably 1.2-5 hours, the pH value is 6.5-10.0, preferably 7.0-9.0; and step two, 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 conditions relaxed in the first aging process are more favorable for generating uniform particle size, the material phase structure in the first aging process generates regular bodies in the closed environment, the microscopic morphology of the material is changed under the action of higher temperature and pressure in the closed environment, the phase of the material is changed from the regular bodies to irregular bodies piled up in irregular sheets, the structural change enables sodium ions in the phase to be transferred to the surface of the phase, the next desalting treatment is more favorable, the specific surface area of the bulk phase catalyst is also favorably 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.
The drying temperature in the step (2) is 50-140 ℃ and the drying time is 0.5-24 hours.
The molding process in the step (2) is well known in the catalyst preparation field, an extrusion aid and a peptizing agent are generally added in the extrusion molding process, the extrusion aid can be one or more of sesbania powder, carbon black, graphite powder or cellulose and the like, the peptizing agent is generally one or more acid solutions containing hydrochloric acid, sulfuric acid, acetic acid and the like, and the consumption of the extrusion aid accounts for 1-10wt% of the total material dry basis.
In the method of the invention, the desalination treatment process of the step (3) comprises the following steps: the method comprises the steps of firstly carrying out health preservation, and then washing to remove salt precipitated on the surface of a formed product, wherein the health preservation 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 the step (3) is preferably performed as follows: the temperature of the first stage is 60-90 ℃, and the first stage is carried out for 5-60 hours, preferably 8-55 hours, so that sodium hydrate ions are separated out and vacancies are reserved; the second stage is at 10-30 deg.c for 1-48 hr, preferably 2-42 hr, to promote the vacancy to remain and shrink, make the catalyst Kong Rongzeng large and possess excellent mechanical strength, and the salt to be separated out is washed to eliminate, and water, ethanol and other solvent with excellent sodium salt dissolving capacity may be used in the washing process.
In the process of the present invention, the drying and firing in step (3) may be carried out under conditions conventional in the art, such as drying at 50 to 200℃for 1 to 48 hours and firing at 450 to 600℃for 0.5 to 24 hours, preferably 1 to 8 hours.
The catalyst of the invention can be prepared into shapes such as sheets, spheres, cylindrical strips, special-shaped strips (clover ) and the like according to the requirements.
The hydrofining catalyst provided by the invention is a bulk hydrofining catalyst and comprises a hydrogenation active metal component WO 3 NiO and MoO 3 And alumina, wherein the total content of Ni, W and Mo in terms of oxide is 50% -95%, preferably 55% -85%, and the content of alumina is 5% -50%, preferably 15% -50% based on the weight of the oxidized hydrofining catalyst.
The invention is thatIn the hydrofining catalyst of (2), the molar ratio of W/Mo is 1: 5-27: 1, preferably 1: 3-24: 1, ni/(Mo+W) molar ratio of 1: 12-18: 1, preferably 1: 10-16: 1, a step of; na in the catalyst 2 The O content is less than 0.12%, preferably less than 0.10%.
The specific surface area of the hydrofining catalyst is 180-500 m 2 And/g, wherein the pore volume is 0.20-0.80 mL/g.
The pore size distribution of the hydrofining catalyst of the present invention is as follows: the pore volume occupied by the pores with the diameter of below 4nm accounts for 1% -10% of the total pore volume, the pore volume occupied by the pores with the diameter of 4-10 nm accounts for 18% -48% of the total pore volume, the pore volume occupied by the pores with the diameter of 10-15 nm accounts for 24% -54% of the total pore volume, and the pore volume with the diameter of above 15nm accounts for 15% -38% of the total pore volume; the preferred pore size distribution is as follows: the pore volume of the pores with the diameter of less than 4nm accounts for 2% -8% of the total pore volume, the pore volume of the pores with the diameter of 4-10 nm accounts for 20% -46% of the total pore volume, the pore volume of the pores with the diameter of 10-15 nm accounts for 26% -52% of the total pore volume, and the pore volume of the pores with the diameter of more than 15nm accounts for 18% -36% of the total pore volume.
The relationship between the active metal content and the pore volume, the specific surface area and the pore distribution of the hydrofining catalyst is as follows: the specific surface area of the active metal is 300-500 m when the active metal is 50-70% 2 Per gram, the pore volume is 0.43-0.80 mL/g, the pore volume with the diameter of more than 10nm accounts for more than 57% of the total pore volume, and when the active metal is 70% -95%, the specific surface area is 180-300 m 2 And/g, wherein the 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% of the total pore volume.
The hydrofining catalyst has larger pore volume and specific surface area, is mainly concentrated at more than 10nm in distribution, has higher hydrodesulfurization and hydrodenitrogenation reaction performances, and is particularly suitable for being applied to the ultra-deep hydrodesulfurization and denitrification reaction of heavy diesel oil fractions.
The invention controls the components of the precipitation slurry in the step (1) and the step (2), so that the particle size obtained in the precipitation process is suitable, the distribution of generated holes is better controlled, and the active metal can be dispersed more uniformly. The catalyst is prepared from a relatively low-price and clean raw material (soluble sodium salt), and a precipitate contains a large amount of sodium ions after gel formation, so that the catalyst has small pore volume and is difficult to form due to the existence of a large amount of sodium ions. The inventor firstly retains sodium salt in the material in the forming process, then carries out desalting treatment on the formed material to remove precipitated sodium salt, and in the forming process, due to the space occupying effect of sodium salt in the forming process, vacancies after sodium removal are more beneficial to the formation of catalyst pore channel structures, pore distribution moves to the macroporous direction, 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 catalyst is difficult to form when the bulk phase catalyst is prepared by adopting clean raw materials in the prior art are solved. Meanwhile, the catalyst has the advantages of multiple active centers, uniform dispersion, high utilization rate and good mechanical strength, and greatly improves the desulfurization and denitrification capability of the bulk phase catalyst when the heavy diesel distillate is processed. The catalyst preparation process is only required to be washed 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 fraction disclosed by the invention 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 -1 The hydrogen-oil ratio is 300:1-1000:1.
Detailed Description
In the invention, the specific surface area and pore volume are measured by adopting a low-temperature liquid nitrogen adsorption method, and the mechanical strength is measured by adopting a side pressure method. In the invention, wt% is mass fraction and v% is volume fraction.
Example 1
(1) An aqueous solution containing nickel chloride, aluminum chloride, citric acid and butanol (the mass concentration of Ni based on NiO is 16g/L, al based on Al) 2 O 3 The mass concentration is 12g/L, the mole ratio of citric acid and butanol is 0.8, the mole ratio of the total mole number of the organic auxiliary agent to Ni is 1.0), 12wt% sodium hydroxide solution and sodium tungstate solution (W is WO 3 40 g/L) and is added into a glue forming tank with certain bottom water in parallel flow for glue forming reaction, the glue forming temperature is 60 ℃, the pH value is 7.8, the glue forming time is 1 hour, precipitate slurry I is obtained after the glue forming is finished, and the slurry I is filtered to obtainA filter cake;
(2) The filter cake obtained in the step (1) and an aqueous solution containing Ni and Al (the mass concentration of Ni is 10g/L in terms of NiO, and Al is Al) 2 O 3 The mass concentration is 10 g/L) and is evenly mixed to obtain a solid-liquid mixture, and the solid-liquid mixture and sodium molybdate solution (Mo is MoO) 3 The mass concentration is 12 g/L) and 12wt% sodium hydroxide solution are added into a reaction tank in parallel to carry out a 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 for 2 hours, the slurry is filtered, the filter cake is dried for 10 hours at 80 ℃, and the formed product is obtained by rolling and extruding strips;
(3) And (3) after the molded product is subjected to health preservation for 45 hours at 85 ℃, cooling to 24 ℃, and continuing to carry out health preservation for 34 hours. Washing with deionized water for 3 times, drying wet strips at 80deg.C for 10 hours, and calcining at 500deg.C for 4 hours to obtain catalyst A, the composition and properties of which 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 based on NiO is 14g/L, al based on Al) 2 O 3 The mass concentration was 8g/L, the molar ratio of maleic acid to ethanol was 1.8, the molar ratio of the total mole number of maleic acid and ethanol to Ni was 1.1), 12% by weight of sodium hydroxide solution and sodium tungstate solution (W in WO 3 44 g/L) and adding the mixture into a glue forming tank with certain bottom water in parallel to carry out a glue forming reaction, wherein the glue forming temperature is 55 ℃, the pH value is 8.3, the glue forming time is 0.9 hour, precipitate slurry I is obtained after the glue forming 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 Al) 2 O 3 The mass concentration is 8 g/L) of the mixture, and the mixture is evenly mixed to obtain a solid-liquid mixture, and the solid-liquid mixture and sodium molybdate solution (Mo is expressed as MoO 3 The mass concentration is 10 g/L) and 10wt% sodium hydroxide solution are added into a reaction tank in parallel to carry out a gelling reaction, the gelling temperature is 58 ℃, the pH value is 11.7, the gelling time is 1.1 hours, the slurry II is obtained, and the aging is carried out, the aging temperature is 72 ℃, and the pH value is 75, aging for 2.2 hours, filtering the slurry, drying a filter cake at 90 ℃ for 10 hours, rolling and extruding to form a formed product;
(3) And (3) after the molded product is subjected to health maintenance at 75 ℃ for 49 hours, cooling to 28 ℃ and continuing to carry out health maintenance for 30 hours. Washing with deionized water for 2 times, drying wet strips at 85deg.C for 13 hr, and calcining at 540 deg.C for 5 hr to obtain catalyst B with the composition and properties shown in Table 1.
Example 3
(1) The aqueous solution containing nickel sulfate, aluminum chloride solution, tartaric acid and propylene glycol (the mass concentration of Ni is 18g/L based on NiO, al is Al) 2 O 3 The mass concentration is 12g/L, the mole ratio of tartaric acid to propylene glycol is 1.8, the mole ratio of the total mole number of the added organic auxiliary agents to Ni in the mixed solution is 0.9), 10wt% of sodium hydroxide solution and sodium tungstate solution (W is WO 3 The mass concentration is 38 g/L), and the mixture is added into a glue forming tank with certain bottom water in parallel to carry out glue forming reaction, the glue forming temperature is 65 ℃, the pH value is 7.6, the glue forming time is 0.8 hour, precipitate slurry I is obtained after the glue forming 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 14g/L in terms of NiO, and Al is Al) 2 O 3 The mass concentration is 9 g/L) of the mixture, and the mixture is evenly mixed to obtain a solid-liquid mixture, and the solid-liquid mixture and sodium molybdate solution (Mo is expressed as MoO 3 The mass concentration is 9 g/L) and 8wt% sodium hydroxide solution are added into a reaction tank in parallel to carry out a gelling reaction, the gelling temperature is 65 ℃, the pH value is 11.0, the gelling time is 1.3 hours, slurry II is obtained, aging is carried out, the aging temperature is 78 ℃, the pH value is 7.6, aging is carried out for 1.6 hours, then the precipitate slurry is continuously aged under high pressure, the pressure is 12MPa, the aging temperature is 150 ℃, the aging time is 1.8 hours, the pH value is 12.4, the slurry is filtered after aging is finished, the filter cake is dried at 70 ℃ for 12 hours, and the formed product is obtained by rolling and extruding strips;
(3) And (3) after the molded product is subjected to health maintenance at 70 ℃ for 48 hours, cooling to 20 ℃ and continuing to carry out health maintenance for 32 hours. Washing with deionized water for 2 times, drying wet strips at 70deg.C for 14 hours, and calcining at 550deg.C for 4 hours to obtain catalyst C, wherein the composition and properties of the catalyst are shown in Table 1.
Example 4
(1) An aqueous solution containing nickel chloride, an aluminum sulfate solution, succinic acid and propylene glycol (the mass concentration of Ni based on NiO is 12g/L, al based on Al) 2 O 3 The mass concentration was 19g/L, the molar ratio of succinic acid to propylene glycol was 2.5, the molar ratio of the total number of added organic auxiliaries to Ni in the mixed solution was 1.3), 8% by weight of sodium hydroxide solution and sodium tungstate solution (W was WO-type 3 The mass concentration is 28 g/L), and the mixture is added into a gel forming tank with certain bottom water in parallel to carry out gel forming reaction, wherein the gel forming temperature is 70 ℃, the pH value is 8.3, the gel forming time is 1.2 hours, precipitate slurry I is obtained after the gel forming 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 10g/L in terms of NiO, and Al is Al) 2 O 3 The mass concentration is 20 g/L) of the mixture, and the mixture is mixed evenly to obtain a solid-liquid mixture, and the solid-liquid mixture and sodium molybdate solution (Mo is MoO 3 The mass concentration is 11 g/L) and 15wt% sodium carbonate solution are added into a reaction tank in parallel to carry out a 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, aging is carried out for 2.1 hours, then 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, the slurry is filtered after aging is finished, the filter cake is dried at 100 ℃ for 8 hours, and the formed product is obtained by rolling and extruding strips;
(3) And (3) after the molded product is subjected to health maintenance at 85 ℃ for 46 hours, cooling to 15 ℃ and continuing the health maintenance for 29 hours. Washing with deionized water for 2 times, drying wet strips at 100deg.C for 7 hours, and calcining at 510 deg.C for 5 hours to obtain catalyst D, the composition and properties of which are shown in Table 1.
Example 5
(1) Mixing nickel chloride, aluminum chloride solution, citric acid and ethanol water solution (Ni is 22g/L based on NiO mass concentration, al is Al 2 O 3 The mass concentration is 7g/L, the mol ratio of the citric acid to the ethanol is 1.8,the molar ratio of the total number of moles of organic auxiliary agent to Ni was 1.3), 10wt% sodium hydroxide solution and sodium tungstate solution (W in WO 3 The mass concentration is 32 g/L) and is added into a glue forming tank with certain bottom water in parallel to carry out glue forming reaction, the glue forming temperature is 70 ℃, the pH value is 7.9, the glue forming time is 0.9 hour, sediment slurry I is obtained after the glue forming 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 18g/L in terms of NiO, and Al is Al) 2 O 3 The mass concentration is 7 g/L) of the mixture is evenly mixed to obtain a solid-liquid mixture, and the solid-liquid mixture and sodium molybdate solution (Mo is MoO 3 The mass concentration is 14 g/L) and 12wt% sodium hydroxide solution are added into a reaction tank in parallel to carry out a 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 for 2.6 hours, the slurry is filtered, a filter cake is dried at 85 ℃ for 11 hours, and the mixture is rolled and extruded to form a formed product;
(3) The molded product was subjected to curing at 65℃for 68 hours, washed with deionized water for 2 times, dried at 80℃for 10 hours, and calcined at 560℃for 3.5 hours to obtain a 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 water solution (Ni is 16g/L based on NiO mass concentration, al is Al 2 O 3 The mass concentration is 9g/L, the mole ratio of tartaric acid and ethanol is 1.8, the mole ratio of the total mole number of the organic auxiliary agents to Ni is 1.1), 12wt% sodium carbonate solution and sodium tungstate solution (W is WO 3 34 g/L) and adding the mixture into a gel forming tank with certain bottom water in parallel to carry out gel forming reaction, wherein the gel forming temperature is 50 ℃, the pH value is 7.7, the gel forming time is 0.9 hour, precipitate slurry I is obtained after the gel forming 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 20g/L in terms of NiO, and Al is Al) 2 O 3 11 g/L) of the components are uniformly mixedTo obtain a solid-liquid mixture, mixing the solid-liquid mixture and sodium molybdate solution (Mo in MoO 3 The mass concentration is 10 g/L) and 8wt% sodium carbonate solution are added into a reaction tank in parallel to carry out a gelling reaction, the gelling temperature is 50 ℃, the pH value is 11.2, the gelling time is 1.3 hours, slurry II is obtained, aging is carried out, the aging temperature is 75 ℃, the pH value is 7.6, aging is carried out for 2.1 hours, then 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, the slurry is filtered after the aging is finished, the filter cake is dried at 85 ℃ for 11 hours, and the formed product is obtained by rolling and extruding strips;
(3) The molded product was subjected to curing at 80℃for 77 hours, washed with deionized water for 2 times, dried at 80℃for 10 hours, and calcined at 550℃for 5 hours to obtain a final catalyst E, the composition, main properties and pore distribution of which are shown in Table 1.
Comparative example 1
Catalyst G was prepared by the method disclosed in CN101172261 for example 1 with unchanged catalyst composition, as follows: 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 WO 3 The mass concentration is 40g/L, sodium metaaluminate is added into a dissolution tank 2 filled with deionized water to prepare an alkaline working solution B, and Al in the solution is Al 2 O 3 The mass concentration of the meter is 22g/L. Deionized water was added to the reaction tank and the temperature was raised to 60 ℃. And (3) adding the solution A and the solution B into a reaction tank in parallel flow under stirring to form gel, wherein the gel forming temperature is 60 ℃, the gel forming time is 1 hour, and the pH value of slurry in the gel forming process is 7.6. Aging for 2 hours after the gel formation. Then filtering, adding 600ml of purified water and 12G of molybdenum trioxide into the filter cake, pulping and stirring uniformly, filtering, drying the filter cake at 80 ℃ for 10 hours, extruding strips for molding, washing 3 times with purified water, 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 main properties are shown in table 1.
Comparative example 2
Reference catalyst H was prepared according to the procedure of example 1, in the proportions of the components of catalyst A in Table 1, without desalting the shaped bars.
(1) An aqueous solution containing nickel chloride, aluminum chloride, citric acid and butanol (the mass concentration of Ni based on NiO is 16g/L, al based on Al) 2 O 3 The mass concentration is 12g/L, the mole ratio of citric acid and butanol is 0.8, the mole ratio of the total mole number of the organic auxiliary agent to Ni is 1.0), 12wt% sodium hydroxide solution and sodium tungstate solution (W is WO 3 40 g/L) and adding the mixture into a gel forming tank with certain bottom water in parallel to carry out gel forming reaction, wherein the gel forming temperature is 60 ℃, the pH value is 7.8, the gel forming time is 1 hour, precipitate slurry I is obtained after gel forming 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 10g/L in terms of NiO, and Al is Al) 2 O 3 The mass concentration is 10 g/L) and is evenly mixed to obtain a solid-liquid mixture, and the solid-liquid mixture and sodium molybdate solution (Mo is MoO) 3 The mass concentration is 12 g/L) and 12wt% sodium hydroxide solution are added into a reaction tank in parallel to carry out a gel forming reaction, the gel forming temperature is 60 ℃, the pH value is 10.8, the gel forming time is 1 hour, the slurry II is obtained, the aging temperature is 75 ℃, the pH value is 8.0, after the aging for 2 hours, the slurry is filtered, the filter cake is dried for 10 hours at 80 ℃, and the formed product is not obtained after rolling, extruding and washing. The method comprises the steps of carrying out a first treatment on the surface of the
(3) The powder was calcined at 500 ℃ for 4 hours to give final catalyst H, the composition, main properties and pore distribution are shown in table 1.
Comparative example 3
According to the catalyst preparation method disclosed in CN106179380a, a reference agent having the same composition as the catalyst of example 1 was prepared. Adding aluminum chloride and nickel chloride solution into a dissolving tank 1 to prepare a working solution A, wherein the mass concentration of Ni in the mixed solution A calculated by NiO is 26g/L, and Al is calculated by Al 2 O 3 The mass concentration of the meter is 12g/L. Adding aluminum chloride, ammonium meta-tungstate and ammonium molybdate into a dissolving tank 2 to prepare a working solution B, wherein W in the mixed solution B is WO 3 The mass concentration of the catalyst is 40g/L, and Mo is expressed as MoO 3 The mass concentration is 12g/L, al is Al 2 O 3 The mass concentration of the meter is 10 g-L. Ammonia water with the concentration of 10wt% is added into the solution A under stirring, the gel forming temperature is kept at 60 ℃, the pH value is controlled at 7.6 at the end, the gel forming time is controlled at 60 minutes, and the precipitate slurry I containing nickel and aluminum is generated. 500mL of deionized water is added into a reaction tank, ammonia water with the concentration of 10wt% and solution B are added into the reaction tank in parallel flow, the gel forming temperature is kept at 60 ℃, the pH value is controlled at 7.6 in the parallel flow gel forming reaction process, and the gel forming time is controlled at 1.0 hour, so that precipitate slurry II containing tungsten, molybdenum and aluminum is generated. Mixing the two precipitate-containing slurries, aging for 2.0 hours at the aging temperature of 72 ℃, controlling the pH value at 7.8 after aging, filtering, and performing hydrothermal treatment on a filter cake under the water vapor containing urea, wherein the hydrothermal treatment conditions are as follows: the molar ratio of urea to the total amount of active metal atoms is 3:1, the temperature is 230 ℃, the pressure is 3.5MPa, the treatment time is 4 hours, the material after the hydrothermal treatment is dried for 10 hours at 80 ℃, rolled and extruded into strips. Washing with deionized water at room temperature for 5 times. The wet strips 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, which had 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 dissolution tank 1 filled with deionized water to prepare an acidic solution A, wherein the mass concentration of Ni in the acidic solution A calculated by NiO is 26g/L, and Al is calculated by Al 2 O 3 The mass concentration of the meter is 12g/L. Respectively adding 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 WO 3 The mass concentration is 20g/L, al is expressed as Al 2 O 3 The mass concentration of the meter is 10g/L. Deionized water is added into a reaction tank, and the mass concentration is WO 3 The sodium tungstate alkaline solution with the mass concentration of 20g/L and the acid solution A are added into a reaction tank in parallel, the gel forming temperature is kept at 60 ℃, the pH value is controlled at 7.6 in the parallel flow gel forming reaction process, the gel forming time is controlled at 60 minutes, and the precipitate slurry I containing nickel, tungsten and aluminum is generated. Aging the obtained precipitate slurry I under stirring at 220 rpmThe temperature is 75 ℃, the aging pH value is controlled to be 7.0, and the aging is carried out for 0.8 hours. After the aging is finished, mo is treated by MoO 3 Adding sodium molybdate alkaline solution and acid solution B with mass concentration of 12g/L into slurry I in parallel, maintaining the gelatinization temperature at 60 ℃, controlling the pH value in the parallel flow gelatinization reaction process at 7.8, controlling the gelatinization time at 2.0 hours to obtain nickel, tungsten, molybdenum and aluminum precipitate slurry II, aging the precipitate slurry II under stirring, controlling the stirring speed at 370 r/min, aging 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 strips and forming. Washing with deionized water at room temperature for 5 times. The wet strips 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. The catalyst A, B, D, E and the comparative catalyst G, I, J are adopted to carry out comparative evaluation tests on a 200mL small hydrogenation device, and catalytic diesel with high nitrogen content and high desulfurization difficulty is adopted as a test raw material, and the main properties of the raw materials 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 -1 The hydrogen oil volume ratio was 500:1, and the evaluation results are shown in Table 3. The type of nitrides in the hydrofinished oils were detected using a gas chromatograph-atomic emission spectroscopy detector (GC-AED), and the results are shown in table 4.
As can be seen from Table 1, the catalyst prepared from clean sodium salt-containing raw materials has less sodium oxide content, increased pore volume and specific surface area, and significantly increased macropores above 10nm, and as can be seen from Table 2, the catalyst activity evaluation uses high nitrogen content of the raw oil, which also increases the difficulty of ultra-deep hydrodesulfurization of the raw oil, compared with the catalyst of the comparative example. As can be seen from tables 3-4, the catalyst of the present invention has excellent hydrodenitrogenation activity when treating heavy diesel oil fractions, effectively eliminates the inhibition of nitrides on hydrodesulfurization reactions, and greatly improves the deep hydrodesulfurization activity. The catalyst of the invention has excellent ultra-deep hydrodesulfurization and denitrification performances when being used for processing diesel oil fraction, especially for processing heavy diesel oil fraction.
Table 1 composition and properties of the catalysts prepared in examples and comparative examples
TABLE 1 compositions and Properties of catalysts prepared in examples and comparative examples
TABLE 2 Main Properties of raw oil
TABLE 3 evaluation results of catalyst Activity
TABLE 3 evaluation results of catalyst Activity
TABLE 4 content of different nitrides in hydrofined oils
Table 4 (subsequent)
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 that: the nitrogen-containing compound which is mainly difficult to remove by hydrodenitrogenation is Carbazole (CB) with larger molecules and steric hindrance, 1-methyl carbazole (1-MCB), 1, 8-dimethyl carbazole (1, 8-DMCB), 1,4, 8-trimethyl carbazole (1, 4, 8-TMCB) and the like.

Claims (16)

1. The preparation method of the heavy diesel fraction hydrofining catalyst is characterized by comprising the following steps: (1) preparing a precipitate containing nickel, tungsten and aluminum: mixing a mixed solution containing Ni, al, organic acid and organic alcohol, a sodium tungstate solution and a precipitator, performing parallel flow gelling reaction, and filtering slurry I to obtain a filter cake; (2) preparing a molded article: 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 parallel flow for gelling reaction, ageing slurry II, and carrying out solid-liquid separation, drying and forming after ageing; (3) Desalting the molded product, washing, drying and roasting to obtain a hydrofining catalyst; the organic acid in the step (1) is selected from one or more of carboxylic acids with carbon numbers of C2-C8; the organic alcohol in the step (1) is selected from one or more of ethanol, isopropanol, butanol, amyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, diethylene methyl glycol, diethylene ethyl glycol, diethylene propyl glycol and diethylene butyl glycol; the precipitants in the step (1) and the step (2) are alkaline compound aqueous solutions without nitrogen elements, and the alkaline compound is one or more of sodium hydroxide, sodium bicarbonate or sodium carbonate; the gelling reaction conditions described in step (1): the gel forming temperature is 30-100 ℃, the gel forming time is 0.5-5.0 hours, and the pH value is controlled to be 7.0-10.0; the gelling reaction conditions described in step (2): the gel forming temperature is 30-100 ℃, the gel forming time is 0.5-5.0 hours, and the pH value is 10.0-12.0; aging conditions described in step (2): the aging temperature is 30-90 ℃, the aging time is 1-5 hours, and the pH value is 7.0-10.0; the desalination treatment process of the step (3): firstly, carrying out health preservation, and then washing to remove salt precipitated on the surface of the formed product, wherein the health preservation condition is that the temperature is 5-100 ℃ and the time is 10-100 hours.
2. The method according to claim 1, characterized in that: in the mixed solution containing Ni, al, organic acid and organic alcohol in the step (1), the mass concentration of Ni calculated by NiO is 3-80 g/L, and Al calculated by Al 2 O 3 The mass concentration of the meter is 2-70 g/L.
3. The method according to claim 1, characterized in that: the molar ratio of organic acid to organic alcohol in step (1) is 0.1:1 to 1:0.1; the molar ratio of the total mole number of the organic acid and the organic alcohol to Ni is 0.2: 1-2: 1.
4. the method according to claim 1, characterized in that: the weight of Ni introduced in the step (1) accounts for 20% -80% of the weight of Ni in the catalyst; the weight of Al introduced in the step (1) accounts for 30-80% of the weight of Al in the catalyst.
5. The method according to claim 1, characterized in that: the organic acid in the step (1) is 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 according to claim 1, characterized in that: in the sodium tungstate solution in the step (1), W is WO 3 The mass concentration of the meter is 5-100 g/L.
7. The method according to claim 1, characterized in that: in the mixed solution containing Ni and Al in the step (2), the mass concentration of Ni in terms of NiO is 3-90 g/L, and Al in terms of Al 2 O 3 The mass concentration of the meter is 1-60 g/L.
8. The method according to claim 1, characterized in that: in the sodium molybdate solution in the step (2), mo is MoO 3 The mass concentration of the meter is 2-60 g/L.
9. The method according to claim 1, characterized in that: the aging condition in the step (2) is carried out in the following manner, wherein the aging is carried out at normal pressure in the first step: the aging temperature is 30-90 ℃, the aging time is 1-6 hours, and the pH value is 6.5-10.0; and step two, high-pressure aging: the temperature is 100-195 ℃, the time is 0.1-4.0 hours, the pressure is not less than 10MPa, and the pH value is 10.0-13.0.
10. The method according to claim 1, characterized in that: the desalination treatment in the step (3) is performed as follows: the temperature of the first stage is 60-90 ℃, and the curing is carried out for 5-60 hours; the temperature of the second stage is 10-30 ℃ for 1-48 hours; then, the precipitated salt was removed by washing.
11. The catalyst prepared by the method according to any one of claims 1 to 10, characterized in that: the specific surface area of the hydrofining catalyst is 180-500 m 2 Per gram, the pore volume is 0.20-0.80 mL/g; the pore size distribution is as follows: the pore volume of the pores with the diameter of less than 4nm accounts for 1% -10% of the total pore volume, the pore volume of the pores with the diameter of 4-10 nm accounts for 18% -48% of the total pore volume, the pore volume of the pores with the diameter of 10-15 nm accounts for 24% -54% of the total pore volume, and the pore volume of the pores with the diameter of more than 15nm accounts for 15% -38% of the total pore volume.
12. The catalyst of claim 11, wherein: the hydrofining catalyst is bulk hydrofining catalyst and comprises a hydrogenation active metal component WO 3 NiO and MoO 3 And alumina, wherein the total content of Ni, W and Mo calculated by oxide is 50% -95% and the content of alumina is 5% -50% based on the weight of the oxidation state hydrofining catalyst.
13. The catalyst of claim 11, wherein: the relationship between the active metal content and the pore volume, the specific surface area and the pore distribution of the hydrofining catalyst is as follows: the specific surface area of the active metal is 300-500 m when the active metal is 50-70% 2 Per gram, the pore volume is 0.43-0.80 mL/g, the pore volume with the diameter of more than 10nm accounts for more than 57% of the total pore volume, and when the active metal is 70% -95%, the specific surface area is 180-300 m 2 And/g, wherein the 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% of the total pore volume.
14. The catalyst of claim 11, wherein: the molar ratio of W/Mo is 1: 5-27: 1, ni/(Mo+W) molar ratio of 1: 12-18: 1.
15. the catalyst of claim 11, wherein: na in hydrofining catalyst 2 The O content is less than 0.12%.
16. The use of the catalyst prepared according to any one of claims 1 to 10 in ultra-deep hydrodesulfurization and denitrification reactions of heavy diesel 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 -1 The hydrogen-oil ratio is 300:1-1000:1.
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