CN114471593B - Preparation method of hydrofining catalyst - Google Patents

Preparation method of hydrofining catalyst Download PDF

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CN114471593B
CN114471593B CN202011151630.0A CN202011151630A CN114471593B CN 114471593 B CN114471593 B CN 114471593B CN 202011151630 A CN202011151630 A CN 202011151630A CN 114471593 B CN114471593 B CN 114471593B
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catalyst
acid
pore volume
hours
aging
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CN114471593A (en
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王继锋
王海涛
徐学军
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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • C10G2300/20—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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/308—Gravity, density, e.g. API
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method of a hydrofining catalyst, which comprises the following steps: (1) Dropwise adding sodium carbonate aqueous solution into aluminum salt aqueous solution containing organic acid and organic alcohol to carry out a gelling reaction to obtain slurry I; (2) Adding nickel salt aqueous solution, sodium tungstate and sodium molybdate aqueous solution and sodium hydroxide aqueous solution into the slurry I in parallel flow for gelling reaction to obtain slurry II; (3) Aging the slurry II, carrying out solid-liquid separation after aging, and drying and forming a solid phase to obtain a formed product; (4) And (3) desalting the molded product, washing, drying and roasting to obtain the catalyst. The method solves the problems of small pore volume and difficult molding of the catalyst when the bulk phase catalyst is prepared by adopting clean raw materials in the prior art, has low preparation cost, clean and pollution-free preparation process, large pore volume and large pore diameter of the catalyst and has high hydrodesulfurization and hydrodenitrogenation reaction performances.

Description

Preparation method of hydrofining catalyst
Technical Field
The invention relates to a preparation method of a hydrofining catalyst, in particular to a preparation method of a bulk hydrofining catalyst.
Background
In recent years, the problems of heavy and poor quality of crude oil in the world are increasingly aggravated, the environmental regulations are increasingly strict on the quality of the finished oil, oil refining enterprises are under great pressure, and meanwhile, the environmental regulations in China are increasingly strict, and the quality standard of the oil product is overtaken to the level of developed western countries. The hydrotreating catalyst plays an increasingly important role in improving the quality of oil products, producing ultra-clean fuel, pretreating raw materials and the like. The development of highly active and stable hydrotreating catalysts is an important approach to address these problems. In particular, in recent years, in order to improve the market competitiveness of the catalyst, a new generation of hydrogenation catalysts is continuously introduced to produce new standard diesel products in all countries of the world. However, the content of active metal in the conventional hydrogenation catalyst is limited by the preparation method, so that the hydrogenation activity is difficult to be greatly improved.
In order to meet the increasingly strict environmental regulations, manufacturers are urgent to prepare catalysts by using raw materials with relatively low price, and to use non-nitrogen raw materials in the preparation process of the catalysts, 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.
The ultra-deep hydrodesulfurization of diesel oil is to remove 4,6-DMDBT macromolecular sulfides. The sulfide has the main way of preventing the contact between the active center of the catalyst and sulfur atoms due to the influence of the steric hindrance effect of methyl substituent groups, namely, the hydrogenation is carried out before the desulfurization, namely, the hydrogenation saturation of polycyclic aromatic hydrocarbon eliminates the steric hindrance effect and then the hydrogenolysis is carried out, meanwhile, in the ultra-deep hydrogenation desulfurization reaction of distillate oil, the organic nitrogen-containing compound in the distillate oil and the sulfur-containing compound are in competitive adsorption on the active site of the catalyst, the active center on the catalyst is occupied, the obvious inhibition effect is generated on the hydrogenation desulfurization reaction, and the hydrogenation desulfurization activity is reduced along with the increase of the nitrogen content in the raw materials. The two characteristics require that the aperture of the catalyst is increased, so that macromolecular sulfides and nitrides smoothly enter the pore canal to perform hydrodenitrogenation and desulfurization reactions. The bulk phase catalyst prepared by the prior art has more hydrogenation active centers, but has smaller pore volume and pore diameter, the pore distribution is mainly concentrated in small pores, and a macromolecular compound containing S, N cannot approach the hydrogenation active centers, so that the utilization of the hydrogenation active centers is reduced, and the improvement of the hydrogenation activity of the bulk phase catalyst is influenced. 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.
The bulk hydrogenation catalyst disclosed in CN102049265A is added with ammonium bicarbonate in the coprecipitation process, the bulk hydrogenation catalyst disclosed in CN102451703A is added with carbon dioxide in the coprecipitation process to generate carbonate or bicarbonate, and the method utilizes the catalyst to release a certain amount of gas in the roasting process, and changes the pore volume and specific surface area of the catalyst 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 process for preparing a catalyst composition according to the invention. Sodium metaaluminate solution and mixed solution containing Ni and W components and salt are adopted to react in parallel to generate precipitate. CN110038581a the present invention 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 hydrofining catalyst. The method solves the problems of small pore volume and difficult molding of the catalyst when the bulk phase catalyst is prepared by adopting clean raw materials in the prior art, has low preparation cost, clean and pollution-free preparation process, large pore volume and large pore diameter of the catalyst and has high hydrodesulfurization and hydrodenitrogenation reaction performances.
The preparation method of the hydrofining catalyst comprises the following steps: (1) Dropwise adding sodium carbonate aqueous solution into aluminum salt aqueous solution containing organic acid and organic alcohol to carry out a gelling reaction to obtain slurry I; (2) Adding nickel salt aqueous solution, sodium tungstate and sodium molybdate aqueous solution and sodium hydroxide aqueous solution into the slurry I in parallel flow for gelling reaction to obtain slurry II; (3) Aging the slurry II, carrying out solid-liquid separation after aging, and drying and forming a solid phase to obtain a formed product; (4) And (3) desalting the molded product, washing, drying and roasting to obtain the catalyst.
In the method of the present invention, the aluminum salt in the step (1) may be one or more of aluminum chloride, aluminum sulfate, aluminum nitrate, etc., preferably an aluminum salt containing no nitrogen element, the mass concentration of the aluminum salt being Al 2 O 3 Counting to be 2-80 g/L; the molar ratio of the organic acid to the organic alcohol 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 the aluminum salt calculated as Al element is 0.2:1 to 3:1, preferably 0.4:1 to 2.5:1.
in the method of the invention, 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, preferably one or more of malic acid, citric acid, tartaric acid, oxalic acid, succinic acid, salicylic acid or maleic acid.
In the method, 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, 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.
In the method, the mass percentage concentration of the sodium carbonate aqueous solution in the step (1) is generally 5% -25%, and the dosage is generally adjusted according to the requirement of the gel forming reaction.
In the method of the invention, the gelling reaction conditions described in step (1) are: the gel forming temperature is 30-90 ℃, the gel forming time is 0.5-5.0 hours, preferably 0.5-3.0 hours, and the pH value is 7.0-9.0.
In the method, the nickel salt in the step (2) is nickel sulfate and/or nickel chloride; the mass concentration of the aqueous nickel salt solution is 3 to 100g/L, preferably 5 to 90g/L, based on NiO.
In the method of the invention, in the aqueous solution of sodium tungstate and sodium molybdate, the sodium tungstate is prepared by the method of WO 3 The mass concentration is 2-110 g/L, preferably 5-90 g/L, sodium molybdate is expressed as MoO 3 The mass concentration of the catalyst is 1 to 50/L, preferably 2 to 40g/L.
In the method of the invention, the concentration of the sodium hydroxide aqueous solution in the step (2) is generally 3-20%, and the dosage is generally adjusted according to the requirement of the gel forming reaction.
In the method of the invention, the gelling reaction conditions described in step (2) are as follows: the gel forming temperature is 30-100 ℃, the gel forming time is 0.5-6.0 hours, preferably 0.5-4.0 hours, and the pH value is 6.0-10.0.
In the method of the invention, the aging conditions described in step (3) are: the aging temperature is 30-90 ℃, the aging time is 1-5 hours, and the pH value is 7.0-10.0.
In the process of the present invention, the aging conditions described in step (3) are preferably carried out as follows, the first step of atmospheric aging: the aging temperature is 30-90 ℃, the optimization is 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 to 195 ℃, preferably 100 to 190 ℃, and the time is 0.1 to 4.0 hours, preferably 0.3 to 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.
In the method, the drying temperature in the step (3) is 50-150 ℃ and the drying time is 0.5-24 hours.
In the method, the forming process in the step (3) is well known in the catalyst preparation field, 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 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 (4) comprises the following steps: firstly, carrying out health preservation, 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 ℃, preferably 10-90 ℃ for 10-100 hours, preferably 24-90 hours,
in the method of the present invention, the desalting treatment in the step (4) 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 (4) 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 prepared by the method can be prepared into shapes such as sheets, spheres, cylindrical strips, special strips (clover and clover) and the like according to the requirements.
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 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.
In the hydrofining catalyst of the invention, the mole 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 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), thereby controlling the growth of precipitate particles, enabling the active metal to be uniformly dispersed, being more beneficial to the utilization of hydrogenation active metal and improving the hydrogenation activity of the catalyst. Meanwhile, the low-cost catalyst is prepared by adopting a clean method, and because the soluble sodium salt is used as a raw material, the precipitate contains a large amount of sodium ions after gel formation, and 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 catalyst is suitable for processing diesel oil fraction, is particularly suitable for being used in ultra-deep hydrodesulfurization and denitrification reactions of heavy diesel oil fraction, has higher hydrodesulfurization and hydrodenitrogenation activity, and particularly has higher hydrodenitrogenation and desulfurization activity when processing low-grade diesel oil with high macromolecular sulfur and nitrogen compound content. [ best gives the key parameter properties of the two types of diesel oil ] the sulfur content in the heavy diesel oil fraction is 2000-20000 [ mu ] g/g, the nitrogen content is 300-2000 [ mu ] g/g, and the density is 0.8550-0.9300 cm 3 And/g, the final distillation point is 355-400 ℃. The sulfur content of thiophene and its derivative in the low-grade diesel oil with high macromolecular sulfur and nitrogen compound content accounts for 40-85 wt% of the total sulfur content of the raw material, and the nitrogen content of carbazole and its derivative accounts for 45-80 wt% of the total nitrogen content of the raw material.
The application of the hydrofining catalyst in the ultra-deep hydrodesulfurization and denitrification reaction of the 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 volume ratio of hydrogen to oil 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. The catalyst surface active metal concentration was measured using Electron Spectroscopy for Chemical Analysis (ESCA). In the invention, wt% is mass fraction and v% is volume fraction.
Example 1
(1) Dropwise adding 10wt% sodium carbonate solution into aqueous solution containing aluminum chloride, citric acid and butanol (aluminum chloride is added as Al) 2 O 3 The mass concentration is 22g/L, the mole ratio of citric acid to butanol is 0.8, the mole ratio of the total mole number of citric acid to butanol to Al is 1.0), the gel forming reaction is carried out, the gel forming temperature is 60 ℃, the pH value is 7.8, and the gel forming time is 1 hour, so that slurry I is obtained;
(2) An aqueous solution of nickel chloride (26 g/L mass concentration based on NiO), an aqueous solution of sodium tungstate and sodium molybdate (W in WO) 3 The mass concentration of the catalyst is 40g/L, and Mo is expressed as MoO 3 The mass concentration is 12 g/L) and 12wt% sodium hydroxide aqueous solution are added into the slurry I in parallel flow for gelling reaction, the gelling temperature is 60 ℃, the pH value is 7.6, and the gelling time is 1 hour, so as to obtain slurry II;
(3) Aging the slurry II at 75 ℃ for 2 hours at the pH value of 7.8, filtering the slurry after aging, drying the filter cake at 80 ℃ for 10 hours, rolling, extruding and molding to obtain a molded product;
(4) And (3) after the molded product is subjected to health maintenance at 85 ℃ for 48 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 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) Dropwise adding 13wt% sodium carbonate solution into aluminum chloride solution, maleic acid and ethanol water solution (aluminum chloride is added with Al 2 O 3 The mass concentration is 18g/L, the mole ratio of maleic acid and ethanol is 1.2, the mole ratio of the total mole number of the organic auxiliary agent to Al is 1.4), the gel forming reaction is carried out, the gel forming temperature is 52 ℃, the pH value is controlled at 8.0, and the gel forming time is 1.2 hours, so that slurry I is obtained;
(2) Nickel chloride (Ni at a mass concentration of 30g/L in terms of NiO), sodium tungstate and sodium molybdate aqueous solution (W in terms of WO) 3 The mass concentration of the catalyst is 44g/L, and Mo is expressed as MoO 3 8 g/L) and 13wt% sodium hydroxide solution were added co-currently to the slurryCarrying out a gel forming reaction in the step I, wherein the gel forming temperature is 50 ℃, the pH value is 8.6, and the gel forming time is 1.1 hours, so as to obtain slurry II;
(3) The slurry II was aged at 72℃and pH 8.3 for 2.8 hours. Filtering the slurry after aging, drying a filter cake at 85 ℃ for 9 hours, rolling, extruding strips and forming to obtain a formed product;
(4) And (3) after curing the molded product at 75 ℃ for 40 hours, cooling to 18 ℃ and continuing to cure for 25 hours. Washing with clean water for 2 times, drying wet strips at 100deg.C for 12 hours, and calcining at 530 deg.C for 4 hours to obtain final catalyst B, the composition and properties of which are shown in Table 1.
Example 3
(1) 10wt% sodium carbonate solution was added dropwise to an aqueous solution containing aluminum chloride, tartaric acid and ethylene glycol (aluminum chloride as Al 2 O 3 The mass concentration is 20g/L, the mole ratio of tartaric acid to ethylene glycol is 1.1, the mole ratio of the total mole number of tartaric acid and ethylene glycol to Al is 1.4), the gel forming reaction is carried out, the gel forming temperature is 50 ℃, the pH value is 7.8, and the gel forming time is 0.9 hour, so as to obtain slurry I;
(2) An aqueous solution of nickel chloride (mass concentration of NiO: 22 g/L), an aqueous solution of sodium tungstate and sodium molybdate (W: WO) 3 The mass concentration of the catalyst is 53g/L, and Mo is expressed as MoO 3 The mass concentration is 5 g/L) and 15wt% sodium hydroxide aqueous solution are added into the slurry I in parallel flow for gelling reaction, the gelling temperature is 60 ℃, the pH value is 8.2, and the gelling time is 1.5 hours, so as to obtain slurry II;
(3) Aging the slurry II at 74 ℃ for 2 hours at a pH of 7.9, and then continuously aging the precipitate slurry under high pressure at 12.5MPa at 170 ℃ for 1.8 hours at a pH of 12.0. Filtering the slurry after aging, drying a filter cake at 90 ℃ for 8 hours, rolling, extruding strips and forming to obtain a formed product;
(4) And (3) after the molded product is subjected to health maintenance at 70 ℃ for 42 hours, cooling to 23 ℃ and continuing the health maintenance for 34 hours. Washing with deionized water for 2 times, drying wet strips at 90 ℃ for 14 hours, and roasting at 550 ℃ for 4 hours to obtain a catalyst C, wherein the composition and properties of the catalyst are shown in Table 1.
Example 4
(1) A12 wt% sodium carbonate solution was added dropwise to an aqueous solution containing aluminum chloride, maleic acid and propylene glycol (aluminum chloride as Al 2 O 3 The mass concentration is 40g/L, the mole ratio of maleic acid and propylene glycol is 1.1, the mole ratio of the total mole number of the maleic acid and the propylene glycol to Al is 1.5), the gel forming reaction is carried out, the gel forming temperature is 70 ℃, the pH value is 8.4, and the gel forming time is 1.3 hours, so that slurry I is obtained;
(2) An aqueous solution of nickel chloride (mass concentration of NiO: 18 g/L), an aqueous solution of sodium tungstate and sodium molybdate (W: WO) 3 The mass concentration of the catalyst is 32g/L, and Mo is expressed as MoO 3 The mass concentration is 10 g/L) and 15wt% sodium hydroxide aqueous solution are added into the slurry I in parallel flow for gelling reaction, the gelling temperature is 65 ℃, the pH value is 7.4, and the gelling time is 1.2 hours, thus obtaining slurry II;
(3) Aging the slurry II at 78 ℃ for 2.8 hours at 7.9, and then continuously aging the precipitate slurry under high pressure at 10.8MPa at 165 ℃ for 1.9 hours at 12.3. Filtering the slurry after aging, drying a filter cake at 85 ℃ for 10 hours, rolling, extruding strips and forming to obtain a formed product;
(4) And (3) after the molded product is subjected to health preservation for 45 hours at 78 ℃, cooling to 28 ℃, and continuing to carry out health preservation for 29 hours. Washing with deionized water for 2 times, drying wet strips at 100deg.C for 10 hours, and calcining at 520 deg.C for 5 hours to obtain catalyst D, the composition and properties of which are shown in Table 1.
Example 5
(1) A12 wt% sodium carbonate solution was added dropwise to an aluminum chloride solution, malic acid and propylene glycol aqueous solution (aluminum chloride as Al) 2 O 3 The mass concentration is 18g/L, the molar ratio of malic acid to propylene glycol is 0.9, the molar ratio of the total mole number of the organic auxiliary agent to Al is 1.5), the gel forming reaction is carried out, the gel forming temperature is 50 ℃, the pH value is 8.3, and the gel forming time is 1.4 hours, so that slurry I is obtained;
(2) An aqueous solution of nickel chloride (the mass concentration of Ni is 38g/L in terms of NiO), sodium tungstate and sodium molybdateAqueous solution (W in WO) 3 The mass concentration of the catalyst is 40g/L, and Mo is expressed as MoO 3 The mass concentration is 4 g/L) and 8wt% sodium hydroxide solution are added into the slurry I in parallel flow for gelling reaction, the gelling temperature is 63 ℃, the pH value is 7.5, and the gelling time is 1.2 hours, thus obtaining slurry II;
(3) The slurry II was aged at 79℃and pH 8.0 for 3.0 hours. Filtering the slurry after aging, drying a filter cake at 80 ℃ for 10 hours, rolling, extruding strips and forming;
(4) The molded product was subjected to a curing at 27℃for 78 hours, washed with clean water for 2 times, dried at 90℃for 13 hours, and calcined at 510℃for 6 hours to obtain a final catalyst E, the composition, main properties and pore distribution of which are shown in Table 1.
Example 6
(1) Dropwise adding 15wt% sodium carbonate solution into aluminum chloride solution, citric acid and ethanol water solution (aluminum chloride is prepared by Al 2 O 3 The mass concentration is 16g/L, the mole ratio of citric acid and ethanol is 0.7, the mole ratio of the total mole number of the organic auxiliary agent to Al is 1.4), the gel forming reaction is carried out, the gel forming temperature is 57 ℃, the pH value is 8.6, and the gel forming time is 0.9 hour, so that slurry I is obtained;
(2) An aqueous solution of nickel chloride (34 g/L of Ni in terms of NiO), an aqueous solution of sodium tungstate and sodium molybdate (W in terms of WO) 3 The mass concentration of the catalyst is 36g/L, and Mo is expressed as MoO 3 The mass concentration is 14 g/L) and 12wt% sodium hydroxide solution are added into the slurry I in parallel flow for gelling reaction, the gelling temperature is 70 ℃, the pH value is 7.9, and the gelling time is 1.0 hour, thus obtaining slurry II;
(3) And (3) aging the slurry II at the aging temperature of 72 ℃ for 2.8 hours at the pH value of 7.5, and then continuously aging the precipitate slurry under high pressure at the pressure of 11.0MPa at the aging temperature of 185 ℃ for 1.9 hours at the pH value of 11.6. Filtering the slurry after aging, drying a filter cake at 100 ℃ for 9 hours, rolling, extruding strips and forming to obtain a formed product;
(4) The molded product was subjected to a curing at 60℃for 69 hours, washed with clean water 2 times, dried at 100℃for 13 hours, and calcined at 540℃for 4 hours to obtain a final catalyst F, 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) Dropwise adding 10wt% sodium carbonate solution into aqueous solution containing aluminum chloride, citric acid and butanol (aluminum chloride is added as Al) 2 O 3 The mass concentration is 22g/L, the mole ratio of citric acid to butanol is 0.8, the mole ratio of the total mole of citric acid and butanol to Al is 1.0), the gel forming reaction is carried out, the gel forming temperature is 60 ℃, the pH value is 7.8, and the gel forming time is 1 hour, so as to obtain slurry I;
(2) An aqueous solution of nickel chloride (26 g/L mass concentration based on NiO), an aqueous solution of sodium tungstate and sodium molybdate (W in WO) 3 The mass concentration of the catalyst is 40g/L, and Mo is expressed as MoO 3 The mass concentration is 12 g/L) and 12wt% sodium hydroxide aqueous solution are added into the slurry I in parallel flow for gel forming reactionThe gel forming temperature is 60 ℃, the pH value is 7.6, and the gel forming time is 1 hour, so as to obtain slurry II;
(3) Aging the slurry II at 75 ℃ for 2 hours at the pH value of 8.0, filtering the slurry after aging, drying the filter cake at 80 ℃ for 10 hours, rolling, extruding strips, and washing to obtain a formed product;
(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 10g/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. Drying the wet strips at 80 ℃ for 10 hours, and roasting at 500 ℃ for 4 hours to obtain the 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. The obtained precipitate slurry I was aged under stirring at a stirring speed of 220 rpm at an aging temperature of 75℃and an aging pH of 7.0 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. Using the catalyst A, B, D, E of the invention and the comparative catalyst G,I. J, performing a comparative evaluation test on a 200mL small hydrogenation device, and adopting catalytic diesel with high nitrogen content and high desulfurization difficulty as a test raw material, wherein the main properties of the raw material are shown in Table 3. 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 4. 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 5.
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 3, 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 4 to 5, the catalyst of the present invention has excellent hydrodenitrogenation activity when treating heavy diesel oil fraction, effectively eliminates the inhibition effect of nitrides on hydrodesulfurization reaction, 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 composition and Properties of the catalysts prepared in the examples and comparative examples
TABLE 2 ESCA determination of catalyst surface Metal relative atomic concentration (molar ratio)
TABLE 3 Main Properties of raw oil
TABLE 4 evaluation results of catalyst Activity
TABLE 5 content of different nitrides in hydrofined oils
Table 5 (subsequent)
Catalyst numbering G I J
Nitrogen content in hydrofined oil, mug/g 87.6 78.2 18.1
1-MCB，µg/g 28.7 25.3 7.4
1，8-DMCB，µg/g 40.3 36.1 6.2
1，4，8-TMCB，µg/g 18.6 16.8 4.5
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 (14)

1. A preparation method of a hydrofining catalyst is characterized by comprising the following steps: (1) Dropwise adding sodium carbonate aqueous solution into aluminum salt aqueous solution containing organic acid and organic alcohol to carry out a gelling reaction to obtain slurry I; (2) Adding nickel salt aqueous solution, sodium tungstate and sodium molybdate aqueous solution and sodium hydroxide aqueous solution into the slurry I in parallel flow for gelling reaction to obtain slurry II; (3) Aging the slurry II, carrying out solid-liquid separation after aging, and drying and forming a solid phase to obtain a formed product; (4) Desalting the molded product, washing, drying and roasting to obtain a hydrofining catalyst; the aluminum salt in the step (1) is aluminum salt without nitrogen element, and the mass concentration of the aluminum salt is Al 2 O 3 Counting to be 2-80 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; the molar ratio of the total mole number of the organic acid and the organic alcohol to the aluminum salt calculated as Al element is 0.2:1 to 3:1, a step of; 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 ethanol, isopropanol, butanol, amyl alcohol, ethylene glycol, propylene glycol and diethyl glycolOne or more of ethylene 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 gelling reaction conditions described in step (1): the gel forming temperature is 30-90 ℃, the gel forming time is 0.5-5.0 hours, and the pH value is 7.0-9.0; the gelling reaction conditions described in step (2): the gel forming temperature is 30-100 ℃, the gel forming time is 0.5-6.0 hours, and the pH value is 6.0-10.0; the aging condition in the step (3) 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; the desalination treatment process of the step (4): firstly, carrying out health preservation, and then washing to remove salt precipitated on the surface of a formed object, wherein the health preservation condition is that the temperature is 5-100 ℃ and the time is 10-100 hours; na in hydrofining catalyst 2 The O content is less than 0.12%; the hydrofining catalyst is bulk hydrofining catalyst and comprises a hydrogenation active metal component WO 3 NiO and MoO 3 And alumina, the total content of Ni, W and Mo calculated by oxide is 50% -95% based on the weight of the oxidation state hydrofining catalyst, and the content of alumina is 5% -50%; the molar ratio of W/Mo is 1: 5-27: 1, ni/(Mo+W) molar ratio of 1: 12-18: 1.
2. the method according to claim 1, characterized in that: the aluminum salt in the step (1) is one or more of aluminum chloride and aluminum sulfate.
3. 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.
4. The method according to claim 1, characterized in that: the nickel salt in the step (2) is nickel sulfate and/or nickel chloride; the mass concentration of the nickel salt aqueous solution is 3-100 g/L calculated by NiO.
5. The method according to claim 1, characterized in that: sodium tungstate and sodium molybdate in water solution, sodium tungstate is prepared by the method of WO 3 The mass concentration is 2-110 g/L, sodium molybdate is calculated by MoO 3 The mass concentration of the meter is 1-50 g/L.
6. The method according to claim 1, characterized in that: the aging condition in the step (3) is carried out in the following manner, wherein the aging is carried out at normal pressure in the first step: the aging temperature is 40-80 ℃, the aging time is 1.2-5 hours, and the pH value is 7.0-9.0; and step two, high-pressure aging: the temperature is 100-190 ℃, the time is 0.3-3.0 hours, the pressure is 10-15 MPa, and the pH value is 10.0-13.0.
7. The method according to claim 1, characterized in that: and (3) adding an extrusion aid and a peptizer in the forming process, wherein the extrusion aid is one or more of sesbania powder, carbon black, graphite powder or cellulose, and the peptizer is one or more acid solutions containing hydrochloric acid, sulfuric acid and acetic acid, and the consumption of the extrusion aid accounts for 1-10wt% of the total material dry basis.
8. The method according to claim 1, characterized in that: the desalination treatment in the step (4) 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 ℃ and the time is 1-48 hours.
9. The method according to claim 1, characterized in that: drying and roasting conditions described in step (4): drying at 50-200 deg.c for 1-48 hr and roasting at 450-600 deg.c for 0.5-24 hr.
10. The method according to claim 1, characterized in that:na in hydrofining catalyst 2 The O content is less than 0.10%.
11. The method according to claim 1, characterized in that: the pore size distribution of the hydrofinishing catalyst 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 method according to claim 1, characterized in that: 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.
13. The method according to claim 1, characterized in that: 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 use of a hydrofining catalyst prepared according to any one of claims 1 to 13 in ultra-deep hydrodesulfurization and denitrification reactions of 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 volume ratio of hydrogen to oil is 300:1-1000:1.
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