CN116943695A - Preparation method of hydrofining catalyst - Google Patents

Preparation method of hydrofining catalyst Download PDF

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CN116943695A
CN116943695A CN202210393483.0A CN202210393483A CN116943695A CN 116943695 A CN116943695 A CN 116943695A CN 202210393483 A CN202210393483 A CN 202210393483A CN 116943695 A CN116943695 A CN 116943695A
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catalyst
solution
aging
reaction
value
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徐学军
王海涛
李娟�
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—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
    • 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
    • B01J37/035—Precipitation on carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • C10G2300/1048—Middle distillates
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method of a hydrofining catalyst. The method comprises the following steps: (1) Performing gel forming reaction on a sodium hydroxide solution, a silicon-containing alkaline solution, a sodium molybdate solution and a Ni-containing solution, and performing first aging after the reaction to obtain first slurry; (2) Adding water and oleaginous liquid into a reactor, then adding a solution containing Ni and Al, a sodium tungstate solution, a sodium phosphate solution and first slurry into the reactor in parallel flow for gelling reaction, and aging for the second time after the reaction to generate second slurry; (3) Aging the second slurry, separating solid from liquid after aging, and drying and molding the solid phase to obtain a molded product; (4) Desalting the molded product, washing, drying and roasting to obtain the hydrofining catalyst with the core-shell structure. The catalyst has the advantages of low preparation cost, clean and pollution-free preparation process, capability of avoiding excessive cracking of diesel oil fraction, good raw material adaptability and capability of treating poor-quality distillate oil raw materials.

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, which is suitable for processes of hydrodesulfurization, denitrification and the like of distillate oil.
Background
In order to improve the market competitiveness of the catalyst and meet the increasingly strict environmental protection regulation requirements, the preparation of the catalyst by using raw materials with relatively low price and the preparation of the catalyst by using raw materials without nitrogen are urgently needed, and the problems of ammonia nitrogen and NO are solved from the source X The pollution problem of the catalyst is reduced.
The bulk phase hydrogenation catalyst is the catalyst with the highest hydrogenation activity center at present, the bulk phase catalyst prepared by the prior method has smaller pore volume and aperture, so that reactant molecules cannot approach the surface of the catalyst to react, and meanwhile, the smaller pore volume and specific surface area cause the excessive accumulation of high-content active metals in the bulk phase catalyst on the surface of the catalyst, thereby reducing the generation of active phases, reducing the activity of the catalyst, affecting the utilization rate of the active metals of the catalyst, and improving the use cost of the catalyst.
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 metal salt 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, even if the washing times are increased (the crushing strength of the catalyst is reduced due to the increase of the washing times), the sodium ions on the surface of the catalyst can only be removed, a large amount of sodium ions still exist in the precipitated material, the residual sodium ions cause poor adhesiveness of the material, and the sodium ions which are not removed are unfavorable for 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 existing coprecipitation method mostly adopts ammonia water as a precipitator and soluble salt containing nitrogenAs raw materials, the precipitation mode and the adhesive tape forming piece are changed to improve the distribution of hydrogenation active metals and the interaction relation between different hydrogenation active metals, but the problems that the pore volume and the specific surface area of a bulk catalyst are small, the pore diameter of the catalyst is small (the pore diameter distribution is mainly concentrated below 8 nm), the metal oxide particles in the catalyst are large, and ammonia nitrogen and NO prepared by the catalyst are not solved X The pollution problem and the higher cost. 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.
CN106179474B discloses a high-activity bulk hydrotreating catalyst and a process for preparing the same. The sediment containing W, ni and Mo is prepared by adopting a forward adding and parallel flow two-step method, and the microporous and mesoporous composite molecular sieve is added, so that the catalyst has high surface active metal content, more uniform active metal dispersion, good coordination among active metals, high active metal utilization rate, reasonable pore structure, high mechanical strength and higher hydrodesulfurization and hydrodenitrogenation activities. The catalyst prepared by the method contains molecular sieve, has stronger acidity, can improve the ultra-deep desulfurization activity of the catalyst, but has cracking reaction, and reduces the yield of diesel products.
CN102451706A discloses a preparation method of a hydrogenation catalyst composition, which adopts sodium metaaluminate solution, mixed solution containing Ni and W components and salt and CO 2 The gases react in parallel flow to form a precipitate. CN110038581a invention discloses a method for preparing hydrofining catalyst. 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 a large amount of sodium ion-containing salt is used as raw materials for carrying out precipitation reaction in the two methods, but the precipitate generated by the method contains a certain amount of sodium ions, the metal oxide particles are larger, the residual sodium ions cause poor adhesiveness of the materials, and the residual sodium ions also cause small pore volume and small specific surface area of the catalyst.
CN106513006a discloses a method for preparing bulk hydrofining catalyst, which comprises: mixing and pre-dispersing a Ni-containing compound and deionized water in an ultrasonic environment, adding a Mo-containing compound to form a Ni-Mo fine grain structure, adding a W-containing compound and a complexing agent to carry out hydrothermal reaction, kneading and extruding the obtained active component powder with aluminum hydroxide dry gel, and drying and roasting to obtain the catalyst. The catalyst prepared by the method of the invention has uniform dispersion among different active phase grains, a W source is embedded into a Ni-Mo skeleton structure, a microcosmic Ni-W active phase is easily wrapped by the Ni-Mo active phase, and the catalyst is not an oxide core-shell structure under a macroscopic state, has smaller pore volume, less effective active phase, larger metal oxide particles and limited removal efficiency of complex sulfur-containing compounds with high nitrogen content.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a hydrofining catalyst. The hydrofining catalyst is a bulk phase hydrogenation catalyst with a core-shell structure, has large pore volume and pore diameter, has high hydrodesulfurization and hydrodenitrogenation reaction performance, is low in preparation cost, clean and pollution-free in preparation process, can avoid excessive cracking of diesel oil fractions, has good raw material adaptability, and can treat poor-quality distillate oil raw materials.
The preparation method of the hydrofining catalyst comprises the following steps:
(1) Carrying out parallel flow reaction on a solution containing Ni, a sodium molybdate solution and a sodium hydroxide solution, stopping the reaction for 5-40 minutes when the volume of the solution containing Ni is still 1/5-1/2, then adding a basic solution containing silicon to continue the gelling reaction, and carrying out first aging after the reaction to obtain a first slurry containing Ni, si and Mo;
(2) Adding water and oleaginous liquid into a reactor, then adding a solution containing Ni and Al, a sodium tungstate solution, a sodium phosphate solution and first slurry into the reactor in parallel flow for a second gelling reaction, and aging for the second time after the reaction to generate second slurry;
(3) Aging the second slurry, separating solid from liquid after aging, and drying and molding the solid phase to obtain a molded product;
(4) Desalting the molded product, washing, drying and roasting to obtain the hydrofining catalyst with the core-shell structure.
In the method, the weight concentration of the sodium hydroxide solution in the step (1) is 5% -30%, and the dosage of the sodium hydroxide solution can be determined according to actual needs by a person skilled in the art.
In the method of the present invention, the alkaline solution containing silicon in the step (1) may be one or more of water glass, silica sol, and the like. Si in alkaline solution containing silicon as SiO 2 The weight concentration is 5-90 g/L, preferably 6-85 g/L.
In the method of the invention, mo in the sodium molybdate solution in the step (1) is MoO 3 The weight concentration is 5-110 g/L, preferably 10-100 g/L.
In the method, in the Ni-containing solution in the step (1), the weight concentration of Ni in terms of NiO is 5-120 g/L, preferably 10-110 g/L; in preparing the Ni-containing solution, the nickel source generally used may be one or more of nickel sulfate, nickel nitrate and nickel chloride.
In the method of the invention, the conditions of the gel forming reaction in the step (1) are as follows: the reaction temperature is 30-90 ℃, preferably 40-85 ℃, the pH value is 7.0-11.0, preferably 7.2-10.0, and the gelling time is 0.2-2.5 hours, preferably 0.3-2.0 hours.
In the method of the present invention, the first aging condition described in step (1) is as follows: the aging temperature is 60-90 ℃, preferably 65-85 ℃, the pH value is 7.0-11.0, preferably 7.2-10.5, and the aging time is 0.3-2.5 hours, preferably 0.5-2.0 hours.
In the method, in the step (1), the weight of the introduced Ni accounts for 30% -80%, preferably 35% -78% of the total Ni weight of the hydrofining catalyst obtained in the step (4), and the rest Ni in the catalyst is introduced in the step (2).
In the method of the invention, in the Ni-and Al-containing solution of the step (2), the weight concentration of Ni in terms of NiO is 5-110 g/L, preferably 10-100 g/L, and Al in terms of Al 2 O 3 The weight concentration is 2-95 g/L, preferably 5-85 g/L; when preparing Ni and Al-containing solution, the nickel source can be one or more of nickel sulfate, nickel nitrate and nickel chloride, and the aluminum source can be aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum acetate, etcOne or more of (a) and (b).
In the method of the invention, W in the sodium tungstate solution in the step (2) is expressed as WO 3 The weight concentration is 4-140 g/L, preferably 6-120 g/L;
in the method of the present invention, P is P in the sodium phosphate solution described in the step (2) 2 O 5 The weight concentration of (C) is 2-70 g/L, preferably 3-65 g/L.
In the method of the present invention, the volume ratio of the added water to the first slurry in the step (2) is 0.1: 1-3: 1.
in the method of the present invention, the oleaginous liquid in step (2) is an unsaturated higher fatty glyceride (vegetable oil), preferably one or more of peanut oil, rapeseed oil, cottonseed oil, sunflower oil, soybean oil, corn oil, tea oil, olive oil. The volume ratio of the oleaginous liquid to the water is 1: 60-1: 4, preferably 1: 40-1: 6.
in the method of the invention, the conditions of the second glue forming reaction in the step (2) are as follows: the reaction temperature is 30-90 ℃, preferably 40-85 ℃, the pH value is initially controlled to be 10.0-14.0, preferably 10.5-13.5, the final pH value is 7.0-8.5, preferably 7.2-8.3 at the end, and the gel forming reaction time is 0.5-6.0 hours, preferably 0.6-5.0 hours. Preferably, the pH value can be adjusted from the initial value to the final pH value by adopting a method of gradually adjusting the pH value to the required value, and the pH value of the reaction slurry is kept constant until the next adjustment, wherein the adjustment is carried out for 2-10 times, preferably 2-8 times. Preferably, the time is constant for 0.1 to 1.2 hours after each down-regulation. The amplitude of each down-regulation may be the same or different, and preferably, when the amplitude of the decrease in pH of the down-regulation is equal to or smaller than the amplitude of the decrease in pH of the last down-regulation. The time taken for each down-regulation process is the sum of the time taken for each down-regulation and the constant time at the pH value, further, the time taken for each down-regulation is from the beginning of the next down-regulation. The time used for each down-regulation process may be the same or different, preferably the same.
In the method of the present invention, the second aging conditions described in step (2) are as follows: the aging temperature is 40-90 ℃, the aging time is 1-5 hours, and the pH value is 7.0-11.0. The aging is generally carried out under stirring.
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 0.1-3.5 hours, preferably 0.3-2.8 hours, the pressure is not less than 10MPa, preferably 10-15 MPa, and the pH value is 10.0-13.0, preferably 10.0-12.5. The conditions relaxed in the aging process are more favorable for generating uniform particle size, the material phase structure in the first step of aging generates regular bodies in the aging process in a 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 formed by stacking irregular sheets, and the structural change enables sodium ions in the phase to be transferred to the surface of the phase, so that the method is more favorable for carrying out the next desalting treatment, the specific surface area of the bulk catalyst is also favorable for increasing, the pore structure is also favorable for improving, 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 of the invention, the solid-liquid separation in the step (3) is generally carried out by adopting modes such as filtration, centrifugation and the like. The drying temperature in the step (3) is 50-140 ℃ and the drying time is 0.5-24 hours. The molding 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 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. 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.
In the method of the invention, the desalination treatment process of the step (4) comprises the following steps: 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 ℃, preferably 10-90 ℃ and the time is 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 method of the present invention, the washing, drying and roasting in the step (4) may employ conditions conventional in the art, and the drying conditions are as follows: drying at 40-150 ℃ for 1-48 hours, preferably at 50-120 ℃ for 4-36 hours. The roasting conditions are as follows: roasting for 1-24 hours at 350-650 ℃, and the preferable roasting conditions are as follows: roasting for 2-12 hours at 400-600 ℃. The washing is generally carried out by adopting deionized water or ethanol solution to wash to neutrality.
The hydrofining catalyst is a bulk phase hydrogenation catalyst with a core-shell structure and comprises composite amorphous oxide particles, wherein a core phase is an amorphous composite oxide containing molybdenum, nickel and silicon, and a shell phase is an amorphous composite oxide containing tungsten, nickel, phosphorus and aluminum; the catalyst of the present invention may be in the form of a sheet, sphere, cylinder or special-shaped bar (clover or clover), preferably cylinder or special-shaped bar (clover or clover). The average particle diameter of the catalyst particles is 8-13 nm; the particle size distribution of the catalyst particles is as follows: the particle number of the particles with the particle size of less than 7nm accounts for 2% -15% of the total particle number, the particle number of the particles with the particle size of 7 nm-13 nm accounts for 66% -88% of the total particle number, and the particle number of the particles with the particle size of more than 13nm accounts for 3% -21% of the total particle number.
In the catalyst, based on the mass of the composite oxide particles with the core-shell structure, the core phase is 20% -90%, preferably 25% -88%, and the shell phase is 10% -80%, preferably 12% -75%.
In the catalyst of the invention, the mole ratio of molybdenum to nickel atoms in the core phase is 1: 28-12:1, preferably 1: 22-10: 1 silicon content as SiO 2 Accounting for 2 to 38 percent of the mass of the hydrofining catalyst, preferably 4 to 36 percent.
In the catalyst of the invention, the mole ratio of tungsten to nickel atoms in the shell phase is 1: 22-8: 1, preferably 1: 20-5: 1, aluminum content is Al 2 O 3 Accounting for 2 to 25 percent, preferably 5 to 22 percent, of the mass of the hydrofining catalyst, and the content of phosphorus is expressed as P 2 O 5 The mass of the catalyst accounts for 3% -20% of the mass of the hydrofining catalyst, and preferably 5% -18%.
In the catalyst, the mass of NiO in the core phase accounts for 30-80% of the total mass of NiO in the hydrofining catalyst, and the mass of NiO in the shell phase accounts for 20-70% of the total mass of NiO in the hydrofining catalyst.
Na in the catalyst of the invention 2 The O content is less than 0.12%, preferably less than 0.1%.
In the catalyst of the invention, the hydrofining catalyst has the following properties: specific surface area of 180-700 m 2 And/g, wherein the pore volume is 0.30-0.90 mL/g. The pore size distribution of the bulk hydrofining catalyst of the present invention is as follows: the pore volume occupied by the pores with the diameter of less than 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 12% -40% of the total pore volume, the pore volume occupied by the pores with the diameter of 10-15 nm accounts for 22% -56% of the total pore volume, and the pore volume with the diameter of more than 15nm accounts for 18% -45% of the total pore volume; the preferred pore size distribution is as follows: the pore volume 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 14% -36% 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 20% -42% of the total pore volume.
The application of the bulk hydrofining catalyst in the diesel hydrofining reaction is that the conditions of the diesel hydrofining reaction are as follows: the reaction temperature is 330-400 ℃, the reaction pressure is 2.5-12 MPa, and the hydrogen-oil volume ratio is 250: 1-1200: 1, the liquid hourly space velocity is 0.3-5.0 h -1 。
Compared with the prior art, the invention has the following advantages:
1. the method of the invention firstly prepares the molybdenum nickel silicon aging slurry, then the slurry, the nickel aluminum mixed solution, the sodium tungstate solution and the sodium phosphate are added into the existing reactor of water and grease liquid in parallel flow for the second glue forming, so that tungsten nickel is uniformly and orderly deposited on molybdenum nickel crystal grains, thereby forming tungsten nickel coated molybdenum nickel nano particles, and the core-shell composite oxide particles have good dispersibility. When the composite oxide of tungsten, nickel and silicon is formed in the first gel forming reaction, the quantity of acid centers at the junction of the core and the shell is better controlled by adjusting the adding mode of the silicon. When the composite oxide of tungsten, nickel and aluminum is formed by the second gel forming reaction, sodium phosphate is adopted as a precipitator to carry out the pH value decreasing method for gel forming, so that the particle size of the core-shell composite oxide is more uniform, and meanwhile, an intermediate formed between hydrogenation active metal at the junction of the auxiliary agent P and the core-shell is beneficial to improving the interaction between the hydrogenation active metal and an acid center at the junction of the core-shell. The hydrofining catalyst prepared by the method is suitable for hydrofining reaction of heavy distillate oil (such as diesel oil), is particularly beneficial to deep hydrodesulfurization and denitrification, and can avoid reducing the yield of the diesel oil.
2. In the method, a clean method is adopted to prepare the low-cost catalyst, and because the soluble sodium salt is adopted as a raw material, the precipitate contains a large amount of sodium ions after gel formation, and the existence of the large amount of sodium ions leads to smaller pore volume of the catalyst and difficult molding. 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. In the catalyst preparation process, the washing times in the conventional catalyst preparation process are reduced through desalting treatment, and the water consumption is reduced. The core-shell composite oxide structure is obtained by comprehensively controlling the preparation steps and the preparation conditions, and is more beneficial to desalting treatment of materials.
3. The hydrorefining catalyst is characterized in that the distribution state of active metal is improved from the nanometer level, namely, the catalyst is mainly composed of composite oxide particles containing tungsten, nickel and aluminum and coated with composite oxide particles containing molybdenum, nickel and silicon, the coating structure is different from a macroscopic (such as millimeter level) structure, the catalytic material structure is controlled from the microscopic level, the integral performance of the catalyst is broken through, the hydrodesulfurization performance of the catalyst is improved, a certain amount of acid centers are formed at the joint of a core-shell structure of the catalyst, the hydrodesulfurization reaction is carried out while the steric hindrance capability of the catalyst is improved, the occurrence of side reactions such as excessive cracking is reduced, and when the distillate oil raw materials containing sulfur and nitrogen (particularly the distillate oil raw materials containing sulfur and nitrogen which are difficult to remove) are contacted with the hydrorefining catalyst, the desulfurization and denitrification activities are obviously improved, meanwhile, the cracking reaction of diesel oil fraction is reduced, and the reduction of the diesel oil yield is avoided. In addition, the catalyst can reduce the content of active metal under the condition of ensuring the desulfurization and denitrification activities, thereby reducing the preparation cost of the catalyst.
Drawings
FIG. 1 is a TEM image of catalyst D obtained in example 2.
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. Measuring specific surface area, pore volume and pore size distribution by using an ASAP-2405 type BET nitrogen adsorption instrument; the crush strength of the catalyst was determined using a ZQJ-2 intelligent particle strength tester.
In the present invention, in the core-shell composite oxide particles, the metal content in the composite oxide in the core and the shell and the thickness of the shell were measured by using a TEM transmission electron microscope (Japanese JSM-2100). The method for measuring the metal content in the composite oxide in the core and the shell comprises the following steps: uniformly mixing the core-shell composite oxide particles with liquid epoxy resin, adding a proper amount of curing agent, uniformly stirring, and heating and curing to form solid particles. Cutting the solid particles into slices with the thickness of 5-20nm by adopting an ultrathin slicer, and putting the obtained slices into a transmission electron microscope for observation to find a core-shell structure (cross section) with a clear interface. The diameter of the electron beam is regulated by a condenser, so that the diameter of the electron beam is basically covered with the outline of the whole core-shell structure, an energy spectrum EDS spectrum is acquired, the intensity of a main energy peak is recorded, the actual content of each element in the known feeding is corresponding to the intensity of the energy peak of each element. And adjusting the diameter of the electron beam to be smaller than or close to the size of the core or the shell, and comparing the peak intensity of energy corresponding to the element with the peak intensity and the corresponding actual value under the condition of full coverage to calculate the metal content in the composite oxide in the core and the shell. In the core-shell structure, the thickness of the shell is distinguished from the image of the transmission electron microscope and measured, and the proportion of the thickness of the shell to the total thickness of the core-shell is the average value obtained by measuring 40-100 core-shell particles.
In the invention, wt% is mass fraction and v% is volume fraction.
Example 1
Nickel chloride was added to a dissolution tank 1 containing deionized water to prepare a Ni-containing solution in which Ni was 28g/L by weight in terms of NiO. Respectively adding nickel chloride and aluminum chloride solution into a dissolving tank 2 filled with deionized water to prepare a solution containing Ni and Al, wherein the weight concentration of Ni in the solution containing Ni and Al calculated by NiO is 24g/L, and Al is calculated by Al 2 O 3 The weight concentration is 26g/L. Wherein, the mass ratio of Ni in the Ni-containing solution used in the reaction of the embodiment to Ni in the Ni-containing solution used in the reaction of the embodiment is 14:12. the Ni-containing solution, sodium hydroxide solution (12% by weight) and sodium molybdate solution (Mo in MoO 3 36 g/L) was added dropwise to the reaction tank 1 to carry out the first gelling reaction, and when the remaining volume of the Ni-containing solution was 1/3, the gelling was stopped and left to stand for 15 minutes, and then the remaining Ni-containing solution, sodium molybdate solution and water glass (SiO) 2 And (2) continuously carrying out parallel flow gel formation until the reaction is finished, wherein the gel formation temperature is kept at 62 ℃, the pH value is controlled at 7.8 when the reaction is finished, the gel formation time is controlled at 1.2 hours, aging is carried out after the reaction is finished, the aging temperature is 78 ℃, the aging pH value is controlled at 7.5, and the aging is carried out for 1.8 hours, so as to obtain the first slurry. 800mL of deionized water and 60mL of rapeseed oil were added to the reaction tank 2, and then a sodium phosphate alkaline solution (P in sodium phosphate solution was P) 2 O 5 Is 20 g/L), a first slurry, a solution containing Ni, al and a sodium tungstate solution (W is WO) 3 Of a meter40 g/L) and then added into a reaction tank 2 in parallel to carry out a second gelling reaction, the gelling temperature is kept at 60 ℃, the pH value is initially controlled to be 13.0, the final pH value at the end is adjusted to be 7.6 by 6 times of downward adjustment of the pH value, the pH value of each downward adjustment is 0.9, the pH value of the reaction slurry after adjustment is constant for 10 minutes after each downward adjustment to the adjustment value, the second gelling reaction is started to age, the aging temperature is 78 ℃, the pH value is controlled to be 8.0, and the aging time is 2.5 hours, so as to obtain a second slurry. Filtering the aged slurry, drying the filter cake at 100 ℃ for 7 hours, rolling, and extruding strips to form clover. And (3) curing the molded strips at the temperature of 70 ℃ for 50 hours, then reducing the temperature to 20 ℃ and continuing curing for 30 hours. Washing with deionized water at room temperature to neutrality. And drying the wet strips at 100 ℃ for 12.0 hours, and roasting the dried materials at 500 ℃ for 4 hours to obtain the catalyst A. The catalyst composition and the main properties are shown in Table 1.
Example 2
Nickel chloride was added to a dissolution tank 1 containing deionized water to prepare a Ni-containing solution in which Ni was 48g/L by weight in terms of NiO. Respectively adding nickel chloride and aluminum chloride solution into a dissolving tank 2 filled with deionized water to prepare a solution containing Ni and Al, wherein the weight concentration of Ni in the solution containing Ni and Al is 20g/L calculated by NiO, and Al is calculated by Al 2 O 3 The weight concentration was 24g/L. Wherein, the mass ratio of Ni in the Ni-containing solution used in the reaction of the embodiment to Ni in the Ni-containing solution used is 24:10. The Ni-containing solution was placed in a reaction tank 1, and a sodium hydroxide solution (12% by weight) and a sodium molybdate solution (Mo in MoO 3 40 g/L) was added dropwise to the reaction tank 1 to carry out the first gelling reaction, and when the remaining volume of the Ni-containing solution was 2/5, the gelling was stopped and left standing for 18 minutes, and then the remaining Ni-containing solution, sodium molybdate solution and water glass (SiO) 2 And (2) continuously carrying out parallel flow gel formation on the sodium hydroxide solution (the weight concentration is 12%) until the reaction is finished, wherein the gel formation temperature is kept at 65 ℃, the pH value is controlled at 8.4 when the reaction is finished, the gel formation time is controlled at 1.6 hours, and after the reaction is finished, the first slurry is obtained by ageing, the ageing temperature is 78 ℃, the ageing pH value is controlled at 8.1 and the ageing time is 1.5 hours. First600mL of deionized water and 70mL of corn oil were added to reaction tank 2, followed by adding sodium phosphate alkaline solution (P in sodium phosphate solution as P) 2 O 5 Is 16 g/L), a first slurry, a solution containing Ni, al and a sodium tungstate solution (W is WO) 3 24 g/L) and then added into a reaction tank 2 in parallel to carry out a second gelling reaction, the gelling temperature is kept at 68 ℃, the pH value is initially controlled to be 12.8, the final pH value at the end is adjusted to be 8.0 by 6 times of downward pH value adjustment, the pH value of each downward pH value adjustment is 0.8, the pH value of the reaction slurry after adjustment is constant for 12 minutes after each downward pH value adjustment, the second gelling reaction is finished, the aging is started, the aging temperature is 75 ℃, the pH value is controlled to be 7.8, and the aging time is 2.9 hours, so as to obtain the second slurry. Filtering the aged slurry, drying the filter cake for the first time, drying at 120 ℃ for 8 hours, rolling, and extruding strips to form clover shape. And (3) curing the molded strips at 68 ℃ for 43 hours, then reducing the temperature to 18 ℃ and continuing curing for 35 hours. Washing with deionized water at room temperature to neutrality. The wet strips were dried at 90℃for 9.0 hours and the dried material was calcined at 540℃for 4 hours to give catalyst B. The catalyst composition and the main properties are shown in Table 1.
Example 3
Nickel chloride was added to a dissolution tank 1 containing deionized water to prepare a Ni-containing solution in which Ni was 20g/L by weight in terms of NiO. Respectively adding nickel chloride and aluminum chloride solution into a dissolving tank 2 filled with deionized water to prepare a solution containing Ni and Al, wherein the weight concentration of Ni in the solution containing Ni and Al calculated by NiO is 24g/L, and Al is calculated by Al 2 O 3 The weight concentration is 32g/L. Wherein, the mass ratio of Ni in the Ni-containing solution used in the reaction of the embodiment to Ni in the Ni-containing and Al-containing solution used is 10:12. The Ni-containing solution was placed in a reaction tank 1, and a sodium hydroxide solution (12% by weight) and a sodium molybdate solution (Mo in MoO 3 34 g/L) was dropped into the reaction tank 1 to perform the first gelling reaction, and when the remaining volume of the Ni-containing solution was 1/4, the gelling was stopped and left standing for 23 minutes, and then the remaining Ni-containing solution, sodium molybdate solution and water glass (SiO) 2 26g/L by weight), sodium hydroxide solution (14% by weight)And continuing parallel flow gel formation until the reaction is finished, keeping the gel formation temperature at 53 ℃, controlling the pH value at 8.0 when the reaction is finished, controlling the gel formation time at 1.2 hours, aging at 80 ℃ after the reaction is finished, controlling the aging pH value at 8.2, and aging for 1.7 hours to obtain the first slurry. 1000mL of deionized water and 80mL of peanut oil were added to reaction tank 2, followed by the addition of an alkaline solution of sodium phosphate (P in sodium phosphate solution with P) 2 O 5 Is at a weight concentration of 18 g/L), a first slurry, a solution containing Ni, al and a sodium tungstate solution (W in WO) 3 The measured weight concentration is 48/L) and is added into a reaction tank 2 in parallel to carry out a second gelling reaction, the gelling temperature is kept at 72 ℃, the pH value is initially controlled to be 12.9, the final pH value at the end is adjusted to be 7.9 by 5 times of downward pH value adjustment, the pH value of each downward pH value adjustment is 1.0, the pH value of the reaction slurry after adjustment is constant for 16 minutes after each downward pH value adjustment, the aging is started after the second gelling reaction is finished, the aging temperature is 82 ℃, the aging pH value is controlled to be 8.4, the aging is carried out for 3.3 hours, then the precipitate slurry is continuously aged under high pressure, the pressure is 13.5MPa, the aging temperature is 170 ℃, the aging time is 1.2 hours, and the aging pH value is 11.7, thereby obtaining the second slurry. Filtering the aged slurry, drying the filter cake at 70 ℃ for 12 hours, rolling, and extruding strips to form clover. The molded strips were subjected to curing at 65℃for 68 hours. Washing with deionized water at room temperature to neutrality. And drying the wet strips at 110 ℃ for 9.0 hours, and roasting the dried materials at 530 ℃ for 6 hours to obtain the catalyst C. The catalyst composition and the main properties are shown in Table 1.
Example 4
Nickel chloride was added to a dissolution tank 1 containing deionized water to prepare a Ni-containing solution in which Ni was 36g/L by weight in terms of NiO. Respectively adding nickel chloride and aluminum chloride solution into a dissolving tank 2 filled with deionized water to prepare a solution containing Ni and Al, wherein the weight concentration of Ni in the solution containing Ni and Al is 20g/L calculated by NiO, and Al is calculated by Al 2 O 3 The weight concentration is 32g/L. Wherein, the mass ratio of Ni in the Ni-containing solution used in the reaction of the embodiment to Ni in the Ni-containing solution used is 18:10. The Ni-containing solution was placed in a reaction tank 1, and a sodium hydroxide solution (weight concentration15% of the degree) and sodium molybdate solution (Mo in MoO 3 28 g/L) was added dropwise to the reaction tank 1 to carry out the first gelling reaction, and when the remaining volume of the Ni-containing solution was 1/3, the gelling was stopped and left standing for 18 minutes, and then the remaining Ni-containing solution, sodium molybdate solution and dilute water glass Solution (SiO) 2 And (2) continuously carrying out parallel flow gel formation on the sodium hydroxide solution (the weight concentration is 10%) until the reaction is finished, wherein the gel formation temperature is kept at 65 ℃, the pH value is controlled at 8.3 when the reaction is finished, the gel formation time is controlled at 1.4 hours, and after the reaction is finished, the first slurry is obtained by ageing the slurry at the ageing temperature of 85 ℃, the ageing pH value is controlled at 8.3 and the ageing time is controlled at 1.5 hours. 800mL of deionized water and 70mL of sunflower seed oil are added into a reaction tank 2, and then sodium phosphate alkaline solution (P is P in sodium phosphate solution) 2 O 5 Is 20 g/L), a first slurry, a solution containing Ni, al and a sodium tungstate solution (W is WO) 3 44 g/L) and then added into a reaction tank 2 for a second gelling reaction, the gelling temperature is kept at 50 ℃, the pH value is initially controlled to be 12.5, the final pH value at the end is adjusted to be 7.1 by 6 down-regulating the pH value, the pH value of each down-regulating is 0.9, the pH value of the reaction slurry after adjustment is constant for 13 minutes after each down-regulating to the regulating value, the aging is started after the second gelling reaction is finished, the aging temperature is 77 ℃, the aging pH value is controlled to be 8.2, the aging time is 2.8 hours, then the precipitate slurry is continuously aged under high pressure, the pressure is 13.2MPa, the aging temperature is 165 ℃, the aging time is 1.8 hours, and the aging pH value is 11.4. A second slurry is obtained. Filtering the aged slurry, drying the filter cake at 90 ℃ for 12 hours, rolling, and extruding strips to form clover. And (3) curing the molded strips at the temperature of 70 ℃ for 47 hours, then reducing the temperature to 23 ℃ and continuing curing for 32 hours. Washing with deionized water at room temperature to neutrality. And drying the wet strips at 120 ℃ for 8.0 hours, and roasting the dried materials at 520 ℃ for 5 hours to obtain the catalyst D. The catalyst composition and the main properties are shown in Table 1.
Comparative example 1
Reference E, which had the same composition as the catalyst of example 1, was prepared as follows:
catalyst according to example 1The composition is that nickel chloride, aluminum chloride and water glass are dissolved in deionized water to prepare a mixed solution, wherein the weight concentration of Ni calculated by NiO is 52g/L, and Al calculated by Al 2 O 3 The weight concentration is 36g/L, siO 2 The weight concentration of (C) is 36g/L. 500mL of deionized water was added to the reaction tank, and 10wt% NaOH solution and sodium molybdate solution (Mo in MoO 3 The weight concentration is 36 g/L), sodium tungstate solution (W is WO 3 40 g/L) and the mixed solution are added into a reaction tank in parallel to form gel, the gel forming temperature is kept at 62 ℃, the pH value is controlled at 7.8 at the end, and the gel forming time is controlled at 1.2 hours, so as to generate the slurry containing nickel and tungsten precipitates. Then aging for 2.0 hours, wherein the aging temperature is 78 ℃, the pH value is controlled to be 7.5 during aging, the reaction slurry is filtered after the aging is finished, the filter cake is dried for 7 hours at 100 ℃, rolled and extruded to form the product. The molded article was washed with deionized water at room temperature, and no molded article was obtained after washing. The powder was dried at 100℃for 12 hours and calcined at 500℃for 4 hours to give catalyst E. The catalyst composition and the main properties are shown in Table 1.
Comparative example 2
Reference F, which was close to the catalyst composition of example 1, was prepared according to the method disclosed in CN102049295a, as follows:
after 1000mL of deionized water is added into a dissolution tank, nickel chloride, ammonium metatungstate and aluminum chloride solution are sequentially added, and the mixture is prepared after uniform stirring. Wherein the weight concentration of Ni in terms of NiO is 52g/L, and W in terms of WO 3 The weight concentration is 40g/L, al is expressed as Al 2 O 3 The weight concentration was 54g/L. 160g of ammonium bicarbonate was prepared as an aqueous solution having a molar concentration of 2.5 mol/L. Then the mixed solution, ammonium bicarbonate aqueous solution and precipitator 10% ammonia water are added into a reaction tank filled with deionized water simultaneously in parallel flow for gelling, the pH value of the gelling is 7.8, and the gelling temperature is 62 ℃. After the gel formation is finished, adding slurry containing the SAPO-11 molecular sieve, aging for 2 hours at the aging temperature of 78 ℃ and controlling the pH value at 7.5 during aging. Filtering after aging, adding 600mL deionized water and 36 g molybdenum trioxide into the filter cake, pulping and stirring uniformly, filtering, drying the obtained filter cake at 100 ℃ for 7 hours, extruding strips for molding, washing with deionized water untilThe neutral, wet strips were dried at 100℃for 12 hours and calcined at 500℃for 4 hours to give the final catalysts F, the composition and the main properties of which are given in Table 1.
The SAPO-11 molecular sieve used in the comparative example was that used in CN102049295a, and can be synthesized by conventional methods, such as hydrothermal crystallization, and has the following properties: siO (SiO) 2 /Al 2 O 3 The molar ratio is 0.85, the infrared acid amount is 0.9mmol/g, the pore volume is 0.24mL/g, and the specific surface area is 250m 2 And/g, particle size of 450nm and crystallinity of 85%.
Comparative example 3
Reference G was prepared according to the procedure of example 1 (no grease was added to the tank during the second step of gelling) and catalyst composition.
Nickel chloride was added to a dissolution tank 1 containing deionized water to prepare a Ni-containing solution in which Ni was 28g/L by weight in terms of NiO. Respectively adding nickel chloride and aluminum chloride solution into a dissolving tank 2 filled with deionized water to prepare a solution containing Ni and Al, wherein the weight concentration of Ni in the solution containing Ni and Al calculated by NiO is 24g/L, and Al is calculated by Al 2 O 3 The weight concentration is 26g/L. Wherein, the mass ratio of Ni in the Ni-containing solution used in the reaction of the embodiment to Ni in the Ni-containing solution used in the reaction of the embodiment is 14:12. the Ni-containing solution, sodium hydroxide solution (12% by weight) and sodium molybdate solution (Mo in MoO 3 36 g/L) was added dropwise to the reaction tank 1 to carry out the first gelling reaction, and when the remaining volume of the Ni-containing solution was 1/3, the gelling was stopped and left to stand for 15 minutes, and then the remaining Ni-containing solution, sodium molybdate solution and dilute water glass Solution (SiO) 2 And (2) continuously carrying out parallel flow gel formation on the sodium hydroxide solution (the weight concentration is 12%) until the reaction is finished, wherein the gel formation temperature is kept at 62 ℃, the pH value is controlled at 7.8 when the reaction is finished, the gel formation time is controlled at 1.2 hours, and after the reaction is finished, the first slurry is obtained by ageing at 78 ℃, the ageing pH value is controlled at 7.5 and the ageing time is 1.8 hours. 800mL of deionized water was added to reaction tank 2, followed by adding sodium phosphate alkaline solution (P in sodium phosphate solution as P) 2 O 5 Is 20 g/L), a first slurry, a solution containing Ni, al and a sodium tungstate solution (W is expressed asWO 3 40 g/L) and the mixture is added into a reaction tank 2 in parallel to carry out a second gelling reaction, the gelling temperature is kept at 60 ℃, the pH value is initially controlled to be 13.0, the final pH value at the end is adjusted to be 7.6 by 6 times of downward pH value adjustment, the pH value of each downward pH value adjustment is 0.9, the pH value of the reaction slurry after adjustment is constant for 10 minutes after each downward pH value adjustment, the second gelling reaction is finished, the aging is started, the aging temperature is 78 ℃, the pH value is controlled to be 8.0, and the aging time is 2.5 hours, so that the second slurry is obtained. Filtering the aged slurry, drying the filter cake at 100 ℃ for 7 hours, rolling, and extruding strips to form clover. And (3) curing the molded strips at the temperature of 70 ℃ for 50 hours, then reducing the temperature to 20 ℃ and continuing curing for 30 hours. Washing with deionized water at room temperature to neutrality. And drying the wet strips at 100 ℃ for 12.0 hours, and roasting the dried materials at 500 ℃ for 4 hours to obtain the catalyst G. The catalyst composition and the main properties are shown in Table 1.
Comparative example 4
Reference H was prepared following the procedure of example 1 (no silicon was added when preparing mixed solution A).
Adding nickel chloride and aluminum chloride solution into a dissolution tank 1 filled with deionized water to prepare a solution A containing Ni and Al, wherein the weight concentration of Ni in the solution A containing Ni and Al calculated as NiO is 28g/L, and Al is calculated as Al 2 O 3 The weight concentration is 26g/L. Respectively adding nickel chloride and aluminum chloride solution into a dissolution tank 2 filled with deionized water to prepare a solution B containing Ni and Al, wherein the weight concentration of Ni in the solution B containing Ni and Al calculated by NiO is 24g/L, and Al is calculated by Al 2 O 3 The weight concentration is 26g/L. Wherein, the mass ratio of Ni in the Ni-containing solution used in the reaction of the embodiment to Ni in the Ni-containing solution used in the reaction of the embodiment is 14:12. a solution A containing Ni and Al, a sodium hydroxide solution (12% by weight) and a sodium molybdate solution (Mo in MoO 3 The measured weight concentration is 36 g/L) is dripped into a reaction tank 1 to carry out a first gel forming reaction, the gel forming temperature is kept at 62 ℃, the pH value is controlled at 7.8 when the reaction is finished, the gel forming time is controlled at 1.2 hours, aging is carried out after the reaction is finished, the aging temperature is 78 ℃, the aging pH value is controlled at 7.5, and the aging is carried out for 1.8 hours, thus obtaining the first slurry. 800mL deionized water and 60m were first added L rapeseed oil is added into a reaction tank 2, and then sodium phosphate alkaline solution (P is P in sodium phosphate solution 2 O 5 Is 20 g/L), a first slurry, a solution B containing Ni and Al, and a sodium tungstate solution (W is WO) 3 40 g/L) and the mixture is added into a reaction tank 2 in parallel to carry out a second gelling reaction, the gelling temperature is kept at 60 ℃, the pH value is initially controlled to be 13.0, the final pH value at the end is adjusted to be 7.6 by 6 times of downward pH value adjustment, the pH value of each downward pH value adjustment is 0.9, the pH value of the reaction slurry after adjustment is constant for 10 minutes after each downward pH value adjustment, the second gelling reaction is finished, the aging is started, the aging temperature is 78 ℃, the pH value is controlled to be 8.0, and the aging time is 2.5 hours, so that the second slurry is obtained. Filtering the aged slurry, drying the filter cake at 100 ℃ for 7 hours, rolling, and extruding strips to form clover. And (3) curing the molded strips at the temperature of 70 ℃ for 50 hours, then reducing the temperature to 20 ℃ and continuing curing for 30 hours. Washing with deionized water at room temperature to neutrality. And drying the wet strips at 100 ℃ for 12.0 hours, and roasting the dried materials at 500 ℃ for 4 hours to obtain the catalyst H. The catalyst composition and the main properties are shown in Table 1.
Comparative example 5
Catalyst I 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.
Nickel chloride was added to a dissolution tank 1 containing deionized water to prepare a Ni-containing solution in which Ni was 28g/L by weight in terms of NiO. Respectively adding nickel chloride and aluminum chloride solution into a dissolving tank 2 filled with deionized water to prepare a solution containing Ni and Al, wherein the weight concentration of Ni in the solution containing Ni and Al calculated by NiO is 24g/L, and Al is calculated by Al 2 O 3 The weight concentration is 26g/L. Wherein, the mass ratio of Ni in the Ni-containing solution used in the reaction of the embodiment to Ni in the Ni-containing solution used in the reaction of the embodiment is 14:12. the Ni-containing solution, sodium hydroxide solution (12% by weight) and sodium molybdate solution (Mo in MoO 3 The weight concentration is 36 g/L) is dripped into the reaction tank 1 to carry out the first gel forming reaction, when the residual volume of the Ni-containing solution is 1/3, the gel forming is stopped, the reaction is kept stand for 15 minutes, and then the residual Ni-containing solution and sodium molybdate solution are addedAnd dilute water glass Solutions (SiO) 2 And sodium hydroxide solution (weight concentration is 12%) are continuously subjected to parallel flow gel formation until the reaction is finished, the gel formation temperature is kept at 62 ℃, the pH value is controlled at 7.8 when the reaction is finished, the gel formation time is controlled at 1.2 hours, aging is performed after the reaction is finished, the aging temperature is 78 ℃, the aging pH value is controlled at 7.5, and the aging is performed for 1.8 hours, so that the first slurry is obtained. 800mL of deionized water and 60mL of rapeseed oil were added to the reaction tank 2, and then a sodium phosphate alkaline solution (P in sodium phosphate solution was P) 2 O 5 Is 20 g/L), a first slurry, a solution containing Ni, al and a sodium tungstate solution (W is WO) 3 40 g/L) and the mixture is added into a reaction tank 2 in parallel to carry out a second gelling reaction, the gelling temperature is kept at 60 ℃, the pH value is initially controlled to be 13.0, the final pH value at the end is adjusted to be 7.6 by 6 times of downward pH value adjustment, the pH value of each downward pH value adjustment is 0.9, the pH value of the reaction slurry after adjustment is constant for 10 minutes after each downward pH value adjustment, the second gelling reaction is finished, the aging is started, the aging temperature is 78 ℃, the pH value is controlled to be 8.0, and the aging time is 2.5 hours, so that the second slurry is obtained. Filtering the aged slurry, drying the filter cake at 100 ℃ for 7 hours, rolling, and extruding strips to form clover. Washing with deionized water at room temperature, no molded article was obtained after washing. The powder was calcined at 500℃for 4 hours to give catalyst I. The catalyst composition and the main properties are shown in Table 1.
Comparative example 6
According to the preparation method disclosed in CN106513006A, a reference agent J close to the catalyst composition of the embodiment 1 of the invention is prepared by the following specific procedures:
adding nickel carbonate and 300ml of deionized water into a 1L high-pressure ultrasonic reaction kettle after uniformly mixing, setting the ultrasonic frequency to be 60KHz, heating the mixture to 80 ℃, keeping the temperature constant for 1h, reducing the ultrasonic frequency to 20KHz, increasing the temperature of the system to 120 ℃, adding ammonium molybdate and 3g of polyvinylpyrrolidone, then adding 10ml of ammonia water with the concentration of 25wt% into the system dropwise, keeping the temperature constant for 2h, closing the ultrasonic, starting stirring, rotating at 300 revolutions per minute, adding ammonium metatungstate, then adding citric acid to the system until the pH value is 4.2, keeping the temperature constant for 2h, closing the heating, cooling the system to room temperature, collecting slurry, carrying out spray drying treatment on the slurry, controlling the inlet temperature and the outlet temperature to be about 200 ℃ and 100 ℃ respectively, and roasting the obtained dry powder in a muffle furnace at 330 ℃ for 3h to obtain active component powder. Mixing the active component powder with aluminum hydroxide dry gel, adding 10% dilute nitric acid aqueous solution, kneading and extruding to obtain strip, drying at 110deg.C for 10 hr, and calcining at 400deg.C for 5 hr in a muffle furnace to obtain reference agent J, wherein the composition and main properties of the catalyst are shown in Table 1.
Comparative example 7
According to the preparation method disclosed in CN1951558A, a reference agent K is prepared, and the specific steps are as follows:
adding deionized water into a dissolving tank, adding nickel chloride, ammonium metatungstate and aluminum chloride for dissolving, preparing an acidic working solution A, wherein the weight concentration of Ni in the solution A calculated by NiO is 74.8g/L, and W is WO 3 The weight concentration is 48.6g/L, al is Al 2 O 3 The weight concentration was 44g/L and the pH of solution A was 1.8. 350mL of deionized water was added to the reaction tank and the temperature was raised to 62 ℃. Under the condition of stirring, adding the solution A and 10wt% ammonia water into a reaction tank in parallel flow for gelling, wherein the gelling temperature is 62 ℃, the gelling time is 1 hour, and the pH value of slurry in the gelling process is 8.5. Aging for 2 hours after the gel forming is finished, wherein the aging temperature is 75 ℃, and the pH value is controlled at 7.6 during aging. Then filtering, adding 600mL deionized water and 32.6g molybdenum trioxide into the filter cake, pulping and stirring uniformly, filtering, drying the filter cake at 120 ℃ for 8 hours, rolling, and extruding strips to form a cylinder. Washing with deionized water at room temperature to neutrality. The wet strips were then dried at 80℃for 10 hours and calcined at 500℃for 4 hours to give catalyst K. The catalyst composition and the main properties are shown in Table 1.
Example 5
This example is an evaluation experiment of the activity of the catalyst of the present invention and is compared with a comparative catalyst. From the physicochemical properties of the catalysts in Table 1, when the sodium-containing raw materials are more raw materials in the preparation process, the catalyst A, B, C and the comparative catalyst F, G, H, J, K are adopted respectively during washing (the activity evaluation is not performed on the powder formed after the comparative catalyst E, F is washed), a comparative evaluation test is performed on a 200mL small hydrogenation device, and the mixed diesel (straight-run diesel and coked diesel) The weight ratio of the catalytic diesel oil is 28:20:52 As a test raw material, and evaluating the catalyst activity under the process conditions: the hydrogen partial pressure is 6.4MPa, the reaction temperature is 365 ℃, and the liquid hourly space velocity is 2.0h -1 The hydrogen oil volume ratio was 500:1, and the main properties of the raw materials are shown in Table 4. The results of the catalyst activity evaluation are shown in Table 5. The type of sulfide in the hydrofinished oil was detected by a gas chromatograph-atomic emission spectroscopy detector (GC-AED), and the results are shown in table 6.
As can be seen from Table 1, when the catalyst of the present invention uses a large amount of sodium-containing raw material in the preparation process, the catalyst has good crush strength after being subjected to desalting treatment and washing after molding, and the molded catalyst strips are turned into powder after washing without desalting treatment.
As can be seen from the evaluation results, compared with the catalyst of the comparative example, the catalyst of the invention shows high hydrodesulfurization activity when removing the refractory 4,6-DMDBT macromolecular sulfides, has excellent ultra-deep hydrodesulfurization activity, and simultaneously has good yield of diesel products. When the activity evaluation reaction space velocity is increased, the catalyst still has excellent ultra-deep desulfurization activity by increasing the reaction temperature, and compared with the evaluation result of the catalyst of the comparative example, the catalyst effectively reduces the influence of the thermodynamic equilibrium of a high-temperature hydrogenation path and has good temperature adaptability. The hydrofining catalyst has larger pore volume and specific surface area, the pore distribution is mainly concentrated above 10nm, and the catalyst has excellent ultra-deep hydrodesulfurization and denitrification performances when being used for processing light distillate oil, especially for processing poor diesel oil fraction.
Table 1 composition and properties of the catalysts prepared in examples and comparative examples
Catalyst numbering A B C D
NiO，wt% 26 34 22 28
WO 3 ，wt% 20 12 24 22
MoO 3 ，wt% 18 20 17 14
SiO 2 ，wt% 13 14 12 10
Al 2 O 3 ，wt% 13 12 16 16
P 2 O 5 ，wt% 10 8 9 10
Na 2 O，% 0.076 0.078 0.084 0.068
Specific surface area, m 2 /g 301 316 305 299
Pore volume, mL/g 0.415 0.433 0.420 0.411
Pore distribution
＜4nm 4.34 4.06 4.25 4.42
4nm~10nm 22.83 22.03 22.25 23.13
10nm~15nm 41.94 42.78 42.56 41.63
＞15nm 30.89 31.13 30.94 30.82
Mechanical strength, N/mm 19.6 19.5 19.6 19.8
TABLE 1 compositions and Properties of catalysts prepared in examples and comparative examples
Catalyst numbering E F G H I J K
NiO，wt% 26 26 26 26 26 26 37.4
WO 3 ，wt% 20 20 20 20 20 20 24.3
MoO 3 ，wt% 18 18 18 18 18 18 16.3
SiO 2 ，wt% 18 4 13 - 13 - -
Al 2 O 3 ，wt% 18 28 13 26 13 36 22
P 2 O 5 ，wt% - 4 10 10 10 - -
Na 2 O，% 0.42 0.14 0.094 0.079 0.551 0.13 0.13
Comparison meterArea, m 2 /g 142 199 259 299 245 283 174
Pore volume, mL/g 0.232 0.252 0.363 0.412 0.357 0.385 0.301
Pore distribution
＜4nm 62.81 22.82 11.85 4.68 15.43 38.21 46.87
4nm~10nm 30.52 71.44 34.13 22.92 40.64 48.61 40.72
10nm~15nm 4.37 4.50 35.44 41.87 29.72 7.28 8.26
＞15nm 2.30 1.24 18.58 30.53 14.21 5.90 4.15
Mechanical strength, N/mm - 17.6 18.8 19.7 - 13.5 19.1
TABLE 2 composition of composite oxides in core and shell of the catalysts obtained in each example
Catalyst numbering A B C D G H I
Based on the mass of the catalyst, the composite oxide composition in the core
NiO，wt% 14 24 10 18 17 14 14
MoO 3 ，wt% 18 20 17 14 13 18 18
SiO 2 ，wt% 13 14 12 10 8 - 13
WO 3 ，wt% - - - - 8 - -
Al 2 O 3 ，wt% - - - - 4 13 -
P 2 O 5 ，wt% - - - - 4
Composition of composite oxide in shell based on catalyst mass
NiO，wt% 12 10 12 10 9 12 12
WO 3 ，wt% 20 12 24 22 12 20 20
Al 2 O 3 ，wt% 13 12 16 16 9 13 13
MoO 3 ，wt% - - - - 5 - -
SiO 2 ，wt% - - - - 5 - -
P 2 O 5 ，wt% 10 8 9 10 6 10 10
Table 3 average particle diameter and particle diameter distribution of the core-shell composite oxide particles of the catalysts obtained in each example
Catalyst numbering A B C D E F
Average particle diameter, nm, of core-shell composite oxide particles 9.5 9.8 9.7 10.0 33.6 23.8
Particle size distribution of core-shell composite oxide particles,%
Particle size of less than 7nm 5.35 5.11 5.24 5.04 3.32 4.05
Particle diameter of 7nm-13nm 84.44 83.56 83.75 83.39 21.22 28.19
Particle size of greater than 13nm 10.21 11.33 11.01 11.57 77.46 67.76
TABLE 3 average particle diameter and particle diameter distribution of the core-shell composite oxide particles of the catalysts obtained in each example
Catalyst numbering G H I J K
Average particle diameter, nm, of core-shell composite oxide particles 31.5 9.6 12.0 24.4 19.4
Particle size distribution of core-shell composite oxide particles,%
Particle size of less than 7nm 3.76 5.27 6.09 8.93 8.42
Particle diameter of 7nm-13nm 28.13 84.55 77.42 28.46 33.62
Particle size of greater than 13nm 68.11 10.18 16.49 62.61 57.96
TABLE 4 Main Properties of raw oil
Project Analysis results
Density (20 ℃), g/cm 3 0.8897
Distillation range, DEG C 175-379
S，µg/g 13100
N，µg/g 922
TABLE 5 evaluation results of catalyst Activity
Catalyst numbering A B C F G H J K
Oil density (20 ℃ C.) g/cm was produced 3 0.8635 0.8633 0.8638 0.8656 0.8718 0.8664 0.8732 0.8707
S，µg/g 7.4 7.2 7.7 38.2 136.9 38.5 236.8 118.8
N，µg/g 3.1 3.0 3.3 16.4 66.2 14.4 112.8 62. 2
Yield of diesel oil, percent 99.2 99.1 99.2 86.6 98.7 99.1 98.3 98.9
TABLE 6 content of different sulfides in hydrofined oils
Catalyst numbering A B C F G H J K
Sulfur content in hydrorefining oil, mug/g 7.4 7.2 7.7 38.2 136.9 38.5 236.8 118.8
C 1 -DBT，µg/g 0 0 0 3.2 9.3 3.9 22.1 9.1
4- MDBT，µg/g 1.6 1.6 1.6 8.1 28.2 10.1 52.2 25.4
6-MDBT，µg/g 2.3 2.2 2.4 9.6 31.3 8.2 60.2 26.3
4，6- DMDBT，µg/g 3.5 3.4 3.7 17.3 68.1 16.3 102.3 58.0

Claims (21)

1. A preparation method of a hydrofining catalyst is characterized by comprising the following steps: (1) Carrying out parallel flow reaction on a solution containing Ni, a sodium molybdate solution and a sodium hydroxide solution, stopping the reaction for 5-40 minutes when the volume of the solution containing Ni is still 1/5-1/2, then adding a basic solution containing silicon to continue the gelling reaction, and carrying out first aging after the reaction to obtain a first slurry containing Ni, si and Mo; (2) Adding water and oleaginous liquid into a reactor, then adding a solution containing Ni and Al, a sodium tungstate solution, a sodium phosphate solution and first slurry into the reactor in parallel flow for gelling reaction, and aging for the second time after the reaction to generate second slurry; (3) Aging the second slurry, separating solid from liquid after aging, and drying and molding the solid phase to obtain a molded product; (4) Desalting the molded product, washing, drying and roasting to obtain the hydrofining catalyst with the core-shell structure.
2. The method according to claim 1, characterized in that: the weight concentration of the sodium hydroxide solution in the step (1) is 5% -30%.
3. The method according to claim 1, characterized in that: the alkaline solution containing silicon in the step (1) can be one or more of water glass and silica sol; si in alkaline solution containing silicon as SiO 2 The weight concentration of the meter is 5-90 g/L.
4. The method according to claim 1, characterized in that: in the sodium molybdate solution in the step (1), mo is expressed as MoO 3 The weight concentration of the meter is 5-110 g/L.
5. The method according to claim 1, characterized in that: in the Ni-containing solution in the step (1), the weight concentration of Ni in terms of NiO is 5-120 g/L.
6. The method according to claim 1, characterized in that: the conditions of the gel forming reaction in the step (1) are as follows: the reaction temperature is 30-90 ℃, the pH value is 7.0-11.0, and the gelling time is 0.2-2.5 hours.
7. The method according to claim 1, characterized in that: the first aging condition described in step (1) is as follows: the aging temperature is 60-90 ℃, the pH value is 7.0-11.0 during aging, and the aging time is 0.3-2.5 hours.
8. The method according to claim 1, characterized in that: in the step (1), the weight of the introduced Ni accounts for 30% -80% of the total weight of Ni in the hydrofining catalyst obtained in the step (4), and the rest Ni in the catalyst is introduced in the step (2).
9. The method according to claim 1, characterized in that: in the Ni and Al-containing solution in the step (2), the weight concentration of Ni in terms of NiO is 5-110 g/L, and Al in terms of Al 2 O 3 The weight concentration of the meter is 2-95 g/L; in the sodium tungstate solution in the step (2), W is WO 3 The weight concentration is 4-140 g/L.
10. The method according to claim 1, characterized in that: p in the sodium phosphate solution described in step (2) to P 2 O 5 The weight concentration of (C) is 2-70 g/L, preferably 3-65 g/L.
11. The method according to claim 1, characterized in that: the volume ratio of the added water to the first slurry in step (2) was 0.1: 1-3: 1.
12. the method according to claim 1, characterized in that: the oleaginous liquid in the step (2) is unsaturated higher fatty glyceride which is one or more of peanut oil, rapeseed oil, cotton seed oil, sunflower seed oil, soybean oil, corn oil, tea oil and olive oil; the volume ratio of the oleaginous liquid to the water is 1: 60-1: 4.
13. the method according to claim 1, characterized in that: the conditions of the gel forming reaction in the step (2) are as follows: the reaction temperature is 30-90 ℃, the pH value is initially controlled to be 10.0-14.0, the final pH value is 7.0-8.5 at the end, and the gel forming reaction time is 0.5-6.0 hours; the pH value is adjusted down from the initial value to the final pH value by adopting a method of multiple times, wherein the method of multiple times of adjustment is that the pH value is adjusted down to the current required value, and the pH value of the reaction slurry is kept constant until the next adjustment is started, and the number of times of adjustment is 2-10.
14. The method according to claim 1, characterized in that: the second aging conditions described in step (2) are as follows: the aging temperature is 40-90 ℃, the aging time is 1-5 hours, and the pH value is 7.0-11.0.
15. The method of claim 1, wherein the aging conditions of step (2) are performed as follows, the first step of atmospheric aging: the aging temperature is 30-90 ℃, preferably 40-80 ℃, the aging time is 1-6 hours, and the pH value is 6.5-10.0; and step two, high-pressure aging: the temperature is 100-195 ℃, the time is 0.1-3.5 hours, the pressure is 10-15 MPa, and the pH value is 10.0-13.0.
16. The method according to claim 1, characterized in that: the desalination treatment process of the step (4): 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.
17. 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 second stage is at 10-30 deg.c for 1-48 hr, and then washing to eliminate salt.
18. The hydrofining catalyst prepared by the method according to any one of claims 1 to 17, which is characterized in that: the catalyst is a bulk phase hydrogenation catalyst with a core-shell structure and comprises composite amorphous oxide particles, wherein the core phase is an amorphous composite oxide containing molybdenum, nickel and silicon, and the shell phase is an amorphous composite oxide containing tungsten, nickel, phosphorus and aluminum; the catalyst is in the shape of a sheet, a sphere, a cylindrical bar and a special-shaped bar; the average particle diameter of the catalyst particles is 8-13 nm; the particle size distribution of the catalyst particles is as follows: the particle number of the particles with the particle size of less than 7nm accounts for 2% -15% of the total particle number, the particle number of the particles with the particle size of 7 nm-13 nm accounts for 66% -88% of the total particle number, and the particle number of the particles with the particle size of more than 13nm accounts for 3% -21% of the total particle number.
19. The catalyst of claim 18, wherein: based on the mass of the composite oxide particles with the core-shell structure, the core phase is 20% -90%, and the shell phase is 10% -80%; the molar ratio of molybdenum to nickel atoms in the core phase is 1: 28-12: 1 silicon content as SiO 2 Accounting for 2-38% of the mass of the hydrofining catalyst; the molar ratio of tungsten to nickel atoms in the shell phase is 1: 22-8: 1, aluminum content is Al 2 O 3 Accounting for 2 to 25 percent of the mass of the hydrofining catalyst, and the content of phosphorus is expressed as P 2 O 5 The calculated mass accounts for 3% -20% of the mass of the hydrofining catalyst, and preferably 5% -18%; na (Na) 2 The O content is less than 0.12%.
20. The catalyst of claim 18, wherein: the hydrofining catalyst has the following properties: specific surface area of 180-700 m 2 Per gram, the pore volume is 0.30-0.90 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 12% -40% of the total pore volume, the pore volume of the pores with the diameter of 10-15 nm accounts for 22% -56% of the total pore volume, and the pore volume of the pores with the diameter of more than 15nm accounts for 18% -45% of the total pore volume.
21. The use of a hydrofining catalyst prepared according to any one of claims 1-17 in a diesel hydrofining reaction.
CN202210393483.0A 2022-04-15 2022-04-15 Preparation method of hydrofining catalyst Pending CN116943695A (en)

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