CN113522353B - Preparation method of hydrotreating catalyst - Google Patents

Preparation method of hydrotreating catalyst Download PDF

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Publication number
CN113522353B
CN113522353B CN202010314422.1A CN202010314422A CN113522353B CN 113522353 B CN113522353 B CN 113522353B CN 202010314422 A CN202010314422 A CN 202010314422A CN 113522353 B CN113522353 B CN 113522353B
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metal
molecular sieve
composite carrier
porous composite
hierarchical porous
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CN113522353A (en
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孙进
郭蓉
李扬
段为宇
姚运海
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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
    • 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)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a preparation method of a hydrotreating catalyst, which comprises the following steps: (1) preparing a metal modified hierarchical porous composite carrier; (2) preparing an active metal impregnation liquid: mixing and dissolving an ionic liquid, a surfactant, a VIB group metal salt and a VIII group metal salt in water to obtain an impregnating solution; (3) And (3) impregnating the metal modified hierarchical porous composite carrier in the step (1) by adopting the impregnating solution in the step (2), and then drying to obtain the hydrotreating catalyst. According to the method, the reduced metal with the hydrogen dissociation function is loaded in the pore canal of the smaller molecular sieve, the hydrogenation active metal is loaded in and on the stacking hole and surface of the larger molecular sieve and the alumina, and the prepared catalyst fully exerts the material diffusion advantage of the large pore canal of the molecular sieve and the acidic and hydrogen overflow effects of the small pore diameter in the molecular sieve, and has very high hydrogenation performance.

Description

Preparation method of hydrotreating catalyst
Technical Field
The invention relates to a preparation method of a hydrotreating catalyst, in particular to a preparation method of a hydrodesulphurization dearomatization catalyst for diesel oil.
Background
With the continuous improvement of the national environmental protection requirements, the low sulfur and low aromatic hydrocarbon of the vehicular diesel oil are the future development trend. The hydrotreating process is used as a main means for producing low-sulfur low-aromatic hydrocarbon diesel oil for vehicles in refineries, and has higher requirements on hydrotreating catalysts. The composite molecular sieve-alumina material has stronger hydrogen adsorption capacity due to the characteristics of multistage pore canal, high specific surface area and proper acid distribution, and is used for preparing desulfurization and dearomatization catalysts in recent years.
However, in the hydrotreating process of the catalyst prepared from the material, the desulfurization reaction and the dearomatization reaction have the problem of mutual restriction, in general, the hydrodesulfurization activity of the catalyst is improved by increasing the reaction temperature, but the condensation reaction of the arene is easier to occur by increasing the temperature, the arene is difficult to desorb from small pore channels of the catalyst, and carbon is accumulated in the pore channels of the catalyst, so that the activity of the catalyst is influenced. Meanwhile, as the sulfide of the macromolecule is influenced by the diffusion effect of the pore canal, the sulfide is not easy to generate adsorption-reaction process with the active metal in the small pore canal, the desulfurization reaction is influenced, and the active metal in the small pore canal is difficult to play a role. How to better match the active metal of the catalyst with the multilevel pore canal of the composite material, fully exert the function of loading the active metal, reduce the carbon deposition generation rate of the catalyst, and improve the conversion rate of sulfides and aromatic hydrocarbons in the hydrotreating process of the catalyst is a problem to be solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a hydrotreating catalyst. According to the method, reduced metal with a hydrogen dissociation function is loaded in a small molecular sieve pore canal, hydrogenation active metal (such as Mo/W-Ni/Co) is loaded in and on a large molecular sieve-alumina stacking hole, and the prepared catalyst fully exerts the material diffusion advantage of the large pore canal of the molecular sieve-alumina carrier and the acid and hydrogen overflow effect of the small pore diameter in the molecular sieve, so that the catalyst has very high hydrogenation performance.
The preparation method of the hydrotreating catalyst comprises the following steps:
(1) Preparing a metal modified hierarchical pore composite carrier;
(2) Preparing an active metal impregnating solution: mixing and dissolving an ionic liquid, a surfactant, a VIB group metal salt and a VIII group metal salt in water to obtain an impregnating solution;
(3) And (3) impregnating the metal modified hierarchical porous composite carrier in the step (1) by adopting the impregnating solution in the step (2), and then drying to obtain the hydrotreating catalyst.
In the method of the present invention, the metal in the step (1) is a group VIII metal, and is selected from one or more of Fe, co, and Ni, preferably Co, ni, and more preferably Ni.
In the method of the invention, the preparation process of the metal modified hierarchical porous composite carrier in the step (1) comprises the following steps: loading the VIII family metal on a molecular sieve, uniformly mixing the material, pseudo-boehmite precursor slurry, organic alcohol and a silane coupling agent I, regulating the pH value to be alkaline, aging, removing certain moisture from the aged material, adding organic amine and a silane coupling agent II, kneading into a plastic body, forming, drying and roasting, and reducing the VIII family metal in a hydrogen atmosphere to obtain the metal modified hierarchical porous composite carrier;
in the above process, the loading mode is generally impregnation by adopting a compound containing VIII group metal, wherein the concentration of the impregnation liquid is determined by the water absorption rate of the molecular sieve and the composition content of the catalyst metal. After impregnation, drying and roasting are carried out, wherein the drying temperature is 80-160 ℃, preferably 90-150 ℃, and the drying effect is 78-99wt% of the dried modified molecular sieve. The roasting temperature is 200-650 ℃, preferably 250-550 ℃, and the roasting time is 1-5 hours.
In the process, the molecular sieve is a molecular sieve commonly used in the hydrogenation field, such as a Y-type molecular sieve, a beta-zeolite, a ZSM-type molecular sieve, a TS-type molecular sieve, a SAPO-type molecular sieve, an MCM-type molecular sieve and an SBA-type molecular sieve. These molecular sieves are well known to those skilled in the art. In order to obtain the desired catalytic properties, the various molecular sieves may be subjected to suitable modification procedures, which are well known to those skilled in the art, such as one or more of hydrothermal treatment, acid treatment, ion exchange, various solvent treatments, and the like.
In the process, the mass ratio of the VIII group metal content to the molecular sieve is 3-8 wt% in terms of oxide.
In the process, the pseudo-boehmite precursor slurry is slurry obtained by filtering and washing a glue-forming material which is not aged after glue forming in the process of preparing pseudo-boehmite in the field, and uniformly mixing the glue-forming material with a certain amount of deionized water. Methods of preparing pseudo-boehmite in the art are generally aluminum alkoxide hydrolysis or acid-base neutralization. The above methods are well known to those skilled in the art.
In the process, the solid content of the pseudo-boehmite precursor slurry is 0.5-20wt%, preferably 3-15 wt%, calculated by alumina.
In the process, the mass ratio of the molecular sieve to the pseudo-boehmite precursor is 1: 19-19: 1, preferably 1: 10-10: 1, pseudo-boehmite precursor is calculated as alumina.
In the process, the mass ratio of the organic alcohol to the water in the pseudo-boehmite precursor slurry is 1:9~9:1, preferably 1:8~3:1. the organic alcohol is one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol or glycerol with carbon number smaller than 4, preferably ethanol, propanol, isopropanol, and ethylene glycol.
In the process, the silane coupling agent I and the silane coupling agent II are oxygen-containing organosilane with the carbon number less than 8; the catalyst may be one or more of trimethoxysilane, tetramethoxysilane, methyldiethoxysilane, dimethylethoxysilane, triethoxysilane, tetraethoxysilane, dimethyldiethoxysilane, dimethylvinylethoxysilane or trimethylallyloxysilane, preferably one or more of tetramethoxysilane, methyldiethoxysilane, dimethylethoxysilane, triethoxysilane, tetraethoxysilane, dimethyldiethoxysilane and dimethylvinylethoxysilane. The silane coupling agent I and the silane coupling agent II can be the same or different.
In the process, the mass ratio of the silane coupling agent I to the organic alcohol is 1: 20-1: 1, preferably 1: 10-1: 1.
in the process, organic alkali and/or inorganic alkali can be adopted to adjust the pH value to be alkaline, and the pH value is adjusted to 7.5-11, preferably 8-10; preferably, an organic amine is used, and more preferably, an organic amine having less than 15 carbon atoms, such as one or more of ethylamine, propylamine, dimethylamine, ethylenediamine, dipropylamine, butylamine, diethylamine, diisopropylamine, hexamethylenediamine, 1, 2-dimethylpropylamine, sec-butylamine, 1, 5-dimethylhexylamine, ethylenediamine, 1, 2-propylenediamine, 1, 4-butylenediamine, monoethanolamine, diethanolamine, triethanolamine, 3-propanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide is used.
In the above process, the aging treatment is generally carried out in a pressure-resistant vessel such as a high-pressure reaction vessel or the like; the aging conditions are as follows: the aging temperature is 100-200 ℃, preferably 150-200 ℃, and the aging time is 6-48 hours, preferably 12-36 hours; the aging pressure is the autogenous pressure of the system.
In the process, the water content of the material from which certain water is removed is 25-70 wt%, preferably 35-55 wt%. The water removal can be performed by filtration or centrifugation.
In the above process, the organic amine is an organic amine with carbon number less than 6, and may be one or more of ethylamine, propylamine, dimethylamine, ethylenediamine, dipropylamine, butylamine, diethylamine or diisopropylamine, preferably ethylamine, propylamine, dimethylamine, ethylenediamine; the total weight of the pseudo-boehmite precursor and the molecular sieve is taken as a reference, the addition amount of the organic amine is 1-10wt%, preferably 5-10wt%, and the addition amount of the silane coupling agent II is 1-10wt%, preferably 4-9wt%, wherein the pseudo-boehmite precursor is calculated by alumina.
In the process, the drying temperature is 80-150 ℃ and the drying time is 2-8 hours; the roasting temperature is 300-900 ℃, and the roasting time is 2-8 hours. The reduction temperature is 250-700 ℃, preferably 300-650 ℃, and the reduction pressure is 0.1-1 MPa.
In the method of the invention, the ionic liquid in the step (2) is BF4 - 、H 2 PO 4- 、CH 3 COO - 、CH 3 C(OH)COO - 、NO 3 - Imidazole salts of radicals hydrophilic acidic ionic liquids, e.g. 1-methyl-3-butylimidazole acetate, 1-carboxyethyl-3-methylimidazole nitrate, 1-methyl-3-carboxyethylimidazole dihydrogen phosphate, 1-methyl-3-butylimidazoleOne or more of tetrafluoroborate and 1-ethyl-3-methylimidazole alpha hydroxy propionate.
In the method of the invention, the surfactant in the step (2) is one or more of nonionic surfactants such as polyvinylpyrrolidone, polyethylene glycol, tween 80 and polyether (such as P123 and F127).
In the method of the invention, the ionic liquid in the step (2): and (2) a surfactant: the sum of the group VIII metal salt and the group VIB metal salt is calculated as oxide: the mass ratio of water is 10-100: 1-10: 20-200:100.
In the method of the invention, the specific preparation process of the impregnating solution in the step (2) is as follows: adding a certain amount of ionic liquid into water, adding a certain amount of surfactant, adding VIB group metal salt and VIII group metal salt after complete dissolution, adjusting the pH value, slowly heating to 60-90 ℃, and naturally cooling after complete dissolution to obtain the impregnating solution.
In the method of the present invention, the group VIII metal in step (2) is one or more of Fe, co, and Ni, preferably Co, ni, and more preferably Ni. The VIB group metal in the step (2) is one or more of Mo and W. The content ratio of the VIII family metal in the step (1) to the VIII family metal in the step (2) is 0.1:1-0.7:1.
In the method of the present invention, the impregnation mode described in step (3) is saturated impregnation or supersaturated impregnation, preferably supersaturated impregnation, wherein the supersaturation degree is expressed as impregnating solution/liquid absorption ratio of 100, and is more than 1.05, preferably 1.2 to 1.8. The drying condition is 95-140 ℃ and the drying time is 2-4 hours.
The invention also provides a hydrotreating catalyst which comprises at least one VIB metal and at least one VIII metal as hydrogenation active metals and a hierarchical porous composite carrier, wherein the weight content of the hydrogenation active metals calculated by oxide is 8% -50%, preferably 10% -40% based on the weight of the catalyst; wherein the group VIB metal is preferably Mo and/or W, and the group VIII metal is preferably Ni and/or Co; the multistage porous composite carrier is 50% -92%, preferably 60% -90%, wherein the multistage porous composite carrier comprises a molecular sieve and alumina, the molecular sieve is 10% -75%, and the alumina is 15% -80%; wherein the weight ratio of the VIII group metal/(the VIB group metal+the VIII group metal) is 0.01-0.70 in terms of oxide.
Compared with the prior art, the invention has the following advantages:
1. the invention fully plays the synergistic effect of the active metal and the carrier by functionally matching the active metal with the carrier multistage pore canal. Firstly, by utilizing the property difference of a multistage pore canal of a molecular sieve-alumina carrier, the reduced VIII metal with a hydrogen dissociation function is loaded in a small molecular sieve pore canal, the hydrogen adsorption and hydrogen overflow functions of the molecular sieve and the reduced VIII metal are fully exerted, and enough activated hydrogen atoms are provided for sulfide and arene hydrogenation. The VIII metal is reduced in advance, so that the condition that the VIII metal is covered by other active metals and is not easy to reduce in the conventional dipping process is avoided. Secondly, the metal is adsorbed by utilizing the hydrogen bond of the macromolecular cationic group of the ionic liquid to generate a metal-ionic liquid macromolecular ligand, and the macromolecular group is formed by the dispersion and stabilization of the surfactant, so that hydrogenation active metal (such as Mo/W-Ni/Co) is loaded in and on the stacking holes of the larger molecular sieve and alumina, the problem that the hydrogenation active metal cannot contact with macromolecular sulfide due to loading in small pore channels of the molecular sieve is reduced, the hydrogenation reaction of the macromolecular sulfide and arene is improved, the residence time of reactant molecules on a catalyst is reduced, the generation of carbon deposit is reduced, the conversion rate of sulfide and arene in the reaction process is improved, and the service life of the catalyst is prolonged.
2. In the process of preparing the hierarchical porous composite carrier, the combination order of the molecular sieve and the alumina is further improved by controlling the preparation conditions, and the composite carrier with improved specific surface, pore volume and strength is obtained, so that the activity of the loaded active metal is exerted.
Detailed Description
The following examples further illustrate the aspects and effects of the present invention, but do not limit the invention.
Example 1
1L aluminum sulfate solution (with the concentration of 0.2 mol/L) and 1L sodium metaaluminate solution (with the concentration of 0.3 mol/L) are respectively placed in a raw material tank, 1L purified water is placed in a reaction tank as base solution, the temperature of the reaction tank is controlled to be 60 ℃ through water circulation, and a small amount of sodium hydroxide is added to enable the pH value of the solution to be 8.5. The aluminum sulfate solution was injected into the reaction tank at a rate of 10. 10 mL/min, while the sodium metaaluminate solution was injected and the rate was adjusted so that the pH of the reaction tank solution was constant at 8.8. After 60min, the neutralization is finished, and Na is removed by full washing + Ions and SO 4 2- After the ions, a certain amount of deionized water is added to obtain pseudo-boehmite slurry with a solid-to-liquid ratio of 8% (calculated by alumina).
Example 2
50g of ZSM-5 molecular sieve (SiO 2 /Al 2 O 3 The molar ratio is 30.0, the unit cell constant is 20A, the relative crystallinity is 85 percent) is placed in a rolling pot, 70mL of aqueous solution containing 8.0g of nickel nitrate hexahydrate is sprayed into a ZSM-5 molecular sieve in the rolling pot in an atomization mode under the rotating condition, the solution is continuously rotated for 30 minutes in the rolling pot after being sprayed, then the solution is placed for 3 hours, dried for 3 hours at 110 ℃, and then the solution is placed in a muffle furnace for roasting for 2 hours at the roasting temperature of 500 ℃ to obtain the modified ZSM-5 molecular sieve.
The modified ZSM-5 molecular sieve obtained in the above was put into 625g of pseudo-boehmite slurry obtained in example 1, 200g of ethanol was added after stirring uniformly, 50g of tetraethoxysilane was added after stirring uniformly continuously, and a small amount of tetramethylammonium hydroxide was added after stirring uniformly to adjust the pH of the slurry to 8.5. Putting the mixture into a closed autoclave, aging for 24 hours at 185 ℃, taking out and filtering until the water content of a filter cake is 39%, adding 8g of ethylenediamine and 6g of tetraethoxysilane, kneading the mixture into a plastic body, extruding the plastic body to form strips, drying the strips at 100 ℃ for 3 hours, roasting the strips at 500 ℃ for 4 hours, and reducing the strips in a hydrogen atmosphere at the reduction temperature of 350 ℃ and the pressure of 0.5MPa to obtain the modified composite carrier.
50g of 1-methyl-3-butyl imidazole acetate ionic liquid is added into 80g of water, 5g of polyvinylpyrrolidone is added, 40.0g of ammonium heptamolybdate and 20.0g of nickel nitrate are added after complete dissolution, and the temperature is slowly increased to 80 ℃ to obtain the impregnating solution after complete dissolution.
The impregnation liquid prepared above was impregnated on the modified composite support prepared above to be supersaturated, and the supersaturation degree was 1.6. Drying at 100 deg.c for 3 hr to obtain catalyst CAT-1.
Example 3
20g of SAPO-34 molecular sieve (SiO 2 /Al 2 O 3 The molar ratio is 0.3) is placed in a rolling pot, 70mL of aqueous solution containing 5.0g of nickel nitrate hexahydrate is sprayed into the SAPO-34 molecular sieve in the rolling pot in an atomization mode under the rotating condition, the rolling pot is continuously rotated for 30 minutes after the solution is sprayed, then the rolling pot is placed for 3 hours, dried for 3 hours at 110 ℃, and then placed in a muffle furnace for roasting for 2 hours, and the roasting temperature is 500 ℃ to obtain the modified SAPO-34 molecular sieve.
The modified SAPO-34 molecular sieve is put into 1000g of pseudo-boehmite slurry obtained in the example 1, 800g of isopropanol is added after the mixture is stirred uniformly, 120g of dimethylvinylethoxysilane is added after the mixture is stirred uniformly continuously, and a small amount of triethanolamine is added after the mixture is stirred uniformly continuously to adjust the pH value of the slurry to 9.0. Putting into a closed autoclave, aging at 160 ℃ for 20 hours, taking out, filtering until the water content of a filter cake is 52%, adding 5.8g of diethylamine and 6.7g of dimethylethoxysilane, kneading into a plastic body, extruding to form strips, drying at 100 ℃ for 3 hours, roasting at 500 ℃ for 4 hours, and reducing in a hydrogen atmosphere at a reduction temperature of 450 ℃ and a pressure of 0.3MPa to obtain the modified composite carrier.
60g of 1-carboxyethyl-3-methylimidazole nitrate ionic liquid is added into 60g of water, 5g of P123 is added, 40.0g of ammonium heptamolybdate and 35.0g of nickel nitrate are added after complete dissolution, and the temperature is slowly increased to 85 ℃ to obtain the impregnating solution after complete dissolution.
The impregnation liquid prepared above was impregnated on the modified composite support prepared above to be supersaturated, and the supersaturation degree was 1.65. Drying at 110 ℃ for 3 hours to obtain the catalyst CAT-2.
Example 4
100g of beta molecular sieve (SiO 2 /Al 2 O 3 The molar ratio is 30.0, the unit cell constant is 13A, the relative crystallinity is 80%) is put into a rolling pot, 80mL of nickel nitrate containing 30.0g of hexahydrate is sprayed into the beta molecular sieve in the rolling pot in an atomization mode under the rotating conditionAfter the spraying of the solution, the solution was continuously rotated in a roll pot for 30 minutes, then left to stand for 3 hours, dried at 110℃for 3 hours, and then put into an atmosphere furnace for roasting for 2 hours at a roasting temperature of 400 ℃.
The modified beta molecular sieve is put into 312.5g of pseudo-boehmite slurry obtained in the example 1, 437.5g of propanol is added after the mixture is stirred uniformly, 125g of dimethyl ethoxysilane is added after the mixture is stirred uniformly continuously, and a small amount of tetraethylammonium hydroxide is added after the mixture is stirred uniformly continuously to adjust the pH value of the slurry to 9.5. Putting into a closed autoclave, aging at 170 ℃ for 30 hours, taking out, filtering until the water content of a filter cake is 46%, adding 8.6g of dimethylamine and 5.7g of triethoxysilane, kneading into a plastic body, extruding to form strips, drying at 100 ℃ for 3 hours, roasting at 500 ℃ for 4 hours, and reducing in a hydrogen atmosphere at a reduction temperature of 500 ℃ and a pressure of 0.8MPa to obtain the modified composite carrier.
20g of 1-methyl-3-carboxyethyl imidazole dihydrogen phosphate ionic liquid is added into 100g of water, 8g of Tween 80 is added, 40.0g of ammonium heptamolybdate and 48.0g of nickel nitrate are added after complete dissolution, and the temperature is slowly increased to 90 ℃ to obtain the impregnating solution after complete dissolution.
The impregnation liquid prepared above was impregnated on the modified composite support prepared above to be supersaturated, and the supersaturation degree was 1.45. Drying at 110 ℃ for 3 hours to obtain the catalyst CAT-3.
Comparative example 1
50g of ZSM-5 molecular sieve (SiO 2 /Al 2 O 3 The molar ratio is 30.0, the unit cell constant is 20A, the relative crystallinity is 85 percent) and 50g SB alumina powder are directly and uniformly mixed, 3g sesbania powder, 20g 10% phosphoric acid and 80mL deionized water are added, the mixture is kneaded into a plastic body, then the plastic body is extruded and formed, and the plastic body is dried at 100 ℃ for 3 hours and then baked at 500 ℃ for 4 hours to obtain the composite carrier.
The obtained composite carrier is placed in a rolling pot, 80mL of aqueous solution containing 40.0g of ammonium heptamolybdate and 28.0g of cobalt nitrate is sprayed into the rolling pot in an atomization mode under the rotating condition, the rolling pot is continuously rotated for 30 minutes after the solution is sprayed, and then the composite carrier is placed for 3 hours and dried at the temperature of 110 ℃ for 3 hours, so that the finished catalyst DCAT-1 is obtained.
Comparative example 2
50g of ZSM-5 molecular sieve (SiO 2 /Al 2 O 3 The molar ratio is 30.0, the unit cell constant is 20A, the relative crystallinity is 85 percent) is placed in a rolling pot, 70mL of aqueous solution containing 8.0g of nickel nitrate hexahydrate is sprayed into a ZSM-5 molecular sieve in the rolling pot in an atomization mode under the rotating condition, the solution is continuously rotated for 30 minutes in the rolling pot after being sprayed, then the solution is placed for 3 hours, dried for 3 hours at 110 ℃, and then the solution is placed in a muffle furnace for roasting for 2 hours at the roasting temperature of 500 ℃ to obtain the modified ZSM-5 molecular sieve.
Directly and uniformly mixing the modified ZSM-5 molecular sieve and 50g of SB alumina powder, adding 3g of sesbania powder, 20g of 10% phosphoric acid and 80mL of deionized water, kneading to form a plastic body, extruding to form strips, drying at 100 ℃ for 3h, roasting at 500 ℃ for 4h, and reducing in a hydrogen atmosphere at the reduction temperature of 350 ℃ and the pressure of 0.5MPa to obtain the modified composite carrier.
50g of 1-methyl-3-butyl imidazole acetate ionic liquid is added into 80g of water, 5g of polyvinylpyrrolidone is added, 40.0g of ammonium heptamolybdate and 20.0g of nickel nitrate are added after complete dissolution, and the temperature is slowly increased to 80 ℃ to obtain the impregnating solution after complete dissolution.
The impregnation liquid prepared above was impregnated on the modified composite support prepared above to be supersaturated, and the supersaturation degree was 1.6. Drying at 100 ℃ for 3 hours to obtain the catalyst DCAT-2.
Comparative example 3
50g of ZSM-5 molecular sieve (SiO 2 /Al 2 O 3 The molar ratio is 30.0, the unit cell constant is 20A, the relative crystallinity is 85 percent) is placed in a rolling pot, 70mL of aqueous solution containing 8.0g of nickel nitrate hexahydrate is sprayed into a ZSM-5 molecular sieve in the rolling pot in an atomization mode under the rotating condition, the solution is continuously rotated for 30 minutes in the rolling pot after being sprayed, then the solution is placed for 3 hours, dried for 3 hours at 110 ℃, and then the solution is placed in a muffle furnace for roasting for 2 hours at the roasting temperature of 500 ℃ to obtain the modified ZSM-5 molecular sieve.
The modified ZSM-5 molecular sieve is put into 625g of pseudo-boehmite slurry A obtained in the example 1, 200g of ethanol is added after the mixture is stirred uniformly, 50g of tetraethoxysilane is added after the mixture is stirred uniformly continuously, and a small amount of tetramethylammonium hydroxide is added after the mixture is stirred uniformly continuously to adjust the pH value of the slurry to 8.5. Putting the mixture into a closed autoclave, aging for 24 hours at 185 ℃, taking out and filtering until the water content of a filter cake is 39%, adding 8g of ethylenediamine and 6g of tetraethoxysilane, kneading the mixture into a plastic body, extruding the plastic body to form strips, drying the strips at 100 ℃ for 3 hours, and roasting the strips at 500 ℃ for 4 hours to obtain the modified composite carrier.
50g of 1-methyl-3-butyl imidazole acetate ionic liquid is added into 80g of water, 5g of polyvinylpyrrolidone is added, 40.0g of ammonium heptamolybdate and 20.0g of nickel nitrate are added after complete dissolution, and the temperature is slowly increased to 80 ℃ to obtain the impregnating solution after complete dissolution.
The impregnation liquid prepared above was impregnated on the modified composite support prepared above to be supersaturated, and the supersaturation degree was 1.6. Drying at 100 ℃ for 3 hours to obtain the catalyst DCAT-3.
Comparative example 4
50g of ZSM-5 molecular sieve (SiO 2 /Al 2 O 3 The molar ratio is 30.0, the unit cell constant is 20A, the relative crystallinity is 85 percent) is placed in a rolling pot, 70mL of aqueous solution containing 8.0g of nickel nitrate hexahydrate is sprayed into a ZSM-5 molecular sieve in the rolling pot in an atomization mode under the rotating condition, the solution is continuously rotated for 30 minutes in the rolling pot after being sprayed, then the solution is placed for 3 hours, dried for 3 hours at 110 ℃, and then the solution is placed in a muffle furnace for roasting for 2 hours at the roasting temperature of 500 ℃ to obtain the modified ZSM-5 molecular sieve.
The modified ZSM-5 molecular sieve obtained in the above was put into 625g of pseudo-boehmite slurry obtained in example 1, 200g of ethanol was added after stirring uniformly, 50g of tetraethoxysilane was added after stirring uniformly continuously, and a small amount of tetramethylammonium hydroxide was added after stirring uniformly to adjust the pH of the slurry to 8.5. Putting the mixture into a closed autoclave, aging for 24 hours at 185 ℃, taking out and filtering until the water content of a filter cake is 39%, adding 8g of ethylenediamine and 6g of tetraethoxysilane, kneading the mixture into a plastic body, extruding the plastic body to form strips, drying the strips at 100 ℃ for 3 hours, roasting the strips at 500 ℃ for 4 hours, and reducing the strips in a hydrogen atmosphere at the reduction temperature of 350 ℃ and the pressure of 0.5MPa to obtain the modified composite carrier.
40.0g of ammonium heptamolybdate and 20.0g of nickel nitrate were added to 120g of water to prepare an impregnation solution. The impregnation liquid prepared above was impregnated on the modified composite support prepared above to be supersaturated, and the supersaturation degree was 1.6. Drying at 100 ℃ for 3 hours to obtain the catalyst DCAT-4.
Comparative example 5
50g of ZSM-5 molecular sieve (SiO 2 /Al 2 O 3 The molar ratio is 30.0, the unit cell constant is 20A, the relative crystallinity is 85 percent) is placed in a rolling pot, 70mL of aqueous solution containing 2.0g of nickel nitrate hexahydrate is sprayed into a ZSM-5 molecular sieve in the rolling pot in an atomization mode under the rotating condition, the solution is continuously rotated for 30 minutes in the rolling pot after being sprayed, then the solution is placed for 3 hours, dried for 3 hours at 110 ℃, and then the solution is placed in a muffle furnace for roasting for 2 hours at the roasting temperature of 500 ℃ to obtain the modified ZSM-5 molecular sieve.
The modified ZSM-5 molecular sieve is put into 625g of pseudo-boehmite slurry A obtained in the example 1, 200g of ethanol is added after the mixture is stirred uniformly, 50g of tetraethoxysilane is added after the mixture is stirred uniformly continuously, and a small amount of tetramethylammonium hydroxide is added after the mixture is stirred uniformly continuously to adjust the pH value of the slurry to 8.5. Putting the mixture into a closed autoclave, aging for 24 hours at 185 ℃, taking out and filtering until the water content of a filter cake is 39%, adding 8g of ethylenediamine and 6g of tetraethoxysilane, kneading the mixture into a plastic body, extruding the plastic body to form strips, drying the strips at 100 ℃ for 3 hours, roasting the strips at 500 ℃ for 4 hours, and reducing the strips in a hydrogen atmosphere at the reduction temperature of 350 ℃ and the pressure of 0.5MPa to obtain the modified composite carrier.
50g of 1-methyl-3-butyl imidazole acetate ionic liquid is added into 80g of water, 5g of polyvinylpyrrolidone is added, 40.0g of ammonium heptamolybdate and 26.0g of nickel nitrate are added after complete dissolution, and the temperature is slowly increased to 80 ℃ to obtain the impregnating solution after complete dissolution.
The impregnation liquid prepared above was impregnated on the modified composite support prepared above to be supersaturated, and the supersaturation degree was 1.6. Drying at 100 ℃ for 3 hours to obtain the catalyst DCAT-5.
Comparative example 6
50g of ZSM-5 molecular sieve (SiO 2 /Al 2 O 3 The molar ratio is 30.0, the unit cell constant is 20A, the relative crystallinity is 85%) is put into a rolling pot, 70mL of aqueous solution containing 16.0g of nickel nitrate hexahydrate is sprayed into ZSM-5 molecular sieve in the rolling pot in an atomization mode under the rotating condition, and after the solution is sprayed, the rolling is carried outThe pot is continuously rotated for 30 minutes, then the pot is placed for 3 hours, dried for 3 hours at 110 ℃, and then put into a muffle furnace for roasting for 2 hours at 500 ℃ to obtain the modified ZSM-5 molecular sieve.
The modified ZSM-5 molecular sieve is put into 625g of pseudo-boehmite slurry A obtained in the example 1, 200g of ethanol is added after the mixture is stirred uniformly, 50g of tetraethoxysilane is added after the mixture is stirred uniformly continuously, and a small amount of tetramethylammonium hydroxide is added after the mixture is stirred uniformly continuously to adjust the pH value of the slurry to 8.5. Putting the mixture into a closed autoclave, aging for 24 hours at 185 ℃, taking out and filtering until the water content of a filter cake is 39%, adding 8g of ethylenediamine and 6g of tetraethoxysilane, kneading the mixture into a plastic body, extruding the plastic body to form strips, drying the strips at 100 ℃ for 3 hours, roasting the strips at 500 ℃ for 4 hours, and reducing the strips in a hydrogen atmosphere at the reduction temperature of 350 ℃ and the pressure of 0.5MPa to obtain the modified composite carrier.
50g of 1-methyl-3-butyl imidazole acetate ionic liquid is added into 80g of water, 5g of polyvinylpyrrolidone is added, 40.0g of ammonium heptamolybdate and 12.0g of nickel nitrate are added after complete dissolution, and the temperature is slowly increased to 80 ℃ to obtain the impregnating solution after complete dissolution.
The impregnation liquid prepared above was impregnated on the modified composite support prepared above to be supersaturated, and the supersaturation degree was 1.6. Drying at 100 ℃ for 3 hours to obtain the catalyst DCAT-6.
Comparative example 7
50g of ZSM-5 molecular sieve (SiO 2 /Al 2 O 3 The molar ratio was 30.0, the unit cell constant was 20 a, and the relative crystallinity was 85%) was added to 625g of pseudo-boehmite slurry a obtained in example 1, 200g of ethanol was added after stirring uniformly, 50g of tetraethoxysilane was added after stirring continuously uniformly, and after stirring continuously uniformly, a small amount of tetramethylammonium hydroxide was added to adjust the pH of the slurry to 8.5. Putting the mixture into a closed autoclave, aging for 24 hours at 185 ℃, taking out and filtering the mixture, adding 8g of ethylenediamine, 6g of tetraethoxysilane, 50g of 1-methyl-3-butyl imidazole acetate ionic liquid, 5g of polyvinylpyrrolidone, 40.0g of ammonium heptamolybdate and 28.0g of nickel nitrate hexahydrate into the mixture, kneading the mixture into a plastic body, extruding the plastic body into strips, and drying the plastic body at 110 ℃ for 3 hours to obtain the finished catalyst DCAT-7.
The molecular sieve and SB powder properties of the raw materials are shown in Table 1, and the catalyst properties are shown in Table 2.
TABLE 1 main Properties of feedstock molecular sieves
TABLE 2 catalyst principal Properties
The catalysts were compared for activity evaluation on a 10mL mini-hydrotreater. The catalyst was presulfided prior to activity evaluation. The catalyst evaluation process condition is that the pressure is 6.0MPa, and the liquid hourly space velocity is 2.0h -1 The volume ratio of hydrogen to oil is 600:1, and the reaction temperature is 340 ℃. The activity evaluation raw materials are 4, 6-dimethyl dibenzothiophene (4, 6-DMDBT) and naphthalene which are dissolved in dodecane solution, wherein the mass percent of the 4,6-DMDBT is 1.0 percent, and the mass percent of the naphthalene is 10 percent. The desulfurization and dearomatization activity evaluation results are shown in Table 3.
Table 3 results of activity evaluation.
From the evaluation results, the catalyst prepared by the method has better saturation activity of removing 4, 6-dimethyl dibenzothiophene (4, 6-DMDBT) and polycyclic aromatic hydrocarbon.
To investigate the stability of the catalysts, the example catalyst CAT-1 and the comparative catalysts DCAT-3, DCAT-4 were subjected to a simulated life test under severe conditions. The evaluation process conditions are as follows: pressure 5.0MPa, liquid hourly space velocity 2.0h -1 The volume ratio of hydrogen to oil is 300:1, and the reaction temperature is 380 ℃. The activity evaluation raw material is catalytic diesel with the aromatic hydrocarbon content up to 66%. The stability results are shown in Table 4.
From the evaluation results, the catalyst prepared by the method has better stability, and the carbon deposition amount in the running process is lower than that of the comparative catalyst.

Claims (30)

1. A method for preparing a hydrotreating catalyst, which is characterized by comprising the following steps: (1) preparing a metal modified hierarchical porous composite carrier; (2) preparing an active metal impregnation liquid: mixing and dissolving an ionic liquid, a surfactant, a VIB group metal salt and a VIII group metal salt in water to obtain an impregnating solution; (3) Impregnating the metal modified hierarchical porous composite carrier in the step (1) by adopting the impregnating solution in the step (2), and then drying to obtain a hydrotreating catalyst; the preparation process of the metal modified hierarchical porous composite carrier comprises the following steps of: loading the VIII family metal on a molecular sieve, uniformly mixing the material, pseudo-boehmite precursor slurry, organic alcohol and a silane coupling agent I, regulating the pH value to be alkaline, aging, removing certain moisture from the aged material, adding organic amine and a silane coupling agent II, kneading into a plastic body, forming, drying and roasting, and reducing the VIII family metal in a hydrogen atmosphere to obtain the metal modified hierarchical porous composite carrier; the surfactant in the step (2) is a nonionic surfactant; the ionic liquid in the step (2): and (2) a surfactant: the sum of the group VIII metal salt and the group VIB metal salt is calculated as oxide: the mass ratio of water is 10-100: 1-10: 20-200:100.
2. The method according to claim 1, characterized in that: the metal in the step (1) is a metal of a VIII group and is selected from one or more of Fe, co and Ni.
3. The method according to claim 1, characterized in that: in the preparation process of the metal modified hierarchical porous composite carrier in the step (1), the loading mode is dipping by adopting a dipping liquid containing VIII family metal; after impregnation, drying and roasting, wherein the drying temperature is 80-160 ℃, and the drying effect is 78-99wt% of the dried modified molecular sieve; the roasting temperature is 200-650 ℃, and the roasting time is 1-5 hours.
4. The method according to claim 1, characterized in that: in the preparation process of the metal modified hierarchical porous composite carrier in the step (1), the molecular sieve is one or more of a Y-type molecular sieve, a beta-zeolite, a ZSM-type molecular sieve, a TS-type molecular sieve, a SAPO-type molecular sieve, an MCM-type molecular sieve, an SBA-type molecular sieve and a modified molecular sieve.
5. The method according to claim 1, characterized in that: in the preparation process of the metal modified hierarchical porous composite carrier in the step (1), the mass ratio of the VIII family metal content to the molecular sieve calculated by oxide is 3-8 wt%.
6. The method according to claim 1, characterized in that: in the preparation process of the metal modified hierarchical porous composite carrier in the step (1), the pseudo-boehmite precursor slurry is slurry obtained by uniformly mixing a non-aged gel-forming material after gel formation, after filtration and washing, with certain deionized water in the process of preparing pseudo-boehmite in the field; the solid content of the pseudo-boehmite precursor slurry is 0.5-20wt% in terms of alumina.
7. The method according to claim 1, characterized in that: in the preparation process of the metal modified hierarchical porous composite carrier in the step (1), the mass ratio of the molecular sieve to the pseudo-boehmite precursor is 1: 19-19: 1, pseudo-boehmite precursor is calculated as alumina.
8. The method according to claim 1, characterized in that: in the preparation process of the metal modified hierarchical porous composite carrier in the step (1), the mass ratio of organic alcohol to water in pseudo-boehmite precursor slurry is 1:9~9:1, a step of; the organic alcohol is an organic alcohol with the carbon number less than 4.
9. The method according to claim 1, characterized in that: in the preparation process of the metal modified hierarchical porous composite carrier in the step (1), the organic alcohol is one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol or glycerol.
10. The method according to claim 1, characterized in that: in the preparation process of the metal modified hierarchical porous composite carrier in the step (1), the silane coupling agent I and the silane coupling agent II are oxygen-containing organosilane with the carbon number smaller than 8.
11. The method according to claim 1, characterized in that: in the preparation process of the metal modified hierarchical porous composite carrier in the step (1), the silane coupling agent I and the silane coupling agent II are selected from one or more of trimethoxy silane, tetramethoxy silane, methyldiethoxy silane, dimethylethoxy silane, triethoxy silane, tetraethoxy silane, dimethyldiethoxy silane, dimethylvinyl ethoxy silane or trimethylallyloxy silane.
12. The method according to claim 1, characterized in that: in the preparation process of the metal modified hierarchical porous composite carrier in the step (1), the mass ratio of the silane coupling agent I to the organic alcohol is 1: 20-1: 1.
13. the method according to claim 1, characterized in that: in the preparation process of the metal modified hierarchical porous composite carrier in the step (1), the aging treatment conditions are as follows: the aging temperature is 100-200 ℃, the aging time is 6-48 hours, and the aging pressure is the autogenous pressure of the system.
14. The method according to claim 1, characterized in that: in the preparation process of the metal modified hierarchical porous composite carrier in the step (1), the water content in the material from which certain water is removed is 25-70 wt%.
15. The method according to claim 1, characterized in that: in the preparation process of the metal modified hierarchical porous composite carrier in the step (1), the organic amine is an organic amine with carbon atoms less than 6, and is selected from one or more of ethylamine, propylamine, dimethylamine, ethylenediamine, dipropylamine, butylamine, diethylamine or diisopropylamine.
16. The method according to claim 1, characterized in that: in the preparation process of the metal modified hierarchical porous composite carrier in the step (1), the addition amount of organic amine is 1-10wt% based on the total weight of the pseudo-boehmite precursor and the molecular sieve, and the addition amount of the silane coupling agent II is 1-10wt%, wherein the pseudo-boehmite precursor is calculated by alumina.
17. The method according to claim 1, characterized in that: in the preparation process of the metal modified hierarchical porous composite carrier in the step (1), the drying temperature is 80-150 ℃ and the drying time is 2-8 hours; the roasting temperature is 300-900 ℃, and the roasting time is 2-8 hours.
18. The method according to claim 1, characterized in that: in the preparation process of the metal modified hierarchical porous composite carrier in the step (1), the reduction temperature is 250-700 ℃, and the reduction pressure is 0.1-1 MPa.
19. The method according to claim 1, characterized in that: the ionic liquid in the step (2) is BF4 - 、H 2 PO 4 - 、CH 3 COO - 、CH 3 C(OH)COO - 、NO 3 - One or more of the imidazole salt hydrophilic acidic ionic liquids of the group.
20. The method according to claim 1, characterized in that: the ionic liquid in the step (2) is one or more of 1-methyl-3-butyl imidazole acetate, 1-carboxyethyl-3-methyl imidazole nitrate, 1-methyl-3-carboxyethyl imidazole dihydrogen phosphate, 1-methyl-3-butyl imidazole tetrafluoroborate or 1-ethyl-3-methyl imidazole alpha hydroxy propionate.
21. The method according to claim 1, characterized in that: the nonionic surfactant in the step (2) is one or more selected from polyvinylpyrrolidone, polyethylene glycol, tween 80 or polyether.
22. The method according to claim 1, characterized in that: the specific preparation process of the impregnating solution in the step (2) is as follows: adding a certain amount of ionic liquid into water, adding a certain amount of surfactant, adding VIB group metal salt and VIII group metal salt after complete dissolution, adjusting the pH value, slowly heating to 60-90 ℃, and naturally cooling after complete dissolution to obtain the impregnating solution.
23. The method according to claim 1, characterized in that: the VIII group metal in the step (2) is one or more of Fe, co and Ni; the VIB metal is one or more of Mo and W.
24. The method according to claim 1, characterized in that: the content ratio of the VIII family metal in the step (1) to the VIII family metal in the step (2) is 0.1:1-0.7:1.
25. The method according to claim 1, characterized in that: the impregnation mode in the step (3) is saturated impregnation or supersaturated impregnation, wherein the supersaturation degree is expressed as impregnation liquid/liquid absorption ratio of 100 and is more than 1.05.
26. The method according to claim 1, characterized in that: and (3) drying at 95-140 ℃ for 2-4 hours.
27. A hydrotreating catalyst characterized by: the method of any one of claims 1 to 26.
28. The catalyst of claim 27, wherein: the catalyst comprises at least one VIB metal, at least one VIII metal which is hydrogenation active metal and a hierarchical porous composite carrier; the weight content of hydrogenation active metal calculated by oxide is 8% -50% based on the weight of the catalyst; the hierarchical porous composite carrier is 50% -92%, wherein the hierarchical porous composite carrier comprises 10% -75% of molecular sieve and 15% -80% of alumina.
29. The catalyst of claim 27, wherein: the weight ratio of the VIII group metal/(the VIB group metal+the VIII group metal) is 0.01-0.70 in terms of oxide.
30. Use of the catalyst of claim 27 in a hydrodesulfurization, dearomatization reaction.
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CN108620081A (en) * 2017-03-24 2018-10-09 中国石油化工股份有限公司 A kind of hydrogenation catalyst maceration extract and preparation method thereof
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CN103801378A (en) * 2012-11-13 2014-05-21 中国石油化工股份有限公司 Hydrogenation catalyst containing molecular sieves and alumina
CN106466623A (en) * 2015-08-14 2017-03-01 中国石油化工股份有限公司 A kind of preparation method of catalyst for hydrogenation de-waxing and the application of the catalyst prepared by the method and this catalyst
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