CN111068750A - Modified alumina carrier, preparation method thereof and hydrofining catalyst - Google Patents

Modified alumina carrier, preparation method thereof and hydrofining catalyst Download PDF

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CN111068750A
CN111068750A CN201811226380.5A CN201811226380A CN111068750A CN 111068750 A CN111068750 A CN 111068750A CN 201811226380 A CN201811226380 A CN 201811226380A CN 111068750 A CN111068750 A CN 111068750A
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slurry
molecular sieve
graphene
pseudo
silane
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CN111068750B (en
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刘丽
郭蓉
孙进
杨涛
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
    • 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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • 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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 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
    • B01J29/40—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
    • B01J29/7007—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
    • B01J29/04—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
    • 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
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a modified alumina carrier, a preparation method thereof and a hydrofining catalyst, wherein the modified alumina carrier comprises a molecular sieve, graphene and alumina with the specific surface area of 300-400m on the basis of the weight of the modified alumina carrier2Per g, poreThe volume is 0.5-0.8cm3(ii)/g, the average pore diameter is 7-9 nm. The preparation method of the carrier comprises the following steps: (1) mixing pseudo-boehmite precursor slurry, a mesoporous molecular sieve, graphene and organic alcohol to obtain slurry A; (2) adding a silane coupling agent into the slurry A, uniformly mixing, and then adjusting the pH value to obtain slurry B; (3) and (3) aging the slurry B, filtering the material after aging to remove certain moisture, adding organic amine and a silane coupling agent, kneading into a plastic body, and forming, drying and roasting to obtain the modified alumina carrier. The modified alumina carrier has better hydrogen molecule adsorption capacity and hydrogen overflow property, and the hydrofining catalyst prepared by the carrier is suitable for a liquid phase circulating hydrogenation process and has good hydrogenation activity.

Description

Modified alumina carrier, preparation method thereof and hydrofining catalyst
Technical Field
The invention relates to the technical field of oil product hydrogenation, in particular to a modified alumina carrier, a preparation method thereof and a hydrofining catalyst.
Background
With increasingly stringent environmental regulations, the development and use of ultra-low sulfur and even sulfur-free diesel is the current trend of clean fuel development worldwide, and hydrogenation of diesel feedstock on conventional trickle bed to produce qualified diesel products is currently the most common way. In the conventional trickle bed hydrogenation process, in order to control the reaction temperature of a catalyst bed layer and ensure that hydrogen is fully contacted with oil, a large volume ratio of hydrogen to oil is usually adopted, and a large amount of hydrogen is necessary to be surplus after the hydrogenation reaction is finished. The surplus hydrogen is generally pressurized by a recycle hydrogen compressor and then mixed with fresh hydrogen to continue to be used as the hydrogen feed for the reaction. Because the operation characteristics of the recycle hydrogen compressor determine, the hydrogen can be recycled only by reducing the lower temperature, so that a large amount of low-temperature heat sources are wasted, and the investment of the recycle hydrogen compressor and high-pressure equipment accounts for a higher proportion of the cost of the whole hydrogenation device.
The liquid phase circulating hydrogenation technology provides hydrogen needed by reaction through saturated liquid circulating materials, a circulating hydrogen system is omitted, energy consumption is reduced, and meanwhile, the influence of a wetting factor of a catalyst can be eliminated. The specific heat capacity of the circulating oil is large, so that the temperature rise of the reactor is greatly reduced, the utilization efficiency of the catalyst is improved, and side reactions such as cracking and the like can be reduced. The hydrodesulfurization catalyst suitable for the conventional trickle bed hydrogenation technology takes modified alumina as a carrier and takes metal sulfides of Mo, W, Co and Ni as active components. The liquid phase circulating hydrogenation technology is greatly different from the traditional trickle bed hydrogenation technology, and particularly the reaction materials in the liquid phase circulating hydrogenation process have high concentration of hydrogen sulfide and ammonia. The hydrogen sulfide has a large inhibiting effect on the hydrogenation reaction. The trickle-bed hydrogenation technology uses a recycle hydrogen sulfide removal facility to reduce the influence of hydrogen sulfide. The hydrogen sulfide generated by the liquid phase circulation hydrogenation technology reaction is dissolved in refined oil, and is difficult to remove by conventional facilities due to the high solubility of the hydrogen sulfide in the oil. The selective adsorption of the catalyst to hydrogen is enhanced, so that the inhibition effect of hydrogen sulfide on the hydrogenation reaction can be weakened, and the aim of producing clean diesel oil with the sulfur content of less than 10 mu g/g by using a liquid-phase circulating hydrogenation technology is fulfilled.
Graphene is a crystal with a two-dimensional space structure formed by hybridization of sp2 of carbon atoms, has excellent mechanical properties and thermal properties and an ultra-large specific surface area, is resistant to acid and alkali corrosion, and is considered to be a novel carbon material with great potential. The thermal stability, the surface modifiability, the flowability of surface electrons, the large conjugated pi-bonds on the surface, the potential high specific surface area and the stable immobilization and dispersion of metal by functionalized and doped graphene all promote the graphene to have excellent catalyst hydrogenation performance.
CN105289636A discloses graphene and MoS2A graphene-like and amorphous carbon composite material and a preparation method thereof. The composite material is mainly applied to electrochemical lithium storage, electrochemical magnesium storage, catalyst carriers and the like, but the preparation method is too complicated.
CN105289636A discloses a nano nickel and molybdenum catalyst loaded on graphene oxide and a preparation method thereof. The catalyst has excellent hydrodesulfurization catalytic effect, but the carrier of the catalyst is completely made of graphene oxide, and the price is high.
Disclosure of Invention
Aiming at the characteristics of a liquid-phase circulating hydrodesulfurization technology and graphene and the defects of the prior art, the invention provides a modified alumina carrier, a preparation method thereof and a hydrofining catalyst.
The modified alumina carrier of the invention takes the weight of the modified alumina carrier as the reference, and comprises 2wt% -20wt%, preferably 5wt% -10wt% of molecular sieve, 2wt% -20wt%, preferably 5wt% -10wt% of graphene, 60wt% -96 wt% of alumina, and the specific surface area of the carrier is 300-400m2Per g, pore volume of 0.5-0.8cm3(ii)/g, average pore diameter of 7-9nm, crush strength of 100-200N/cm.
The preparation method of the modified alumina carrier comprises the following steps:
(1) uniformly mixing pseudo-boehmite precursor slurry, a mesoporous molecular sieve, graphene and organic alcohol to obtain slurry A;
(2) adding a silane coupling agent into the slurry A obtained in the step (1), uniformly mixing, and then adjusting the pH value of the slurry to 7.5-11 to obtain slurry B;
(3) and (3) aging the slurry B obtained in the step (2) under a certain pressure, filtering the material after aging to remove a certain amount of water, adding organic amine and a silane coupling agent, kneading into a plastic body, and forming, drying and roasting to obtain the modified alumina carrier.
In the method, the pseudoboehmite precursor slurry in the step (1) is a gelatinizing material which is not aged after gelatinizing in the process of preparing the pseudoboehmite in the field, and the gelatinized material is filtered and washed, and then is uniformly mixed with certain deionized water again to obtain the slurry. The methods for preparing pseudoboehmite in the field are generally aluminum alkoxide hydrolysis or acid-base neutralization. The acid-base neutralization process generally adopts an operation mode of parallel-flow gelling of two materials, or an operation mode of continuously adding one material into a gelling tank and the other material into gelling. The gelling material typically comprises a source of aluminum (Al)2(SO4)3、AlCl3、Al(NO3)3And NaAlO2One or more of the above), precipitant (NaOH, NH)4OH or CO2Etc.), can be selected according to different gelling processes. The conventional operation modes mainly comprise: (1) acidic aluminum salt (Al)2(SO4)3、AlCl3、Al(NO3)3) With alkaline aluminium salts (NaAlO)2) Or alkaline precipitants (NaOH, NH)4OH) neutralization to form gel, 2 alkaline aluminum salt (NaAlO)2) With acidic precipitants (CO)2) Neutralizing to form gel. The above methods are well known to those skilled in the art.
In the method, the solid content of the pseudo-boehmite precursor slurry in the step (1) is 0.5-20 wt% calculated by alumina, and preferably 3-15 wt%.
In the method of the present invention, the molecular sieve in step (1) is a molecular sieve commonly used in the hydrogenation field, such as Y-type molecular sieve, β zeolite, ZSM, TS series molecular sieve, SAPO series molecular sieve, MCM series molecular sieve, SBA series molecular sieve, which are well known to those skilled in the art2/Al2O3The molar ratio is 20-60, preferably 40-50, the BET specific surface area is 300-400m2(g) external specific surface area of 100-2Per g, pore volume of micropores is 0.05-0.10cm3Per g, the mesoporous volume is 0.35-0.5cm3/g。
In the method, the graphene in the step (1) can be one or two of single-layer graphene, double-layer graphene, few-layer graphene and multi-layer graphene. The preparation method of the graphene is well known to those skilled in the art. Ultrasonically stripping graphite oxide in water for 0.5-3h to prepare a graphene oxide suspension, and then adding hydrazine hydrate and/or sodium borohydride to reduce the graphene oxide into graphene.
In the method, the mass ratio of the molecular sieve and the pseudo-boehmite precursor in the step (1) is 1: 48-1: 3, preferably 1: 18-1: and 8, the pseudo-boehmite precursor is calculated by alumina.
In the method, the mass ratio of the graphene to the pseudo-boehmite precursor in the step (1) is 1: 48-1: 3, preferably 1: 18-1: and 8, the pseudo-boehmite precursor is calculated by alumina.
In the method, the mass ratio of the organic alcohol in the step (1) to the water in the pseudo-boehmite precursor slurry is 1: 9-9: 1, preferably 1: 8-8: 1.
in the method of the present invention, the organic alcohol in step (1) is an organic alcohol with a carbon number less than 4, such as one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol and glycerol, preferably ethanol, propanol, isopropanol and ethylene glycol.
In the method, the silane coupling agent in the step (2) and the step (3) is oxygen-containing organosilane with the carbon atom number less than 8; can be one or more of trimethoxy silane, tetramethoxy silane, methyl diethoxy silane, dimethyl ethoxy silane, triethoxy silane, tetraethoxy silane, dimethyl diethoxy silane, dimethyl vinyl ethoxy silane or trimethyl allyloxy silane, and preferably one or more of tetramethoxy silane, methyl diethoxy silane, dimethyl ethoxy silane, triethoxy silane, tetraethoxy silane, dimethyl diethoxy silane and dimethyl vinyl ethoxy silane. The silane coupling agent in the step (2) and the silane coupling agent in the step (3) may be the same or different.
In the method, the mass ratio of the silane coupling agent in the step (2) to the organic alcohol in the slurry A is 1: 20-1: 1, preferably 1: 10-1: 1.
in the method of the present invention, in step (2), organic base and/or inorganic base may be used to adjust the pH, organic amine is preferably used, and organic amine with carbon number less than 15 is further preferably used, such as one or more of ethylamine, propylamine, dimethylamine, ethylenediamine, dipropylamine, butylamine, diethylamine, diisopropylamine, hexyldiamine, 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 or tetrapropylammonium hydroxide.
In the method, the pH value is preferably adjusted to 8-10 in the step (2).
In the method of the present invention, the aging process of step (3) is generally performed in a pressure-resistant vessel, such as a high-pressure reaction vessel; 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 method, the water content in the filter cake subjected to certain water removal in the step (3) is 25-70 wt%, and preferably 35-55 wt%.
In the method, the organic amine in the step (3) is an organic amine with a carbon atom number less than 6, and can be one or more of ethylamine, propylamine, dimethylamine, ethylenediamine, dipropylamine, butylamine, diethylamine or diisopropylamine, preferably ethylamine, propylamine, dimethylamine and ethylenediamine; based on the total weight of the pseudo-boehmite precursor, the graphene and the molecular sieve, the adding amount of the organic amine is 1wt% -10wt%, preferably 5wt% -10wt%, and the adding amount of the silane coupling agent is 1wt% -10wt%, preferably 4wt% -9 wt%, wherein the pseudo-boehmite precursor is calculated by alumina.
In the method, the drying temperature in the step (3) is 80-150 ℃, and the drying time is 2-8 h; roasting under the protection of nitrogen or inert gas, wherein the roasting temperature is 300-900 ℃, and the roasting time is 2-8 h.
The invention also provides a hydrofining catalyst, which takes the modified alumina as a carrier, and the hydrogenation active components are VIB group metals and VIII group metals, wherein the VIB group metals are preferably Mo and/or W, and the VIII group metals are preferably Co and/or Ni. Based on the total weight of the catalyst, the VIB group metal accounts for 2.0-30% of the total weight of the catalyst, and the VIII group metal accounts for 0.1-10% of the total weight of the catalyst.
The preparation method of the hydrofining catalyst is well known to those skilled in the art, and generally adopts a conventional impregnation method to impregnate the VIB group metal and/or VIII group metal active component onto the carrier, and the catalyst is obtained by drying and roasting; the preparation of the hydrogenation active component solution is generally that cobalt nitrate or nickel nitrate and molybdenum ammonium nitrate or tungsten nitrate are dissolved in nitric acid or ammonia water, and citric acid or ammonium citrate complexing agent is added to prepare impregnation liquid. The drying conditions are as follows: drying at the temperature of 100 ℃ and 120 ℃ for 3-6h, wherein the roasting conditions are as follows: roasting for 3-6h at the temperature of 300-500 ℃ under the protection of nitrogen or inert gas.
Compared with the prior art, the invention has the following advantages:
1. according to the modified alumina carrier, graphene has strong hydrogen molecule adsorption capacity and can store a large amount of hydrogen, the molecular sieve has a hydrogen overflow property, and the combination of the graphene and the molecular sieve can effectively activate hydrogen molecules into active hydrogen, so that the reaction activity is improved. The conjugated structure of the graphene enables the graphene to have strong adsorption capacity on reaction raw materials, and the excellent electron transport performance of the graphene can promote electron migration in catalytic reaction, so that the catalytic activity is improved.
2. The hydroxyl on the surface of the neutralized pseudo-boehmite crystal nucleus and the silicon-oxygen bond on the surface of the molecular sieve generate hydrogen bond adsorption with the silanol bond generated by a silane coupling agent in the hydrolysis process, and a covalent bond is formed in the dehydration process, so that the alumina and the molecular sieve are uniformly and firmly bonded, and the highly dispersed graphene in the organic alcohol has a high specific surface area, so that the alumina and the molecular sieve react on the graphene, the agglomeration of the alumina and the molecular sieve particles is prevented, the migration and agglomeration cannot occur in the subsequent carrier forming process, and the carrier property is more uniform.
3. The hydrolysis rate of the silane coupling agent is controlled to be matched with the crystallization rate of the pseudo-boehmite crystal nucleus through the conditions of the hydrolysis reaction process, so that the alumina and the molecular sieve are combined orderly and are better dispersed on the graphene, and the phenomenon of non-uniformity in the reaction process is avoided. The alumina aged at high temperature and under autogenous pressure by utilizing a solvent system has higher crystallinity, so that the pore structure is not easy to damage in the molding process, and the acidity is higher.
4. The wet slurry obtained by reacting the pseudo-boehmite with the molecular sieve and the graphene does not need to be dehydrated and dried, but is formed by one-step extrusion by adding the silane coupling agent and the organic amine after partial moisture is directly removed, and the characteristics that the surface of the wet slurry containing water is rich in hydroxyl and is easy to peptize are utilized, and meanwhile, the wet slurry containing water is easy to form by utilizing the caking property of the silane coupling agent, so that the alumina pore channel structure is prevented from being damaged by adding acid, and the carrier strength is improved.
Detailed Description
The following examples further illustrate the present invention and the effects thereof, but are not intended to limit the present invention.
Example 1
1L of aluminum sulfate solution (with the concentration of 0.2 mol/L) and 1L of sodium metaaluminate solution (with the concentration of 0.3 mol/L) are respectively placed in a raw material tank, 1L of purified water is placed in a reaction tank to be used as a 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 ensure that the pH value of the solution is 8.5. The aluminum sulfate solution was injected into the reactor at a rate of 10 mL/min, and simultaneously, the sodium metaaluminate solution was injected and the rate was adjusted so that the pH of the reactor solution was constant at 8.8. Neutralizing after 60min, and washing to remove Na+Ions and SO4 2-After ionization, a certain amount of deionized water is added to obtain the pseudo-boehmite slurry A with the solid-to-liquid ratio of 8 percent (calculated by alumina).
Adding 300g of graphene oxide into 1.5L of deionized water, uniformly stirring, performing ultrasonic treatment for 1h to prepare a graphene oxide suspension, then adding 600g of sodium borohydride, reducing the graphene oxide into graphene, filtering, washing and drying to obtain the graphene.
Example 2
13g of graphene and 13g of ZSM-5 molecular Sieve (SiO)2/Al2O330.0 molar ratio, 20 Å unit cell constant and 85% relative crystallinity) into 625g of the pseudo-boehmite slurry A obtained in example 1, stirring uniformly, adding 200g of ethanol, stirring uniformly, adding 50g of tetraethoxysilane, stirring uniformly, adding a small amount of tetramethylammonium hydroxide to adjust the pH value of the slurry to 8.5, placing into a closed autoclave, aging at 185 ℃ for 24h, taking out, filtering until the water content of a filter cake is 39%, adding 8g of ethylenediamine and 6g of tetraethoxysilane, kneading into a plastic body, extruding into strips, drying at 100 ℃ for 3h, roasting at 500 ℃ for 4h under the protection of nitrogen to obtain the final modified aluminaBody S-1.
93.1g of Co (NO)3)2. 6H2Dissolving O in 200mL deionized water, adding ammonium citrate 1.5 times of total mole of metal ions, heating to dissolve, cooling to room temperature, adding 175.5g (NH)4)6Mo7O24.4H2And O, adjusting with ammonia water until ammonium molybdate is completely dissolved, and fixing the volume with a 1000mL volumetric flask.
And (3) soaking 120g of S-1 carrier in Mo-Co solution in the same volume, then placing the soaked strip in a drying oven for 3h at 120 ℃, and roasting for 3h at 500 ℃ under the protection of nitrogen to obtain the catalyst CS-1.
Example 3
10g of graphene and 10g of ZSM-5 molecular Sieve (SiO)2/Al2O330.0 molar ratio, 20 Å unit cell constant and 85% relative crystallinity) into 180g of the pseudo-boehmite slurry A obtained in example 1, stirring uniformly, adding 200g of ethanol, stirring uniformly, adding 50g of tetraethoxysilane, stirring uniformly, adding a small amount of tetramethylammonium hydroxide to adjust the pH value of the slurry to 8.5, placing into a closed autoclave, aging at 185 ℃ for 24h, taking out, filtering until the water content of a filter cake is 39%, adding 8g of ethylenediamine and 6g of tetraethoxysilane, kneading into a plastic body, extruding into strips, drying at 100 ℃ for 3h, and roasting at 500 ℃ for 4h under the protection of nitrogen to obtain the final modified alumina carrier S-2.
93.1g of Co (NO)3)2. 6H2Dissolving O in 200mL deionized water, adding ammonium citrate 1.5 times of total mole of metal ions, heating to dissolve, cooling to room temperature, adding 175.5g (NH)4)6Mo7O24.4H2And O, adjusting with ammonia water until ammonium molybdate is completely dissolved, and fixing the volume with a 1000mL volumetric flask.
And (3) soaking 120g of S-2 carrier in Mo-Co solution in the same volume, then placing the soaked strip in a drying oven for 3h at 120 ℃, and roasting for 3h at 500 ℃ under the protection of nitrogen to obtain the catalyst CS-2.
Example 4
50g of graphene and 50g of ZSM-5 molecular Sieve (SiO)2/Al2O330.0 molar ratio, 20 Å unit cell constant and 85% relative crystallinity) into 400g of the pseudo-boehmite slurry A obtained in example 1, stirring uniformly, adding 200g of ethanol, stirring uniformly, adding 50g of tetraethoxysilane, stirring uniformly, adding a small amount of tetramethylammonium hydroxide to adjust the pH value of the slurry to 8.5, placing into a closed autoclave, aging at 185 ℃ for 24h, taking out, filtering until the water content of a filter cake is 39%, adding 8g of ethylenediamine and 6g of tetraethoxysilane, kneading into a plastic body, extruding into strips, drying at 100 ℃ for 3h, and roasting at 500 ℃ for 4h under the protection of nitrogen to obtain the final modified alumina carrier S-3.
93.1g of Co (NO)3)2. 6H2Dissolving O in 200mL deionized water, adding ammonium citrate 1.5 times of total mole of metal ions, heating to dissolve, cooling to room temperature, adding 175.5g (NH)4)6Mo7O24.4H2And O, adjusting with ammonia water until ammonium molybdate is completely dissolved, and fixing the volume with a 1000mL volumetric flask.
And (3) soaking 120g of S-3 carrier in Mo-Co solution in the same volume, then placing the soaked strip in a drying oven for 3h at 120 ℃, and roasting for 3h at 500 ℃ under the protection of nitrogen to obtain the catalyst CS-3.
Example 5
13g of graphene and 13g of SBA-15 mesoporous molecular Sieve (SiO)2/Al2O3Molar ratio 35.0) was added to 625g of the pseudo-boehmite slurry a obtained in example 1, 500g of isopropyl alcohol was added after stirring uniformly, 75g of dimethylvinylethoxysilane was added after stirring uniformly, and a small amount of triethanolamine was added after stirring uniformly to adjust the pH of the slurry to 9.0. Placing the mixture into a closed high-pressure kettle, aging the mixture at 160 ℃ for 20h, taking out the mixture, filtering the mixture until the water content of a filter cake is 52%, adding 3.5g of diethylamine and 4g of dimethylethoxysilane, kneading the mixture into a plastic body, extruding the plastic body into strips, forming the strips, drying the strips at 100 ℃ for 3h, and roasting the strips at 500 ℃ for 4h under the protection of nitrogen to obtain the final composite carrier S-4.
93.1g of Co (NO)3)2. 6H2Dissolving O in 200mL deionized water, adding ammonium citrate 1.5 times of total mole of metal ions, heating to dissolve, cooling to room temperature, adding 175.5g (NH)4)6Mo7O24.4H2And O, adjusting with ammonia water until ammonium molybdate is completely dissolved, and fixing the volume with a 1000mL volumetric flask.
And (3) soaking 120g of S-4 carrier in Mo-Co solution in the same volume, then placing the soaked strip in a drying oven for 3h at 120 ℃, and roasting for 3h at 500 ℃ under the protection of nitrogen to obtain the catalyst CS-4.
Example 6
10g of graphene and 31g of β molecular Sieve (SiO)2/Al2O330.0 molar ratio, 13 unit cell constant 13 Å and 80% relative crystallinity) into 250g of the pseudo-boehmite slurry A obtained in example 1, stirring uniformly, adding 350g of propanol, stirring uniformly, adding 100g of dimethylethoxysilane, stirring uniformly, adding a small amount of tetraethylammonium hydroxide to adjust the pH value of the slurry to 9.5, placing into a closed autoclave, aging at 175 ℃ for 30h, taking out, filtering until the water content of a filter cake is 46%, adding 6g of dimethylamine and 4g of triethoxysilane, kneading into a plastic mass, extruding into strips, drying at 100 ℃ for 3h, and roasting at 500 ℃ for 4h to obtain the final composite carrier S-5.
93.1g of Co (NO)3)2. 6H2Dissolving O in 200mL deionized water, adding ammonium citrate 1.5 times of total mole of metal ions, heating to dissolve, cooling to room temperature, adding 175.5g (NH)4)6Mo7O24.4H2And O, adjusting with ammonia water until ammonium molybdate is completely dissolved, and fixing the volume with a 1000mL volumetric flask.
And (3) soaking 120g of S-5 carrier in Mo-Co solution in the same volume, then placing the soaked strip in a drying oven for 3h at 120 ℃, and roasting for 3h at 500 ℃ under the protection of nitrogen to obtain the catalyst CS-5.
Comparative example 1
625g of pseudo-boehmite slurry A is taken, 200g of ethanol is added after uniform stirring, 50g of tetraethoxysilane is added after continuous uniform stirring, and a small amount of tetramethyl ammonium hydroxide is added after continuous uniform stirring to adjust the pH value of the slurry to 8.5. Putting the mixture into a closed high-pressure kettle, aging the mixture for 24 hours at 185 ℃, taking out the mixture, filtering the mixture until the water content of a filter cake is 39 percent, adding 8g of ethylenediamine and 6g of tetraethoxysilane, kneading the mixture into a plastic body, extruding the plastic body into strips, forming the strips, drying the strips at 100 ℃ for 3 hours, and roasting the strips at 500 ℃ for 4 hours to obtain the alumina carrier DS-1.
93.1g of Co (NO)3)2. 6H2Dissolving O in 200mL deionized water, adding ammonium citrate 1.5 times of total mole of metal ions, heating to dissolve, cooling to room temperature, adding 175.5g (NH)4)6Mo7O24.4H2And O, adjusting with ammonia water until ammonium molybdate is completely dissolved, and fixing the volume with a 1000mL volumetric flask.
And (3) soaking 120g of DS-1 carrier in Mo-Co solution in the same volume, then placing the soaked strip in a drying oven for 3h at 120 ℃, and roasting for 3h at 500 ℃ under the protection of nitrogen to obtain the catalyst CDS-1.
Comparative example 2
13g of ZSM-5 molecular Sieve (SiO)2/Al2O330.0 molar ratio, 20 Å unit cell constant and 85% relative crystallinity) into 625g of the pseudo-boehmite slurry A obtained in example 1, stirring uniformly, adding 200g of ethanol, stirring uniformly, adding 50g of tetraethoxysilane, stirring uniformly, adding a small amount of tetramethylammonium hydroxide to adjust the pH value of the slurry to 8.5, placing into a closed autoclave, aging at 185 ℃ for 24h, taking out, filtering until the water content of a filter cake is 39%, adding 8g of ethylenediamine and 6g of tetraethoxysilane, kneading into a plastic body, extruding into strips, drying at 100 ℃ for 3h, and roasting at 500 ℃ for 4h to obtain the final composite carrier DS-2.
93.1g of Co (NO)3)2. 6H2Dissolving O in 200mL deionized water, adding ammonium citrate 1.5 times of total mole of metal ions, heating to dissolve, cooling to room temperature, adding 175.5g (NH)4)6Mo7O24.4H2O, with ammoniaAdjusting the water until the ammonium molybdate is completely dissolved, and fixing the volume by using a 1000mL volumetric flask.
And (3) soaking 120g of DS-2 carrier in Mo-Co solution in the same volume, then placing the soaked strip in a drying oven for 3h at 120 ℃, and roasting for 3h at 500 ℃ under the protection of nitrogen to obtain the catalyst CDS-2.
Comparative example 3
Adding 13g of graphene into 625g of the pseudo-boehmite slurry A obtained in example 1, stirring uniformly, adding 200g of ethanol, stirring uniformly, adding 50g of tetraethoxysilane, stirring uniformly, adding a small amount of tetramethylammonium hydroxide, and adjusting the pH value of the slurry to 8.5. Placing the mixture into a closed high-pressure kettle, aging the mixture for 24 hours at 185 ℃, taking out the mixture, filtering the mixture until the water content of a filter cake is 39 percent, adding 8g of ethylenediamine and 6g of tetraethoxysilane, kneading the mixture into a plastic body, extruding the plastic body into strips, forming the strips, drying the strips for 3 hours at 100 ℃, and roasting the strips for 4 hours at 500 ℃ in a nitrogen atmosphere to obtain the final composite carrier DS-3.
93.1g of Co (NO)3)2. 6H2Dissolving O in 200mL deionized water, adding ammonium citrate 1.5 times of total mole of metal ions, heating to dissolve, cooling to room temperature, adding 175.5g (NH)4)6Mo7O24.4H2And O, adjusting with ammonia water until ammonium molybdate is completely dissolved, and fixing the volume with a 1000mL volumetric flask.
And (3) soaking 120g of DS-3 carrier in Mo-Co solution in the same volume, then placing the soaked strip in a drying oven for 3h at 120 ℃, and roasting for 3h at 500 ℃ under the protection of nitrogen to obtain the catalyst CDS-3.
Comparative example 4
The preparation method comprises the steps of uniformly stirring 13g of graphene, 13g of ZSM-5 molecular sieve and 625g of pseudo-boehmite slurry A, drying at 110 ℃ until the water content is 20%, directly and uniformly mixing, adding 3g of sesbania powder, 20g of 10% phosphoric acid and 80ml of deionized water, kneading into a plastic body, extruding into strips, drying at 100 ℃ for 3 hours, and roasting at 500 ℃ for 4 hours under the protection of nitrogen to obtain the final modified alumina carrier DS-4.
93.1g of Co (NO)3)2. 6H2Dissolving O into 200mL of deionized water, and dissolving to obtain the productAdding ammonium citrate 1.5 times of total mole of metal ions, heating to dissolve, cooling to room temperature, adding 175.5g (NH)4)6Mo7O24.4H2And O, adjusting with ammonia water until ammonium molybdate is completely dissolved, and fixing the volume with a 1000mL volumetric flask.
And (3) soaking 120g of S-1 carrier in Mo-Co solution in the same volume, then placing the soaked strip in a drying oven for 3h at 120 ℃, and roasting for 3h at 500 ℃ under the protection of nitrogen to obtain the catalyst DS-4.
Comparative example 5
50g of ZSM-5 molecular sieve and 50g of SB alumina powder are directly and uniformly mixed, 3g of sesbania powder, 20g of 10% phosphoric acid and 80ml of deionized water are added, the mixture is kneaded into a plastic body, then the plastic body is extruded into strips for forming, the strips are dried at 100 ℃ for 3 hours, and then the strips are roasted at 500 ℃ for 4 hours to obtain the final composite carrier DS-5.
93.1g of Co (NO)3)2. 6H2Dissolving O in 200mL deionized water, adding ammonium citrate 1.5 times of total mole of metal ions, heating to dissolve, cooling to room temperature, adding 175.5g (NH)4)6Mo7O24.4H2And O, adjusting with ammonia water until ammonium molybdate is completely dissolved, and fixing the volume with a 1000mL volumetric flask.
And (3) soaking 120g of DS-4 carrier in Mo-Co solution in the same volume, then placing the soaked strip in a drying oven for 3h at 120 ℃, and roasting for 3h at 500 ℃ under the protection of nitrogen to obtain the catalyst CDS-5.
Comparative example 6
The synthesis of example 2 was repeated, but without addition of tetramethylammonium hydroxide and tetraethoxysilane, to give the comparative support DS-6 and catalyst CDS-6.
Comparative example 7
The synthesis of example 2 was repeated, but without the addition of the solvent ethanol, to give the comparative support DS-7 and catalyst CDS-7.
Comparative example 8
The synthesis of example 2 was repeated, but the aging temperature was 70 ℃ to give the comparative support DS-8 and catalyst CDS-8.
Comparative example 9
The synthesis of example 2 was repeated, but instead of adding ethylenediamine and tetraethoxysilane during kneading to form a plastomer, ammonia was added to obtain the comparative support DS-9 and catalyst CDS-9.
Comparative example 10
The synthesis of example 2 was repeated, but ethylenediamine and tetraethoxysilane were not added, and after adding a proper amount of nitric acid and sesbania powder, kneading was carried out to give a plastic molding, to obtain a comparative support DS-10 and a catalyst CDS-10.
Comparative example 11
The synthesis of example 2 was repeated, but without the addition of ethylenediamine during kneading to form a plastomer, giving the comparative support DS-11 and catalyst CDS-11.
Comparative example 12
The synthesis of example 2 was repeated, but without addition of tetraethoxysilane during kneading to a plastomer, giving a comparative support DS-12 and catalyst CDS-12.
Comparative example 13
The synthesis of example 2 was repeated except that 625g of pseudo-boehmite slurry A was changed to 50gSB alumina powder and 575g of aqueous solution were mixed to give comparative support DS-13 and catalyst CDS-13.
The properties of the raw material molecular sieve and SB powder are shown in Table 1, and the properties of the obtained carrier are shown in Table 2.
Table 1 main properties of the feedstock molecular sieves
Figure 478161DEST_PATH_IMAGE002
TABLE 2 Main Properties of the vector
Figure 208351DEST_PATH_IMAGE004
Table 2 (continuation)
Figure 988088DEST_PATH_IMAGE006
As can be seen from Table 2, the carrier prepared according to the present invention has improved bulk properties, higher specific surface area and pore volume, higher amount of infrared acid, and better crush strength, as compared to the comparative examples.
Example 7
This example demonstrates the hydrodesulfurization reaction performance of the catalyst provided by the present invention for diesel fuel.
The adopted evaluation raw oil is straight-run diesel oil provided by a certain refinery of China petrochemicals.
The catalysts CS-1 to CS-6 and the comparative examples CDS-1 to CDS-12 were subjected to hydrogenation performance evaluation using a 200mL fixed bed liquid phase circulating hydrogenation apparatus.
Presulfurizing conditions of the catalyst: using a catalyst containing 3wt% of CS2The space velocity of the aviation kerosene is 1.0h-1Presulfurizing the catalyst at an operating pressure of 5.0MPa with a hydrogen-oil volume ratio of 500: 1.
The prevulcanisation process is as follows: feeding pre-vulcanized oil at 120 ℃, feeding oil for 2h, vulcanizing at constant temperature for 2h, heating to 150 ℃ at 15 ℃/h, vulcanizing at constant temperature for 4h, heating to 230 ℃ at 6 ℃/h, vulcanizing at constant temperature for 10h, heating to 290 ℃ at 6 ℃/h, vulcanizing at constant temperature for 6h, heating to 340 ℃ at 10 ℃/h, vulcanizing at constant temperature for 6h, naturally cooling to 200 ℃, and finishing the pre-vulcanization.
The evaluation reaction conditions were: the operating pressure is 10.0MPa, the reaction temperature is 360 ℃, the circulation ratio is 2, and the volume space velocity of the fresh raw material is 1.2h-1The results of the three hydrogen mixtures are shown in Table 3.
TABLE 3 Properties of catalyst and evaluation results
Figure DEST_PATH_IMAGE008
Table 3 (continuation)
Figure DEST_PATH_IMAGE010
The evaluation results in Table 3 can show that the catalyst of the invention is used in the liquid phase cycle hydrogenation of diesel oil, and has the operating pressure of 10.0MPa, the reaction temperature of 360 ℃, the circulation ratio of 2 and the volume space velocity of fresh raw material of 1.2h-1Under the process condition of tertiary hydrogen mixing, the high desulfurization performance is achieved, and the high denitrification performance is achieved。

Claims (18)

1. A modified alumina carrier is characterized in that: based on the weight of the modified alumina, the modified alumina comprises 2-20 wt% of molecular sieve, 2-20 wt% of graphene and 60-96 wt% of alumina; the specific surface area of the carrier is 300-400m2Per g, pore volume of 0.5-0.8cm3(ii)/g, average pore diameter of 7-9nm, crush strength of 100-200N/cm.
2. A method for preparing a modified alumina carrier as claimed in claim 1, which comprises: (1) uniformly mixing pseudo-boehmite precursor slurry, a mesoporous molecular sieve, graphene and organic alcohol to obtain slurry A; (2) adding a silane coupling agent into the slurry A obtained in the step (1), uniformly mixing, and then adjusting the pH value of the slurry to 7.5-11 to obtain slurry B; (3) and (3) aging the slurry B obtained in the step (2) under a certain pressure, filtering the material after aging to remove a certain amount of water, adding organic amine and a silane coupling agent, kneading into a plastic body, and forming, drying and roasting to obtain the modified alumina carrier.
3. The method of claim 2, wherein: the solid content of the pseudo-boehmite precursor slurry in the step (1) is 0.5-20 wt% calculated by alumina.
4. The method according to claim 2, wherein the molecular sieve in the step (1) is one or more of a Y-type molecular sieve, β zeolite, ZSM, TS series molecular sieve, SAPO series molecular sieve, MCM series molecular sieve or SBA series molecular sieve.
5. The method of claim 2, wherein: the molecular sieve in the step (1) has the following properties: SiO 22/Al2O3The molar ratio is 20-60, the BET specific surface area is 300-2(g) external specific surface area of 100-2Per g, pore volume of micropores is 0.05-0.10cm3Per g, mesoporous pore volume of 0.35-0.5cm3/g。
6. The method of claim 2, wherein: the graphene in the step (1) is one or two of single-layer graphene, double-layer graphene, few-layer graphene or multi-layer graphene.
7. The method of claim 2, wherein: the mass ratio of the molecular sieve to the pseudo-boehmite precursor in the step (1) is 1: 48-1: and 3, counting the pseudo-boehmite precursor by alumina.
8. The method of claim 2, wherein: the mass ratio of the graphene to the pseudo-boehmite precursor in the step (1) is 1: 48-1: and 3, counting the pseudo-boehmite precursor by alumina.
9. The method of claim 2, wherein: the mass ratio of the organic alcohol to the water in the pseudo-boehmite precursor slurry in the step (1) is 1: 9-9: 1.
10. the method of claim 2, wherein: the organic alcohol in the step (1) is an organic alcohol with the carbon number less than 4.
11. The method of claim 2, wherein: the silane coupling agent in the step (2) and the step (3) is oxygen-containing organosilane with the carbon number less than 8.
12. The method of claim 2, wherein: the silane coupling agent in the step (2) and the step (3) is one or more of trimethoxy silane, tetramethoxy silane, methyl diethoxy silane, dimethyl ethoxy silane, triethoxy silane, tetraethoxy silane, dimethyl diethoxy silane, dimethyl vinyl ethoxy silane or trimethyl allyloxy silane.
13. The method of claim 2, wherein: the mass ratio of the silane coupling agent in the step (2) to the organic alcohol in the slurry A is 1: 20-1: 1.
14. the method of claim 2, wherein: the aging process of the step (3) is carried out in a pressure-resistant container, and the aging conditions are as follows: the aging temperature is 100-200 ℃, the aging time is 6-48 hours, and the aging pressure is the system autogenous pressure.
15. The method of claim 2, wherein: and (4) the water content in the filter cake subjected to certain water removal in the step (3) is 25-70 wt%.
16. The method of claim 2, wherein: the organic amine in the step (3) is organic amine with carbon atom number less than 6, and can be one or more of ethylamine, propylamine, dimethylamine, ethylenediamine, dipropylamine, butylamine, diethylamine or diisopropylamine; based on the total weight of the pseudo-boehmite precursor, the graphene and the molecular sieve, the adding amount of the organic amine is 1wt% -10wt%, and the adding amount of the silane coupling agent is 1wt% -10wt%, wherein the pseudo-boehmite precursor is calculated by alumina.
17. A hydrorefining catalyst characterized by: the catalyst takes the modified alumina as the carrier in claim 1, the hydrogenation active components are VIB group metals and VIII group metals, and based on the total weight of the catalyst, the VIB group metals account for 2.0-30% of the total weight of the catalyst, and the VIII group metals account for 0.1-10% of the total weight of the catalyst.
18. Use of the hydrofinishing catalyst according to claim 16 in the liquid phase hydrogenation of oils.
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