CN114433210B - Hydrodearene catalyst and preparation method and application thereof - Google Patents

Hydrodearene catalyst and preparation method and application thereof Download PDF

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Publication number
CN114433210B
CN114433210B CN202011115930.3A CN202011115930A CN114433210B CN 114433210 B CN114433210 B CN 114433210B CN 202011115930 A CN202011115930 A CN 202011115930A CN 114433210 B CN114433210 B CN 114433210B
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molecular sieve
catalyst
silicon source
sba
content
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CN114433210A (en
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樊宏飞
孙晓艳
于正敏
陈玉晶
王继锋
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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
    • B01J29/80—Mixtures of different zeolites
    • B01J35/397—
    • B01J35/615—
    • B01J35/617—
    • B01J35/633—
    • B01J35/635—
    • B01J35/638—
    • B01J35/647—
    • 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
    • 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
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0325—Noble metals
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/12—Noble metals
    • B01J29/126—Y-type faujasite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1062—Lubricating oils
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/14—White oil, eating oil

Abstract

The invention discloses a hydrodearomatization catalyst and a preparation method and application thereof, wherein the catalyst comprises an Al-SBA-15/Y composite molecular sieve, amorphous silicon aluminum and platinum group metal, the content of the Al-SBA-15/Y composite molecular sieve is 5 to 25 weight percent, the content of the amorphous silicon aluminum is 60 to 90 weight percent, the content of the platinum group metal is 0.1 to 0.5 weight percent based on elements, and the content of Pd is 0.2 to 0.8 weight percent based on the weight of the catalyst. The catalyst has higher hydrodearene activity, and is especially suitable for hydrodearene and decoloring processes of naphthenic high-viscosity white oil and solvent oil containing heavy arene.

Description

Hydrodearene catalyst and preparation method and application thereof
Technical Field
The invention relates to a hydrodearomatization catalyst, a preparation method and application thereof, wherein the method is suitable for hydrogenation of aromatic hydrocarbon, in particular for hydrodearomatization of naphthenic oil containing heavy aromatic hydrocarbon.
Background
The white oil is deeply refined mineral oil, has the characteristics of water white color, transparency, low impurity content of sulfur, nitrogen and oxygen containing heterocyclic compounds, aromatic hydrocarbon and the like, and can be classified into industrial grade, cosmetic grade/medical grade and food grade according to the characteristics of impurity content, color and the like. Wherein, the food-grade white oil has the deepest refining degree and the strictest quality requirement. Domestic industrial white oil is in a situation of being supplied more than needed, and cosmetic grade white oil, medical white oil and food grade white oil, especially high grade white oil, still need to depend on import. The hydrogenation process of producing food grade white oil includes the technological content including the steps of taking hydrotreated distillate oil, hydrotreated light deoiling, hydrocracked tail oil, etc. as material, isomerizing dewaxing in the presence of hydrogen and hydroisomerizing catalyst, replenishing hydrofining the liquid phase of the reacted effluent, and fractionating the replenishing hydrofined liquid phase effluent to obtain the required white oil product. Meeting the requirements of food-grade white oil index, the most effective method is to deeply hydrogenate and saturate the product with aromatic hydrocarbon because the product has extremely strict limitation on the aromatic hydrocarbon content. The product color is improved and the peculiar smell is eliminated by deep dearomatization in the refining process.
To solve the above problems, the most effective method is to deeply hydrogenate aromatic hydrocarbon saturation. CN1769379A, CN1140748A, CN1070215a refers to conventional metal catalysts, which have the defect of low activity and can not effectively solve the problem of deep dearomatization of lubricating oil; the catalyst support components of CN98117511.2, CN90100187.2 and US5393408 are described as having A1 2 O 3 And amorphous silica alumina, the dearomatization effect is poor due to the structural defect of the carrier pores of the catalyst. The carrier of the lubricating oil hydrofining catalyst such as CN1317368C, CN201010197869.1 consists of a Y-type molecular sieve and amorphous silica-alumina, and the active components mainly comprise Pd and Pt. Because the naphthenic base thick oil fraction has the characteristics of high viscosity, high molecular weight and multiple condensed ring structures, the pore structure of the Y molecular sieve still cannot fully hydrogenate and saturate polycyclic aromatic hydrocarbon in the macromolecular fraction, and high-grade white oil cannot be prepared. Therefore, a catalyst with a special structure is required to improve the ring-opening selectivity of the catalyst so as to obtain higher-grade white oil.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a hydrodearene catalyst, and a preparation method and application thereof. The catalyst prepared by the method has higher hydrodearene activity, and is particularly suitable for hydrodearene and decoloring processes of naphthenic high-viscosity white oil and solvent oil containing heavy arene.
A hydrodearene catalyst comprises an Al-SBA-15/Y composite molecular sieve, amorphous silicon aluminum and platinum group metal, wherein the content of the Al-SBA-15/Y composite molecular sieve is 5 to 25 weight percent, preferably 10 to 18 weight percent, the content of the amorphous silicon aluminum is 60 to 90 weight percent, preferably 70 to 85 weight percent, the content of the platinum group metal is 0.1 to 0.5 weight percent, preferably 0.2 to 0.4 weight percent, and the content of Pd is 0.2 to 0.8 weight percent, preferably 0.3 to 0.6 weight percent based on the weight of the catalyst.
In the catalyst of the present invention, the platinum group metal is one or more of ruthenium, rhodium, palladium, osmium, iridium and platinum, preferably palladium and/or platinum, more preferably palladium and platinum,
in the catalyst, the Al-SBA-15/Y composite molecular sieve is of a shell-core structure, the Y-type molecular sieve is of a core, the content of the Y-type molecular sieve in the Al-SBA-15/Y composite molecular sieve is 30% -90%, preferably 40% -80%, and the content of the SBA-15 molecular sieve in the Al-SBA-15/Y composite molecular sieve is 20% -90%, preferably 20% -60%.
In the catalyst of the invention, the content of silicon dioxide in the amorphous silicon aluminum is 5 to 30 weight percent, preferably 8 to 20 weight percent based on the weight of the amorphous silicon aluminum.
In the catalyst of the invention, the hydrodearomatic hydrocarbon catalyst has the following properties: specific surface area of 300-600 m 2 Preferably 350 to 500m 2 Per g, pore volume of 0.4-1.2 ml/g, preferably 0.5-0.9 ml/g, infrared acid amount of 0.1-1.0 mmol/g, preferably 0.2-0.6 mmol/g, pore distribution of 40-15nm pore volume accounting for 80-95% of total pore volume.
In the catalyst of the present invention, the hydrodearomatic hydrocarbon catalyst contains a binder, and the content of the binder in the catalyst is 10wt% to 30wt%, preferably 13wt% to 25wt%, and more preferably 16wt% to 22wt% by weight.
The preparation method of the hydrodearene catalyst comprises the following steps: kneading, molding, drying and roasting an Al-SBA-15/Y composite molecular sieve, preferably a core-shell type Al-SBA-15/Y composite molecular sieve, amorphous silica-alumina and an adhesive to obtain a catalyst carrier; platinum group metals, preferably Pd and Pt, are loaded on the catalyst carrier by an impregnation method, and then the catalyst is dried and roasted to obtain the hydrodearene catalyst.
In the method of the invention, the preparation process of the Al-SBA-15/Y shell-core composite molecular sieve comprises the following steps:
(1) Mixing a template agent, a silicon source and a Y-type molecular sieve for reaction, and carrying out solid-liquid separation on the reacted materials to obtain a solid phase and a liquid phase;
(2) Taking 10% -50%, preferably 15% -30% of the volume fraction of the liquid phase obtained in the step (1), adjusting the mass content of the template agent in the taken liquid phase to be 0.05-0.8, preferably 0.1-0.6, further preferably 0.25-0.5, adding the template agent into the solid phase separated in the step (1) for crystallization, and carrying out solid-liquid separation, drying and roasting after the crystallization is finished to obtain the SBA-15/Y shell-core composite molecular sieve;
(3) And (3) treating the SBA-15/Y shell-core composite molecular sieve obtained in the step (2) by adopting an acidic aluminum salt solution, and drying and roasting to obtain the final composite carrier.
In the step (1) of the method, the silicon source is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate and butyl orthosilicate.
In the method step (1), the silicon source is prepared by prehydrolysis, and the prehydrolysis process of the silicon source is as follows: adding a silicon source into an acidic solution, and aging to obtain the silicon source, wherein the acid is one or more of hydrochloric acid, sulfuric acid and phosphoric acid.
In the step (1) of the method, a specific process of prehydrolysis of the silicon source is as follows: and adding the silicon source into a dilute acid solution with the pH value of 1-4, preferably, stirring for 1-12 h at room temperature, standing and ageing for 4-120 h to obtain the silicon source, preferably, adding the silicon source into a dilute acid solution with the pH value of 2.5-3.5, stirring for 6-8 h at room temperature, and standing and ageing for 24-96 h to obtain the silicon source.
In the step (1) of the method, the template agent is P123, and the template agent P123 can be dissolved in an acidic aqueous solution first and then mixed with materials such as a silicon source, a Y-type molecular sieve and the like for reaction.
In the step (1) of the method, the Y-type molecular sieve is a modified Y-type molecular sieve, the particle size of the Y-type molecular sieve is 200 nm-5000 nm, and SiO 2 /Al 2 O 3 =40 to 85; preferably 45 to 70, and more preferably 55 to 70.
In the step (1) of the method, the molar concentration of the acid solution in the template agent, the silicon source and the Y-type molecular sieve mixture is 0.1-1.0 mol/L, preferably 0.2-0.4 mol/L, and the mass content of the template agent is 0.2-3%, preferably 0.2-2%; the mass content of the silicon source is 1% -10%, preferably 3% -8%; the mass content of the Y-type molecular sieve is 1% -15%, preferably 3% -10%.
In the step (1) of the method, the reaction temperature is 20-40 ℃, preferably 25-30 ℃; the reaction time is 2-12 hours, preferably 4-8 hours.
In the step (1) of the method, a specific template agent, a silicon source and a Y-type molecular sieve are mixed and reacted as follows: and dissolving a certain amount of template agent (such as P123) in an acidic aqueous solution, adding water into Y, adding into the solution, stirring for 10-15 min, adding a prehydrolyzed silicon source, and stirring at a constant temperature for 2-12 h.
In the step (2), the crystallization process is to add alkaline substances or alkaline solutions into the crystallization system to adjust the pH of the system to be 3-11, preferably pH to be 7.5-10, and more preferably 8-9.5; the crystallization temperature is 80-140 ℃, preferably 100-120 ℃; the crystallization time is 4 to 48 hours, preferably 24 to 30 hours.
In the step (2), one or more of centrifugal separation and filtering separation are adopted, preferably, the solid content of the separated liquid phase is controlled to be 0.05-3 wt%, preferably 0.1-2.5 wt%, and more preferably 0.3-0.2 wt%; at this time, part of the liquid is the same as the solid phase mixture in the step (1) for crystallization; the rest liquid phase can be mixed with the template agent, the silicon source and the Y-type molecular sieve to repeat the operation process of the step (1); the mass content of the template agent added into the mixed system is 0.2% -3%, preferably 0.2% -2%; the mass content of the added silicon source in the system is 1% -10%, preferably 3% -8%; the mass content of the added Y-type molecular sieve in the system is 1% -15%, preferably 3% -10%, and the mass fraction of the rest liquid phase is 10% -50%; the process can be repeatedly carried out, the repeated times are not limited, and the optimization adjustment can be carried out according to the actual production condition.
In the step (2) of the method, the drying temperature is 80-120 ℃, the drying time is 4-10h, the roasting temperature is 450-600 ℃, and the roasting time is 4-8h.
In the step (3) of the method, the aluminum salt is one or more of aluminum sulfate, aluminum chloride and aluminum nitrate, the pH value of the acidic aluminum salt solution is 1-4, preferably 2-3, and the mass content of the aluminum salt in the acidic aluminum salt solution is 0.1% -1%, preferably 0.2% -0.8%; the treatment time is 3-10, and the treatment temperature is 25-35 ℃.
In the step (3) of the method, a specific operation process is as follows: dissolving a certain amount of aluminum source in an acidic solution, wherein the pH value of the acidic aluminum salt solution is 1-4, preferably 2-3, adding the SBA-15/Y shell-core composite molecular sieve prepared in the step (2), stirring for 10-20h at 28-32 ℃, washing, drying for 4-10h at 80-120 ℃, and roasting for 4-6h at 500-560 ℃ to obtain the Al-SBA-15/Y molecular sieve.
In the method, the liquid phase material with proper solid content is adopted to inhibit phase separation of the phase-separated SBA-15 material and the Y molecular sieve and instability of the Y molecular sieve in a strong acid medium, so that the composite material with more uniform morphology and more complete core-shell structure SBA-15/Y is synthesized.
In the preparation method of the hydrodearomatic hydrocarbon catalyst, the adhesive is preferably small-pore alumina with pore volume of 0.3-0.5 mL/g and specific surface area of 200-400 m 2 /g。
In the preparation method of the hydrodearene catalyst, the catalyst can be molded according to actual needs, and the catalyst can be in the shape of a cylindrical bar, clover and the like. The carrier strips are dried at 100-130 ℃ for 12-14 hours and baked at 450-550 ℃ for 5-10 hours.
In the preparation method of the hydrodearene catalyst, the method for loading Pt and Pd adopts an impregnation method. The impregnation method can adopt a saturated impregnation or excessive impregnation method, and after Pt and Pd are impregnated, the catalyst is dried and roasted under the following conditions: drying at 100-130 ℃ for 18-14 hours, and roasting at 500-600 ℃ for 4-10 hours.
The hydrodearene method adopts the hydrodearene catalyst, and the operation conditions are as follows: the reaction pressure is 8-20 MPa, the hydrogen-oil volume ratio is 500-2000, and the liquid hourly space velocity is 0.5-7.0 h -1 The reaction temperature is 180-250 ℃, and the raw material is the hydrocracking tail after hydroisomerizationOil and solvent oil.
The hydrodearomatization catalyst disclosed by the invention can not only meet the hydrofining of smaller molecules, but also meet the hydrofining of the ultra-high viscosity naphthenic base distillate oil, is more beneficial to the selective ring opening of aromatic hydrocarbons, is particularly suitable for hydrodearomatization and decolorization processes of naphthenic base white oil, solvent oil and hydrocracking tail oil containing heavy aromatic hydrocarbons, and can obtain good use effects.
Detailed Description
The specific surface area and pore volume of the product are measured by adopting an ASAP2405 low-temperature liquid nitrogen adsorption method. The acid amount was measured by infrared spectrometer, and the adsorbent used was pyridine. Relative crystallinity was measured by XRD, with standard NaY of 100. In the invention, the mass fraction is as follows unless otherwise specified. The solid content of the liquid phase in the process according to the invention is defined as the ratio of the weight of the solid after evaporation of the water removed to the total mass of the liquid phase.
Example 1:
1. (a) 5.0g of teos was added to 15.0g of 15.0gpH =3 HCl solution with stirring, and after stirring at room temperature for 4 hours, the solution was changed from turbid solution to clear solution, and left stand for 24 hours for use. (b) 1.5g of P123 surfactant is dissolved in 130g of 0.3mol/L hydrochloric acid solution, 1.53g of modified Y-1 molecular sieve (specific surface area 835 m) 2 Per gram, pore volume 0.58 mL/g, siO 2 /Al 2 O 3 55, relative crystallinity 96, acid content 0.332 mmol/g) was dissolved in water, stirred for 5min, and then the pre-hydrolysis solution of TEOS prepared in advance in (1) was added, stirred at constant temperature of 30℃for 6h, and separated to obtain a solid phase and a liquid phase. The solid content of the liquid phase was controlled to be 0.5%.
2. The liquid phase obtained in step (1) was added to 1.0g of P123, 15.8g of concentrated HCL and 37g of water. Repeating the step 1; and (3) carrying out solid-liquid separation on the reacted materials to obtain a solid phase and a liquid phase, and controlling the solid content of the liquid phase to be 0.5%.
3. And (3) hydrothermal crystallization: adding the solid obtained in the step 2 into 30g of the liquid phase obtained in the step (1), uniformly stirring, adjusting the pH of the reaction liquid of the step (2) to 8.0 by using ammonia water, crystallizing at 100 ℃ for 24 hours, filtering, washing, drying, and roasting at 550 ℃ for 6 hours to obtain the core-shell structure SBA-15/Y-1 material.
4. 1.5g of aluminum isopropoxide is dissolved in 200ml of 0.2mol/LHCl solution, 30g of SBA-15/Y-1 material with a core-shell structure is added, the mixture is stirred for 20 hours at 30 ℃, and the mixture is washed, dried and roasted for 5 hours at 550 ℃ to obtain the aluminum supplementing material with the AlSBA-15/Y-1 mesoporous shell layer. The physical parameters of the composite molecular sieve are shown in Table 1.
Example 2:
1. (a) 5.0g of teos was added to 15.0g of 15.0gpH =3 HCl solution with stirring, and after stirring at room temperature for 4 hours, the solution was changed from turbid solution to clear solution, and left stand for 24 hours for use. (b) 1.4g of P123 surfactant was dissolved in 120g of 0.3mol/L hydrochloric acid solution, and 2.3g of modified Y-1 molecular sieve (specific surface area 835 m) 2 Per gram, pore volume 0.58 mL/g, siO 2 /Al 2 O 3 55, relative crystallinity 96, acid content 0.332 mmol/g) was dissolved in water, stirred for 5min, and then the pre-hydrolysis solution of TEOS prepared in advance in (1) was added, stirred at constant temperature for 4h at 30℃to separate, thereby obtaining a solid phase and a liquid phase. The solid content of the liquid phase was controlled to be 0.5%.
2. The liquid phase obtained in step (1) was added to 0.96P123, 12.1g of concentrated HCl and 34g of water. Repeating the step 1; and (3) carrying out solid-liquid separation on the reacted materials to obtain a solid phase and a liquid phase, and controlling the solid content of the liquid phase to be 0.5%.
3. And (3) hydrothermal crystallization: adding 28g of the liquid phase obtained in the step (1) into the solid obtained in the step (2), uniformly stirring, adjusting the pH of the reaction solution of the step (2) to 4.5 by using ammonia water, crystallizing at 100 ℃ for 24 hours, filtering, washing, drying, and roasting at 550 ℃ for 6 hours to obtain the core-shell structure SBA-15/Y-2 material.
4. 1.5g of aluminum isopropoxide is dissolved in 200ml of 0.2mol/LHCl solution, 30g of SBA-15/Y-2 material with a core-shell structure is added, the mixture is stirred for 20 hours at 30 ℃, and the mixture is washed, dried and roasted for 5 hours at 550 ℃ to obtain the aluminum supplementing material with the AlSBA-15/Y-2 mesoporous shell layer. The physical parameters of the composite molecular sieve are shown in Table 1.
Example 3:
1. (a) 5.0g of teos was added to 15.0g of 15.0gpH =3 HCl solution with stirring, and after stirring at room temperature for 4 hours, the solution was changed from turbid solution to clear solution, and left stand for 24 hours for use. (b) 1.3g of P123 surfactant is dissolved in 110g of 0.3mol/L hydrochloric acid solution, 3.5g of modified Y-1 molecular sieve (specific surface area 835 m) 2 /g，Pore volume 0.58 mL/g, siO 2 /Al 2 O 3 55, relative crystallinity 96, acid content 0.332 mmol/g) was dissolved in water, stirred for 5min, and then the pre-hydrolysis solution of TEOS prepared in advance in (1) was added, stirred at constant temperature for 4h at 30℃to separate, thereby obtaining a solid phase and a liquid phase. The solid content of the liquid phase was controlled to be 0.8%.
2. The liquid phase obtained in step (1) was added to 0.88P123, 12.1g of concentrated HCl and 31g of water. Repeating the step 1; and (3) carrying out solid-liquid separation on the reacted materials to obtain a solid phase and a liquid phase, and controlling the solid content of the liquid phase to be 0.8%.
3. And (3) hydrothermal crystallization: adding the solid obtained in the step 2 into 22g of the liquid phase obtained in the step (1), uniformly stirring, adjusting the pH of the reaction liquid of the step (2) to 9.0 by ammonia water, crystallizing at 100 ℃ for 24 hours, filtering, washing, drying, and roasting at 550 ℃ for 6 hours to obtain the core-shell structure SBA-15/Y-3 material.
4. 1.5g of aluminum isopropoxide is dissolved in 200ml of 0.2mol/LHCl solution, 30g of SBA-15/Y-3 material with a core-shell structure is added, the mixture is stirred for 20 hours at 30 ℃, and the mixture is washed, dried and roasted for 5 hours at 550 ℃ to obtain the aluminum supplementing material with an AlSBA-15/Y-3 mesoporous shell layer, wherein the physical parameters of the composite molecular sieve are shown in the table 1.
Example 4:
1. (a) 5.0g of teos was added to 15.0g of 15.0gpH =3 HCl solution with stirring, and after stirring at room temperature for 4 hours, the solution was changed from turbid solution to clear solution, and left stand for 24 hours for use. (b) 1.2g of P123 surfactant was dissolved in 100g of 0.3mol/L hydrochloric acid solution, and 5.6g of modified Y-1 molecular sieve (specific surface area 835 m) 2 Per gram, pore volume 0.58 mL/g, siO 2 /Al 2 O 3 55, relative crystallinity 96, acid content 0.332 mmol/g) was dissolved in water, stirred for 5min, and then the pre-hydrolysis solution of TEOS prepared in advance in (1) was added, stirred at constant temperature for 4h at 30℃to separate, thereby obtaining a solid phase and a liquid phase. The solid content of the liquid phase was controlled to be 1.0%.
2. The liquid phase obtained in step (1) was added to 0.66P123, 9.3g of concentrated HCl and 24g of water. Repeating the step 1; and (3) carrying out solid-liquid separation on the reacted materials to obtain a solid phase and a liquid phase, and controlling the solid content of the liquid phase to be 1.0%.
3. And (3) hydrothermal crystallization: adding 18g of the liquid phase obtained in the step (1) into the solid obtained in the step (2), uniformly stirring, adjusting the pH of the reaction solution of the step (2) to 9.5 by using ammonia water, crystallizing at 100 ℃ for 24 hours, filtering, washing, drying, and roasting at 550 ℃ for 6 hours to obtain the core-shell structure SBA-15/Y-1 material.
4. 1.5g of aluminum isopropoxide is dissolved in 200ml of 0.2mol/LHCl solution, 30g of SBA-15/Y-4 material with a core-shell structure is added, the mixture is stirred for 20 hours at 30 ℃, and the mixture is washed, dried and roasted for 5 hours at 550 ℃ to obtain the aluminum supplementing material with an AlSBA-15/Y-4 mesoporous shell layer, wherein the physical parameters of the composite molecular sieve are shown in the table 1.
Example 4-1:
1. (a) 5.0g of teos was added to 15.0g of 15.0gpH =3 HCl solution with stirring, and after stirring at room temperature for 4 hours, the solution was changed from turbid solution to clear solution, and left stand for 24 hours for use. (b) 1.2g of P123 surfactant was dissolved in 100g of 0.3mol/L hydrochloric acid solution, and 5.6g of modified Y-1 molecular sieve (specific surface area 835 m) 2 Per gram, pore volume 0.58 mL/g, siO 2 /Al 2 O 3 55, relative crystallinity 96, acid content 0.332 mmol/g) was dissolved in water, and stirred for 5min, and then the pre-hydrolysis solution of TEOS prepared in advance in (1) was added thereto, and stirred at constant temperature for 4h at 30 ℃.
2. And (3) hydrothermal crystallization: 2, regulating the pH value of the reaction solution in the step 1 to 4.5 by ammonia water, crystallizing at 100 ℃ for 24 hours, filtering, washing, drying, and roasting at 550 ℃ for 6 hours to obtain the core-shell structure SBA-15/Y-4-1 material.
3. 1.5g of aluminum isopropoxide is dissolved in 200ml of 0.2mol/LHCl solution, 30g of SBA-15/Y-4-1 material with a core-shell structure is added, the mixture is stirred for 20 hours at 30 ℃, and the mixture is washed, dried and roasted for 5 hours at 550 ℃ to obtain the aluminum supplementing material with an AlSBA-15/Y-4-1 mesoporous shell layer, and the physical parameters of the composite molecular sieve are shown in Table 1
Example 5
12 g of AlSBA-15/Y-1 molecular sieve and 100g of amorphous silica-alumina (pore volume 0.85mL/g, specific surface area 370 m) 2 And (2) adding an adhesive prepared from 20 small-pore alumina and dilute nitric acid (the molar ratio of nitric acid to small-pore alumina is 0.18) into a rolling machine, mixing and rolling, adding water, rolling into paste, extruding, drying the extruded strip at 110 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours to obtain the carrier TCAT-1. By adopting a conventional method of equal volume impregnation,PdC1 is added to the mixture 2 (analytically pure) and Pt (NH) 4 ） 4 C1 2 The (analytically pure) solution was impregnated stepwise onto the shaped support according to the final catalyst metal content (Pt 0.2wt%; pd0.5 wt%), left to stand for 12h, dried at 110℃for 6 hours, and calcined at 480℃for 4 hours to give catalyst cat1. The corresponding catalyst properties are shown in Table 2.
Example 6
14.3 g of AlSBA-15/Y-2 molecular sieve and 97.3 g of amorphous silica alumina (pore volume 0.85mL/g, specific surface area 370m 2 And (2) adding an adhesive prepared from 20g of small-pore alumina and dilute nitric acid (the molar ratio of nitric acid to small-pore alumina is 0.18) into a rolling machine, mixing and rolling, adding water, rolling into paste, extruding, drying the extruded strip at 110 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours to obtain the carrier TCAT-2.
The metal loading method was the same as in example 5 to produce catalyst cat2.
The corresponding catalyst properties are shown in Table 2.
Example 7
16.6 g of AlSBA-15/Y-3 molecular sieve and 94.6 g of amorphous silica alumina (pore volume 0.85mL/g, specific surface area 370m 2 And (3) adding an adhesive prepared from 20g of small-pore alumina and dilute nitric acid (the molar ratio of nitric acid to small-pore alumina is 0.21) into a rolling machine, mixing and rolling, adding water, rolling into paste, extruding, drying the extruded strip at 110 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours to obtain the carrier TCAT-3.
The metal loading method was the same as in example 5 to produce catalyst cat3.
Example 8
18.9 g of AlSBA-15/Y-4 molecular sieve and 91.9 g of amorphous silica alumina (pore volume 0.85mL/g, specific surface area 370m 2 And (3) adding a binder prepared from 20g of small-pore alumina and dilute nitric acid (the molar ratio of nitric acid to small-pore alumina is 0.18) into a rolling machine, mixing and rolling, adding water, rolling into paste, extruding, drying the extruded bars for 4 hours at 110 ℃, and roasting at 550 ℃ for 4 hours to obtain the carrier TCAT-4.
The metal loading method was the same as in example 5 to produce catalyst cat4.
Example 8-1
The preparation method of AlSBA-15/Y molecular sieve and catalyst is the same as that of example 5, SBA-15/Y-4-1 is substituted for SBA-15/Y-1 to obtain catalyst CCAT-4.
Table 1 physicochemical properties of composite molecular sieves
The composite molecular sieve is a core-shell SBA-15/Y composite molecular sieve. Compared with SBA-15/Y-1, SBA-15/Y-1 has less split-phase SBA-15, more uniform appearance and more complete 'core-shell' structure. As can be seen from Table 1, the molecular sieve prepared by the present invention has larger pore volume and specific surface area, more acid and higher crystallinity.
TABLE 2 physicochemical Properties of the catalysts
As can be seen from Table 2, compared with the comparative examples, the molecular sieve prepared by the method has more uniform morphology and more complete core-shell structure, so that the metal of the catalyst is more uniformly dispersed, and the catalyst has larger pore volume and specific surface area. The total acidity of the infrared ray is also increased.
The catalysts of the present invention CAT-1, CAT-2, CAT-3, CAT-4 and comparative catalyst CCAT-4 were evaluated for activity. The experiments were performed on a 200mL small hydrogenation unit with low pressure hydroisomerization of the product>The properties of the 320℃lubricating oil material are shown in Table 3. Adopts the high-pressure hydrofining process, and the hydrogen partial pressure is 13.0MPa, the hydrogen-oil volume ratio is 1250 and the volume space velocity is 0.8h -1 The process test of hydrogenation to produce white oil was performed under the process conditions, and the results of the reaction performance evaluation test are shown in Table 4.
Table 3 low pressure hydroisomerization >320 ℃ lube oil properties
TABLE 4 evaluation results of catalyst Activity
As can be seen from the evaluation results of the catalysts in Table 4, the catalyst prepared by the invention has higher activity, and the key technical index of the produced high-grade food-grade white oil is superior to that of the reference agent.

Claims (42)

1. A hydrodearene catalyst, characterized in that: the catalyst comprises an Al-SBA-15/Y composite molecular sieve, amorphous silicon aluminum, platinum group metal and Pd, wherein the content of the Al-SBA-15/Y composite molecular sieve is 5 to 25 weight percent, the content of the amorphous silicon aluminum is 60 to 90 weight percent, the platinum group metal is one or more of ruthenium, rhodium, osmium, iridium and platinum, and the content of the platinum group metal is 0.1 to 0.5 weight percent based on the element; pd is also included in the catalyst, and the content of Pd is 0.2-0.8 wt%; the Al-SBA-15/Y composite molecular sieve is of a shell-core structure, the Y-type molecular sieve is a core, the mass content of the Y-type molecular sieve in the Al-SBA-15/Y composite molecular sieve is 30% -90%, and the mass content of the SBA-15 molecular sieve in the Al-SBA-15/Y composite molecular sieve is 20% -90%; the content of silicon dioxide in the amorphous silicon aluminum is 5 to 30 weight percent based on the weight of the amorphous silicon aluminum; the hydrodearene catalyst contains a binder, wherein the content of the binder in the catalyst is 10-30wt% based on the weight; the hydrodearene catalyst has the following properties: specific surface area of 300-600 m 2 Per g, the pore volume is 0.4-1.2 mL/g, the infrared acid amount is 0.1-1.0 mmol/g, the pore distribution is that 40-15nm pore volume accounts for 80-95% of the total pore volume;
the preparation method of the hydrodearene catalyst comprises the following steps: kneading the Al-SBA-15/Y composite molecular sieve, amorphous silica-alumina and an adhesive, forming, drying and roasting to obtain a catalyst carrier; loading platinum group metals and Pd on a catalyst carrier by adopting an impregnation method, and drying and roasting to obtain a hydrodearene catalyst; the preparation method of the Al-SBA-15/Y composite molecular sieve specifically comprises the following steps:
(1) Mixing a template agent, a silicon source and a Y-type molecular sieve for reaction, and carrying out solid-liquid separation on the reacted materials to obtain a solid phase and a liquid phase;
(2) Taking 10% -50% of the volume fraction of the liquid phase obtained in the step (1), adjusting the mass content of the template agent in the taken liquid phase to be 0.05-0.8, adding the template agent into the solid phase separated in the step (1) for crystallization, and carrying out solid-liquid separation, drying and roasting after the crystallization is finished to obtain the SBA-15/Y shell-core composite molecular sieve;
(3) Treating the SBA-15/Y shell-core composite molecular sieve obtained in the step (2) by adopting an acidic aluminum salt solution, and drying and roasting to obtain a final composite carrier;
in the step (1), the silicon source is prepared by prehydrolysis, and the prehydrolysis process of the silicon source is as follows: adding a silicon source into an acidic solution, and aging to obtain the silicon source, wherein the acid is one or more of hydrochloric acid, sulfuric acid and phosphoric acid; the specific process is as follows: adding a silicon source into a dilute acid solution with pH=1-4, stirring for 1-12 hours at room temperature, and standing and aging for 4-120 hours to obtain the silicon source;
in the step (1), the mixing reaction process of the template agent, the silicon source and the Y-type molecular sieve is as follows: and dissolving the template agent in an acidic aqueous solution, adding water into the solution after adding water into the Y-type molecular sieve, stirring for 10-15 min, adding a prehydrolyzed silicon source, and stirring for 2-12 h at constant temperature.
2. The catalyst of claim 1, wherein: the content of the Al-SBA-15/Y composite molecular sieve is 10 to 18 weight percent, the content of amorphous silicon aluminum is 70 to 85 weight percent, the content of platinum group metal is 0.2 to 0.4 weight percent and the content of Pd is 0.3 to 0.6 weight percent based on the weight of the catalyst.
3. The catalyst of claim 1, wherein: the platinum group metal is platinum.
4. The catalyst of claim 1, wherein: the mass content of the Y-type molecular sieve in the Al-SBA-15/Y composite molecular sieve is 40% -80%, and the mass content of the SBA-15 molecular sieve in the Al-SBA-15/Y composite molecular sieve is 20% -60%.
5. The catalyst of claim 1, wherein: the silicon dioxide content in the amorphous silicon aluminum is 8-20wt% based on the weight of the amorphous silicon aluminum.
6. The catalyst of claim 1, wherein: the hydrodearene catalyst has the following properties: specific surface area of 350-500 m 2 Per gram, the pore volume is 0.5-0.9 ml/g, and the infrared acid amount is 0.2-0.6 mmol/g.
7. The catalyst of claim 1, wherein: the content of the binder in the catalyst is 13-25 wt% based on the weight of the catalyst.
8. The catalyst according to claim 1 or 7, characterized in that: the content of the binder in the catalyst is 16-22 wt% based on the weight of the catalyst.
9. A process for the preparation of a catalyst according to any one of claims 1 to 8, characterized in that: comprising the following steps: kneading the Al-SBA-15/Y composite molecular sieve, amorphous silica-alumina and an adhesive, forming, drying and roasting to obtain a catalyst carrier; the hydrogenation dearomatization catalyst is obtained by loading platinum group metal and Pd on a catalyst carrier by adopting an impregnation method, drying and roasting.
10. The method according to claim 9, wherein: comprising the following steps: the Al-SBA-15/Y composite molecular sieve is a core-shell type Al-SBA-15/Y composite molecular sieve.
11. The method according to claim 9, wherein: the preparation process of the Al-SBA-15/Y shell-core composite molecular sieve comprises the following steps:
(1) Mixing a template agent, a silicon source and a Y-type molecular sieve for reaction, and carrying out solid-liquid separation on the reacted materials to obtain a solid phase and a liquid phase;
(2) Taking 10% -50% of the volume fraction of the liquid phase obtained in the step (1), adjusting the mass content of the template agent in the taken liquid phase to be 0.05-0.8, adding the template agent into the solid phase separated in the step (1) for crystallization, and carrying out solid-liquid separation, drying and roasting after the crystallization is finished to obtain the SBA-15/Y shell-core composite molecular sieve;
(3) And (3) treating the SBA-15/Y shell-core composite molecular sieve obtained in the step (2) by adopting an acidic aluminum salt solution, and drying and roasting to obtain the final composite carrier.
12. The method according to claim 11, wherein: in the step (2), 15% -30% of the volume fraction of the liquid phase obtained in the step (1) is taken; adjusting the mass content of the template agent in the liquid phase to be 0.1-0.6.
13. The method according to claim 11 or 12, characterized in that: in the step (2), the mass content of the template agent in the liquid phase is adjusted to be 0.25-0.5.
14. The method according to claim 11, wherein: in the step (1), the silicon source is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate and butyl orthosilicate.
15. The method according to claim 11, wherein: in the step (1), the silicon source is prepared by prehydrolysis, and the prehydrolysis process of the silicon source is as follows: adding a silicon source into an acidic solution, and aging to obtain the silicon source, wherein the acid is one or more of hydrochloric acid, sulfuric acid and phosphoric acid.
16. The method according to claim 11, wherein: in the step (1), the prehydrolysis process of the silicon source is as follows: and adding a silicon source into a dilute acid solution with pH=1-4, stirring for 1-12 hours at room temperature, and standing and aging for 4-120 hours to obtain the silicon source.
17. The method according to claim 11 or 16, characterized in that: in the step (1), the prehydrolysis process of the silicon source is as follows: and adding a silicon source into a dilute acid solution with the pH value of 2.5-3.5, stirring for 6-8 hours at room temperature, and standing and aging for 24-96 hours to obtain the silicon source.
18. The method according to claim 11, wherein: in the step (1), the template agent is P123, and the template agent P123 is firstly dissolved in an acidic aqueous solution and then is mixed with materials such as a silicon source, a Y-type molecular sieve and the like for reaction.
19. The method according to claim 11, wherein: in the step (1), the Y-type molecular sieve is a modified Y-type molecular sieve, the particle size of the Y-type molecular sieve is 200 nm-5000 nm, and SiO 2 /Al 2 O 3 =40~85。
20. The method according to claim 19, wherein: in the step (1), siO of the Y-type molecular sieve 2 /Al 2 O 3 =45-70。
21. The method according to claim 19, wherein: in the step (1), siO of the Y-type molecular sieve 2 /Al 2 O 3 =55-70。
22. The method according to claim 11, wherein: in the step (1), the molar concentration of the acidic solution in the template agent, the silicon source and the Y-type molecular sieve mixture is 0.1-1.0 mol/L, and the mass content of the template agent is 0.2% -3%; the mass content of the silicon source is 1% -10%; the mass content of the Y-type molecular sieve is 1% -15%.
23. The method according to claim 11 or 22, characterized in that: in the step (1), the molar concentration of the acidic solution in the template agent, the silicon source and the Y-type molecular sieve mixture is 0.2-0.4 mol/L, and the mass content of the template agent is 0.2% -2%; the mass content of the silicon source is 3% -8%; the mass content of the Y-type molecular sieve is 3% -10%.
24. The method according to claim 11, wherein: in the step (1), the reaction temperature is 20-40 ℃; the reaction time is 2-12 h.
25. The method according to claim 11 or 24, characterized in that: in the step (1), the reaction temperature is 25-30 ℃; the reaction time is 4-8h.
26. The method according to claim 11, wherein: in the step (1), the mixing reaction process of the template agent, the silicon source and the Y-type molecular sieve is as follows: and dissolving the template agent in an acidic aqueous solution, adding water into the solution after adding water into the Y-type molecular sieve, stirring for 10-15 min, adding a prehydrolyzed silicon source, and stirring for 2-12 h at constant temperature.
27. The method according to claim 11, wherein: in the step (2), the crystallization process is to add alkaline substances or alkaline solutions into a crystallization system to adjust the pH value of the system to be 3-11; the crystallization temperature is 80-140 ℃; the crystallization time is 4-48 h.
28. The method according to claim 11 or 27, characterized in that: in the step (2), the crystallization process is to add alkaline substances or alkaline solution into the crystallization system to adjust the pH=7.5-10; the crystallization temperature is 100-120 ℃; the crystallization time is 24-30 h.
29. The method according to claim 11 or 27, characterized in that: in the step (2), the crystallization process is to add alkaline substances or alkaline solution into the crystallization system to adjust the pH=8-9.5 of the system.
30. The method according to claim 11, wherein: in the step (2), one or more of centrifugal separation and filtering separation are adopted for separation; at this time, part of the liquid is the same as the solid phase mixture in the step (1) for crystallization; the rest liquid phase can be mixed with the template agent, the silicon source and the Y-type molecular sieve to repeat the operation process of the step (1); the mass content of the template agent added into the mixed system is 0.2% -3% in the system; the mass content of the added silicon source in the system is 1% -10%; the mass content of the added Y-type molecular sieve in the system is 1% -15%, and the mass fraction of the rest liquid phase accounts for 10% -50% of the mass fraction of the system.
31. The method according to claim 30, wherein: in the step (2), controlling the solid content of the separated liquid phase to be 0.05-3wt%; the mass content of the template agent added into the mixed system is 0.2% -2% in the system; the mass content of the added silicon source in the system is 3% -8%; the mass content of the added Y-type molecular sieve in the system is 3% -10%.
32. The method according to claim 30, wherein: in the step (2), the solid content of the separated liquid phase is controlled to be 0.1-2.5wt%.
33. The method according to claim 30, wherein: in the step (2), the solid content of the separated liquid phase is controlled to be 0.3-0.2 wt%.
34. The method according to claim 11, wherein: in the step (2), the drying temperature is 80-120 ℃, the drying time is 4-10h, the roasting temperature is 450-600 ℃, and the roasting time is 4-8h.
35. The method according to claim 11, wherein: in the step (3), the aluminum salt is one or more of aluminum sulfate, aluminum chloride and aluminum nitrate, the pH value of the acidic aluminum salt solution is 1-4, and the mass content of the aluminum salt in the acidic aluminum salt solution is 0.1% -1%; the treatment time is 3-10h, and the treatment temperature is 25-35 ℃.
36. The method according to claim 11 or 35, characterized in that: in the step (3), the pH value of the acidic aluminum salt solution is 2-3, and the mass content of aluminum salt in the acidic aluminum salt solution is 0.2% -0.8%.
37. The method according to claim 11, wherein: in the step (3), an aluminum source is dissolved in an acid solution, the pH value of the acid aluminum salt solution is 1-4, the SBA-15/Y shell-core composite molecular sieve prepared in the step (2) is added, stirring is carried out for 10-20h at 28-32 ℃, washing is carried out, drying is carried out for 4-10h at 80-120 ℃, and roasting is carried out for 4-6h at 500-560 ℃ to obtain the Al-SBA-15/Y molecular sieve.
38. The method according to claim 37, wherein: the pH value of the acidic aluminum salt solution is 2-3.
39. The method according to claim 9, wherein: the adhesive is small-pore alumina with pore volume of 0.3-0.5 mL/g and specific surface area of 200-400 m 2 /g。
40. The method according to claim 9, wherein: the catalyst is molded according to actual needs, and the carrier is dried at 100-130 ℃ for 12-14 hours and baked at 450-550 ℃ for 5-10 hours.
41. The method according to claim 9, wherein: the method for loading Pt and Pd adopts an impregnation method, wherein the impregnation method is saturated impregnation or excessive impregnation, and after the Pt and Pd are impregnated, the catalyst is dried and roasted under the following conditions: drying at 100-130 ℃ for 18-14 hours, and roasting at 500-600 ℃ for 4-10 hours.
42. A process for hydrodearomatization, characterized by: the use of the catalyst according to any one of claims 1 to 8, under the following operating conditions: the reaction pressure is 8-20 MPa, the hydrogen-oil volume ratio is 500-2000, and the liquid hourly space velocity is 0.5-7.0 h -1 The reaction temperature is 180-250 ℃.
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