CN116060112A - Hydrodearene catalyst and preparation method and application thereof - Google Patents

Hydrodearene catalyst and preparation method and application thereof Download PDF

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CN116060112A
CN116060112A CN202111269676.7A CN202111269676A CN116060112A CN 116060112 A CN116060112 A CN 116060112A CN 202111269676 A CN202111269676 A CN 202111269676A CN 116060112 A CN116060112 A CN 116060112A
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molecular sieve
beta
catalyst
phase product
liquid
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CN116060112B (en
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孙晓艳
樊宏飞
于政敏
王继锋
陈玉晶
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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
    • 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
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/54—Hydrogenation of the aromatic hydrocarbons 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
    • 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
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B01J29/068—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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/7215—Zeolite Beta
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical Kinetics & Catalysis (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The invention discloses a hydrodearene catalyst, which comprises the following components in percentage by weight: 0.1 to 0.5 weight percent of active component, 0.2 to 0.8 weight percent of auxiliary component and 98.7 to 99.7 weight percent of carrier; wherein, based on the weight of the carrier, the carrier comprises: 9 to 20 weight percent of Al-SBA-15/beta core-shell composite molecular sieve, 55 to 80 weight percent of amorphous silicon aluminum and 10 to 25 weight percent of adhesive component. The catalyst has higher hydrodearene activity, is especially suitable for hydrodearene and decoloring processes of naphthenic oil, solvent oil and hydrocracking tail oil containing heavy arene, and has the characteristics of high liquid yield, high flash point of target products, high Sagnac chromaticity number and the like.

Description

Hydrodearene catalyst and preparation method and application thereof
Technical Field
The invention relates to a hydrodearene catalyst, a preparation method and application thereof.
Background
At present, domestic white oil products are classified into the following grades: industrial grade, cosmetic grade, food grade and pharmaceutical grade. 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 new standard released in 2018 is more to put forward higher index requirements on pour point, sulfur content and aromatic hydrocarbon content of white oil products. After the new standard is implemented, the refinery white oil product has to be further desulfurized and dearomatized, so as to upgrade the product quality.
To solve the above problems, the most effective method is to deeply hydrogenate aromatic hydrocarbon saturation. The conventional hydrofining catalyst is adopted, and due to the structural defect of the catalyst and the characteristics of large viscosity, high molecular weight and multiple condensed ring structures of the cycloalkyl thickened oil fraction, polycyclic aromatic hydrocarbon in the macromolecular fraction is difficult to obtain sufficient hydrogenation saturation, the catalyst is required to have high catalytic activity for deeply removing aromatic hydrocarbon, in particular polycyclic aromatic hydrocarbon, and meanwhile, the catalyst also has good selectivity and does not influence the viscosity, pour point and flash point of a hydrofining product. And the catalyst adopts Y, beta and other molecular sieves. CN104826649B discloses a process for preparing hydrodearene catalysts. The method adopts NaY type molecular sieve raw materials with high silicon-aluminum ratio, high crystallinity and good stability, and the small-grain Y type molecular sieve is obtained after alkali washing, ammonium exchange, dealumination and silicon supplementing, hydrothermal treatment and treatment by using mixed solution of acid and ammonium salt. The small-grain Y-shaped molecular sieve is used as an acidic component and is matched with amorphous silica-alumina, an active component and an auxiliary component. However, when the traditional Y, beta and other microporous molecular sieves are used as hydrogenation catalysts of acidic components, the heavy aromatics with high sulfur and nitrogen contents, complex molecular structures and high carbon number are treated, the heavy aromatics are limited by micropores of the molecular sieves, and large molecular heavy oil cannot effectively enter the inner pore of the molecular sieves, so that the treatment capacity of the catalyst on the heavy oil is severely restricted.
In recent years, the microporous-mesoporous composite material combining the high catalytic activity and the high hydrothermal stability of the microporous molecular sieve with the pore channel characteristics of the mesoporous molecular sieve ensures that the microporous molecular sieve and the mesoporous molecular sieve are complementary in acidity and pore structure, and has good hydrothermal stability and catalytic performance and wide application prospect in the aspect of catalytic conversion of hydrocarbons.
CN201010228038.6 discloses a method for preparing a mesoporous-microporous core-shell composite molecular sieve catalyst, wherein microporous zeolite is used as a core, and mesoporous silica or mesoporous silica containing aluminum is used as a shell. The obtained composite molecular sieve has a reserved zeolite micropore framework and an ordered two-dimensional hexagonal mesoporous structure, mesoporous pore channels are vertical to the surfaces of zeolite particles, the pore channel openness is high, the thickness of mesoporous shell layers is adjustable, and after the mesoporous shell layers are wrapped, the high smoothness between the mesoporous and micropores can be maintained. The mesoporous shell pore size of the shell-core composite zeolite molecular sieve is generally smaller than 3nm, and is smaller for complex heavy oil and residual oil molecules.
The catalyst is used in the processes of hydrodearomatization and decoloration of naphthenic oil, solvent oil and hydrocracking tail oil containing heavy aromatic hydrocarbon, is not easy to deeply remove aromatic hydrocarbon, has low liquid yield and poor product quality, and is especially a composite molecular sieve with a shell-core structure, and the shell-core separation condition or the damage of a framework caused by the influence of external environment is unavoidable, so that the catalytic performance of the shell-core structure composite molecular sieve is affected. Therefore, the further research is suitable for hydrodearomatic hydrocarbon catalysts, and has great significance.
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 has higher hydrodearene activity, is especially suitable for hydrodearene and decoloring processes of naphthenic oil, solvent oil and hydrocracking tail oil containing heavy arene, and has the characteristics of high liquid yield, high flash point of target product, high Sagnac chromaticity number and the like.
The first aspect of the invention provides a hydrodearomatic hydrocarbon catalyst, which comprises the following components in percentage by weight: 0.1 to 0.5 weight percent of active component, 0.2 to 0.8 weight percent of auxiliary component and 98.7 to 99.7 weight percent of carrier;
wherein, based on the weight of the carrier, the carrier comprises: 9 to 20 weight percent of Al-SBA-15/beta core-shell composite molecular sieve, 55 to 80 weight percent of amorphous silicon aluminum and 10 to 25 weight percent of adhesive component.
According to the invention, the active component is Pt; the auxiliary agent component is Pd.
According to the invention, the content of silicon dioxide in the amorphous silicon aluminum is 5 to 20 weight percent, preferably 8 to 15 weight percent; the pore volume is 0.6-1.0 mL/g; specific surface area of 300-500 m 2 Preferably 350 to 500m 2 /g；
According to the invention, the specific surface area of the catalyst is 300-600 m 2 Preferably 350 to 505m 2 /g; the pore volume is 0.4-1.2 mL/g, preferably 0.5-0.9 mL/g, and the infrared acid amount is 0.1-1.0 mmol/g, preferably 0.2-0.5 mmol/g.
According to the present invention, the composite molecular sieve comprises: al-SBA-15 is taken as a shell, and beta-type molecular sieve is taken as a core; the mass ratio of the shell to the core is 45:55-50:50; siO of the composite molecular sieve 2 /Al 2 O 3 The molar ratio is 100-130.
According to the invention, the mass ratio of framework aluminum to non-framework aluminum in the composite molecular sieve is 95:5-99:1.
The second aspect of the present invention provides a method for preparing the hydrodearomatic hydrocarbon catalyst, comprising the steps of: mixing Al-SBA-15/beta core-shell composite molecular sieve, amorphous silicon-aluminum and adhesive, molding, drying and roasting to obtain a catalyst carrier; the catalyst is obtained after the carrier is loaded with active components and auxiliary components.
According to the invention, the Al-SBA-15/beta core-shell composite molecular sieve is prepared according to the following preparation method, which comprises the following steps:
(1) Adding a silicon source into the acid solution, uniformly mixing, standing and aging to obtain a silicon source hydrolysate;
(2) Uniformly mixing part of the silicon source hydrolysate in the step (1), the first beta molecular sieve and the first template agent, performing a first reaction, and performing first solid-liquid separation to obtain a first solid-phase product and a first liquid-phase product;
controlling the solid content of the first liquid phase product to be 0.1-10wt%, preferably 0.5-3wt%, and more preferably 0.5-1wt%;
(3) Uniformly mixing part of the silicon source hydrolysate in the step (1), the second beta molecular sieve, part of the first liquid phase product obtained in the step (2) and the second template agent, and performing a second reaction and second solid-liquid separation to obtain a second solid phase product and a second liquid phase product; controlling the solid content of the second liquid phase product to be 0.1-10wt%, preferably 0.5-3wt%, and more preferably 0.5-1wt%;
(4) And taking the mixture of the first solid-phase product and the second solid-phase product and the first liquid-phase product and/or the second liquid-phase product as raw materials, carrying out hydrothermal crystallization, washing, drying and roasting to obtain the Al-SBA-15/beta core-shell composite molecular sieve.
According to the preparation method of the core-shell composite molecular sieve, the silicon source in the step (1) is one or more of methyl orthosilicate, ethyl orthosilicate TEOS, propyl orthosilicate, isopropyl orthosilicate and butyl orthosilicate. The acid is one or more of hydrochloric acid, sulfuric acid and phosphoric acid. The pH of the acid solution is 1 to 4, preferably 2.0 to 3.5.
According to the preparation method of the core-shell composite molecular sieve, in the step (1), the mechanical stirring mode is adopted for mixing, and the stirring time is 1-12 hours, preferably 4-8 hours; the standing aging time is 4 to 120 hours, preferably 24 to 96 hours.
According to the preparation method of the core-shell composite molecular sieve, in the step (2), the first template agent is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, which is abbreviated as P123; preferably, the template P123 is first dissolved in an acid solution and then mixed with the other raw materials. The acid is one or more of hydrochloric acid, sulfuric acid and phosphoric acid. The molar concentration of hydrogen ions in the acid solution is 0.1 to 0.6mol/L, preferably 0.3 to 0.5mol/L.
According to the preparation method of the core-shell composite molecular sieve, the molar concentration of hydrogen ions in the mixed material obtained in the step (2) is 0.1-0.6 mol/L, preferably 0.3-0.5 mol/L; the mass content of the first template agent in the system is 0.3-3%, preferably 0.5-2%; the mass content of the silicon source in the system is 1-10%, preferably 2-8%; the mass content of the first beta molecular sieve in the system is 0.5-15%, preferably 1.0-10%.
According to the preparation method of the core-shell composite molecular sieve, the conditions of the first reaction in the step (2) are as follows: the reaction temperature is 30-60 ℃, preferably 35-50 ℃, and the reaction time is 2-12 h, preferably 4-8 h.
According to the preparation method of the core-shell composite molecular sieve, in the step (2), one or more of centrifugal separation and filtering separation are adopted for the first solid-liquid separation; the first solid-liquid separation is not as aimed at as conventional separation, and this separation requires the retention of a suitable solid content in the liquid phase.
According to the preparation method of the core-shell composite molecular sieve, the first beta molecular sieve in the step (2) is a hydrogen beta molecular sieve.
According to the invention, in the preparation method of the core-shell composite molecular sieve, the first beta molecular sieve Na in the step (2) 2 The weight content of O is less than 0.3 percent; silicon to aluminum molar ratio SiO 2 /Al 2 O 3 50 to 65; specific surface area of 400-700 m 2 /g; the pore volume is 0.3-0.6 mL/g; the grain diameter is 500-1000 nm.
According to the preparation method of the core-shell composite molecular sieve, the second beta molecular sieve in the step (3) is a hydrogen beta molecular sieve.
According to the invention, in the preparation method of the core-shell composite molecular sieve, the second beta molecular sieve Na in the step (3) 2 The weight content of O is less than 0.3 percent; silicon to aluminum molar ratio SiO 2 /Al 2 O 3 50 to 65; the specific surface area is 450-700 m 2 /g; the pore volume is 0.35-0.70 mL/g, and the particle size is 500-1000 nm.
According to the preparation method of the core-shell composite molecular sieve, in the step (3), the second template agent is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, which is abbreviated as P123; preferably, the template P123 is first dissolved in an acid solution and then mixed with the other raw materials. The acid is one or more of hydrochloric acid, sulfuric acid and phosphoric acid. The molar concentration of hydrogen ions of the acid solution is 0.1 to 0.6mol/L, preferably 0.3 to 0.5mol/L.
According to the preparation method of the core-shell composite molecular sieve, the molar concentration of hydrogen ions in the mixed material obtained in the step (3) is 0.1-0.6 mol/L, preferably 0.3-0.5 mol/L. The mass content of the added second template agent in the system is 0.3-3%, preferably 0.2-2%; the mass content of the added silicon source in the system is 1-10%, preferably 2-8%; the mass content of the added second beta molecular sieve in the system is 0.5-15%, preferably 1.0-10%. The addition amount of the first liquid phase product accounts for 60-80% of the mass fraction of the mixed material system in the step (3), and preferably 60-70%.
According to the preparation method of the core-shell composite molecular sieve, the conditions of the second reaction in the step (3) are as follows: the reaction temperature is 30-60 ℃, preferably 35-50 ℃, and the reaction time is 2-12 h, preferably 4-8 h.
According to the preparation method of the core-shell composite molecular sieve, in the step (3), one or more of centrifugal separation and filtering separation are adopted for the second solid-liquid separation.
According to the preparation method of the core-shell composite molecular sieve, in the step (4), the liquid-solid mass ratio of the mixed raw materials is controlled to be 1:1-10:1, preferably 1:1-8:1, and more preferably 1:1-5:1 by adjusting the addition amount of the first liquid-phase product and/or the second liquid-phase product. The first liquid phase product and/or the second liquid phase product are/is used for hydrothermal crystallization to synthesize the raw materials of the molecular sieve, and the rest part can be recycled.
According to the preparation method of the core-shell composite molecular sieve, ammonia water is added into the mixed material until the pH value is 3-6, preferably 4-5, before the hydrothermal crystallization in the step (4).
According to the preparation method of the core-shell composite molecular sieve, the hydrothermal crystallization condition in the step (4) is as follows: the crystallization temperature is 80-140 ℃, preferably 100-120 ℃; the crystallization time is 4 to 48 hours, preferably 24 to 30 hours. The drying temperature is 100-120 ℃, and the drying time is 6-10 h. The roasting temperature is 500-550 ℃ and the roasting time is 4-6 h.
According to the preparation method of the core-shell composite molecular sieve, siO in the raw material in the step (4) 2 /Al 2 O 3 Molar ratio to the composite molecular sieve SiO in step (4) 2 /Al 2 O 3 The ratio of the molar ratio is 97% -100%.
In the method for preparing the hydrodearomatic hydrocarbon catalyst according to the present invention, the binder may be a binder commonly used in the art, preferably, a small-pore alumina. The pore volume of the small pore alumina is 0.3-0.5 mL/g, and the specific surface area is 200-400 m 2 /g。
According to the method for preparing the hydrodearomatic hydrocarbon catalyst, the molding can be selected conventionally according to the need. The shape can be cylindrical strips, clover, etc. The drying is carried out for 12-14 hours at the temperature of 100-130 ℃. The roasting is carried out for 5-10 hours at 450-550 ℃.
In the method for preparing the hydrodearomatic hydrocarbon catalyst according to the present invention, the loading method may employ a conventional loading method, preferably an impregnation method, and may be saturated leaching, excessive leaching or complex leaching. Further, the impregnation method is to impregnate the carrier with a solution containing an active component and an auxiliary component, dry and bake the carrier to obtain the product. The drying is carried out for 8-14 hours at 100-130 ℃. The roasting is carried out for 4-10 hours at 500-600 ℃.
The third aspect of the invention provides the application of the hydrodearene catalyst in hydrodearene reaction.
According to the invention, the application is that the raw oil is prepared into white oil under the action of hydrogen and a hydrodearomatization catalyst in the hydrodearomatization reaction.
According to the invention, the raw oil in the hydrodearomatization reaction is the hydroisomerized raw material of naphthenic oil containing heavy aromatics, solvent oil and hydrocracking tail oil. The aromatic hydrocarbon content in the raw oil is 10-30wt%.
According to the invention, the hydrodearene process is a hydrofining process. The hydrogenation dearomatization reaction conditions are as follows: the reaction temperature is 180-250 ℃, the total reaction pressure is 8-20 MPa, and the liquid hourly space velocity is 0.5-7 h -1 Hydrogen oil volume ratio 500:1 to 2000:1.
compared with the prior art, the invention has the following beneficial technical effects:
(1) In the invention, the catalyst comprises the following components by weight of the catalyst: 0.1 to 0.5 weight percent of active component, 0.2 to 0.8 weight percent of auxiliary component and 98.7 to 99.7 weight percent of carrier; wherein, based on the weight of the carrier, the carrier comprises: 9 to 20 weight percent of Al-SBA-15/beta core-shell composite molecular sieve, 55 to 80 weight percent of amorphous silicon aluminum and 10 to 25 weight percent of adhesive component. The special Al-SBA-15/beta core-shell type composite molecular sieve is selected in the catalyst composition, the morphology of the composite molecular sieve is more uniform, the 'core-shell' structure is more complete, the catalyst has larger pore volume, specific surface area and gradient acid distribution and pore distribution pore channels consisting of mesopores and micropores, and the size of a macromolecular material can be reduced and the capability of treating the macromolecular material of the microporous molecular sieve can be enhanced through the pre-cracking of weak acid sites of a shell layer; and secondly, the free and smooth pore channels with different gradients are beneficial to the rapid escape of reaction molecules from the catalytic surface, so that the excessive reaction is avoided. The method is more favorable for the selective ring opening of aromatic hydrocarbon, is particularly suitable for the hydrodearomatization and decoloration process of naphthenic oil, solvent oil and hydrocracking tail oil containing heavy aromatic hydrocarbon, can obtain good use effect, and has the characteristics of high liquid yield, good product quality and the like.
(2) In the method, in particular to the preparation step of the Al-SBA-15/beta core-shell type composite molecular sieve, the solid content of a liquid phase product is controlled, and the shell type molecular sieve is introduced in a plurality of steps, so that the phase separation of the phase separation SBA-15 material and the beta molecular sieve is restrained, the morphology of the formed composite molecular sieve is more uniform, and the 'core-shell' structure is more complete. In the method, the silicon source is hydrolyzed in advance, and the method maintains the complete structure and higher crystallinity of the beta molecular sieve. In the method, SBA-15 is synthesized in an acid system, non-framework aluminum formed by dealumination is free from pore channels of a microporous molecular sieve in the system by utilizing the dealumination characteristic of a beta molecular sieve in a specific acid concentration, and is used as an aluminum source for synthesizing a mesoporous molecular sieve, the synthesis of the composite molecular sieve fully utilizes the non-framework aluminum removed by the microporous molecular sieve,the aluminum source added in the conventional preparation of the SBA-15 molecular sieve is avoided, and the removed Al is removed by adjusting the pH value of the system 3+ Hydrolysis to form Al-OH, which polymerizes with Si-OH to form Si-OH into SBA-15 skeleton. Meanwhile, the in-situ aluminum supplementing of SBA-15 and the acidic dealumination modification of the beta molecular sieve are completed. Meanwhile, the silicon-aluminum ratio of the beta molecular sieve is improved, and the structure and crystallinity of the beta molecular sieve are well maintained. The Al-SBA-15/beta molecular sieve prepared by the method has larger pore volume, specific surface area, and gradient acid distribution and pore distribution pore canal composed of mesopores and micropores, and is suitable for the field of macromolecular catalysis. The prepared catalyst is suitable for hydrodearomatization reaction, is particularly suitable for preparing white oil by hydrodearomatization and decoloration reaction of naphthenic oil, solvent oil and hydrocracking tail oil containing heavy aromatics, and has the characteristics of high liquid yield, good product quality and the like.
(3) In the invention, the catalyst is suitable for hydrodearomatization reaction, and is especially suitable for preparing white oil by hydrodearomatization and decoloration reaction of naphthenic oil containing heavy aromatics, solvent oil and hydrocracking tail oil. The catalyst has the characteristics of high liquid yield, good product quality and the like in the hydrodearomatization reaction. The liquid yield can reach 99.3wt%, the flash point can reach 225 ℃, and the Saint color can be 32 #.
Drawings
FIG. 1 is a small angle XRD spectrum of an example molecular sieve;
wherein: line 1 is the composite molecular sieve Al-SBA-15/beta-1 of example 1, line 2 is the composite molecular sieve Al-SBA-15/beta-2 of example 2, and line 3 is the composite molecular sieve Al-SBA-15/beta-3 of example 3;
FIG. 2 is a small angle XRD spectrum of the molecular sieves of the examples and comparative examples;
wherein: line 1 is the composite molecular sieve Al-SBA-15/beta-3-1 of comparative example 1, line 2 is the composite molecular sieve Al-SBA-15/beta-3 of example 3, line 3 is the composite molecular sieve Al-SBA-15/beta-3-2 of comparative example 2, and line 4 is the composite molecular sieve Al-SBA-15/beta-3-3 of comparative example 3;
FIG. 3 is a high angle XRD spectrum of the molecular sieves of the examples and comparative examples;
wherein: line 1 is molecular sieve beta-1, line 2 is composite molecular sieve Al-SBA-15/beta-1 of example 1, line 3 is composite molecular sieve Al-SBA-15/beta-2 of example 2, and line 4 is composite molecular sieve Al-SBA-15/beta-3 of example 3;
FIG. 4 is XRD spectra of molecular sieves of examples and comparative examples;
wherein: line 1 is molecular sieve beta-1, line 2 is comparative example 4 molecular sieve beta-2, line 3 is comparative example 5 molecular sieve beta-3, and line 4 is comparative example 1 composite molecular sieve Al-SBA-15/beta-3-1; line 5 is the composite molecular sieve Al-SBA-15/beta-3-2 of comparative example 2, and line 6 is the composite molecular sieve Al-SBA-15/beta-3-3 of comparative example 3;
FIG. 5 is a TEM image of the composite molecular sieve Al-SBA-15/beta-3 prepared in example 3;
FIG. 6 is a TEM image of the composite molecular sieve Al-SBA-15/beta-3-1 prepared in comparative example 1.
Detailed Description
In the invention, the specific surface area and pore volume of the product are measured by adopting ASAP2405 and a low-temperature liquid nitrogen adsorption method.
In the invention, the acid amount is measured by an infrared spectrometer, and the adsorbent used is pyridine.
In the present invention, TEM analysis was performed on a JEM-2100 high resolution transmission electron microscopy device.
In the present invention, the relative crystallinity was measured by XRD, and the hydrogen form beta molecular sieve in the step (2) of example 1 was 100. The molar ratio of silicon to aluminum is determined by a chemical method.
In the present invention, both skeletal aluminum and non-skeletal aluminum 27 Al MAS NMR characterization used a Bruker AV-500 Nuclear magnetic resonance instrument, switzerland.
In the invention,% is mass fraction 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) 10.0g of TEOS was added to 25.0g of HCl solution with pH=2.6 under stirring, and after stirring at 20℃for 4 hours, the solution was changed from a turbid solution to a clear solution, and left to stand for 24 hours to obtain a silicon source hydrolysate.
(2) 1.2g of P123 are dissolved in 80g of 0.45mol/L hydrochloric acid solution; 2.2g of hydrogen form beta molecular sieve was designated beta-1 (specific surface area 580m 2 Per g, pore volume 0.42mL/g, particle size 800nm, siO 2 /Al 2 O 3 Molar ratio 60, na 2 O weight content is 0.1%) and 13g of water, then adding the mixture into the mixed solution of hydrochloric acid and P123, stirring for 5min, and then adding 1/2 of the silicon source hydrolysate obtained in the step (1) and uniformly mixing. The molar concentration of hydrogen ions in the mixed material is 0.4mol/L; stirring at constant temperature of 45 ℃ for 4h. And then centrifugal separation is carried out to obtain a solid-phase product and a liquid-phase product. The solid content of the liquid phase product was controlled to be 0.5wt%.
(3) And (2) dissolving P123 in 0.45mol/L hydrochloric acid solution, adding 2/3 of the liquid phase product obtained in the step (2), adding hydrogen type beta molecular sieve with the same property as the beta-1 molecular sieve in the step (2), and mixing the rest silicon source hydrolysate uniformly. The molar concentration of hydrogen ions in the mixed material is 0.4mol/L, and the mass content of the added P123 in the system is 0.73%; the mass content of the added silicon source TEOS in the system is 5%; the mass content of the added hydrogen type beta molecular sieve in the system is 1.8 percent. The added amount of the liquid phase product in the step (2) accounts for 65% of the mass fraction of the mixed material system in the step (3). Stirring at constant temperature of 45 ℃ for 4h. And then filtering and separating to obtain a solid-phase product and a liquid-phase product. The solid content of the liquid phase product was controlled to be 0.5wt%.
(4) And (3) hydrothermal crystallization: mixing the solid-phase products obtained in the step (2) and the step (3) to obtain a solid-phase raw material of the step (4); mixing the liquid-phase product remained in the step (2) with the liquid-phase product obtained in the step (3) to obtain a liquid-phase raw material of the step (4); and feeding according to the metering ratio, and controlling the liquid-solid mass ratio of the mixed materials to be 2:1. Stirring uniformly, adding ammonia water to regulate pH to 4.0, crystallizing at 100deg.C for 24 hr, filtering, washing, drying at 100deg.C for 6 hr, and calcining at 550deg.C for 4 hr to obtain core-shell composite molecular sieve, which is designated as Al-SBA-15/beta-1. Step (4) SiO in the raw material 2 /Al 2 O 3 Molar ratio and composite molecular sieve SiO 2 /Al 2 O 3 The molar ratio was 99%. The physical parameters of the composite molecular sieve are shown in Table 1.XRD patterns are shown in fig. 1 and 3.
24 g of Al-SBA-15/beta-1 molecular sieve and 120 g of amorphous silica-alumina (pore volume 0)78mL/g, specific surface area 350m 2 Per gram, 9% by weight of silica), 25 g of small-pore alumina (pore volume 0.35mL/g, specific surface area 330 m) 2 And (2) adding 35 g of an adhesive made of 10wt% dilute nitric acid into a rolling machine, mixing and grinding, adding water, grinding into paste, extruding strips, drying the extruded strips at 110 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours to obtain the carrier TCAT-1. PdC1 is impregnated by a conventional isovolumetric impregnation method 2 (analytically pure) and Pt (NH) 4 ) 4 C1 2 The (analytically pure) solution was then impregnated stepwise onto the shaped support according to the final catalyst metal amount, allowed to stand for 12 hours, dried at 110℃for 6 hours, and calcined at 480℃for 4 hours to produce catalyst CAT-1. The corresponding catalyst properties are shown in Table 2.
The above catalyst was subjected to an activity evaluation test. 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 hydrogenation complementary refining process, and the hydrogen partial pressure is 12.0MPa, the hydrogen oil volume ratio is 1100 and the volume space velocity is 1.1h at the reaction temperature of 220 DEG C -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.
Example 2:
(1) 10.0g of TEOS was added to 25.0g of HCl solution with pH=2.8 under stirring, and after stirring at 20℃for 4 hours, the solution was changed from a turbid solution to a clear solution, and left to stand for 24 hours to obtain a silicon source hydrolysate.
(2) 1.3g of P123 are dissolved in 80g of a 0.42mol/L hydrochloric acid solution; mixing 2.0g of hydrogen beta molecular sieve (raw material beta-1 obtained in the step (2) of the example 1) with 15g of water, adding the mixture into the mixed solution of hydrochloric acid and P123, stirring for 5min, and then adding the silicon source hydrolysate obtained in the step (1) of 1/2, and uniformly mixing. The molar concentration of hydrogen ions in the mixed material is 0.39mol/L; stirring at 48 ℃ for 4 hours at constant temperature. And then centrifugal separation is carried out to obtain a solid-phase product and a liquid-phase product. The solid content of the liquid phase product was controlled to be 0.8wt%.
(3) And (2) dissolving P123 in 0.42mol/L hydrochloric acid solution, adding 2/3 of the liquid phase product obtained in the step (2), adding hydrogen type beta molecular sieve with the same property as the beta-1 molecular sieve in the step (2), and mixing the rest silicon source hydrolysate uniformly. The molar concentration of hydrogen ions in the mixed material is 0.39mol/L, and the mass content of the added P123 in the system is 0.80%; the mass content of the added silicon source TEOS in the system is 4.6%; the mass content of the added hydrogen type beta molecular sieve in the system is 2.6 percent. The added amount of the liquid phase product in the step (2) accounts for 62% of the mass fraction of the mixed material system in the step (3). Stirring at constant temperature of 45 ℃ for 4h. And then filtering and separating to obtain a solid-phase product and a liquid-phase product. The solid content of the liquid phase was controlled to be 0.8wt%.
(4) And (3) hydrothermal crystallization: mixing the solid-phase products obtained in the step (2) and the step (3) to obtain a solid-phase raw material of the step (4); mixing the liquid-phase product remained in the step (2) with the liquid-phase product obtained in the step (3) to obtain a liquid-phase raw material of the step (4); and feeding according to the metering ratio, and controlling the liquid-solid mass ratio of the mixed materials to be 2:1. Stirring uniformly, adding ammonia water to regulate pH to 4.5, crystallizing at 100deg.C for 24 hr, filtering, washing, drying at 100deg.C for 6 hr, and calcining at 550deg.C for 4 hr to obtain core-shell composite molecular sieve, which is designated as Al-SBA-15/beta-2. Step (4) SiO in the raw material 2 /Al 2 O 3 Molar ratio and composite molecular sieve SiO 2 /Al 2 O 3 The molar ratio was 98%. The physical parameters of the composite molecular sieve are shown in Table 1.XRD patterns are shown in fig. 1 and 3.
30 g of Al-SBA-15/beta-2 molecular sieve and 120 g of amorphous silica-alumina (pore volume 0.78mL/g, specific surface area 350 m) 2 Per gram, 9% by weight of silica), 25 g of small-pore alumina (pore volume 0.35mL/g, specific surface area 330 m) 2 And (2) adding 30 g of an adhesive made of 10wt% dilute nitric acid into a rolling machine, mixing and grinding, adding water, grinding into paste, extruding strips, drying the extruded strips at 110 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours to obtain the carrier TCAT-2. PdC1 is impregnated by a conventional isovolumetric impregnation method 2 (analytically pure) and Pt (NH) 4 ) 4 C1 2 The (analytically pure) solution is dipped on the shaped carrier step by step according to the final catalyst metal amount, and is kept stand for 12h, dried for 6 hours at 110 ℃, and baked for 4 hours at 480 ℃ to prepare the catalyst CAT-2. The corresponding catalyst properties are shown in Table 2.
The above catalyst was subjected to an activity evaluation test. 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 hydrogenation complementary refining process, and the hydrogen partial pressure is 12.0MPa, the hydrogen oil volume ratio is 1100 and the volume space velocity is 1.1h at the reaction temperature of 220 DEG C -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.
Example 3:
(1) Under stirring, 10.0g of TEOS was added to 25.0g of HCl solution having ph=2.9, and after stirring at 20 ℃ for 4 hours, the solution was changed from a turbid solution to a clear solution, and was left to stand for 24 hours, to obtain a silicon source hydrolysate.
(2) 1.4g of P123 are dissolved in 80g of 0.50mol/L hydrochloric acid solution; mixing 1.8g of hydrogen beta molecular sieve (raw material beta-1 obtained in the step (2) of the example 1) with 15g of water, adding the mixture into the mixed solution of hydrochloric acid and P123, stirring for 5min, and then adding the silicon source hydrolysate obtained in the step (1) of 1/2, and uniformly mixing. The molar concentration of hydrogen ions in the mixed material is 0.46mol/L; stirring at 48 ℃ for 4 hours at constant temperature. And then centrifugal separation is carried out to obtain a solid-phase product and a liquid-phase product. The solid content of the liquid phase product was controlled to be 0.7wt%.
(3) And (2) dissolving P123 in 0.50mol/L hydrochloric acid solution, adding 2/3 of the liquid phase product obtained in the step (2), adding hydrogen beta molecular sieve with the same property as the beta-1 molecular sieve in the step (2), and mixing the rest silicon source hydrolysate uniformly. The molar concentration of hydrogen ions in the mixed material is 0.46mol/L, and the mass content of the added P123 in the system is 0.78%; the mass content of the added silicon source TEOS in the system is 4%; the mass content of the added beta-1 molecular sieve in the system is 3.5 percent. The added amount of the liquid phase product in the step (2) accounts for 64% of the mass fraction of the mixed material system in the step (3). Stirring at 48 ℃ for 4 hours at constant temperature. And then filtering and separating to obtain a solid-phase product and a liquid-phase product. The solid content of the liquid phase was controlled to be 0.7wt%.
(4) And (3) hydrothermal crystallization: mixing the solid-phase products obtained in the step (2) and the step (3) to obtain a solid-phase raw material of the step (4); residual step (2)Mixing the liquid-phase product with the liquid-phase product obtained in the step (3) to obtain a liquid-phase raw material of the step (4); and feeding according to the metering ratio, and controlling the liquid-solid mass ratio of the mixed materials to be 3:1. Stirring uniformly, adding ammonia water to regulate pH to 4.8, crystallizing at 100deg.C for 24 hr, filtering, washing, drying at 100deg.C for 6 hr, and calcining at 550deg.C for 4 hr to obtain core-shell composite molecular sieve, which is designated as Al-SBA-15/beta-3. Step (4) SiO in the raw material 2 /Al 2 O 3 Molar ratio and composite molecular sieve SiO 2 /Al 2 O 3 The molar ratio was 99%. The physical parameters of the composite molecular sieve are shown in Table 1.XRD patterns are shown in fig. 1 and 3. The TEM image is shown in FIG. 5.
18 g of Al-SBA-15/beta-3 molecular sieve and 120 g of amorphous silica-alumina (pore volume 0.78mL/g, specific surface area 350 m) 2 Per gram, 9% by weight of silica), 25 g of small-pore alumina (pore volume 0.35mL/g, specific surface area 330 m) 2 And (2) adding 45 g of an adhesive made of 10wt% dilute nitric acid into a rolling machine, mixing and grinding, adding water, grinding into paste, extruding strips, drying the extruded strips at 110 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours to obtain the carrier TCAT-3. PdC1 is impregnated by a conventional isovolumetric impregnation method 2 (analytically pure) and Pt (NH) 4 ) 4 C1 2 The (analytically pure) solution is dipped on the shaped carrier step by step according to the final catalyst metal amount, and is kept stand for 12h, dried for 6 hours at 110 ℃, and baked for 4 hours at 480 ℃ to obtain the catalyst CAT-3. The corresponding catalyst properties are shown in Table 2.
The above catalyst was subjected to an activity evaluation test. 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 hydrogenation complementary refining process, and the hydrogen partial pressure is 12.0MPa, the hydrogen oil volume ratio is 1100 and the volume space velocity is 1.1h at the reaction temperature of 220 DEG C -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.
Comparative example 1:
(1) 5.0g of TEOS was added to 12.5g of HCl solution with pH=2.9 under stirring, and after stirring at 20℃for 4 hours, the solution was changed from turbid solution to clear solution, and left to stand for 24 hours to obtain silicon source hydrolysate.
(2) 1.4g of P123 are dissolved in 80g of 0.50mol/L hydrochloric acid solution; mixing 1.8g of hydrogen beta molecular sieve (raw material beta-1 in the step (2) of the example 1) with 15g of water, adding the mixture into the mixed solution of hydrochloric acid and P123, stirring for 5min, and then adding the silicon source hydrolysate obtained in the step (1) to mix uniformly. The molar concentration of hydrogen ions in the mixed material is 0.46mol/L; stirring at 48 ℃ for 4 hours at constant temperature.
(3) And (3) hydrothermal crystallization: adding ammonia water into the product of the step (2) to adjust the pH of the system to 4.8, crystallizing at 100 ℃ for 24 hours, filtering, washing, drying at 100 ℃ for 6 hours, and roasting at 550 ℃ for 4 hours to obtain the core-shell composite molecular sieve, which is denoted as Al-SBA-15/beta-3-1. SiO in the raw material 2 /Al 2 O 3 Molar ratio and composite molecular sieve SiO 2 /Al 2 O 3 The ratio of the molar ratios was 92%. The physical parameters of the composite molecular sieve are shown in Table 1.XRD patterns are shown in FIG. 2 and FIG. 4, and TEM patterns are shown in FIG. 6.
18 g of Al-SBA-15/beta-3-1 molecular sieve and 120 g of amorphous silica-alumina (pore volume 0.78mL/g, specific surface area 350 m) 2 Per gram, 9% by weight of silica), 25 g of small-pore alumina (pore volume 0.35mL/g, specific surface area 330 m) 2 And (2) adding 45 g of 10wt% dilute nitric acid into a rolling machine, mixing and grinding, adding water, grinding into paste, extruding strips, drying the extruded strips for 4 hours at 110 ℃, and roasting for 4 hours at 550 ℃ to obtain the carrier TCAT-3-1. PdC1 is impregnated by a conventional isovolumetric impregnation method 2 (analytically pure) and Pt (NH) 4 ) 4 C1 2 The (analytically pure) solution was then impregnated stepwise onto the shaped support according to the final catalyst metal amount, allowed to stand for 12 hours, dried at 110℃for 6 hours, and calcined at 480℃for 4 hours to produce catalyst CCAT-3-1. The corresponding catalyst properties are shown in Table 2.
The above catalyst was subjected to an activity evaluation test. 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 hydrogenation complementary refining process, and the hydrogen partial pressure is 12.0MPa, the hydrogen oil volume ratio is 1100 and the volume space velocity is 1.1h at the reaction temperature of 220 DEG C -1 The process test of producing white oil by hydrogenation is carried out under the process conditions of (1) reactionThe results of the performance evaluation test are shown in Table 4.
Comparative example 2:
(1) 1.4g of P123 are dissolved in 80g of 0.50mol/L hydrochloric acid solution; 1.8g of hydrogen form beta molecular sieve (raw material beta-1 in the same way as in the step (2) of the example 1) and 15g of water are mixed and added into the mixed solution of the hydrochloric acid and the P123, and the mixture is stirred for 5min, and then 5g of TEOS is slowly added dropwise by a pipette. The molar concentration of hydrogen ions in the mixture is 0.42mol/L, and the mixture is stirred for 30 hours at a constant temperature of 48 ℃.
(2) And (3) hydrothermal crystallization: adding ammonia water to regulate pH to 4.8, crystallizing at 100deg.C for 24 hr, filtering, washing, drying at 100deg.C for 6 hr, and calcining at 550deg.C for 4 hr to obtain core-shell composite molecular sieve, which is designated as Al-SBA-15/beta-3-2. SiO in the raw material 2 /Al 2 O 3 Molar ratio and composite molecular sieve SiO 2 /Al 2 O 3 The molar ratio was 65%. The physical parameters of the composite molecular sieve are shown in Table 1.XRD patterns are shown in fig. 2 and 4.
18 g of Al-SBA-15/beta-3-2 molecular sieve and 120 g of amorphous silica-alumina (pore volume 0.78mL/g, specific surface area 350 m) 2 Per gram, 9% by weight of silica), 25 g of small-pore alumina (pore volume 0.35mL/g, specific surface area 330 m) 2 And (2) adding 45 g of 10wt% dilute nitric acid into a rolling machine, mixing and grinding, adding water, grinding into paste, extruding strips, drying the extruded strips for 4 hours at 110 ℃, and roasting for 4 hours at 550 ℃ to obtain the carrier TCAT-3-2. PdC1 is impregnated by a conventional isovolumetric impregnation method 2 (analytically pure) and Pt (NH) 4 ) 4 C1 2 The (analytically pure) solution was then impregnated stepwise onto the shaped support according to the final catalyst metal amount, allowed to stand for 12 hours, dried at 110℃for 6 hours, and calcined at 480℃for 4 hours to produce catalyst CCAT-3-2. The corresponding catalyst properties are shown in Table 2.
The above catalyst was subjected to an activity evaluation test. 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 hydrogenation complementary refining process, the reaction temperature is 220 ℃, and the hydrogen partial pressure is 12.0MPa, the hydrogen-oil volume ratio is 1100, and the volume space velocity is 1.1h -1 The process test of producing white oil by hydrogenation is carried out under the process conditions,the results of the reaction performance evaluation test are shown in Table 4.
Comparative example 3:
(1) 10.0g of TEOS was added to 25.0g of HCl solution with pH=2.9 under stirring, and after stirring at 20℃for 4 hours, the solution was changed from a turbid solution to a clear solution, and left to stand for 24 hours to obtain a silicon source hydrolysate.
(2) 1.4g of P123 are dissolved in 80g of 0.50mol/L hydrochloric acid solution; mixing 1.8g of hydrogen beta molecular sieve (raw material beta-1 in the step (2) in the example 1) with 15g of water, adding the mixture into the mixed solution of hydrochloric acid and P123, stirring for 5min, and then adding the silicon source hydrolysate obtained in the step (1) in the 1/2, and uniformly mixing. The molar concentration of hydrogen ions in the mixed material is 0.46mol/L; stirring at 48 ℃ for 4 hours at constant temperature.
(3) And (3) hydrothermal crystallization: crystallizing the product in the step (2) for 24 hours at 100 ℃, filtering, washing, drying for 6 hours at 100 ℃, and roasting for 4 hours at 550 ℃ to obtain the core-shell structure Al-SBA-15/beta-3-3 material. SiO in the raw material 2 /Al 2 O 3 Molar ratio and composite molecular sieve SiO 2 /Al 2 O 3 The ratio of the molar ratio was 41%. The physical parameters of the composite molecular sieve are shown in Table 1.XRD patterns are shown in fig. 2 and 4.
18 g of Al-SBA-15/beta-3-3 molecular sieve and 120 g of amorphous silica-alumina (pore volume 0.78mL/g, specific surface area 350 m) 2 Per gram, 9% by weight of silica), 25 g of small-pore alumina (pore volume 0.35mL/g, specific surface area 330 m) 2 And (2) adding 45 g of 10wt% dilute nitric acid into a rolling machine, mixing and grinding, adding water, grinding into paste, extruding strips, drying the extruded strips for 4 hours at 110 ℃, and roasting for 4 hours at 550 ℃ to obtain the carrier TCAT-3-3. PdC1 is impregnated by a conventional isovolumetric impregnation method 2 (analytically pure) and Pt (NH) 4 ) 4 C1 2 The (analytically pure) solution was then impregnated stepwise onto the shaped support according to the final catalyst metal amount, allowed to stand for 12 hours, dried at 110℃for 6 hours, and calcined at 480℃for 4 hours to produce catalyst CCAT-3-3. The corresponding catalyst properties are shown in Table 2.
The above catalyst was subjected to an activity evaluation test. 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. By high pressureIn the hydrofining process, the reaction temperature is 220 ℃, the hydrogen partial pressure is 12.0MPa, the hydrogen-oil volume ratio is 1100, and the volume space velocity is 1.1h -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.
Comparative example 4:
10g of hydrogen beta molecular sieve (raw material beta-1 in the step (2) of the example 1) is taken and added into hydrochloric acid solution with the molar concentration of hydrogen ions of 0.42mol/L, and the mixture is stirred for 4 hours at the constant temperature of 45 ℃ under the condition that the liquid-solid mass ratio is controlled to be 10:1. Filtering, washing, drying at 120 ℃ for 6 hours, and roasting at 550 ℃ for 4 hours to obtain the beta-2 material. The physical parameters of the molecular sieve are shown in Table 1. The XRD spectrum is shown in FIG. 4.
Comparative example 5:
10g of hydrogen beta molecular sieve (raw material beta-1 in the step (2) of the example 1) is taken and added into hydrochloric acid solution with the molar concentration of hydrogen ions of 5mol/L, the liquid-solid mass ratio is controlled to be 10:1, and the mixture is stirred for 4 hours at the constant temperature of 45 ℃. Filtering, washing, drying at 120 ℃ for 6 hours, and roasting at 550 ℃ for 4 hours to obtain the beta-3 material. The physical parameters of the molecular sieve are shown in Table 1. The XRD spectrum is shown in FIG. 4.
Table 1 physicochemical properties of molecular sieves
Figure BDA0003328255220000161
Figure BDA0003328255220000171
The composite molecular sieve is shown in FIG. 5 as a core-shell Al-SBA-15/beta composite molecular sieve. As can be seen from FIGS. 5 and 6, the Al-SBA-15/beta-3 has less split-phase SBA-15, more uniform morphology and more complete "core-shell" structure than the Al-SBA-15/beta-3-1. As can be seen from Table 1, the molecular sieve prepared by the invention simultaneously completes in-situ aluminum supplementation of SBA-15. Meanwhile, the silicon-aluminum ratio of the beta molecular sieve is improved, and the structure and crystallinity of the beta molecular sieve are well maintained.
TABLE 2 physicochemical Properties of the catalysts
Figure BDA0003328255220000172
As can be seen from Table 2, compared with the catalyst of comparative example, the catalyst of the present invention has more uniform morphology and more complete core-shell structure, so that the catalyst has more uniform metal dispersion and larger pore volume and specific surface area. The total acidity of the infrared ray is also increased.
Table 3 low pressure hydroisomerization >320 ℃ lube oil properties
Analysis item
Density (20 ℃ C.)/kg.m -3 868.6
Sulfur/. Mu.g.g -1 4.2
Nitrogen/. Mu.g.g -1 1.4
Pour point/. Degree.C -32
Viscosity (100 ℃ C.)/mm 2 ·s -1 5.241
Viscosity (40 ℃ C.)/mm 2 ·s -1 25.62
Carbon residue, wt% 0.01
Aromatic hydrocarbon, wt% 13.4
TABLE 4 evaluation results of catalyst Activity
Figure BDA0003328255220000181
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As can be seen from the evaluation results of the catalysts in Table 4, the catalyst prepared in the invention produced food-grade white oil with key technical indexes superior to those of the comparative examples.

Claims (15)

1. A hydrodearomatization catalyst, comprising, based on catalyst weight: 0.1 to 0.5 weight percent of active component, 0.2 to 0.8 weight percent of auxiliary component and 98.7 to 99.7 weight percent of carrier;
wherein, based on the weight of the carrier, the carrier comprises: 9 to 20 weight percent of Al-SBA-15/beta core-shell composite molecular sieve, 55 to 80 weight percent of amorphous silicon aluminum and 10 to 25 weight percent of adhesive component.
2. The catalyst of claim 1, wherein the active component is Pt; the auxiliary agent component is Pd.
3. The catalyst according to claim 1, characterized in that the silica content of the amorphous silica alumina is between 5% and 20% by weight, preferably between 8% and 15% by weight; the pore volume is 0.6-1.0 mL/g; specific surface area of 300-500 m 2 Preferably 350 to 500m 2 /g。
4. The catalyst according to claim 1, characterized in thatThe composite molecular sieve takes Al-SBA-15 as a shell and beta-type molecular sieve as a core; the mass ratio of the shell to the core is 45:55-50:50; siO of the composite molecular sieve 2 /Al 2 O 3 The molar ratio is 100-130;
further preferably, the mass ratio of framework aluminum to non-framework aluminum in the composite molecular sieve is 95:5-99:1.
5. The catalyst according to claim 1, wherein the specific surface area of the catalyst is 300 to 600m 2 Preferably 350 to 505m 2 /g; the pore volume is 0.4-1.2 mL/g, preferably 0.5-0.9 mL/g, and the infrared acid amount is 0.1-1.0 mmol/g, preferably 0.2-0.5 mmol/g.
6. A process for preparing the catalyst of any one of claims 1 to 5, comprising the steps of: mixing Al-SBA-15/beta core-shell composite molecular sieve, amorphous silicon-aluminum and adhesive, molding, drying and roasting to obtain a catalyst carrier; the catalyst is obtained after the carrier is loaded with active components and auxiliary components.
7. The preparation method according to claim 6, wherein the Al-SBA-15/β core-shell composite molecular sieve is prepared according to a method comprising the steps of:
(1) Adding a silicon source into the acid solution, uniformly mixing, standing and aging to obtain a silicon source hydrolysate;
(2) Uniformly mixing part of the silicon source hydrolysate in the step (1), the first beta molecular sieve and the first template agent, performing a first reaction, and performing first solid-liquid separation to obtain a first solid-phase product and a first liquid-phase product;
controlling the solid content of the first liquid phase product to be 0.1-10wt%, preferably 0.5-3wt%, and more preferably 0.5-1wt%;
(3) Uniformly mixing part of the silicon source hydrolysate in the step (1), the second beta molecular sieve, part of the first liquid phase product obtained in the step (2) and the second template agent, and performing a second reaction and second solid-liquid separation to obtain a second solid phase product and a second liquid phase product; controlling the solid content of the second liquid phase product to be 0.1-10wt%, preferably 0.5-3wt%, and more preferably 0.5-1wt%;
(4) And taking the mixture of the first solid-phase product and the second solid-phase product and the first liquid-phase product and/or the second liquid-phase product as raw materials, carrying out hydrothermal crystallization, washing, drying and roasting to obtain the Al-SBA-15/beta core-shell composite molecular sieve.
8. The process according to claim 7, wherein the molar concentration of hydrogen ions in the mixed material obtained by the mixing in the step (2) is 0.1 to 0.6mol/L, preferably 0.3 to 0.5mol/L; the mass content of the first template agent in the system is 0.3-3%, preferably 0.5-2%; the mass content of the silicon source in the system is 1-10%, preferably 2-8%; the mass content of the first beta molecular sieve in the system is 0.5-15%, preferably 1.0-10%;
and/or, in the mixed material obtained by the step (3), the molar concentration of hydrogen ions is 0.1-0.6 mol/L, preferably 0.3-0.5 mol/L; the mass content of the added second template agent in the system is 0.3-3%, preferably 0.2-2%; the mass content of the added silicon source in the system is 1-10%, preferably 2-8%; the mass content of the added second beta molecular sieve in the system is 0.5-15%, preferably 1.0-10%; the addition amount of the first liquid phase product accounts for 60-80% of the mass fraction of the mixed material system in the step (3), and is preferably 60-70%.
9. The method according to claim 7, wherein the silicon source in the step (1) is one or more of methyl orthosilicate, ethyl orthosilicate TEOS, propyl orthosilicate, isopropyl orthosilicate, butyl orthosilicate; the acid is one or more of hydrochloric acid, sulfuric acid and phosphoric acid; the pH of the acid solution is 1-4, preferably 2.0-3.5;
and/or, in the step (2), the first template agent is P123;
and/or, in the step (2), the first beta molecular sieve is a hydrogen beta molecular sieve;
further preferably, the first beta molecular sieve Na in step (2) 2 The weight content of O is less than 0.3 percent; silicon to aluminum molar ratio SiO 2 /Al 2 O 3 50 to 65; specific surface area of 400-700 m 2 /g; the pore volume is 0.3-0.6 mL/g; the grain diameter is 500-1000 nm;
and/or, in the step (3), the second beta molecular sieve is a hydrogen beta molecular sieve;
further preferably, the second beta molecular sieve Na in step (3) 2 The weight content of O is less than 0.3 percent; silicon to aluminum molar ratio SiO 2 /Al 2 O 3 50 to 65; the specific surface area is 450-700 m 2 /g; the pore volume is 0.35-0.70 mL/g, and the particle size is 500-1000 nm.
10. The method according to claim 7, wherein the conditions of the first reaction in step (2) are: the reaction temperature is 30-60 ℃, preferably 35-50 ℃, and the reaction time is 2-12 h, preferably 4-8 h;
and/or, the conditions of the second reaction in step (3) are: the reaction temperature is 30-60 ℃, preferably 35-50 ℃, and the reaction time is 2-12 h, preferably 4-8 h.
11. The process according to claim 7, wherein SiO in the raw material of step (4) 2 /Al 2 O 3 Molar ratio to the composite molecular sieve SiO in step (4) 2 /Al 2 O 3 The ratio of the molar ratio is 97% -100%.
12. The method according to claim 7, wherein in the step (4), the liquid-solid mass ratio after mixing the raw materials is controlled to be 1:1 to 10:1, preferably 1:1 to 8:1, and more preferably 1:1 to 5:1 by adjusting the addition amount of the first liquid-phase product and/or the second liquid-phase product.
13. The method according to claim 7, wherein the hydrothermal crystallization conditions in the step (4) are: the crystallization temperature is 80-140 ℃, preferably 100-120 ℃; the crystallization time is 4-48 h, preferably 24-30 h;
and/or, in the step (4), the drying temperature is 100-120 ℃, and the drying time is 6-10 h;
and/or, the roasting temperature in the step (4) is 500-550 ℃ and the roasting time is 4-6 h.
14. The method according to claim 6, wherein the drying is for 12 to 14 hours at a temperature of 100 to 130 ℃; the roasting is carried out for 5 to 10 hours at the temperature of 450 to 550 ℃;
and/or the method for loading the active metal is an impregnation method.
15. Use of a catalyst according to any one of claims 1 to 5 or a catalyst prepared by a process according to any one of claims 6 to 14 in hydrodearomatization reactions.
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