CN116637651A - Hydrocracking catalyst - Google Patents

Hydrocracking catalyst Download PDF

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Publication number
CN116637651A
CN116637651A CN202210138547.2A CN202210138547A CN116637651A CN 116637651 A CN116637651 A CN 116637651A CN 202210138547 A CN202210138547 A CN 202210138547A CN 116637651 A CN116637651 A CN 116637651A
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Prior art keywords
hydrocracking catalyst
sapo
composite material
spraying
silica gel
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Inventor
李海岩
谢方明
田宏宇
关旭
孙发民
郭金涛
颜子金
王甫村
张铁珍
王亮
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Petrochina Co Ltd
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Petrochina Co Ltd
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Priority to CN202210138547.2A priority Critical patent/CN116637651A/en
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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
    • B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • 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
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • 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
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/64—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/66—Tungsten
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • 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
    • B01J29/084—Y-type faujasite
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    • 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
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • 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
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    • 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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Abstract

The invention discloses a hydrocracking catalyst, which is prepared by a carrier loaded with a metal complex, wherein the carrier is prepared by a Y/SAPO-34/ASP composite material containing a crystal pore wall structure and alumina sol, and the preparation method of the composite material comprises the following steps: (1) Uniformly adsorbing the slurry obtained after mixing the Y molecular sieve, the long-chain surfactant and the alkaline aqueous solution on macroporous silica gel to prepare a Y/silica gel solid mixture; (2) Mixing the Y/silica gel solid mixture obtained in the step (1) serving as a silicon-aluminum source with a template agent, phosphoric acid, an aluminum source and water, adjusting pH, and crystallizing to obtain Y/SAPO-34 composite material slurry; (3) And (3) mixing the Y/SAPO-34 composite material slurry obtained in the step (2) with a silicon source and a long-chain surfactant, regulating the pH to 8-10, and crystallizing to obtain the Y/SAPO-34/ASP composite material with a crystal pore wall structure.

Description

Hydrocracking catalyst
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a hydrocracking catalyst.
Background
The hydrocracking technology has the advantages of strong raw material adaptability, flexible processing scheme, high liquid product yield, good product quality and the like, particularly has high aromatic hydrocarbon potential content of heavy naphtha, and is a high-quality raw material for producing aromatic hydrocarbon or high-octane gasoline; the hydrogenated tail oil and the light naphtha are rich in alkane, and are high-quality feeds of a device for preparing ethylene by steam cracking; meanwhile, high-quality No. 3 jet fuel and national VI diesel blending components can be produced simultaneously, the core of the hydrocracking technology is a hydrocracking catalyst, the hydrocracking catalyst is generally prepared by loading a metal solution onto a carrier by adopting an equal-volume impregnation method or an excessive impregnation method, the hydrocracking catalyst is also prepared by the existing technology, the solution part in the impregnation process is not uniform, the excessive metal easily causes the blocking of holes after the catalyst is dried and roasted, and the specific surface area and the pore volume loss of the catalyst are larger.
CN201410711529 is a hydrocracking catalyst carrier and a preparation method thereof, and discloses a hydrocracking catalyst carrier and a preparation method thereof. The catalyst carrier adopts a modified Y-type molecular sieve with large crystal grains, high silicon and concentrated effective pore diameter distribution as a main cracking component, and the hydrocracking catalyst prepared by the carrier is suitable for being used as a hydrocracking catalyst for flexibly producing high-quality heavy naphtha, aviation kerosene and diesel oil, and has higher activity and selectivity; the disadvantages of this technique or the shortcomings with respect to the present invention: the metal loading method adopts a conventional isovolumetric impregnation method, and the metal loading content is high, so that the specific surface area of the carrier material loaded with the metal is low. The defect of the technology is that a mesoporous structure rich in crystal pore walls is not formed, and the content of mesoporous pore channels is low.
CN201811521961.1 a hydrocracking catalyst, and a preparation method and application thereof. The catalyst comprises a carrier, an active component and silicon dioxide formed by roasting after silane loading, wherein the carrier contains a Y molecular sieve and a SAPO-34 molecular sieve; the active components comprise VIB metal and VIII metal, and the weight content of silica formed by roasting the supported silane in the catalyst is 0.5-5 wt%. The preparation method of the hydrocracking catalyst comprises the following steps: (1) Uniformly mixing materials containing a Y molecular sieve and an SAPO-34 molecular sieve, adding an acidic solution, and drying and roasting after molding to obtain a carrier; (2) And (3) introducing active components into the carrier prepared in the step (1), wherein the active components are VIB-group and VIII-group metals, and drying and roasting after introducing to prepare the hydrocracking catalyst. The catalyst prepared by the method is used for well matching the reactivity and the medium oil selectivity in the hydrocracking reaction process, and has excellent product properties. The disadvantages of this technique or the shortcomings with respect to the present invention: the method is only mechanical mixing of the Y molecular sieve and the SAPO-34 molecular sieve, and the technology has the defect that a mesoporous structure rich in crystal pore walls is not formed, and the mesoporous pore channel content is low, so that the method is mainly used for producing the middle distillate oil in a plurality of yields.
CN201811522285.X, a hydrocracking catalyst carrier, a preparation method and application thereof, wherein the carrier contains a Y molecular sieve and an SAPO-34 molecular sieve, the weight content of the Y molecular sieve is 2-35 wt% and the content of the SAPO-34 molecular sieve is 2-25 wt% based on the carrier. The preparation method of the carrier comprises the following steps: uniformly mixing materials containing the Y molecular sieve and the SAPO-34 molecular sieve, adding an acidic solution for molding, and drying and roasting after molding to obtain the hydrocracking catalyst carrier. The catalyst prepared by the carrier has higher reactivity, medium oil selectivity and excellent product properties when used in the hydrocracking reaction process. The defect of the technology is that the method is only mechanical mixing of the Y molecular sieve and the SAPO-34 molecular sieve, and compared with the technology, a mesoporous structure rich in crystal pore walls is not formed, and the mesoporous pore channel content is low, so that the method is mainly used for producing middle distillate in a plurality of yields.
Disclosure of Invention
The invention aims to provide a hydrocracking catalyst, which solves the problems that the existing catalyst does not form a mesoporous structure rich in crystal pore walls and the content of mesoporous pore channels is low.
In order to achieve the above object, the present invention provides a hydrocracking catalyst prepared from a carrier-supported metal complex, the carrier being prepared from a Y/SAPO-34/ASP composite material having a crystal pore wall structure and an alumina sol, the preparation method of the Y/SAPO-34/ASP composite material having a crystal pore wall structure comprising the steps of:
(1) Uniformly adsorbing the slurry obtained after mixing the Y molecular sieve, the long-chain surfactant and the alkaline aqueous solution on macroporous silica gel to prepare a Y/silica gel solid mixture;
(2) Mixing the Y/silica gel solid mixture obtained in the step (1) with a template agent, phosphoric acid, an aluminum source and water, wherein the silicon aluminum source is SiO 2 Counting the amount of phosphoric acid and adding P 2 O 5 Metering Al as Al source 2 O 3 Metering, controlling the feeding mole ratio to be (1-1.5) Al 2 O 3 :(1～1.5)P 2 O 5 :(1～1.5)SiO 2 (1-2) template agent (40-80) H 2 O, regulating the pH value, and crystallizing to obtain Y/SAPO-34 composite material slurry;
(3) And (2) mixing the Y/SAPO-34 composite slurry obtained in the step (2) with a silicon source and a long-chain surfactant according to the mass ratio of (0.01-0.1), regulating the pH value, and crystallizing to obtain the Y/SAPO-34/ASP composite material containing a crystal pore wall structure.
The hydrocracking catalyst disclosed by the invention comprises the following steps: long chain surfactants: alkali: the mass ratio of water is 1 (0.05-0.1) (0.05-0.2) (5-10), the materials are prepared, the materials are mixed and stirred for 4-10 hours at 70-90 ℃ to obtain mixed slurry containing Y molecular sieve microcrystals, the mixed slurry is dispersed in a container by a high-pressure and airflow crushing method to form a moist atmosphere, and the moist atmosphere is adsorbed on macroporous silica gel to obtain a Y/silica gel solid mixture.
In the hydrocracking catalyst, in the step (2), phosphoric acid is added into water, then an aluminum source is added, and stirring is carried out to form a solution B; mixing the Y/silica gel solid mixture, a template agent and water to obtain a solid-liquid mixture C, adding the solid-liquid mixture C into the solution B, adjusting the pH value, and crystallizing.
The hydrocracking catalyst of the invention, in the step (2), the pH value is regulated to 6.5-7.5, and the slurry of the Y/SAPO-34 composite material is obtained after crystallization for 12-24 hours at 150-200 ℃.
The hydrocracking catalyst of the invention, in the step (3), pH is regulated to 8-10, and stirred crystallization is carried out for 10-24 hours at 80-100 ℃ to obtain the Y/SAPO-34/ASP composite material containing a crystal pore wall structure, wherein ASP is mesoporous amorphous silicon phosphorus aluminum oxide.
The hydrocracking catalyst provided by the invention further comprises the steps of filtering, washing, ammonium ion exchange and roasting after crystallization in the step (3).
The hydrocracking catalyst is roasted for 3-5 hours at 500-550 ℃.
The preparation method of the hydrocracking catalyst comprises the steps of loading 10-20wt% of aluminum sol into a high-pressure container, pressurizing to 2-6 MPa, spraying, and enabling the flow velocity perpendicular to the spraying direction of the aluminum sol to be 10-20 m 3 The high-speed airflow per min is carried and sprayed out after being crushed, an alumina sol moist atmosphere is formed in a container, so that the Y/SAPO-34/ASP composite material with a crystal pore wall structure and macroporous alumina are fully and uniformly adsorbed in the container, and the hydrogenation catalyst carrier is obtained after molding.
The hydrocracking catalyst of the invention, the specific surface area of the catalyst carrier is 450-610m 2 Per g, pore volume 0.50-0.80 mL/g, pore size distribution 4-15 nm.
The hydrocracking catalyst disclosed by the invention has the advantages that the long-chain surfactant comprises one or more of hexadecyl trimethyl ammonium bromide, PEG1000 and PEG 2000; the aluminum source comprises pseudo-boehmite; the silicon source comprises silica sol and/or water glass; the template agent comprises one or more of triethylamine, morpholine and tetraethylammonium hydroxide.
The hydrocracking catalyst of the present invention has Y molecular sieve unit cell of 24.32-24.42.
The preparation method of the hydrocracking catalyst provided by the invention comprises the following steps: pressurizing 15-25wt% metal complex solution to 2-6 MPa, spraying, and spraying at a flow rate of 10-20 m perpendicular to the spraying direction 3 Spraying out high-speed gas flow per min to form a wet atmosphere containing metal solution in a container, placing the carrier in the container, and fully adsorbing to obtain hydrocracking catalyst with specific surface area of 350-500m 2 Per g, pore volume 0.35-0.65 mL/g, pore size distribution 4-12 nm.
The preparation method of the hydrocracking catalyst provided by the invention comprises the following steps: the metal complex solution comprises a solution formed by one or more of tungsten salt, molybdenum salt and nickel salt and 2, 2-bipyridine and/or 1, 10-phenanthroline chelate.
The invention has the beneficial effects that:
according to the invention, the Y/SAPO-34/ASP composite material containing a crystal pore wall structure is used for preparing the hydrogenation catalyst, so that the stability of a mesoporous pore channel of the catalyst is improved; because the technology ensures that the metal solution is highly dispersed into the moist atmosphere, in the metal feeding process, the metal dispersity is improved, the number of effective active centers is increased, the problems of blocking holes, loss of specific surface area and pore volume of the catalyst caused by local excessive metal are reduced, and the specific surface area, pore volume and pore diameter of the catalyst are improved. The invention adopts the Y/SAPO-34/ASP composite material containing the crystal pore wall structure to prepare the hydrogenation catalyst carrier, and the carrier contains the mesoporous structure of Y molecular sieve, SAPO-34 molecular sieve microcrystal and secondary structural unit microcrystal, thereby improving the mesoporous stability in the carrier.
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of illustration and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and variations of the invention will become apparent to those skilled in the art in light of the above disclosure.
Example 1
(1) Using unit cells 24.32, specific surface area 550m 2 A Y molecular sieve with a pore volume of 0.40mL/g and an average pore diameter of 2.6nm, according to the following formula: cetyl trimethylammonium bromide: potassium hydroxide: dispersing a Y molecular sieve in an aqueous solution of hexadecyl trimethyl ammonium bromide and potassium hydroxide according to the mass ratio of water of 1:0.05:0.05:5, and stirring at a constant temperature of 70 ℃ for 10 hours to obtain mixed slurry containing Y molecular sieve microcrystals;
(2) Adding the mixed slurry containing Y molecular sieve microcrystals into a container, pressurizing to 2MPa, spraying the solution, and enabling the flow velocity perpendicular to the spraying direction to be 10m 3 And spraying out the high-speed air flow per minute, forming a moist atmosphere in a container, placing macroporous silica gel with a pore volume of 1.0ml/g in the moist atmosphere, and fully adsorbing the mixed slurry by the macroporous silica gel to obtain a Y/silica gel solid mixture A.
(3) 23g of phosphoric acid was added to 41g of deionized water, and 13.5g of alumina sol (65% Al2O 3) was added thereto, followed by stirring for 5 hours to obtain a solution B. 6g of the Y/silica gel solid mixture A was mixed with 15g of triethylamine and 50g of water to obtain a solid-liquid mixture C. And adding the solid-liquid mixture C into the solution B, regulating the pH value to 6.5 to obtain a solid-liquid mixture D, and crystallizing at 200 ℃ for 12 hours to obtain the Y/SAPO-34 molecular sieve composite material slurry.
(4) 10g of silica Sol (SiO) is added into the slurry of the Y/SAPO-34 molecular sieve composite material 2 30wt percent) and 3g of PEG2000, regulating the pH value of the system to 10, stirring and crystallizing at 80 ℃ for 24 hours, filtering, washing and exchanging ammonium ions, roasting at 500 ℃ for 4 hours to obtain the mesoporous Y/SAPO-34/ASP composite material containing a crystal pore wall structure, wherein the specific surface area is 680m 2 Per g, pore volume 0.60mL/g, pore size distribution 4-12 nm.
(5) 27g of the prepared Y/SAPO-34/ASP composite material containing a crystal pore wall structure and 27g of macroporous alumina (specific surface area 400m 2 Per gram, pore volume of 1.0mL/g, pore size distribution of 4-8 nm) and then placing the mixture in a container, and then placing 50g of 10wt% concentrationThe aluminum sol is filled into the container, pressurized to 2MPa and sprayed out, and then the aluminum sol is sprayed out at a flow rate of 10m 3 Carrying out high-speed air flow/min, spraying, forming aluminum sol humid atmosphere in a container, fully and uniformly adsorbing the composite material and aluminum oxide, and forming to obtain hydrogenation catalyst carrier with specific surface area of 610m 2 Per g, pore volume 0.50mL/g, pore size distribution 4-12 nm.
(6) 15g of 17wt% ammonium molybdate, 5g of 3wt% ammonium metatungstate, 5g of 3wt% nickel nitrate aqueous solution and 4g of 12wt%2, 2-bipyridine form a metal complex solution, the metal complex solution is pressurized to 6MPa and then sprayed out, and the flow rate perpendicular to the spraying direction is 20m 3 Spraying out the high-speed airflow per min to form a wet atmosphere containing a metal solution in a container, placing the carrier in the container, and fully and uniformly adsorbing to obtain the hydrocracking catalyst, wherein the metal complex solution is the carrier with the mass ratio of 3:7, and the specific surface area of the prepared catalyst is 500m 2 Per g, pore volume 0.35mL/g, pore size distribution 4-12 nm.
Example 2
(1) Using unit cells 24.37, specific surface area 560m 2 /g, pore volume 0.41mL/g, average pore size 2.7nm, according to the following molecular sieve: PEG2000: potassium hydroxide: dispersing a Y molecular sieve in an aqueous solution of PEG2000 and potassium hydroxide according to the mass ratio of water of 1:0.07:0.07:5, and stirring at the constant temperature of 80 ℃ for 7 hours to obtain mixed slurry containing Y molecular sieve microcrystals;
(2) Adding the mixed slurry containing Y molecular sieve microcrystals into a container, pressurizing to 4MPa, spraying the solution, and enabling the flow velocity perpendicular to the spraying direction to be 15m 3 The high-speed air flow of/min is sprayed out to form a moist atmosphere in the container. Macroporous silica gel with a pore volume of 2.5ml/g was allowed to fully adsorb the above mixed slurry in a moist atmosphere to obtain a Y/silica gel solid mixture A.
(3) 28.7g of phosphoric acid was added to 51g of deionized water, followed by 16.8g of aluminum sol (65% Al2O 3) and stirred well for 7.5 hours to form solution B. 6.5g of Y/silica gel solid mixture A was mixed with 17g of tetraethylammonium hydroxide and 55g of water to give a solid-liquid mixture C. And adding the solid-liquid mixture C into the solution B, regulating the pH value to 7.5 to obtain a solid-liquid mixture D, and crystallizing at 200 ℃ for 18 hours to obtain the Y/SAPO-34 molecular sieve composite material slurry.
(4) 10g of silica Sol (SiO) is added into the slurry of the Y/SAPO-34 molecular sieve composite material 2 30wt percent) and 5g of PEG1000, regulating the pH value of the system to 8, stirring and crystallizing at 90 ℃ for 16 hours, filtering, washing and exchanging ammonium ions, roasting at 550 ℃ for 3 hours to obtain the mesoporous Y/SAPO-34/ASP composite material containing a crystal pore wall structure, wherein the specific surface area is 590m 2 Per g, pore volume 0.80mL/g, pore size distribution 4-14 nm.
(5) 32.5g of the prepared Y/SAPO-34/ASP composite material containing a crystal pore wall structure and 32.5g of macroporous alumina (specific surface area 350m 2 Per gram, pore volume of 1.2mL/g, pore size distribution of 6-10 nm), then placing the mixture in a container, placing 43g of 15wt% concentration aluminum sol in a high-pressure container, pressurizing to 2MPa, spraying out, and then using the flow rate of 10m 3 Carrying out high-speed air flow/min, spraying, forming aluminum sol humid atmosphere in a container, fully and uniformly adsorbing the composite material and aluminum oxide, and forming to obtain hydrogenation catalyst carrier with specific surface area of 520m 2 Per g, pore volume 0.65mL/g, pore size distribution 4-13 nm.
(6) 15g of 14.5wt% ammonium molybdate, 5g of 3wt% ammonium metatungstate, 5g of 3wt% nickel nitrate aqueous solution and 4g of 10wt%1, 10-phenanthroline form a metal complex solution, the metal complex solution is pressurized to 4MPa and sprayed out, and the flow rate perpendicular to the spraying direction is 15m 3 Spraying out the high-speed airflow per min to form a wet atmosphere containing a metal solution in a container, placing the carrier in the container, and fully and uniformly adsorbing to obtain the hydrocracking catalyst, wherein the metal complex solution is the carrier with the mass ratio of 3:7, and the specific surface area of the prepared catalyst is 410m 2 Per g, pore volume 0.55mL/g, pore size distribution 4-13 nm.
Example 3
(1) Using unit cells 24.42 and specific surface area 580m 2 /g, pore volume 0.42mL/g, average pore size 3.0nm, according to the following molecular sieve: PEG1000: potassium hydroxide: dispersing a Y molecular sieve in an aqueous solution of PEG1000 and potassium hydroxide according to the mass ratio of water of 1:0.1:0.2:10, and stirring for 4 hours at a constant temperature of 90 ℃ to obtain mixed slurry containing Y molecular sieve microcrystals;
(2) Adding the mixed slurry containing Y molecular sieve microcrystals into a container, pressurizing to 6MPa, spraying out high-pressure solution, and enabling the flow velocity perpendicular to the spraying direction to be 20m 3 The high-speed air flow of/min is sprayed out to form a moist atmosphere in the container. Macroporous silica gel with a pore volume of 3.5ml/g was allowed to fully adsorb the above mixed slurry in a moist atmosphere to obtain a Y/silica gel solid mixture A.
(3) 34.5g of phosphoric acid was added to 61.5g of deionized water, followed by 20.2g of aluminum sol (65% Al2O 3) and stirred well for 10 hours to form solution B. 9g of Y/silica gel solid mixture A was mixed with 26g of morpholine and 75g of water to give a solid-liquid mixture C. And adding the solid-liquid mixture C into the solution B, regulating the pH value to 7, obtaining a solid-liquid mixture D, and crystallizing at 200 ℃ for 24 hours to obtain the Y/SAPO-34 molecular sieve composite slurry.
(4) 15g of water glass (SiO) is added into the slurry of the Y/SAPO-34 molecular sieve composite material 2 35 wt%) and 8g of hexadecyl trimethyl ammonium bromide, regulating pH value of system to 9, crystallizing at 100 deg.C for 10 hr, filtering, washing and ammonium ion-exchanging product, roasting at 600 deg.C for 2 hr to obtain the invented mesoporous Y/SAPO-34/ASP composite material with crystal pore wall structure and specific surface area of 500m 2 And/g, pore volume is 1.0mL/g, and pore size distribution is 4-15 nm.
(5) 40g of the prepared Y/SAPO-34/ASP composite material containing a crystal pore wall structure and 40g of macroporous alumina (specific surface area 300m 2 Per gram, pore volume of 1.4mL/g, pore size distribution of 8-12 nm), placing the mixture in a container, placing 40g of 20wt% concentration aluminum sol in a high-pressure container, pressurizing to 2MPa, spraying out, and then spraying the aluminum sol at a flow rate of 10m 3 Carrying out high-speed air flow/min, spraying, forming aluminum sol wet atmosphere in a container to enable the composite material and aluminum oxide to be fully and uniformly adsorbed, and forming to obtain the hydrogenation catalyst carrier with the specific surface area of 450m 2 Per g, pore volume 0.80mL/g, pore size distribution 4-15 nm.
(6) Placing a carrier in a container, forming a metal complex solution by 15g of 13wt% ammonium metatungstate and 5g of 2wt% nickel salt water solution and 4g of 8wt% 1, 10-phenanthroline, pressurizing the metal complex solution to 2MPa, spraying out, and sprayingThe flow velocity in the vertical direction is 10m 3 Spraying out the high-speed airflow per min, forming a wet atmosphere containing a metal solution in a container, fully adsorbing a carrier to obtain the hydrocracking catalyst, wherein the metal complex solution is used as the carrier, the mass ratio of the metal complex solution to the carrier is 3:7, and the specific surface area of the prepared catalyst is 350m 2 Per g, pore volume 0.65mL/g, pore size distribution 4-14 nm.
Comparative example 1
(1) Using unit cells 24.44, specific surface area 530m 2 A Y molecular sieve with a pore volume of 0.39mL/g and an average pore diameter of 2.2nm, according to the following formula: cetyl trimethylammonium bromide: potassium hydroxide: dispersing a Y molecular sieve in an aqueous solution of hexadecyl trimethyl ammonium bromide and potassium hydroxide according to the mass ratio of water of 1:0.03:0.03:15, and stirring for 5 hours at a constant temperature of 100 ℃ to obtain mixed slurry containing Y molecular sieve microcrystals;
(2) Adding the mixed slurry containing Y molecular sieve microcrystals into a container, pressurizing to 1.5MPa, spraying the solution, and enabling the flow velocity vertical to the spraying direction to be 5m 3 And spraying out the high-speed air flow per minute, forming a moist atmosphere in a container, placing macroporous silica gel with a pore volume of 1.0ml/g in the moist atmosphere, and fully adsorbing the mixed slurry by the macroporous silica gel to obtain a Y/silica gel solid mixture A.
(3) 11g of phosphoric acid was added to 20g of deionized water, followed by 7g of aluminum sol (65% Al2O 3), and stirred well for 3 hours to form solution B. 3g of the Y/silica gel solid mixture A was mixed with 7g of triethylamine and 25g of water to obtain a solid-liquid mixture C. And adding the solid-liquid mixture C into the solution B, regulating the pH value to 6.2, obtaining a solid-liquid mixture D, and crystallizing at 180 ℃ for 15 hours to obtain the Y/SAPO-34 molecular sieve composite material slurry.
(4) 5g of silica Sol (SiO) is added into the slurry of the Y/SAPO-34 molecular sieve composite material 2 35 wt%) and 2g of PEG2000, regulating pH value of system to 10, stirring and crystallizing at 85 deg.C for 20 hr, filtering, washing and ammonium ion-exchanging the product, roasting at 470 deg.C for 5 hr to obtain the invented mesoporous Y/SAPO-34/ASP composite material with crystal pore wall structure and specific surface area of 640m 2 Per g, pore volume 0.50mL/g, pore size distribution 4-8 nm.
(5) 27g of the prepared Y/SAPO-34 containing a crystal pore wall structureASP composite and 27g macroporous alumina (specific surface area 300m 2 Per gram, pore volume of 0.8mL/g, pore size distribution of 4-8 nm), placing the mixture in a container, placing 50g of 10wt% concentration aluminum sol in a high-pressure container, pressurizing to 2MPa, spraying out, and then flowing at a speed of 10m 3 Carrying out high-speed air flow/min, spraying, forming aluminum sol wet atmosphere in a container to make the composite material and aluminum oxide fully and uniformly adsorbed, and forming to obtain hydrogenation catalyst carrier with specific surface area of 410m 2 Per g, pore volume 0.45mL/g, pore size distribution 4-8 nm.
(6) Placing a carrier in a container, forming a metal complex solution by 15g of 13wt% tungsten salt and 5g of 2wt% nickel salt water solution and 4g of 8wt% 1, 10-phenanthroline, pressurizing the metal complex solution to 2MPa, spraying the metal complex solution, and spraying the metal complex solution at a flow rate of 10m perpendicular to the spraying direction 3 Spraying out the high-speed airflow per min, forming a wet atmosphere containing a metal solution in a container, fully adsorbing a carrier to obtain the hydrocracking catalyst, wherein the metal complex solution is used as the carrier, the mass ratio of the metal complex solution to the carrier is 3:7, and the specific surface area of the prepared catalyst is 350m 2 Per g, pore volume 0.43mL/g, pore size distribution 4-9 nm.
The catalysts prepared in examples 1 to 3 and comparative example 1 were subjected to hydrocracking performance test.
TABLE 1 oil Properties of raw materials
Table 2 results of catalyst evaluation
Project Example 1 Implementation of the embodimentsExample 2 Example 3 Comparative example 1
Reaction temperature, DEG C 378 375 372 378
Light naphtha wt% 9.0 13.7 11.80 6.0
Heavy naphtha wt% 17.5 34.4 52.50 15.5
Aviation kerosene, wt% 34 43.9 15.00 35
Diesel oil, wt% 38 8.0 5.5 41
Tail oil, wt% / / 12.70 /
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (13)

1. A hydrocracking catalyst characterized by being prepared by a carrier loaded with a metal complex, wherein the carrier is prepared from a Y/SAPO-34/ASP composite material containing a crystal pore wall structure and an alumina sol, and the preparation method of the Y/SAPO-34/ASP composite material containing the crystal pore wall structure comprises the following steps:
(1) Uniformly adsorbing the slurry obtained after mixing the Y molecular sieve, the long-chain surfactant and the alkaline aqueous solution on macroporous silica gel to prepare a Y/silica gel solid mixture;
(2) Mixing the Y/silica gel solid mixture obtained in the step (1) with a template agent, phosphoric acid, an aluminum source and water, wherein the silicon aluminum source is SiO 2 Counting the amount of phosphoric acid and adding P 2 O 5 Metering Al as Al source 2 O 3 Metering, controlling the feeding mole ratio to be (1-1.5) Al 2 O 3 :(1～1.5)P 2 O 5 :(1～1.5)SiO 2 (1-2) template agent (40-80) H 2 O, regulating the pH value, and crystallizing to obtain Y/SAPO-34 composite material slurry;
(3) And (2) mixing the Y/SAPO-34 composite slurry obtained in the step (2) with a silicon source and a long-chain surfactant according to the mass ratio of (0.01-0.1), regulating the pH value, and crystallizing to obtain the Y/SAPO-34/ASP composite material containing a crystal pore wall structure.
2. The hydrocracking catalyst of claim 1 wherein step (1) is carried out in accordance with the Y molecular sieve: long chain surfactants: alkali: the mass ratio of water is 1 (0.05-0.1) (0.05-0.2) (5-10), the materials are prepared, the materials are mixed and stirred for 4-10 hours at 70-90 ℃ to obtain mixed slurry containing Y molecular sieve microcrystals, the mixed slurry is dispersed in a container by a high-pressure and airflow crushing method to form a moist atmosphere, and the moist atmosphere is adsorbed on macroporous silica gel to obtain a Y/silica gel solid mixture.
3. The hydrocracking catalyst of claim 1 wherein in step (2) phosphoric acid is added to water followed by the addition of an aluminum source and agitation to form solution B; mixing the Y/silica gel solid mixture, a template agent and water to obtain a solid-liquid mixture C, adding the solid-liquid mixture C into the solution B, adjusting the pH value, and crystallizing.
4. A hydrocracking catalyst according to claim 1 or 3, wherein the pH is adjusted to 6.5-7.5 in step (2), and the slurry is crystallized at 150-200 ℃ for 12-24 hours to obtain the slurry of the Y/SAPO-34 composite material.
5. The hydrocracking catalyst according to claim 1, wherein the step (3) is to adjust the pH to 8-10, and to stir and crystallize at 80-100 ℃ for 10-24 hours to obtain a Y/SAPO-34/ASP composite material having a crystalline pore wall structure, wherein ASP is a mesoporous amorphous silicoaluminophosphate.
6. The hydrocracking catalyst of claim 1, wherein the crystallization in step (3) further comprises filtration, washing, ammonium ion exchange and calcination steps.
7. The hydrocracking catalyst as claimed in claim 6, wherein the calcination condition is 500 to 550 ℃ for 3 to 5 hours.
8. The hydrocracking catalyst as claimed in claim 1, wherein the carrier is prepared by charging 10 to 20wt% of the alumina sol into a high pressure vessel, pressurizing to 2 to 6MPa, spraying, and then spraying at a flow rate of 10 to 20m perpendicular to the spraying direction of the alumina sol 3 High-speed airflow breaking per minuteCarrying and spraying after crushing, forming an alumina sol moist atmosphere in a container, fully and uniformly adsorbing the Y/SAPO-34/ASP composite material with a crystal pore wall structure and macroporous alumina in the container, and forming to obtain the hydrogenation catalyst carrier.
9. The hydrocracking catalyst as claimed in claim 1, wherein the specific surface area of the catalyst support is 450-610m 2 Per g, pore volume 0.50-0.80 mL/g, pore size distribution 4-15 nm.
10. The hydrocracking catalyst of claim 1, wherein the long chain surfactant comprises one or more of cetyltrimethylammonium bromide, PEG1000 and PEG 2000; the aluminum source comprises pseudo-boehmite; the silicon source comprises silica sol and/or water glass; the template agent comprises one or more of triethylamine, morpholine and tetraethylammonium hydroxide.
11. The hydrocracking catalyst of claim 1 wherein the unit cells of the Y molecular sieve are 24.32 to 24.42.
12. The hydrocracking catalyst according to claim 1, wherein the catalyst is prepared by a process comprising: pressurizing 15-25wt% metal complex solution to 2-6 MPa, spraying, and spraying at a flow rate of 10-20 m perpendicular to the spraying direction 3 Spraying out high-speed gas flow per min to form a wet atmosphere containing metal solution in a container, placing the carrier in the container, and fully adsorbing to obtain hydrocracking catalyst with specific surface area of 350-500m 2 Per g, pore volume 0.35-0.65 mL/g, pore size distribution 4-12 nm.
13. The hydrocracking catalyst according to claim 1, wherein the catalyst is prepared by a process comprising: the metal complex solution comprises a solution formed by one or more of tungsten salt, molybdenum salt and nickel salt and 2, 2-bipyridine and/or 1, 10-phenanthroline chelate.
CN202210138547.2A 2022-02-15 2022-02-15 Hydrocracking catalyst Pending CN116637651A (en)

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