CN116637652A - Hydrogenation catalyst carrier - Google Patents

Hydrogenation catalyst carrier Download PDF

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Publication number
CN116637652A
CN116637652A CN202210138548.7A CN202210138548A CN116637652A CN 116637652 A CN116637652 A CN 116637652A CN 202210138548 A CN202210138548 A CN 202210138548A CN 116637652 A CN116637652 A CN 116637652A
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sapo
hydrogenation catalyst
composite material
silica gel
asp
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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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    • 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
    • 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
    • B01J35/635—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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a hydrogenation catalyst carrier, which is prepared from a Y/SAPO-34/ASP composite material containing a crystal pore wall structure and alumina sol, wherein 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) The Y/silica gel solid mixture is a silicon-aluminum source, is mixed with a template agent, phosphoric acid, an aluminum source and water, the pH value is regulated, and after crystallization, the Y/SAPO-34 composite slurry is obtained; (3) And mixing the Y/SAPO-34 composite material slurry with a silicon source and a long-chain surfactant, regulating the pH value, and crystallizing to obtain the Y/SAPO-34/ASP composite material containing a crystal pore wall structure. The aluminum sol in the technology can be highly dispersed, so that the bonding effect is improved, and the loss of pore volume in the carrier forming process is reduced.

Description

Hydrogenation catalyst carrier
Technical Field
The invention belongs to the technical field of catalyst carriers, and particularly relates to a hydrogenation catalyst carrier.
Background
The preparation method of the hydrogenation catalyst carrier generally comprises the steps of directly and mechanically mixing materials such as molecular sieve, amorphous silica-alumina, binder and the like, kneading, rolling, extruding, forming, drying and roasting to obtain the catalyst carrier, but the mechanical mixing method has the defects of uneven material dispersion, longer rolling time of the mixed materials, larger specific surface area and pore volume loss of the carrier and poor pore channel connectivity. The carrier prepared from the molecular sieve composite material has the characteristics of good pore channel connectivity, large specific surface area, large pore volume retention, large pore diameter and the like, and is beneficial to improving the performance of the carrier.
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 is a hydrocracking catalyst, and a preparation method and application thereof, wherein the catalyst comprises a carrier, an active component and silicon dioxide formed by roasting after silane is loaded, and the carrier contains a Y molecular sieve and an 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 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.
Disclosure of Invention
The invention aims to provide a hydrogenation catalyst carrier to solve the problem that the existing carrier 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 hydrogenation catalyst carrier 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 hydrogenation catalyst carrier disclosed by the invention comprises the following steps of: 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 hydrogenation catalyst carrier, 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 hydrogenation catalyst carrier disclosed by the invention is prepared by the step (2) of adjusting the pH value to 6.5-7.5 and crystallizing at 150-200 ℃ for 12-24 hours to obtain Y/SAPO-34 composite slurry.
The hydrogenation catalyst carrier disclosed by the invention is prepared by the step (3) of adjusting pH to 8-10, and stirring and crystallizing at 80-100 ℃ for 10-24 hours to obtain a Y/SAPO-34/ASP composite material containing a crystal pore wall structure, wherein ASP is mesoporous amorphous silicon phosphorus aluminum oxide.
The hydrogenation catalyst carrier provided by the invention further comprises the steps of filtering, washing, ammonium ion exchange and roasting after crystallization in the step (3).
The hydrogenation catalyst carrier is roasted for 3-5 hours at the temperature of 500-550 ℃.
The preparation method of the hydrogenation catalyst carrier comprises the steps of loading 10-20wt% of aluminum sol into a high-pressure container, pressurizing to 2-6 MPa, spraying, and then spraying with 10-20 m perpendicular to the spraying direction of the aluminum sol 3 And carrying out spraying after crushing the high-speed airflow per min, forming an aluminum sol wetting atmosphere in a container, uniformly mixing the Y/SAPO-34/ASP composite material containing a crystal pore wall structure and macroporous alumina powder, placing the mixture in the container, fully and uniformly adsorbing, and forming to obtain the hydrogenation catalyst carrier.
The hydrogenation catalyst carrier has a specific surface area of 450-610m 2 Per g, pore volume 0.50-0.80 mL/g, pore size distribution 4-15 nm.
The hydrogenation catalyst carrier 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 invention has the beneficial effects that:
the technology adopts the Y/SAPO-34/ASP composite material containing a crystal pore wall structure to prepare the hydrogenation catalyst carrier, and the carrier contains a mesoporous structure of Y molecular sieve and SAPO-34 molecular sieve microcrystals, so that the mesoporous stability in the carrier is improved. Because the aluminum sol in the technology can be highly dispersed, the bonding effect is improved, the loss of pore volume in the carrier molding process is reduced, and the specific surface area of the prepared carrier is 450-610m 2 And/g, the pore volume is 0.50-0.80 mL/g, the pore size distribution is 4-15 nm, and the specific surface area, pore volume and pore size of the carrier are improved.
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 spraying the solution at a flow rate of 10m perpendicular to the spraying direction of the mixed slurry 3 And carrying out high-speed airflow at/min, crushing, carrying out spraying, 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, wherein the mass of the mixed slurry is 1% of that of the macroporous silica gel, so as 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), then placing the mixture in a container, placing 50g of 10wt% concentration aluminum sol into the container, pressurizing to 2MPa, spraying out, and then making flow rate be 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.
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 spraying the solution at a flow rate of 15m perpendicular to the spraying direction of the mixed slurry 3 The high-speed airflow per min is crushed and then carried and sprayed out, so that a moist atmosphere is formed in the container. And (3) enabling macroporous silica gel with the pore volume of 2.5ml/g to be in a humid atmosphere container, enabling the macroporous silica gel to fully absorb the mixed slurry, wherein the mass of the mixed slurry is 10% of that of the macroporous silica gel, and obtaining the 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 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.
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 microcrystals of 0.1-5 nm of the Y molecular sieve;
(2) Adding mixed slurry containing Y molecular sieve 0.1-5 nm microcrystal into a container, pressurizing to 6MPa, spraying high-pressure solution, directly impacting with smooth metal wall, and making flow velocity perpendicular to the spraying direction of mixed slurry be 20m 3 High-speed airflow disruption per minuteThen carrying out the ejection, and forming a moist atmosphere in the container. And placing macroporous silica gel with a pore volume of 3.5ml/g in the moist atmosphere, and fully contacting and adsorbing the mixed slurry with the macroporous silica gel, wherein the mass of the mixed slurry is 30% of that of the macroporous silica gel, so as 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.
Comparative 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 Y molecular sieve in water solution of hexadecyl trimethyl ammonium bromide and potassium hydroxide in the mass ratio of water being 1:0.03:0.03:15, and stirring at 70 ℃ at constant temperatureStirring for 10h 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 spraying the solution at a flow rate of 10m perpendicular to the spraying direction of the mixed slurry 3 And carrying out high-speed airflow at/min, crushing, carrying out spraying, 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, wherein the mass of the mixed slurry is 1% of that of the macroporous silica gel, so as 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 6.5 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) Adding 5g of 30wt% silica sol and 2g of PEG2000 into the Y/SAPO-34 molecular sieve composite material slurry, 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 with a crystal pore wall structure, wherein the specific surface area is 640m 2 Per g, pore volume 0.50mL/g, pore size distribution 4-8 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 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.
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 (11)

1. The hydrogenation catalyst carrier is characterized by being prepared from a Y/SAPO-34/ASP composite material containing a crystal pore wall structure and an alumina sol, wherein 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 hydrogenation catalyst support according to claim 1, wherein step (1) is carried out according to the molecular sieve Y: 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 hydrogenation catalyst support according to claim 1, wherein in step (2) phosphoric acid is added to water, followed by adding an aluminum source and stirring 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. The hydrogenation catalyst carrier according to claim 1 or 3, wherein the pH value is adjusted to 6.5-7.5 in the 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 hydrogenation catalyst carrier 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 hydrogenation catalyst support according to claim 1, wherein the crystallization in step (3) further comprises filtration, washing, ammonium ion exchange and calcination steps.
7. The hydrogenation catalyst support according to claim 6, wherein the calcination conditions are 500 to 550 ℃ for 3 to 5 hours.
8. The hydrogenation catalyst carrier according to claim 1, wherein said carrier is prepared by charging 10 to 20 wt.% of an alumina sol into a high pressure vessel, pressurizing to 2 to 6MPa, spraying, and then spraying with 10 to 20m perpendicular to the direction of alumina sol spraying 3 And carrying out spraying after crushing the high-speed airflow per min, forming an aluminum sol wetting atmosphere in a container, uniformly mixing the Y/SAPO-34/ASP composite material containing a crystal pore wall structure and macroporous alumina powder, placing the mixture in the container, fully and uniformly adsorbing, and forming to obtain the hydrogenation catalyst carrier.
9. The hydrogenation catalyst support according to 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 hydrogenation catalyst support 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 hydrogenation catalyst support of claim 1 wherein the unit cells of the Y molecular sieve are 24.32 to 24.42.
CN202210138548.7A 2022-02-15 2022-02-15 Hydrogenation catalyst carrier Pending CN116637652A (en)

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