CN111889132B - Metal oxide-molecular sieve catalyst, and preparation method and application thereof - Google Patents

Metal oxide-molecular sieve catalyst, and preparation method and application thereof Download PDF

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CN111889132B
CN111889132B CN202010805398.1A CN202010805398A CN111889132B CN 111889132 B CN111889132 B CN 111889132B CN 202010805398 A CN202010805398 A CN 202010805398A CN 111889132 B CN111889132 B CN 111889132B
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metal oxide
molecular sieve
composite
water
sieve catalyst
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CN111889132A (en
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王森
樊卫斌
秦张峰
董梅
王建国
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Shanxi Institute of Coal Chemistry of CAS
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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
    • B01J29/82—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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/783—CHA-type, e.g. Chabazite, LZ-218
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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

Abstract

The invention provides a metal oxide-molecular sieve catalyst, a preparation method and application thereof, belonging to the technical field of catalysts. The metal oxide-molecular sieve catalyst provided by the invention comprises a composite metal oxide and an acidic molecular sieve; the composite metal oxide has a chemical composition represented by formula I: m1aM2bOcFormula I; in the formula I, M1Is a group IIIA metal, M2Is a metal in VIB group, a, b and c are atomic ratio, and the total valence of the composite metal oxide is zero. In the invention, the composite metal oxide can form a solid solution structure, the surface oxygen hole concentration is high, and CO is favorably generated2Adsorption and low carbon olefin production. The metal oxide-molecular sieve catalyst provided by the invention is used for CO2The low-carbon olefin can be prepared by hydrogenation, and the CO can be obviously improved2Conversion rate, selectivity and yield of low-carbon olefin, and effectively reducing the selectivity of byproduct CO.

Description

Metal oxide-molecular sieve catalyst, and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a metal oxide-molecular sieve catalyst and a preparation method and application thereof.
Background
The rapid consumption of fossil resources leads to a drastic increase in the carbon dioxide content of the atmosphere, thereby bringing about a serious greenhouse effect. By means of hydrogenation, carbon dioxide is converted into high value-added chemicals such as methanol, formic acid, low-carbon olefin and aromatic hydrocarbon, so that the carbon dioxide can be reasonably utilized, the greenhouse effect is controlled, a new route for preparing important chemical products is developed, and the energy crisis caused by reduction of petroleum resources can be effectively solved. Among them, low-carbon olefins represented by ethylene, propylene, etc. are important basic organic chemical raw materials, and it has important strategic significance to directly convert rich carbon dioxide resources into low-carbon olefins.
At present, there are two main methods for preparing low-carbon olefins by carbon dioxide hydrogenation: the Fischer-tropsch (ft) synthesis route and the Methanol-intermediate (Methanol-intermediate) route. The catalyst commonly used in the Fischer-Tropsch synthesis route is a Fe-based, Co-based or Rh-based catalyst, but is limited by the product distribution rule of Fischer-Tropsch synthesis (ASF), the selectivity of low-carbon olefin is generally lower than 60%, and the selectivity of methane is more than 25%. For example, chinese patent CN104437504A discloses that a Fe-based catalyst generates a large amount of methane and other long-chain alkanes in the preparation of olefins by hydrogenation of carbon dioxide, and the selectivity of low-carbon olefins is only about 60%. The methanol intermediate route is generally: the carbon dioxide is converted into methanol under the action of the metal oxide, and then the methanol is dehydrated under the action of the acidic molecular sieve to form the low-carbon olefin. For example, the Shanghai high research institute (ACS Catalysis,2018,8,571-With In2O3the/H-SAPO-34 composite catalyst catalyzes the carbon dioxide hydrogenation reaction, the selectivity of low-carbon olefin in total hydrocarbon can reach 80 percent, but the selectivity of the byproduct carbon monoxide is close to 90 percent; chinese patent CN106423263A discloses a method for preparing olefin by carbon dioxide hydrogenation, ZnZrO is hydrogenatedxThe catalyst prepared by physically mixing the oxide and the H-SAPO-34 molecular sieve has the selectivity of low-carbon olefin prepared by the catalysis of the catalyst of about 60-80 percent, but the conversion rate of carbon dioxide is low (<15 percent) and simultaneously generates a large amount of carbon monoxide by-products, and the selectivity to CO is over 60 percent; chinese patent CN110327969A discloses a nitrogen-doped metal oxide and molecular sieve composite catalyst used in the preparation of olefin by carbon dioxide hydrogenation, but the carbon dioxide conversion rate is only 9-13%, and the yield of low-carbon olefin is less than 7.2%.
Disclosure of Invention
In view of the above, the present invention provides a metal oxide-molecular sieve catalyst for CO, and a preparation method and applications thereof2The low-carbon olefin can be prepared by hydrogenation, and the CO can be obviously improved2The conversion rate, the selectivity and the yield of the low-carbon olefin, and the generation of a byproduct CO can be effectively reduced.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a metal oxide-molecular sieve catalyst, which comprises a composite metal oxide and an acidic molecular sieve; the composite metal oxide has a chemical composition represented by formula I:
M1aM2bOcformula I;
in the formula I, M1Is a group IIIA metal, M2Is a metal in VIB group, a, b and c are atomic ratio, and the total valence of the composite metal oxide is zero.
Preferably, the group IIIA metal comprises Al, Ga or In; the group VIB metal comprises Cr, Mo or W;
the molar ratio of a to b is (0.1-5): (0.01-1).
Preferably, the acidic molecular sieve comprises H-SAPO-34, H-RUB-13, or H-SSZ-13.
Preferably, the mass ratio of the composite metal oxide to the acidic molecular sieve is 1: 4-4: 1.
Preferably, the particle size of the metal oxide-molecular sieve catalyst is 10-60 meshes.
The invention provides a preparation method of the metal oxide-molecular sieve catalyst in the technical scheme, which comprises the following steps:
mixing water-soluble IIIA group metal salt, water-soluble VIB group metal salt and water to obtain mixed metal ion solution;
mixing the mixed metal ion solution with an auxiliary agent, and carrying out a composite reaction to obtain a precursor; the auxiliary agent comprises a complexing agent or a precipitating agent;
roasting the precursor to obtain a composite metal oxide;
and mixing the composite metal oxide and the acidic molecular sieve to obtain the metal oxide-molecular sieve catalyst.
Preferably, the complexing agent comprises one or more of glucose, citric acid, tartaric acid, salicylic acid and adipic acid;
the precipitant comprises one or more of water-soluble carbonate and water-soluble bicarbonate;
the molar ratio of the total metal ions in the mixed metal ion solution to the auxiliary agent is 1: (0.5 to 6).
Preferably, the temperature of the composite reaction is 60-95 ℃ and the time is 2-10 h.
Preferably, the roasting temperature is 350-750 ℃, and the roasting time is 3-12 h.
The invention provides an application of the metal oxide-molecular sieve catalyst or the metal oxide-molecular sieve catalyst prepared by the preparation method in the technical scheme in preparation of low-carbon olefin by carbon dioxide hydrogenation.
The invention provides a metal oxide-molecular sieve catalyst, which comprises a composite metal oxide and an acidic molecular sieve; the composite metal oxide has a chemical composition represented by formula I: m1aM2bOcFormula I;in the formula I, M1Is a group IIIA metal, M2Is a metal in VIB group, a, b and c are atomic ratio, and the total valence of the composite metal oxide is zero. In the invention, the acidic molecular sieve has the characteristics of low strong acid content, low acid strength and high specific surface area, can selectively generate low-carbon olefin, can reduce the secondary hydrogenation rate of the low-carbon olefin, and reduces the generation of byproduct alkane; the IIIA group metal element in the composite metal oxide can promote H2Active hydrogen is formed by adsorption and dissociation, and the doping of VIB group metal elements promotes the formation of surface oxygen holes, which is beneficial to CO2The absorption and activation of the methanol are carried out, the formate/methoxy intermediate is hydrogenated to form methanol, the methanol is quickly diffused to the molecular sieve acid site to form low-carbon olefin, and further CO is improved2Conversion rate; meanwhile, the generation of carboxylate intermediates can be inhibited, the reaction rate of reverse water gas is reduced, and the generation of by-products CO is reduced. The invention adopts composite metal oxide as active component, and uses acid molecular sieve for CO2The low-carbon olefin can be prepared by hydrogenation, and the CO can be obviously improved2Conversion rate, selectivity and yield of low-carbon olefin, and can effectively reduce the generation of byproducts CO and alkane. As shown by the results of the examples of the present invention, the metal oxide-molecular sieve catalyst provided by the present invention is used for CO2The low-carbon olefin is prepared by hydrogenation, the conversion rate of carbon dioxide is up to 33.6%, the selectivity of the low-carbon olefin is up to 88.4%, and the yield of the low-carbon olefin is up to 11.4%. The catalyst provided by the invention has high CO2Conversion rate, high low-carbon olefin selectivity and low CO selectivity.
The preparation method of the metal oxide-molecular sieve catalyst provided by the invention is simple to operate, low in cost, free of secondary pollution and suitable for industrial production.
Drawings
FIG. 1 is an XRD spectrum of a composite metal oxide prepared in example 1;
fig. 2 is a schematic diagram of performance results of the metal oxide-molecular sieve catalyst in the reaction of preparing low-carbon olefin by carbon dioxide hydrogenation in application example 9.
Detailed Description
The invention provides a metal oxide-molecular sieve catalyst, which comprises a composite metal oxide and an acidic molecular sieve; the composite metal oxide has a chemical composition represented by formula I:
M1aM2bOcformula I;
in the formula I, M1Is a group IIIA metal, M2Is a metal in VIB group, a, b and c are atomic ratio, and the total valence of the composite metal oxide is zero.
In the invention, the mole ratio of the IIIA group metal to the VIB group metal in the composite metal oxide is preferably (0.1-5): (0.01-1), more preferably (0.1-2.5): (0.1 to 0.8), most preferably (0.5 to 2): (0.2-0.5). In the present invention, the group IIIA metal (M)1) Preferably, Al, Ga or In, more preferably In; the group VIB metal (M)2) Preferably, Cr, Mo or W is included, more preferably Cr. In the present invention, the chemical composition of the composite metal oxide is preferably InaCrbOcWherein a is 0.1-5.0, b is 0.01-1.0, the value of c is not specially limited, and the total valence of the composite metal oxide is zero. In the examples of the present invention, the InaCrbOcIn is preferred1.5Cr0.2O2.55、In1.4Cr0.3O2.55、In1.2Cr0.5O2.55Or In0.85Cr0.85O2.55. In the present invention, the composite metal in the composite metal oxide forms a solid solution structure.
In the present invention, the acidic molecular sieve preferably comprises H-SAPO-34, H-RUB-13 or H-SSZ-13. The acidic molecular sieve utilized by the invention has a super-cage structure and is connected through an eight-membered ring orifice, and the generation and diffusion of long-chain hydrocarbons can be effectively limited, so that the selectivity of low-carbon olefins is improved.
In the invention, the mass ratio of the composite metal oxide to the acidic molecular sieve is preferably 1: 4-4: 1, more preferably 1: 3-3: 1, and most preferably 1: 2-2: 1.
In the invention, the particle size of the metal oxide-molecular sieve catalyst is preferably 10-60 meshes, more preferably 20-50 meshes, and most preferably 30-40 meshes.
The invention adopts composite metal oxide as active component, and uses acid molecular sieve for CO2The low-carbon olefin can be prepared by hydrogenation, and the CO can be obviously improved2The conversion rate and the yield of the low-carbon olefin are improved, and the generation of byproducts CO and alkane can be effectively reduced.
The invention provides a preparation method of the metal oxide-molecular sieve catalyst in the technical scheme, which comprises the following steps:
mixing water-soluble IIIA group metal salt, water-soluble VIB group metal salt and water to obtain mixed metal ion solution;
mixing the mixed metal ion solution with an auxiliary agent, and carrying out a composite reaction to obtain a precursor; the auxiliary agent comprises a complexing agent or a precipitating agent;
roasting the precursor to obtain a composite metal oxide;
and mixing the composite metal oxide and the acidic molecular sieve to obtain the metal oxide-molecular sieve catalyst.
According to the invention, water-soluble IIIA group metal salt, water-soluble VIB group metal salt and water are mixed to obtain mixed metal ion solution. In the present invention, the water-soluble group IIIA metal salt preferably includes a water-soluble aluminum salt, a water-soluble gallium salt, or a water-soluble indium salt, and the water-soluble aluminum salt preferably includes aluminum nitrate, aluminum chloride, or aluminum sulfate; the water-soluble gallium salt preferably comprises gallium nitrate or gallium chloride; the water-soluble indium salt preferably comprises indium nitrate or indium chloride. In the present invention, the water-soluble group VIB metal salt preferably comprises a water-soluble chromium salt, a water-soluble molybdenum salt or a water-soluble tungsten salt, and the water-soluble aluminum salt preferably comprises chromium nitrate, chromium chloride or chromium sulfate; the water-soluble molybdenum salt preferably comprises molybdenum nitrate or molybdenum chloride; the water-soluble tungsten salt preferably comprises tungsten nitrate. In the present invention, when the chemical composition of the composite metal oxide is InaCrbOcIn the case of the above, the water-soluble group IIIA metal salt is more preferably indium nitrate, and the water-soluble group VIB metal salt is more preferably chromium nitrate.
In the invention, the water-soluble group IIIA metal salt and the water-soluble group VIB metal salt are respectively used in amounts of group IIIA metal ions and group VIB metal ions, and the molar ratio of the water-soluble group IIIA metal salt to the water-soluble group VIB metal salt is preferably (0.1-5): (0.01-1), more preferably (0.1-2.5): (0.1 to 0.8), most preferably (0.5 to 2): (0.2-0.5). In the present invention, the water is preferably deionized water. In the invention, the concentration of the IIIA group metal ions in the mixed metal ion solution is preferably 0.1-5.0 mol/L, more preferably 1-4 mol/L, and most preferably 2-3 mol/L; the concentration of the VIB group metal ions is preferably 0.01-1.0 mol/L, more preferably 0.1-0.8 mol/L, and most preferably 0.2-0.5 mol/L.
In the present invention, the mixing method is preferably stirring mixing, and the speed and time of stirring mixing are not particularly limited in the present invention, and the raw materials may be uniformly mixed.
After obtaining the mixed metal ion solution, mixing the mixed metal ion solution with an auxiliary agent, and carrying out a composite reaction to obtain a precursor; the auxiliary agent comprises a complexing agent or a precipitating agent.
In the invention, the complexing agent preferably comprises one or more of glucose, citric acid, tartaric acid, salicylic acid and adipic acid; when the complexing agent is a mixed complexing agent of two or more, the mass ratio of different complexing agents is not particularly limited in the invention, and any ratio can be adopted.
In the present invention, the precipitant preferably includes one or more of water-soluble carbonate and water-soluble bicarbonate; the water-soluble carbonate preferably comprises one or more of sodium carbonate, ammonium carbonate and potassium carbonate; the water-soluble bicarbonate preferably comprises one or more of ammonium bicarbonate, sodium bicarbonate and potassium bicarbonate. When two or more mixed precipitants are used as the precipitant, the mass ratio of the different precipitants is not particularly limited in the present invention, and any ratio may be used. In the invention, the precipitant is preferably used in the form of a precipitant aqueous solution, and the concentration of the precipitant aqueous solution is preferably 0.5-5.0 mol/L, more preferably 1-4 mol/L, and most preferably 2-3 mol/L.
In the present invention, the molar ratio of the total metal ions in the mixed metal ion solution to the auxiliary agent is preferably 1: (0.5 to 6), more preferably 1: (1-5), most preferably 1: (2-4).
In the present invention, the mixing method is preferably stirring mixing, and the speed and time of stirring mixing are not particularly limited in the present invention, and the raw materials may be uniformly mixed.
In the present invention, when the assistant is a precipitant, the mixed metal ion solution and the assistant (precipitant aqueous solution) are preferably mixed by dropping the mixed metal ion solution and the precipitant aqueous solution together into a reaction vessel containing water, and adjusting the pH to 7. The dropping speed is not specially limited, and the dropping can be carried out at a constant speed. The volume of water contained in the reaction container is not specially limited, and metal ions can be fully contacted with the precipitator; in the embodiment of the present invention, the volume ratio of the mixed metal ion solution to the water contained in the reaction vessel is preferably 1.5: 1. In the present invention, the adjustment of the pH is preferably achieved by controlling the addition amount of the precipitant.
In the invention, the temperature of the composite reaction is preferably 60-95 ℃, more preferably 65-90 ℃, and most preferably 70-80 ℃; the time of the composite reaction is preferably 3-12 h, more preferably 5-10 h, and most preferably 6-8 h. In the invention, when the auxiliary agent is a complexing agent, the composite metal ions are combined with the hydroxyl groups of the complexing agent in the composite reaction process and are tightly distributed around the complexing agent to form a composite coordination complex. In the invention, when the auxiliary agent is a precipitator, the composite metal ions and the precipitator interact to form composite metal carbonate precipitates in the composite reaction process.
In the invention, when the auxiliary agent is a complexing agent, after the complex reaction, the invention preferably further comprises aging and drying a system of the complex reaction to obtain a precursor. In the invention, the aging temperature is preferably 60-95 ℃, more preferably 65-90 ℃, and most preferably 70-80 ℃; the aging time is preferably 2-5 h, more preferably 2.5-4.5 h, and most preferably 3-4 h; the aging process ensures that the mixed metal ions fully form a coordination complex. In the invention, the drying temperature is preferably 80-120 ℃, more preferably 90-110 ℃, and most preferably 100 ℃; the aging time is preferably 4-12 h, more preferably 5-10 h, and most preferably 6-8 h.
In the invention, when the auxiliary agent is a precipitating agent, after the composite reaction, the invention preferably further comprises aging, solid-liquid separation, water washing and drying of the system of the composite reaction to obtain a precursor. In the invention, the aging temperature is preferably 60-95 ℃, more preferably 65-90 ℃, and most preferably 70-80 ℃; the aging time is preferably 2-5 h, more preferably 2.5-4.5 h, and most preferably 3-4 h; the aging process ensures that the mixed metal ions completely form a composite metal precipitate. The solid-liquid separation mode is not particularly limited, and a solid-liquid separation mode known to those skilled in the art can be adopted, specifically centrifugal separation; the conditions for the centrifugal separation are not particularly limited in the present invention, and the solid component and the liquid component can be separated. The washing frequency of the water is not particularly limited, and the unreacted precipitator and the water-soluble impurities can be removed completely. In the invention, the drying temperature is preferably 80-120 ℃, more preferably 90-110 ℃, and most preferably 100 ℃; the aging time is preferably 4-12 h, more preferably 5-10 h, and most preferably 6-8 h.
After the precursor is obtained, the precursor is roasted to obtain the composite metal oxide.
In the invention, the roasting temperature is preferably 350-750 ℃, more preferably 400-700 ℃, and most preferably 500-600 ℃; the roasting time is preferably 3-12 h, more preferably 5-10 h, and most preferably 6-8 h; the atmosphere for the calcination is preferably air. The temperature rise rate for raising the temperature to the calcination temperature in the present invention is not particularly limited, and a temperature rise rate well known to those skilled in the art may be used. In the present invention, in the calcination process, the complex or the composite metal precipitate undergoes a decomposition reaction to produce a composite metal oxide.
After the calcination, the present invention preferably cools the calcined product to room temperature to obtain a composite metal oxide. The cooling method of the present invention is not particularly limited, and a cooling method known to those skilled in the art may be used, specifically, natural cooling.
After the composite metal oxide is obtained, the composite metal oxide and the acidic molecular sieve are mixed to obtain the metal oxide-molecular sieve catalyst. In the invention, the mass ratio of the composite metal oxide to the acidic molecular sieve is preferably 1: 4-4: 1, more preferably 1: 3-3: 1, and most preferably 1: 2-2: 1.
In the present invention, the mixing is preferably mechanical mixing, more preferably milling mixing. The grinding and mixing of the present invention is not particularly limited, and a grinding method known to those skilled in the art may be used. The invention adopts a grinding and mixing mode, can ensure that the composite metal oxide is tightly contacted with the molecular sieve, and is beneficial to the rapid transfer and diffusion of intermediate substances in the reaction process.
After the mixing, the invention preferably further comprises the step of sequentially tabletting, crushing and screening the composite catalyst obtained by mixing to obtain the metal oxide-molecular sieve catalyst. The present invention is not particularly limited with respect to the specific procedures of tabletting, crushing and sieving, and the procedures of tabletting, crushing and sieving known to those skilled in the art may be employed. In the present invention, the pressure of the compressed tablet is preferably 8 to 25MPa, and more preferably 10 to 20 MPa. In the invention, the particle size of the metal oxide-molecular sieve catalyst is preferably 10-60 meshes, more preferably 20-50 meshes, and most preferably 30-40 meshes.
The preparation method provided by the invention is simple to operate, low in cost, green and environment-friendly by taking water as a solvent, free of secondary pollution and suitable for industrial production.
The invention also provides the application of the metal oxide-molecular sieve catalyst or the metal oxide-molecular sieve catalyst prepared by the preparation method in the technical scheme in preparing low-carbon olefin by carbon dioxide hydrogenation.
In the present invention, the metal oxide-molecular sieve catalyst is preferably subjected to a reduction treatment before application; the reduction treatment is preferably carried out in H2Is carried out in the atmosphere; the temperature of the reduction treatment is preferably 350-450 ℃, more preferably 400 ℃, and the time is preferably 1-4 hours, more preferably 2-3 hours. In the present invention, the reduction treatment is carried out by passing through H2The reduction treatment can promote the generation of more surface oxygen cavities of the metal oxide-molecular sieve catalyst, and is beneficial to CO2The adsorption of (1) is activated.
In the invention, the application of the metal oxide-molecular sieve catalyst in the preparation of low-carbon olefin by carbon dioxide hydrogenation comprises the following steps:
catalysis of H with metal oxide-molecular sieve catalysts2-CO2And (3) carrying out hydrogenation reaction on the mixed gas to obtain the low-carbon olefin. In the present invention, the hydrogenation reaction is preferably carried out in a reaction tube, and specifically, a metal oxide-molecular sieve catalyst is filled in the reaction tube, and then H is introduced into the reaction tube2-CO2And (4) mixing the gases. In the present invention, said H2-CO2H in the mixed gas2And CO2The volume ratio of (1-6): 1, more preferably (2-5): 1, most preferably (3-4): 1; the space velocity of the mixed gas is preferably 800-10000 mL/(h.g), more preferably 1000-9000 mL/(h.g), and most preferably 3000-5000 mL/(h.g); the temperature of the hydrogenation reaction is preferably 260-400 ℃, more preferably 300-380 ℃, and most preferably 320-360 ℃; the time of the hydrogenation reaction is preferably 10-500 h, and more preferably 20-250 h; the pressure of the hydrogenation reaction is preferably 0.1-5 MPa, more preferably 1-4 MPa, and most preferably 2-3 MPa.
In the invention, the number of carbon atoms of the low-carbon olefin is preferably 2 to 4.
The yield of low-carbon olefin of the composite catalyst provided by the invention is CO2Conversion x (1-CO selectivity) x low carbon olefin selectivity. The catalyst provided by the invention has high CO2Conversion rate, high low carbon olefin selectivity and lower CO selectivity.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
47.8245g of indium nitrate and 8.0020g of chromium nitrate are dissolved In 1500mL of deionized water, 101.0667g of glucose is added and mixed uniformly, the mixture is subjected to complex reaction for 8 hours at 80 ℃ under the stirring condition, then the mixture is placed In a 100 ℃ oven to be dried for 12 hours, then the mixture is roasted for 3 hours In a muffle furnace at 500 ℃ under the air atmosphere, and the mixture is naturally cooled to obtain the composite metal oxide In1.5Cr0.2O2.55。
In with the mass ratio of 1:21.5Cr0.2O2.55And H-SAPO-34 molecular sieve (Si/Al is 0.025), uniformly grinding, tabletting under 10.0MPa, crushing and sieving to obtain the metal oxide-molecular sieve catalyst with the particle size of 20-40 meshes.
In prepared In this example1.5Cr0.2O2.55The XRD spectrum of the compound is shown In FIG. 1, and In is known from FIG. 11.5Cr0.2O2.55An indium-chromium solid solution structure is formed without separate indium oxide or chromium oxide phase separation.
Example 2
44.6362g of indium nitrate and 12.0030g of chromium nitrate are dissolved In 1500mL of deionized water, 101.0667g of glucose is added and mixed uniformly, the mixture is subjected to complex reaction for 8 hours at 80 ℃ under the stirring condition, then the mixture is placed In a 100 ℃ oven to be dried for 12 hours, then the mixture is roasted for 3 hours In a muffle furnace at 500 ℃ under the air atmosphere, and the mixture is naturally cooled to obtain the composite metal oxide In1.4Cr0.3O2.55。
In with the mass ratio of 1:21.4Cr0.3O2.55And H-SAPO-34 molecular sieve (Si/Al is 0.025), uniformly grinding, tabletting under 10.0MPa, crushing and sieving to obtain the metal oxide-molecular sieve catalyst with the particle size of 20-40 meshes.
Example 3
38.2569g of indium nitrate and 20.0050g of chromium nitrate are dissolved In 1500mL of deionized water, 101.0667g of glucose is added and mixed uniformly, the mixture is subjected to complex reaction for 8 hours at 80 ℃ under the stirring condition, then the mixture is placed In a 100 ℃ oven to be dried for 12 hours, then the mixture is roasted for 3 hours In a muffle furnace at 500 ℃ under the air atmosphere, and the mixture is naturally cooled to obtain the composite metal oxide In1.2Cr0.5O2.55。
In with the mass ratio of 1:21.2Cr0.5O2.55And H-SAPO-34 molecular sieve (Si/Al is 0.025), uniformly grinding, tabletting under 10.0MPa, crushing and sieving to obtain the metal oxide-molecular sieve catalyst with the particle size of 20-40 meshes.
Example 4
27.1005g of indium nitrate and 34.0080g of chromium nitrate are dissolved In 1500mL of deionized water, 101.0667g of glucose is added and mixed uniformly, the mixture is subjected to complex reaction for 8 hours at 80 ℃ under the stirring condition, then the mixture is placed In a 100 ℃ oven to be dried for 12 hours, then the mixture is roasted for 3 hours In a muffle furnace at 500 ℃ under the air atmosphere, and the mixture is naturally cooled to obtain the composite metal oxide In0.85Cr0.85O2.55。
In with the mass ratio of 1:20.85Cr0.85O2.55And H-SAPO-34 molecular sieve (Si/Al is 0.025), uniformly grinding, tabletting under 10.0MPa, crushing and sieving to obtain the metal oxide-molecular sieve catalyst with the particle size of 20-40 meshes.
Example 5
47.8245g of indium nitrate and 8.002g of chromium nitrate are dissolved in 1500mL of deionized water to obtain a mixed metal ion solution; 100.1513g of ammonium carbonate is dissolved in 200mL of deionized water to obtain an ammonium carbonate aqueous solution; dropwise adding the mixed metal ion solution and ammonium carbonate aqueous solution into a container containing 1000mL of deionized water, adjusting the pH value to 7, carrying out coprecipitation reaction for 3h at 80 ℃ under the stirring condition, washing and centrifuging, drying the obtained solid product In a 100 ℃ drying oven for 12h, then roasting for 3h In a muffle furnace at 500 ℃ under the air atmosphere, and naturally cooling to obtain the composite metal oxide In1.5Cr0.2O2.55。
In with the mass ratio of 1:21.5Cr0.2O2.55And H-SAPO-34 molecular sieve (Si/Al is 0.025), uniformly grinding, tabletting under 10.0MPa, crushing and sieving to obtain the metal oxide-molecular sieve catalyst with the particle size of 20-40 meshes.
Example 6
47.8245g of indium nitrate and 8.0020g of chromium nitrate are dissolved In 1500mL of deionized water, 101.0667g of glucose is added and mixed uniformly, the mixture is subjected to complex reaction for 8 hours at 80 ℃ under the stirring condition, then the mixture is placed In a 100 ℃ oven to be dried for 12 hours, then the mixture is roasted for 3 hours In a muffle furnace at 500 ℃ under the air atmosphere, and the mixture is naturally cooled to obtain the composite metal oxide In1.5Cr0.2O2.55。
In with the mass ratio of 1:21.5Cr0.2O2.55And H-RUB-13 molecular sieve (Si/Al is 200) are uniformly ground, and the mixture is tableted, crushed and sieved under 10.0MPa to obtain the metal oxide-molecular sieve catalyst with the granularity of 20-40 meshes.
Example 7
47.8245g of indium nitrate and 8.0020g of chromium nitrate are dissolved In 1500mL of deionized water, 101.0667g of glucose is added and mixed uniformly, the mixture is subjected to complex reaction for 8 hours at 80 ℃ under the stirring condition, then the mixture is placed In a 100 ℃ oven to be dried for 12 hours, then the mixture is roasted for 3 hours In a muffle furnace at 500 ℃ under the air atmosphere, and the mixture is naturally cooled to obtain the composite metal oxide In1.5Cr0.2O2.55。
In with the mass ratio of 1:21.5Cr0.2O2.55And H-SSZ-13 molecular sieve (Si/Al is 25) are uniformly ground, and the mixture is tableted, crushed and sieved under 10.0MPa to obtain the metal oxide-molecular sieve catalyst with the granularity of 20-40 meshes.
Comparative example 1
47.8245g of indium nitrate is dissolved In 1500mL of deionized water, 89.1765g of glucose is added and uniformly mixed, the complex reaction is carried out for 8h under the conditions of 80 ℃ and stirring, then the mixture is placed In a 100 ℃ oven for drying for 12h, then the mixture is roasted for 3h In a muffle furnace at 500 ℃ under the air atmosphere, and the natural cooling is carried out to obtain the composite metal oxide In2O3。
In with the mass ratio of 1:22O3And H-SAPO-34 componentAnd uniformly grinding the sub-sieve (Si/Al is 0.025), tabletting under 10.0MPa, crushing and sieving to obtain the metal oxide-molecular sieve catalyst with the granularity of 20-40 meshes.
Comparative example 2
47.8245g of indium nitrate and 8.6844g of cerium nitrate are dissolved In 1500mL of deionized water, 101.0667g of glucose is added and mixed uniformly, the mixture is subjected to complex reaction for 8 hours at 80 ℃ under the stirring condition, then the mixture is placed In a 100 ℃ oven to be dried for 12 hours, then the mixture is roasted for 3 hours at 500 ℃ In a muffle furnace under the air atmosphere, and the mixture is naturally cooled to obtain the composite metal oxide In1.5Ce0.2O2.55。
In with the mass ratio of 1:21.5Ce0.2O2.55And H-SAPO-34 molecular sieve (Si/Al is 0.025), uniformly grinding, tabletting under 10.0MPa, crushing and sieving to obtain the metal oxide-molecular sieve catalyst with the particle size of 20-40 meshes.
Comparative example 3
47.8245g of indium nitrate and 5.9498g of zinc nitrate are dissolved In 1500mL of deionized water, 101.0667g of glucose is added and mixed uniformly, the mixture is subjected to complex reaction for 8 hours at 80 ℃ under the stirring condition, then the mixture is placed In a 100 ℃ oven to be dried for 12 hours, then the mixture is roasted for 3 hours at 500 ℃ In a muffle furnace under the air atmosphere, and the mixture is naturally cooled to obtain the composite metal oxide In1.5Zn0.2O2.45。
In with the mass ratio of 1:21.5Zn0.2O2.45And H-SAPO-34 molecular sieve (Si/Al is 0.025), uniformly grinding, tabletting under 10.0MPa, crushing and sieving to obtain the metal oxide-molecular sieve catalyst with the particle size of 20-40 meshes.
Comparative example 4
47.8245g of indium nitrate and 8.5864g of zirconium nitrate are dissolved In 1500mL of deionized water, 101.0667g of glucose is added and mixed uniformly, the mixture is subjected to complex reaction for 8 hours at 80 ℃ under the condition of stirring, then the mixture is placed In a 100 ℃ oven to be dried for 12 hours, then the mixture is roasted for 3 hours In a muffle furnace at 500 ℃ under the air atmosphere, and the composite metal oxide In is obtained after natural cooling1.5Zr0.2O2.65。
In with the mass ratio of 1:21.5Zr0.2O2.65And H-SAPO-34 molecular sieve (Si/Al is 0.025), uniformly grinding, tabletting under 10.0MPa, crushing and sieving to obtain the metal oxide-molecular sieve catalyst with the particle size of 20-40 meshes.
Comparative example 5
8.9247g of zinc nitrate and 85.8640g of zirconium nitrate are dissolved in 1500mL of deionized water, 136.7373g of glucose is added and mixed uniformly, the mixture is subjected to complex reaction for 8 hours at 80 ℃ under the stirring condition, then the mixture is placed in a 100 ℃ oven to be dried for 12 hours, then the mixture is roasted for 3 hours at 500 ℃ in a muffle furnace under the air atmosphere, and the mixture is naturally cooled to obtain the composite metal oxide Zn0.3Zr2.0O4.3。
Zn with the mass ratio of 1:20.3Zr2.0O4.3And H-SAPO-34 molecular sieve (Si/Al is 0.025), uniformly grinding, tabletting under 10.0MPa, crushing and sieving to obtain the metal oxide-molecular sieve catalyst with the particle size of 20-40 meshes.
Application examples 1 to 9
The composite catalyst prepared in the embodiment 1 to 7 is added in H2Reducing at 400 ℃ for 2h in atmosphere, and then applying to catalyzing CO2And (3) carrying out a reaction for preparing low-carbon olefins by hydrogenation, wherein the reaction conditions of application examples 1-9 are shown in Table 1.
Comparative examples 6 to 12
The composite catalyst prepared in comparative examples 1-5 is added in H2Reducing at 400 ℃ for 2h in atmosphere, and then applying to catalyzing CO2And (3) carrying out a reaction for preparing the low-carbon olefin by hydrogenation, wherein the reaction conditions of comparative examples 6-12 are shown in Table 1.
TABLE 1 reaction conditions of application examples 1 to 9 and application examples 6 to 12
Figure BDA0002628933160000131
The catalytic results of the composite catalysts of application examples 1 to 9 and comparative examples 6 to 12 are shown in table 2, and the catalytic effect of application example 9 is shown in fig. 2:
TABLE 2 catalytic Properties of application examples 1 to 9 and comparative examples 6 to 12
Figure BDA0002628933160000132
Figure BDA0002628933160000141
In Table 2 and FIG. 2, C2 ＝Represents ethylene, C3 ＝Represents propylene, C4 ＝Represents butene, C2 ＝-C4 ＝C represents C2-4 olefins (i.e., ethylene, propylene and butylene)2 0-C4 0C represents C2-4 alkane (i.e. ethane, propane and butane)5 +The carbon number of the alkane and the olefin is 5 or more, and DME is dimethyl ether.
As is clear from Table 2 and FIG. 2, the composite metal oxide In of the present inventionaCrbOcThe composite catalyst composed of the carbon dioxide and the acidic molecular sieve has excellent catalytic performance of preparing the low-carbon olefin by hydrogenating the carbon dioxide, wherein the low-carbon olefin (C)2 ＝-C4 ＝Olefin) selectivity of 75-88.4%, CO2The conversion rate is 16.3-33.6%, the selectivity of the low-carbon olefin is 65.0-71.6%, and the maximum yield of the low-carbon olefin reaches 11.4%, which is higher than that of the comparative examples 6-12 by 3.9-5.7%. CO, the composite catalyst prepared in comparative examples 6 to 122The conversion rate is only 8.7-13.3%.
Wherein the yield of the low-carbon olefin is CO2Conversion x (1-CO selectivity) x low carbon olefin selectivity. The catalyst provided by the invention has high CO2Conversion rate, high low carbon olefin selectivity and lower CO selectivity.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (7)

1. A metal oxide-molecular sieve catalyst, comprising a composite metal oxide and an acidic molecular sieve; the composite metal oxide has a chemical composition represented by formula I:
InaCrbOcformula I;
in the formula I, a, b and c are atomic ratios, and the total valence of the composite metal oxide is zero; the molar ratio of a to b is (0.5-2): (0.2 to 1);
the mass ratio of the composite metal oxide to the acidic molecular sieve is 1: 4-4: 1;
the acidic molecular sieve comprises H-RUB-13;
the preparation method of the metal oxide-molecular sieve catalyst comprises the following steps:
mixing water-soluble indium salt, water-soluble chromium salt and water to obtain mixed metal ion solution;
mixing the mixed metal ion solution with an auxiliary agent, and carrying out a composite reaction to obtain a precursor; the auxiliary agent comprises a complexing agent or a precipitating agent;
roasting the precursor to obtain a composite metal oxide;
and mixing the composite metal oxide and the acidic molecular sieve to obtain the metal oxide-molecular sieve catalyst.
2. The metal oxide-molecular sieve catalyst of claim 1, wherein the metal oxide-molecular sieve catalyst has a particle size of 10 to 60 mesh.
3. The method of any of claims 1-2, comprising the steps of:
mixing water-soluble indium salt, water-soluble chromium salt and water to obtain mixed metal ion solution;
mixing the mixed metal ion solution with an auxiliary agent, and carrying out a composite reaction to obtain a precursor; the auxiliary agent comprises a complexing agent or a precipitating agent;
roasting the precursor to obtain a composite metal oxide;
and mixing the composite metal oxide and the acidic molecular sieve to obtain the metal oxide-molecular sieve catalyst.
4. The preparation method of claim 3, wherein the complexing agent comprises one or more of glucose, citric acid, tartaric acid, salicylic acid and adipic acid;
the precipitant comprises one or more of water-soluble carbonate and water-soluble bicarbonate;
the molar ratio of the total metal ions in the mixed metal ion solution to the auxiliary agent is 1: (0.5 to 6).
5. The preparation method according to claim 3, wherein the temperature of the composite reaction is 60-95 ℃ and the time is 2-10 h.
6. The preparation method according to claim 3, wherein the roasting temperature is 350-750 ℃ and the roasting time is 3-12 h.
7. Use of the metal oxide-molecular sieve catalyst according to any one of claims 1 to 2 or the metal oxide-molecular sieve catalyst prepared by the preparation method according to any one of claims 3 to 6 in the preparation of lower olefins by hydrogenation of carbon dioxide.
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Publication number Priority date Publication date Assignee Title
CN112479223A (en) * 2020-11-26 2021-03-12 厦门大学 Low-silicon nano sheet SAPO-34 molecular sieve and preparation method and application thereof
CN112588315B (en) * 2020-12-21 2022-03-04 中国科学院山西煤炭化学研究所 Chromium-based metal oxide-molecular sieve catalyst and preparation method and application thereof
CN113134386B (en) * 2021-04-25 2022-02-11 中国科学院山西煤炭化学研究所 Gallium-zirconium composite oxide-molecular sieve catalyst, and preparation method and application thereof
CN113600199B (en) * 2021-09-07 2023-07-14 中国华能集团清洁能源技术研究院有限公司 Metal copper catalyst and preparation method and application thereof
CN113996337B (en) * 2021-12-06 2023-08-22 陕西延长石油（集团）有限责任公司 Catalyst for preparing acetic acid from high-hydrocarbon-ratio synthesis gas and preparation method and application thereof
CN115430438B (en) * 2022-05-31 2023-12-29 南京工业大学 Preparation method of HZSM-5 supported solid super acid catalyst
CN114939435A (en) * 2022-06-30 2022-08-26 山东能源集团有限公司 Integral type bifunctional catalyst and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103182308A (en) * 2011-12-29 2013-07-03 中国石油化工股份有限公司 Perovskite/metal composite oxide catalyst and preparation method thereof
CN108160105A (en) * 2017-12-12 2018-06-15 南开大学 Redox molecule sieve catalyst and its synthetic method are catalyzed for methane selectively
CN111068760A (en) * 2020-01-08 2020-04-28 中国石油大学(北京) Fast controllable preparation method of SSZ-13 zeolite and catalyst for preparing olefin from H-SSZ-13 zeolite and methanol
CN111111760A (en) * 2018-10-30 2020-05-08 中国石油化工股份有限公司 Catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2593989C2 (en) * 2010-03-11 2016-08-10 Джонсон Мэттей Паблик Лимитед Компани CARRIERS BASED ON UNORDERED MOLECULAR SIEVES FOR SELECTIVE CATALYTIC REDUCTION OF NOx

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103182308A (en) * 2011-12-29 2013-07-03 中国石油化工股份有限公司 Perovskite/metal composite oxide catalyst and preparation method thereof
CN108160105A (en) * 2017-12-12 2018-06-15 南开大学 Redox molecule sieve catalyst and its synthetic method are catalyzed for methane selectively
CN111111760A (en) * 2018-10-30 2020-05-08 中国石油化工股份有限公司 Catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation and application thereof
CN111068760A (en) * 2020-01-08 2020-04-28 中国石油大学(北京) Fast controllable preparation method of SSZ-13 zeolite and catalyst for preparing olefin from H-SSZ-13 zeolite and methanol

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Direct Production of Lower Olefins from CO2 Conversion via Bifunctional Catalysis;Peng Gao等;《ACS Catalysis》;20171205;第8卷(第1期);全文 *
Methanol to olefins over H-RUB-13 zeolite: regulation of framework aluminum siting and acid density and their relationship to the catalytic performance;Li Zhang等;《Catalysis Science & Technology》;20200128;第10卷(第6期);全文 *
Selective Transformation of CO2 and H2 into Lower Olefins over In2O3-ZnZrOx/SAPO-34 Bifunctional Catalysts;Shanshan Dang等;《ChemSusChem》;20190613;第12卷(第15期);全文 *
金属离子改性SAPO分子筛催化甲醇制烯烃反应的研究;钟家伟;《中国博士学位论文全文数据库 工程科技I辑》;20200115(第1期);正文第15-16页 *

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