CN114425437B - Catalyst containing silicon aluminum phosphate molecular sieve, preparation method thereof and diesel catalytic conversion method - Google Patents

Catalyst containing silicon aluminum phosphate molecular sieve, preparation method thereof and diesel catalytic conversion method Download PDF

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CN114425437B
CN114425437B CN202011106667.1A CN202011106667A CN114425437B CN 114425437 B CN114425437 B CN 114425437B CN 202011106667 A CN202011106667 A CN 202011106667A CN 114425437 B CN114425437 B CN 114425437B
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molecular sieve
catalyst
oxide
content
metal
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CN114425437A (en
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王丽霞
王鹏
宋海涛
韩蕾
赵留周
凤孟龙
林伟
周翔
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
    • 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
    • B01J29/16—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C07C2529/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • C07C2529/14—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C07C2529/16—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
    • 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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Abstract

The invention relates to the field of petrochemical industry, and provides a catalyst containing a silicon aluminum phosphate molecular sieve, a preparation method thereof and a diesel catalytic conversion method, wherein the catalyst comprises natural mineral substances, inorganic oxides, metals and molecular sieves, the content of the natural mineral substances is 10-70wt% based on the total weight of the catalyst, the content of the inorganic oxides is 10-60wt% based on dry basis, the content of the molecular sieves is 10-70wt% based on dry basis, the content of the metals is 0.01-10wt% based on elements, and the molecular sieves comprise the silicon aluminum phosphate molecular sieve and FAU structure molecular sieves; the metal comprises one or more of W, cu, fe, co, mg, mo, zr and Ca, and the diesel catalytic conversion method comprises: diesel, carbon dioxide and catalyst, and optionally diluent gas, are contacted to react. The method can improve the yield of the low-carbon olefin.

Description

Catalyst containing silicon aluminum phosphate molecular sieve, preparation method thereof and diesel catalytic conversion method
Technical Field
The invention relates to the field of petrochemical industry, in particular to a catalyst containing a silicon aluminum phosphate molecular sieve, a preparation method thereof and a diesel catalytic conversion method.
Background
The low-carbon olefin is an indispensable chemical raw material, including ethylene, propylene and butylene. Wherein, ethylene is mainly used for producing polyethylene, ethylene oxide, dichloroethane and the like, and propylene is mainly used for producing polypropylene, acrylonitrile, propylene oxide and the like. In recent years, the demand for low-carbon olefins has increased rapidly, driving the production capacity to increase continuously. Currently, the main modes for producing low-carbon olefins are steam cracking, catalytic cracking, propane dehydrogenation, MTO, catalytic reforming and the like. Wherein, the ratio of the products of the low-carbon olefin produced by adopting a steam cracking mode can not be flexibly adjusted, the reaction temperature is as high as 840-860 ℃, and the energy consumption accounts for about 40% of the energy consumption in petrochemical industry. Therefore, the catalytic cracking of the diesel fraction is very promising because of the advantages of low reaction temperature, flexible and easily-regulated product distribution, small pollution of the product, environmental protection and the like. From the current results, there is still a need for further improvements and enhancements to the diesel conversion process and catalyst performance.
CO 2 As an important greenhouse gas, a series of problems such as desertification of land, climate change, glacier thawing, etc. are caused, and thus, CO is required 2 And (5) emission reduction is carried out. At the same time, however, CO 2 And the low-cost and abundant C1 resource can react with hydrogen to generate CO, methanol, dimethyl ether, low-carbon hydrocarbon and the like, and can also react with methane to generate synthetic gas, ethane to generate ethylene and the like. However, these reactions are generally carried out under high pressure, and the reaction conditions are relatively severe.
The catalyst containing the silicoaluminophosphate molecular sieve can be used for hydrocarbon oil conversion, but the prior art does not disclose how to make the catalyst have better effect of producing low-carbon olefin when the silicoaluminophosphate molecular sieve is used.
Disclosure of Invention
The invention aims to provide a method suitable for CO 2 A catalyst for converting diesel oil in the presence, which contains a silicon aluminum phosphate molecular sieve and can improve the selectivity of low-carbon olefin when used for diesel oil conversion; the invention aims to provide a preparation method of the catalyst; the third technical problem to be solved by the invention is to provide a diesel oil conversion method.
The invention provides a catalyst containing a silicon aluminum phosphate molecular sieve, which comprises natural mineral substances, inorganic oxides, metals and molecular sieves, wherein the content of the natural mineral substances is 10-70wt% based on the total weight of the catalyst, the content of the inorganic oxides is 10-60wt% based on dry basis, the content of the molecular sieves is 10-70wt% based on dry basis, the content of the metals is 0.01-10wt% based on elements, and the molecular sieves comprise the silicon aluminum phosphate molecular sieve and FAU structure molecular sieve; the metal includes one or more of W, cu, fe, co, mg, mo, zr and Ca. wt represents the weight.
The invention provides a method for catalytic conversion of diesel oil, which comprises the following steps: diesel fuel, carbon dioxide and optionally diluent gas are contacted with a catalyst comprising the above-described silicoaluminophosphate molecular sieve-containing catalyst.
The invention adopts the silicon aluminum phosphate molecular sieve, FAU structure molecular sieve and natural mineral, inorganic oxide and metal to match to obtain the catalyst containing the silicon aluminum phosphate molecular sieve, which is used for CO 2 In the catalytic conversion process of diesel oil in the presence, CO can be utilized 2 Improves the selectivity of low-carbon olefin, especially propylene and butene, and can realize CO under mild conditions 2 Is effectively utilized. The catalyst provided by the invention can also be used for catalytic cracking of hydrocarbon oil, and has good low-carbon olefin selectivity.
The diesel catalytic conversion method provided by the invention uses the catalyst containing the silicoaluminophosphate molecular sieve and utilizes CO 2 Is coupled with catalytic cracking or thermal cracking reaction of diesel oil, and can improve propylene and/or butylThe yield of alkene and/or the yield of ethylene and/or the yield of liquefied gas are increased. Surprisingly, coke selectivity can also be reduced.
The diesel catalytic conversion method provided by the invention can fully utilize CO under mild conditions such as lower pressure 2 The resource can reduce the environmental problems caused by greenhouse gases, and has very good economic value and industrial application value.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The catalyst comprises natural mineral substances, inorganic oxides, molecular sieves and metals, wherein the content of the natural mineral substances is 10-70wt% based on the total weight of the catalyst containing the silicon aluminum phosphate molecular sieves, the content of the inorganic oxides is 10-60wt% based on dry basis, the content of the molecular sieves is 10-70wt% based on dry basis, the content of the metals is 0.01-10wt% based on elements, and the molecular sieves comprise the silicon aluminum phosphate molecular sieves and FAU structure molecular sieves.
Preferably, the catalyst containing the silicoaluminophosphate molecular sieve provided by the invention contains 20-60wt% of natural minerals, 10-50wt% of inorganic oxides, 10-55wt% of molecular sieves and 0.1-5wt% of metals in terms of elements based on the total weight of the catalyst containing the silicoaluminophosphate molecular sieve.
More preferably, the catalyst containing the silicoaluminophosphate molecular sieve provided by the invention comprises 25-50wt% of natural minerals, 10-44wt% of inorganic oxides, 30-45wt% of the silicoaluminophosphate molecular sieve and 1-3.5wt% of metals in terms of elements by taking the total weight of the catalyst as a reference.
Such as one or more of a SAPO-11 molecular sieve, a SAPO-31 molecular sieve, a SAPO-34 molecular sieve, and a SAPO-47 molecular sieve; preferably, the silicoaluminophosphate molecular sieve is SAPO-34 and/or SAPO-11, further preferably, the silicoaluminophosphate molecular sieve is SAPO-11. The SAPO-11 molecular sieve is adopted to be matched with other components, so that the yield of the target product is improved.
The FAU structure molecular sieve is preferably a Y-type molecular sieve. The Y-type molecular sieve is one or more of HY molecular sieve, DASY molecular sieve, HSY molecular sieve and SOY.
The weight ratio of FAU structure molecular sieve to silicoaluminophosphate molecular sieve is 0.05 to 1:1, preferably 0.1 to 0.8:1, for example 0.3 to 0.6:1.
In the present invention, the silicoaluminophosphate molecular sieve may be commercially available or may be prepared according to a conventional method in the art, and the present invention is not particularly limited thereto.
In the present invention, the natural minerals may be selected as conventional in the art, and preferably, the natural minerals are selected from one or more of kaolin, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite, and rectorite.
In the present invention, the inorganic oxide may be a conventional choice in the art, preferably, the inorganic oxide is selected from one or more of silicon oxide, aluminum oxide-silicon oxide, zirconium oxide, titanium oxide, boron oxide, amorphous silicon aluminum, aluminum phosphate, tungsten oxide-zirconium oxide, molybdenum oxide-zirconium oxide, molybdenum oxide-titanium oxide, tungsten oxide-titanium oxide, tin oxide, zinc oxide, copper oxide, nickel oxide, cobalt oxide, vanadium oxide, and niobium oxide; for example, the inorganic oxide is selected from one or more of silicon oxide, aluminum oxide-silicon oxide, titanium oxide, boron oxide, amorphous silicon aluminum, aluminum phosphate, tin oxide, zinc oxide, nickel oxide, vanadium oxide, and niobium oxide, and more preferably, the inorganic oxide is selected from one or more of aluminum oxide, silicon oxide, and aluminum oxide-silicon oxide. Preferably, the inorganic oxide comprises one or more of an inorganic oxide binder.
The metal (or modified metal) is one or more of W, cu, co, mg, mo, zr and Ca, preferably one or more of Cu, co and Mg. The metal content of the catalyst is preferably 0.1 to 5% by weight, for example 0.2 to 4% by weight or 0.3 to 3.5% by weight or 0.8 to 3.5% by weight or 1.5 to 3.5% by weight, based on the element.
Preferably, in the catalyst, the weight ratio of the silicoaluminophosphate molecular sieve to the FAU structure molecular sieve is 2.1-3.5:1, and the metal content is 0.8-3.5 wt%, for example 1.5-3.5 wt%.
The method for producing the catalyst is not particularly limited as long as the catalyst having the above composition can be produced.
In one embodiment, the catalyst is prepared by a process comprising slurrying a natural mineral, an inorganic oxide and/or inorganic oxide precursor, a metal compound, a molecular sieve, and water, spray drying, or slurrying a natural mineral, an inorganic oxide and/or inorganic oxide precursor, a molecular sieve, and water, spray drying, and contacting the metal compound; the metal compound is preferably in the molecular sieve, and the molecular sieve comprises a silicon aluminum phosphate molecular sieve and a FAU structure molecular sieve; optionally calcining.
In the present invention, the inorganic oxide precursor may be a substance that can be converted into an inorganic oxide in the subsequent process (e.g., calcination) of the method provided by the present invention, and a person skilled in the art can properly select the inorganic oxide precursor based on the present disclosure. Specifically, the inorganic oxide precursor may be a sol of an inorganic oxide, for example, at least one of a silica sol, an alumina sol, a peptized pseudo-boehmite, a silica-alumina sol, and a phosphorus-containing alumina sol.
The method of the catalyst provided by the present invention is not particularly limited, and the spray drying may be performed according to conventional technical means in the art. Preferably, the spray-drying is performed under such conditions that the average particle diameter of the particles obtained by the spray-drying is 60 to 80 μm and the particle diameter distribution is mainly in the range of 40 to 100. Mu.m, and more preferably, the spray-drying is performed under such conditions that the particles obtained by the spray-drying have a particle diameter of 60 to 80. Mu.m, optionally 50% or more.
In the catalyst preparation method provided by the present invention, preferably, a sodium washing exchange (or referred to as sodium washing) step is further included before or after the calcination, and the sodium washing exchange method is well known to those skilled in the art. In one embodiment, the sodium wash exchange is contacting the spray dried catalyst particles (which may or may not be calcined catalyst particles) with an ammonium salt solution to wash away sodium from the catalyst, which may be ammonium salts commonly used in the art, preferably one or more of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium acetate and ammonium nitrate.
The firing conditions may be firing conditions conventional in the art, preferably, the firing conditions include: the calcination temperature is 400-800 ℃, preferably 400-600 ℃, and the calcination time is 0.5-8 hours, preferably 1-5 hours.
According to the present invention, the calcination may be performed under an air atmosphere, an inert atmosphere or a water vapor atmosphere, preferably the calcination is performed under an air atmosphere. In the present invention, the inert atmosphere may be provided by at least one of nitrogen, argon, helium and neon, preferably nitrogen.
The preparation method of the catalyst containing the silicon aluminum phosphate molecular sieve comprises the following steps of:
(1) Mixing and pulping molecular sieves comprising a silicoaluminophosphate molecular sieve, natural minerals, inorganic oxides and/or inorganic oxide precursors and water, and spray-drying to obtain a solid product a;
(2) The metal is supported on the solid product a and then calcined.
According to the catalyst preparation method provided by the invention, in the first specific embodiment, preferably, the slurry obtained by mixing and pulping in the step (1) has a solid content of 30-40 wt%.
According to the catalyst preparation method provided by the present invention, in the first embodiment, in the step (2), the metal is supported on the solid product a by a method which is conventional in the art, and specifically, one of an impregnation method, an ion exchange method, a chemical deposition method and a plasma method may be used. The present invention is illustrated in the examples section by the impregnation method, and the present invention is not limited thereto.
According to a first embodiment, step (2) may impregnate the solid product a with a solution containing a metal salt, followed by drying and calcination. The drying and firing conditions may be performed according to conventional conditions, and the present invention will not be described herein.
According to the invention, the second embodiment of the preparation method of the catalyst comprises the following steps: forming a slurry comprising molecular sieves, metal compounds, natural minerals, inorganic oxides and/or inorganic oxide precursors, water, spray drying, calcining, optionally sodium or ammonium washing. The washing may be performed with ammonium salts or aqueous ammonia to wash free sodium ions.
According to a preferred embodiment of the present invention, the method for preparing the catalyst comprises the steps of:
(1) Impregnating a molecular sieve with an aqueous solution of a metal salt, drying and roasting to prepare a metal-loaded mixed molecular sieve; the molecular sieve comprises a Y molecular sieve and a silicon aluminum phosphate molecular sieve; the calcination temperature may be 400-800 ℃, preferably 400-600 ℃, and the calcination time may be 0.5-8 hours, preferably 1-5 hours;
(2) Mixing natural mineral substances, inorganic oxide and/or inorganic oxide precursor and the prepared metal-loaded mixed molecular sieve, pulping, spray drying, and preparing into catalyst particles; wherein the mixed beaten slurry has a solids content of 20 to 45wt%, for example 30 to 40 wt%;
(3) Optionally drying and roasting the catalyst particles obtained in the step (2); the calcination temperature may be 400-800 ℃, preferably 400-600 ℃, and the calcination time may be 0.5-8 hours, preferably 1-5 hours, to obtain the calcined catalyst particles;
(4) Contacting the calcined catalyst particles obtained in step (3) with an ammonium salt solution, such as an ammonium sulfate solution, for sodium washing exchange, and then drying; or alternatively
(3') contacting the catalyst particles obtained in step (2) with an ammonium salt solution such as an ammonium sulfate solution for sodium washing exchange, and then drying;
(4 ') calcining the catalyst particles obtained in the step (3'). The firing temperature may be 400 to 800 ℃, preferably 400 to 600 ℃, and the firing time may be 0.5 to 8 hours, preferably 1 to 5 hours.
In the catalytic conversion of diesel oil provided by the invention, diesel oil and carbon dioxide are contacted with a catalyst and optionally diluent gas to react, and preferably, the contact reaction conditions comprise: the reaction temperature is 400-800 ℃, the reaction pressure is 0.1-2MPa, the weight ratio of carbon dioxide to diesel oil is 0.2-3:1, and the mass airspeed of diesel oil is 0.3-10h -1 The method comprises the steps of carrying out a first treatment on the surface of the More preferably, the conditions of the contact reaction include: the temperature is 480-650deg.C, such as 500-650deg.C, the pressure is 0.1-0.3MPa, the weight ratio of carbon dioxide to diesel oil is 0.25-2:1, and the mass space velocity of diesel oil is 0.5-5h -1 。
In the catalytic conversion of the diesel oil provided by the invention, the diesel oil can mainly comprise C10-C22 aliphatic hydrocarbon and naphthene hydrocarbon, and can also comprise a certain amount of aromatic hydrocarbon, and concretely, the diesel oil can comprise one or more of catalytic cracking diesel oil, coking diesel oil, straight-run diesel oil, reforming diesel oil, superposition diesel oil and alkyl diesel oil.
In the method for catalytic conversion of diesel oil provided by the invention, the diluent gas can be N 2 、H 2 O、O 2 Air, N 2 O、NO 2 、NO、H 2 And SO 2 One or more of (a), preferably N 2 。
According to the method for catalytic conversion of diesel oil provided by the invention, preferably, the content of carbon dioxide is 10-100% by volume based on the total volume of carbon dioxide and diluent gas.
The present invention will be described in detail by examples.
In the following examples:
the parameters of the diesel oil used are shown in table 1 below:
TABLE 1
Parameters (parameters) Parameter value
Density (20 ℃), g/cm 3 0.8415
Viscosity at 20 ℃ mm 2 /s 7.665
Paraffin/wt% 47.7
Naphthenes/wt% 31.4
Aromatic hydrocarbon/wt% 20.9
Initial point of distillation, DEG C 235
50% recovery temperature, DEG C 301
End point, DEG C 337
Kaolin (available from china kaolin company, su zhou, with a solids content of 75% by weight);
rectorite (from Hubei's lucky rectorite ore, 75% solids by weight);
montmorillonite (75% solids by weight available from red stone bentonite, koku yang, jean, liaoning);
alumina sol (from ziluta corporation, a catalyst of petrochemical Co., ltd., alumina content of 22.5% by weight);
silica sol (available from Qingdao ocean chemical Co., ltd., silica content 25.5 wt%, pH 3.0);
SAPO-34 molecular sieves were prepared as disclosed in "j.am.chem.soc.,106, 6092-6093 (1984)".
The Y-type molecular sieve is HSY-4, the catalyst of China petrochemical catalyst Co., ltd, the product of Qilu division, the silicon-aluminum ratio (Si/Al molar ratio) is 4, the sodium oxide content is 1.1 weight percent, and the crystallinity is 63 percent.
The content of each component in the following catalyst is calculated by the feeding amount.
Example 1
This example is intended to illustrate the catalyst of the invention, its method of preparation and the method of catalytic conversion of diesel fuel.
And (3) preparing a catalyst:
(1) Impregnating a molecular sieve mixture containing 24.9g of SAPO-34 (the same applies below) and 10.6. 10.6gY molecular sieves (the same applies below) on a dry basis with an aqueous solution containing 10.6g of cobalt nitrate hexahydrate, drying at 110 ℃ for 5 hours, and roasting at 550 ℃ for 2 hours to obtain a metal supported mixed molecular sieve;
(2) Preparing 75.6g of aluminum sol, 60.5g of kaolin and the metal-loaded mixed molecular sieve into slurry with the solid content of 31 weight percent by using decationizing water, uniformly stirring, and performing spray drying on the slurry to prepare a microsphere catalyst (the average particle size is 65 mu m, and 60-80 mu m of particles account for 60 percent);
(3) Drying at 100deg.C for 2h, and roasting at 450deg.C for 4h;
(4) And (3) performing sodium washing exchange on the roasted catalyst obtained in the step (3) and ammonium sulfate, and then drying at 100 ℃ for 2 hours to obtain a catalyst C-1. The results of the content of each component in the catalyst are shown in Table 2. Wherein the sodium washing exchange method comprises the following steps: the concentration of the ammonium sulfate solution is 2 weight percent, the weight ratio of the ammonium sulfate solution to the catalyst is 10:1, the sodium washing exchange temperature is 60 ℃ and the time is 40 minutes; washing twice; the following is the same.
Catalytic conversion of diesel oil:
aging the catalyst at 800deg.C under 100 vol% steam for 15 hr, mixing diesel oil, carbon dioxide and the catalyst at 556 deg.C under 0.16MPa, with weight ratio of carbon dioxide to diesel oil of 0.3:1 and mass space velocity of diesel oil of 1.0 hr -1 And (3) carrying out contact reaction under the condition of (2) to obtain a diesel catalytic conversion product. The yields of the respective products were tested and the results are shown in table 3.
Example 2
This example is intended to illustrate the catalyst of the invention, its method of preparation and the method of catalytic conversion of diesel fuel.
And (3) preparing a catalyst:
(1) Impregnating 35.0g of SAPO-34 and 11.7. 11.7gY molecular sieves with an aqueous solution containing 4.4g of cobalt nitrate hexahydrate, drying at 110 ℃ for 5 hours, and roasting at 550 ℃ for 2 hours to obtain a metal loaded mixed molecular sieve;
(2) Preparing slurry with solid content of 31 wt% from 97.8g aluminum sol, 40.7g kaolin and the metal-loaded mixed molecular sieve by using decationizing water, uniformly stirring, and performing spray drying on the slurry to prepare a microsphere catalyst (the average particle size is 65 mu m, and 60-80 mu m of particles account for 60%);
(3) Drying at 100deg.C for 2h, and roasting at 450deg.C for 4h;
(4) And (3) carrying out sodium washing exchange on the roasted catalyst obtained in the step (3) and ammonium sulfate, and then drying at 100 ℃ for 2 hours. Catalyst C-2 was obtained. The results of the content of each component in the catalyst are shown in Table 2.
Catalytic conversion of diesel oil:
the diesel catalytic conversion was carried out with catalyst C-2 as in example 1. The yields of the respective products were tested and the results are shown in table 3.
Example 3
This example is intended to illustrate the catalyst of the invention, its method of preparation and the method of catalytic conversion of diesel fuel.
And (3) preparing a catalyst:
(1) Impregnating 19.0g of SAPO-34 and 9.0g of gY molecular sieve with an aqueous solution containing 16.3g of cobalt nitrate hexahydrate, drying at 110 ℃ for 5 hours, and roasting at 550 ℃ for 2 hours to obtain a metal loaded mixed molecular sieve;
(2) Preparing slurry with solid content of 31 wt% from 66.7g aluminum sol, 70.9g montmorillonite and the metal-loaded mixed molecular sieve by using decationizing water, uniformly stirring, and performing spray drying on the slurry to prepare a microsphere catalyst (the average particle size is 65 mu m, and 60-80 mu m of particles account for 60%);
(3) Drying at 100deg.C for 2h, and roasting at 450deg.C for 4h;
(4) And (3) carrying out sodium washing exchange on the roasted catalyst obtained in the step (3) and ammonium sulfate, and then drying at 100 ℃ for 2 hours. Catalyst C-3 was obtained. The results of the content of each component in the catalyst are shown in Table 2.
Catalytic conversion of diesel oil:
the diesel catalytic conversion was carried out with catalyst C-3 as in example 1. The yields of the respective products are shown in table 3.
Example 4
This example is intended to illustrate the catalyst of the invention, its method of preparation and the method of catalytic conversion of diesel fuel.
And (3) preparing a catalyst:
(1) Impregnating 23.0g of SAPO-34 and 11.0g of gY molecular sieve with an aqueous solution containing 1.8g of magnesium nitrate, drying at 110 ℃ for 5 hours, and roasting at 550 ℃ for 2 hours to obtain a metal loaded mixed molecular sieve;
(2) Preparing 71.1g of aluminum sol, 66.8g of montmorillonite and the metal-loaded mixed molecular sieve into slurry with 31 weight percent of solid content by using decationizing water, uniformly stirring, and performing spray drying on the slurry to prepare a microsphere catalyst (the average particle size is 65 mu m, and 60-80 mu m of particles account for 60 percent);
(3) Drying at 100deg.C for 2h, and roasting at 450deg.C for 4h;
(4) And (3) carrying out sodium washing exchange on the roasted catalyst obtained in the step (3) and ammonium sulfate, and then drying at 100 ℃ for 2 hours. Catalyst C-4 was obtained. The results of the content of each component in the catalyst are shown in Table 2.
Catalytic conversion of diesel oil:
the diesel catalytic conversion was carried out with catalyst C-4 as in example 1. The yields of the respective products were tested and the results are shown in table 3.
Example 5
This example is intended to illustrate the catalyst of the invention, its method of preparation and the method of catalytic conversion of diesel fuel.
(1) Impregnating 15.0g of SAPO-34 and 8.0g of gY molecular sieve with an aqueous solution containing 7.4g of cobalt nitrate hexahydrate, drying at 110 ℃ for 5 hours, and roasting at 550 ℃ for 2 hours to obtain a metal loaded mixed molecular sieve;
(2) Preparing slurry with solid content of 31 wt% from 117.6g silica sol, 60.7g kaolin and the metal-loaded mixed molecular sieve by using decationizing water, uniformly stirring, and performing spray drying on the slurry to prepare a microsphere catalyst (the average particle size is 65 mu m, and 60-80 mu m of particles account for 60%);
(3) Drying at 100deg.C for 2h, and roasting at 450deg.C for 4h;
(4) And (3) carrying out sodium washing exchange on the roasted catalyst obtained in the step (3) and ammonium sulfate, and then drying at 100 ℃ for 2 hours. Catalyst C-5 was obtained. The results of the content of each component in the catalyst are shown in Table 2.
Catalytic conversion of diesel oil:
the diesel catalytic conversion was carried out with catalyst C-5 as in example 1. The yields of the respective products were tested and the results are shown in table 3.
Comparative example 1
This comparative example is used to illustrate a comparative catalyst, a method of preparing the same, and a method of catalytic conversion of diesel fuel.
Catalyst preparation and diesel catalytic conversion were the same as in example 1 except that no cobalt nitrate was added.
Wherein the prepared catalyst is named as D-1. The results of the content of each component in the catalyst are shown in Table 2. The diesel catalytic conversion was carried out with catalyst D-1 according to the procedure of example 1, and the yield of each product is shown in Table 3.
Comparative example 2
This comparative example is used to illustrate a comparative catalyst, a method of preparing the same, and a method of catalytic conversion of diesel fuel.
Catalyst preparation and diesel catalytic conversion were the same as in example 1 except that no molecular sieve was added. The catalyst thus prepared was designated D-2. The results of calculating the contents of the components in the catalyst according to the total weight and the feeding amount of the finally obtained catalyst are shown in Table 2. The results of the diesel catalytic conversion with catalyst D-2 according to example 1 gave the yields of the respective products are shown in Table 3.
Comparative example 3
The diesel catalytic conversion was performed in the same manner as in example 1 except that carbon dioxide gas was not introduced during the diesel catalytic conversion. The yields of the respective products were tested and the results are shown in table 3.
TABLE 2
wt% refers to weight%.
TABLE 3 Table 3
From the data in Table 3, it can be seen that the selectivity of propylene and butene can be improved by using the catalyst provided by the present invention. In addition, the catalyst and CO provided by the invention 2 The catalyst is matched in the catalytic conversion process of diesel oil, is more beneficial to improving the selectivity of low-carbon olefin, and can realize CO 2 Effective utilization under mild conditions. Unexpectedly, it is possible to have lower coke yields. Preferably, it is also possible to have a higher liquefied gas yield.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (13)

1. A method of catalytic conversion of diesel fuel comprising: contacting diesel, carbon dioxide with a catalyst and optionally a diluent gas, the contacting reaction conditions comprising: the temperature is 400-800 ℃, the pressure is 0.1-2MPa, and the weight ratio of carbon dioxide to diesel oil is 0.2-3:1, the diesel oil mass airspeed is 0.3-10h -1 The method comprises the steps of carrying out a first treatment on the surface of the The catalyst comprises a catalyst containing a silicoaluminophosphate molecular sieve; the catalyst of the silicon aluminum phosphate molecular sieve comprises natural mineral substances, inorganic oxides, metals and molecular sieves, wherein the content of the natural mineral substances is 10-70wt% based on the total weight of the catalyst of the silicon aluminum phosphate molecular sieve, the content of the inorganic oxides is 10-60wt% based on dry basis, the content of the molecular sieves is 10-70wt% based on dry basis, the content of the metals is 0.01-10wt% based on elements, and the molecular sieves comprise the silicon aluminum phosphate molecular sieve and FAU structure molecular sieve; the metal includes one or more of W, cu, fe, co, mg, mo, zr and Ca.
2. The process according to claim 1, wherein the natural minerals are present in an amount of 20 to 60wt%, the inorganic oxides are present in an amount of 10 to 50wt%, the molecular sieves are present in an amount of 10 to 55wt%, and the metals are present in an amount of 0.1 to 5wt%, based on the total weight of the catalyst comprising the silicoaluminophosphate molecular sieve.
3. The process of claim 1, wherein the natural minerals are present in an amount of 25 to 50wt%, the inorganic oxides are present in an amount of 10 to 44wt%, the molecular sieves are present in an amount of 28 to 48wt%, and the metals are present in an amount of 0.7 to 3.5wt%, based on the total weight of the silicoaluminophosphate molecular sieve-containing catalyst.
4. The method of claim 1, wherein the metal is one or more of Cu, co, and Mg.
5. The method of claim 1, wherein the silicoaluminophosphate molecular sieve is selected from one or more of a SAPO-11 molecular sieve, a SAPO-31 molecular sieve, a SAPO-34 molecular sieve, and a SAPO-47 molecular sieve.
6. The method of claim 1, wherein the weight ratio of FAU structural molecular sieve to silicoaluminophosphate molecular sieve is 0.05-1: 1.
7. the process of claim 1, wherein the weight ratio of silicoaluminophosphate molecular sieve to FAU structure molecular sieve is from 1.5 to 3.5:1, a step of; and the content of the metal is 0.1-5wt%.
8. The method of claim 1, wherein the natural mineral is selected from one or more of kaolin, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite, and rectorite;
the inorganic oxide is selected from one or more of silicon oxide, aluminum oxide-silicon oxide, zirconium oxide, titanium oxide, boron oxide, amorphous silicon aluminum, tungsten oxide-zirconium oxide, molybdenum oxide-titanium oxide, tungsten oxide-titanium oxide, zinc oxide and niobium oxide.
9. The process of any one of claims 1-8, wherein the catalyst comprising a silicoaluminophosphate molecular sieve is prepared by a process comprising the steps of:
(1) Impregnating the Y and the silicon aluminum phosphate molecular sieve with an aqueous solution of a metal salt, drying and roasting to prepare a metal-loaded mixed molecular sieve;
(2) Mixing natural mineral substances, inorganic oxide and/or inorganic oxide precursor and the prepared metal-loaded mixed molecular sieve, pulping, spray drying, and preparing into catalyst particles;
(3) Drying and roasting the catalyst particles to obtain roasted catalyst particles;
(4) Sodium washing and exchanging are carried out on the roasted catalyst particles, and then drying is carried out;
alternatively, (1') impregnating the Y and silicoaluminophosphate molecular sieves with an aqueous solution of a metal salt, followed by drying and calcination to produce a metal-loaded hybrid molecular sieve;
(2') mixing and pulping natural minerals, inorganic oxides and/or inorganic oxide precursors and the prepared metal-loaded mixed molecular sieve, and spray-drying to prepare catalyst particles;
(3') carrying out sodium washing exchange on the catalyst particles to obtain catalyst particles subjected to sodium washing exchange;
(4') drying and calcining the catalyst particles after sodium exchange.
10. The method of claim 9, wherein the firing conditions of step (1) and step (3) each comprise: the roasting temperature is 400-800 ℃ and the roasting time is 0.5-8 hours.
11. The method of claim 1, wherein the FAU-structured molecular sieve is a Y-type molecular sieve.
12. The method of claim 1, wherein the contacting reaction conditions comprise: the temperature is 480-650 ℃, the pressure is 0.1-0.3MPa, and the weight ratio of carbon dioxide to diesel oil is 0.25-2:1, the diesel oil mass airspeed is 0.5 to 5 hours -1 。
13. The process of claim 7, wherein the weight ratio of silicoaluminophosphate molecular sieve to FAU structure molecular sieve is from 2.1 to 3.5:1, a step of; the metal content is 0.8-3.5 wt%.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102814194A (en) * 2011-06-09 2012-12-12 中国石油化工股份有限公司 Catalyst containing modified silicoaluminophosphate molecular sieve
CN107971017A (en) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 A kind of catalytic cracking catalyst and preparation method thereof
CN108452835A (en) * 2017-02-22 2018-08-28 中国石油化工股份有限公司 A kind of catalytic cracking catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102814194A (en) * 2011-06-09 2012-12-12 中国石油化工股份有限公司 Catalyst containing modified silicoaluminophosphate molecular sieve
CN107971017A (en) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 A kind of catalytic cracking catalyst and preparation method thereof
CN108452835A (en) * 2017-02-22 2018-08-28 中国石油化工股份有限公司 A kind of catalytic cracking catalyst

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