CN112742385A - Catalyst for gasoline catalytic conversion, preparation method thereof and gasoline catalytic conversion method - Google Patents
Catalyst for gasoline catalytic conversion, preparation method thereof and gasoline catalytic conversion method Download PDFInfo
- Publication number
- CN112742385A CN112742385A CN202010906429.2A CN202010906429A CN112742385A CN 112742385 A CN112742385 A CN 112742385A CN 202010906429 A CN202010906429 A CN 202010906429A CN 112742385 A CN112742385 A CN 112742385A
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- Prior art keywords
- oxide
- catalyst
- noble metal
- gasoline
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- 239000003054 catalyst Substances 0.000 title claims abstract description 125
- 239000003502 gasoline Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 73
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000011973 solid acid Substances 0.000 claims abstract description 71
- 239000002131 composite material Substances 0.000 claims abstract description 67
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 49
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 30
- 239000011707 mineral Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000003085 diluting agent Substances 0.000 claims abstract description 7
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- 229910000510 noble metal Inorganic materials 0.000 claims description 76
- 239000012752 auxiliary agent Substances 0.000 claims description 33
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- 239000002243 precursor Substances 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
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- 238000001694 spray drying Methods 0.000 claims description 18
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 17
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- 239000011733 molybdenum Substances 0.000 claims description 4
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
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- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims 1
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Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- 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
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention relates to the field of petrochemical industry, and discloses a catalyst for catalytic conversion of gasoline, a preparation method thereof and a catalytic conversion method of gasoline, wherein the catalyst comprises natural mineral substances, inorganic oxides, composite oxide solid acids and precious metals, wherein the total weight of the catalyst is taken as a reference, the content of the natural mineral substances is 15-70 wt%, the content of the inorganic oxides is 5-60 wt%, the content of the composite oxide solid acids is 10-65 wt%, and the content of the precious metals is 0.1-10 wt% calculated by elements. The method for catalytically converting gasoline comprises the following steps: mixing gasolineCarbon dioxide and optionally a diluent gas are contacted with the catalyst for reaction. The catalyst provided by the invention has high activity, and can realize catalytic conversion and CO of gasoline under very mild conditions2The method can be used for producing the low-carbon olefin.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a catalyst for gasoline catalytic conversion, a preparation method thereof and a gasoline catalytic conversion method.
Background
The low-carbon olefin is an indispensable chemical raw material. The low-carbon olefin comprises 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 other products.
In recent years, the demand of low-carbon olefins is rapidly increased, and the productivity is continuously improved. At present, the main modes for producing low-carbon olefins include steam cracking, catalytic cracking, propane dehydrogenation, MTO, catalytic reforming and the like. Wherein, the proportion of the products of the low-carbon olefin produced by adopting a steam cracking mode can not be flexibly adjusted, the reaction temperature is up to 840-860 ℃, and the energy consumption is about 40 percent of the energy consumption of the petrochemical industry. Therefore, the method for increasing the yield of the low-carbon olefin in large quantity by catalytic cracking is an efficient way for meeting the increase of demand, wherein the catalytic cracking of gasoline fractions such as naphtha and the like is promising due to the advantages of low reaction temperature, flexible and easily-adjustable product distribution, small product pollution, environmental friendliness and the like. However, from the current results, further improvements and enhancements in process and catalyst performance are still needed.
As is well known, CO2Is an important greenhouse gas, the greenhouse effect of the greenhouse gas causes a series of problems such as land desertification, aggravation of plant diseases and insect pests, climate change, glacier melting and the like, and therefore, the international society calls for CO2And (5) emission reduction. But on the other hand, CO2It is also a cheap and rich C1 resource, which can react with hydrogen to produce CO, methanol, dimethyl ether, low carbon hydrocarbon, gasoline, etc., and can react with methane to produce synthetic gas and ethane to produce ethylene, etc. However, these reactions generally need to be carried out under high pressure, and the reaction conditions are relatively severe.
Disclosure of Invention
The invention aims to overcome the reaction conditions of gasoline catalytic conversion and CO in the prior art2The defects of harsh conditions are utilized to provide a catalyst for gasoline catalytic conversion, a preparation method thereof and a method for gasoline catalytic conversion. The catalyst provided by the invention can realize the catalytic conversion and CO of gasoline under very mild conditions2The method effectively utilizes the catalyst and further improves the yield of the product (low-carbon olefin).
In order to achieve the above object, a first aspect of the present invention provides a catalyst for catalytic conversion of gasoline, the catalyst comprising natural minerals, inorganic oxides, solid acids of composite oxides, and noble metals, the natural minerals being contained in an amount of 15 to 70 wt%, the inorganic oxides being contained in an amount of 5 to 60 wt%, the solid acids of composite oxides being contained in an amount of 10 to 65 wt%, and the noble metals being contained in an amount of 0.1 to 10 wt%, calculated as elements, based on the total weight of the catalyst.
Preferably, the composite oxide solid acid is selected from at least two of tungsten oxide, zirconium oxide, and molybdenum oxide.
A second aspect of the present invention provides a method for preparing the above catalyst for catalytic conversion of gasoline, comprising: mixing noble metal salt and/or supported noble metal, composite oxide solid acid, natural mineral, inorganic oxide and/or inorganic oxide precursor, pulping, spray drying, and roasting.
A third aspect of the present invention provides a process for preparing the above catalyst for catalytic conversion of gasoline, which comprises:
1) loading noble metal on the composite oxide solid acid to obtain the composite oxide solid acid containing the noble metal;
2) mixing the noble metal-containing composite oxide solid acid, natural mineral substances and inorganic oxides and/or inorganic oxide precursors, pulping, spray-drying and then roasting.
In a fourth aspect, the present invention provides a catalyst for catalytic conversion of gasoline prepared by the above-described process.
In a fifth aspect, the present invention provides a method for catalytic conversion of gasoline, the method comprising: gasoline, carbon dioxide and catalyst, and optionally diluent gas are contacted and reacted, wherein the catalyst comprises the catalyst for the catalytic conversion of the gasoline.
The invention can realize the catalytic conversion of the gasoline under mild conditions by adopting the catalyst containing natural minerals, inorganic oxides, noble metals and composite oxide solid acids. The catalyst provided by the invention is used in the catalytic conversion process of gasoline, carbon dioxide and diluent gas are in contact reaction with the catalyst, and CO is utilized2The weak oxidation performance of the catalyst can be coupled with the catalytic cracking/thermal cracking reaction of the gasoline fraction, and the yield of ethylene, propylene and butylene can be improved in a normal pressure range. In addition, the method for catalytically converting the gasoline can also fully utilize CO under mild conditions2Resources, reduces the problems caused by greenhouse gases, and has very good economic value and industrial application value.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a catalyst for catalytic conversion of gasoline, which comprises natural minerals, inorganic oxides, composite oxide solid acids and precious metals, wherein the content of the natural minerals is 15-70 wt%, the content of the inorganic oxides is 5-60 wt%, the content of the composite oxide solid acids is 10-65 wt%, and the content of the precious metals is 0.1-10 wt% calculated by elements.
Preferably, the content of the natural mineral matter is 20-60 wt%, the content of the inorganic oxide is 10-55 wt%, the content of the composite oxide solid acid is 10-55 wt%, and the content of the noble metal is 0.1-5 wt% calculated by element based on the total weight of the catalyst.
More preferably, the content of natural minerals is 30-55 wt%, the content of inorganic oxides is 10-43 wt%, the content of composite oxide solid acids is 25-40 wt%, and the content of noble metals is 1.2-4 wt% calculated by elements, based on the total weight of the catalyst.
In the present invention, the noble metal may be various noble metals conventionally used in the art, for example, the noble metal may be selected from one or more of Au, Pd, and Rh.
According to a specific embodiment of the present invention, the complex oxide solid acid is selected from at least two of transition metal oxides; preferably, the composite oxide solid acid is selected from at least two of tungsten oxide, zirconium oxide, molybdenum oxide, titanium oxide, tin oxide, zinc oxide, copper oxide, nickel oxide, cobalt oxide, vanadium oxide, and niobium oxide; preferably, the composite oxide solid acid is selected from at least two of tungsten oxide, zirconium oxide, and molybdenum oxide.
According to a preferred embodiment of the present invention, the composite oxide solid acid includes tungsten oxide and zirconium oxide, or the composite oxide solid acid includes molybdenum oxide and zirconium oxide.
Further preferably, the composite oxide solid acid comprises tungsten oxide and zirconium oxide, and still further preferably, the molar ratio of tungsten oxide to zirconium oxide is 0.05 to 0.5: 1, more preferably 0.1 to 0.4: 1. preferably, the tungsten oxide and the zirconium oxide are used in a specific ratio, so that the yield of the target product is improved.
Further preferably, the composite oxide solid acid comprises molybdenum oxide and zirconium oxide, and still further preferably, the molar ratio of molybdenum oxide to zirconium oxide is 0.05-0.5: 1, more preferably 0.1 to 0.4: 1. preferably, the molybdenum oxide and the zirconium oxide are used in a specific ratio, so that the yield of the target product is improved.
In the present invention, the complex oxide solid acid may be obtained commercially or may be prepared by a method generally used in the art, and the present invention is not particularly limited thereto.
In the present invention, the natural mineral may be selected conventionally in the art, and preferably, the natural mineral is selected from one or more of kaolin, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite; more preferably, the natural mineral is selected from one or more of kaolin, halloysite, rectorite and montmorillonite.
In the present invention, the inorganic oxide may be conventionally selected in the art, and preferably, the inorganic oxide is selected from one or more of silicon oxide, aluminum oxide, alumina-silica, zirconium oxide, titanium oxide, boron oxide, amorphous silica-alumina, aluminum phosphate, tungsten oxide, molybdenum oxide, tin oxide, zinc oxide, copper oxide, nickel oxide, cobalt oxide, vanadium oxide, and niobium oxide; more preferably, the inorganic oxide is selected from one or more of alumina, silica and alumina-silica.
In the invention, preferably, the catalyst also contains an auxiliary agent; the promoter may be present in the catalyst in the form of an oxide. The auxiliary agent is selected from at least one of group IIA, group IIIA, group IVA, group VA, lanthanide, Y, Cr, Mn, Re, Fe and Cd, preferably at least one of Ca, Fe, Ga, In, Bi, La and Mn.
The group IIA element can be Mg and/or Ca; the group IIIA element may be at least one of B, Al and Ga; the group IVA element may be at least one of Si, Ge and Sn; the group VA element may be at least one of N, P, As, Sb and Bi.
Further preferably, the additive is at least one selected from Ca, Fe, Ga, In, Bi, La and Mn, and further preferably Ga.
In the present invention, the content of the promoter is preferably 0.5 to 9 wt% in terms of oxide, based on the total weight of the catalyst.
In the present invention, the catalyst may also contain a molecular sieve, which may be a conventional choice in the art. For example, the molecular sieve may be one or more selected from the group consisting of FAU structure molecular sieve, BEA structure molecular sieve, MFI structure molecular sieve, FER structure molecular sieve, MCM molecular sieve, MTT structure molecular sieve, TON structure molecular sieve, MEL structure molecular sieve, SBA molecular sieve and silicoaluminophosphate molecular sieve.
The present invention provides a method for producing the catalyst, which is not particularly limited as long as the catalyst having the above composition can be produced, and a method for producing the catalyst is provided to further improve the catalytic performance of the catalyst.
In a second aspect, the present invention provides a process (denoted as process a) for preparing the above-described catalyst for catalytic conversion of gasoline, which process comprises: mixing noble metal salt and/or supported noble metal, composite oxide solid acid, natural mineral, inorganic oxide and/or inorganic oxide precursor, pulping, spray drying, and roasting.
In the method provided by the invention, the noble metal can be introduced in the form of a noble metal salt or in the form of a supported noble metal.
In the present invention, the noble metal salt may be a water-soluble noble metal salt, such as a nitrate and/or chloride of a noble metalThe noble metal salt may be selected from, but not limited to, (NH)4)3RhCl6、PdCl2And AuCl3At least one of (1).
In the method provided by the invention, preferably, the supported noble metal comprises a carrier and a noble metal supported on the carrier; preferably, the support is selected from one or more of alumina, silica, alumina-silica, zirconia, tungsten oxide-zirconia, molybdenum oxide-zirconia, titania, molybdenum oxide-titania, tungsten oxide-titania, tin oxide, zinc oxide, copper oxide, nickel oxide, cobalt oxide, vanadium oxide and niobium oxide, more preferably alumina.
The method provided by the invention preferably comprises 0.5-20 wt% of the noble metal calculated by element based on the total weight of the supported noble metal.
The supported noble metal of the present invention may be prepared by a method conventionally used in the art, for example, by an impregnation method, and specifically, the support may be impregnated with a solution containing a noble metal salt, followed by drying and calcination. The drying and calcining conditions may be carried out according to conventional conditions, and the present invention will not be described herein.
In the preparation method of the catalyst of the present invention, unless otherwise specified, when the noble metal is mixed and beaten with other raw materials in the form of a supported noble metal, the weight content of the carrier of the supported noble metal is taken into account in the content of the inorganic oxide.
According to the method provided by the invention, the inorganic oxide precursor can be a substance which can be converted into an inorganic oxide in the subsequent process (such as roasting) of the method provided by the invention, and the inorganic oxide precursor can be correctly selected by a person skilled in the art on the basis of the disclosure of the invention. Specifically, the inorganic oxide precursor may be a sol of an inorganic oxide, for example, at least one of a silica sol, an aluminum sol, a peptized pseudo-boehmite, a silica-alumina sol, and a phosphorus-containing aluminum sol.
According to the present invention, preferably, the method a further comprises introducing an auxiliary agent into the catalyst, wherein the kind of the auxiliary agent is as described above and is not described herein again.
Further preferably, the introduction manner of the auxiliary agent comprises: mixing and pulping an auxiliary agent precursor, a noble metal salt and/or a supported noble metal, a composite oxide solid acid, a natural mineral substance, an inorganic oxide and/or an inorganic oxide precursor; and/or mixing and pulping the supported noble metal containing the auxiliary agent, the composite oxide solid acid, the natural mineral substance, the inorganic oxide and/or the inorganic oxide precursor.
The auxiliary agent can be introduced in a form of mixing and pulping with other materials in the form of an auxiliary agent precursor, or can be introduced in a form of loading the auxiliary agent and the noble metal on a carrier together and then mixing and pulping with other materials.
According to the method provided by the invention, the auxiliary agent precursor can be an oxide of the auxiliary agent and/or a substance which can be converted into an auxiliary agent oxide in a subsequent process (such as roasting) of the method provided by the invention, and the auxiliary agent precursor can be correctly selected by a person skilled in the art on the basis of the disclosure of the invention. May be an oxide and/or a water-soluble salt of the adjuvant (e.g. a nitrate and/or chloride of the adjuvant).
The invention has no special limitation on the preparation method, the assistant and the noble metal can be introduced onto the carrier by adopting an impregnation method, the assistant precursor and the noble metal salt can be introduced onto the carrier together (co-impregnation) or introduced onto the carrier step by step (step-by-step impregnation), and when the assistant precursor and the noble metal salt are introduced onto the carrier step by step, the invention has no special limitation on the introduction sequence of the assistant precursor and the noble metal salt.
According to the method A provided by the invention, preferably, the method comprises the steps of firstly mixing the inorganic oxide and/or the precursor of the inorganic oxide and the natural mineral by adding water, then adding the composite oxide solid acid, the noble metal salt and/or the supported noble metal, mixing, pulping, spraying, drying and then roasting.
According to a preferred embodiment of the present invention, an inorganic oxide and/or an inorganic oxide precursor, a natural mineral and water are mixed and stirred uniformly to obtain a slurry; adding composite oxide solid acid, noble metal salt and/or supported noble metal after 0.5-2 hours, and stirring to obtain catalyst slurry with solid content of 30-40 wt%; spray drying to obtain microsphere catalyst; then the microspherical catalyst is roasted.
A third aspect of the invention provides a process (denoted as process B) for preparing the above-described catalyst for catalytic conversion of gasoline, which process comprises:
1) loading noble metal on the composite oxide solid acid to obtain the composite oxide solid acid containing the noble metal;
2) mixing the noble metal-containing composite oxide solid acid, natural mineral substances and inorganic oxides and/or inorganic oxide precursors, pulping, spray-drying and then roasting.
In step 1) of the present invention, the noble metal may be supported on the composite oxide solid acid by a conventional method 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 examples of the present invention are illustrated in part by the dipping method and the present invention is not limited thereto.
According to an embodiment of the present invention, step 1) may be to impregnate the composite oxide solid acid with a solution containing a noble metal salt, followed by drying and firing. The drying and calcining conditions may be carried out according to conventional conditions, and the present invention will not be described herein. The noble metal salt is as described above.
In the present invention, preferably, the method further comprises introducing an auxiliary agent into the catalyst, wherein the kind of the auxiliary agent is as described above and is not described herein again; further preferably, the method further comprises introducing an auxiliary agent into the catalyst in step 1); still further preferably, step 1) comprises: and loading the noble metal and the auxiliary agent on the composite oxide solid acid to obtain the composite oxide solid acid containing the noble metal and the auxiliary agent. Specifically, the method B includes:
1) loading noble metal and an auxiliary agent on the composite oxide solid acid to obtain the composite oxide solid acid containing the noble metal and the auxiliary agent;
2) mixing the composite oxide solid acid containing the noble metal and the auxiliary agent, natural mineral substances and inorganic oxide and/or inorganic oxide precursor, pulping, spray drying and then roasting.
The invention can adopt an impregnation method to load the auxiliary agent and the noble metal on the composite oxide solid acid, the auxiliary agent precursor and the noble metal salt can be jointly impregnated on the composite oxide solid acid (co-impregnation) or can be impregnated on the composite oxide solid acid step by step (step-impregnation), when the auxiliary agent precursor and the noble metal salt are impregnated on the composite oxide solid acid step by step, the invention has no special limitation on the introduction sequence of the auxiliary agent precursor and the noble metal salt.
According to the method C provided by the invention, the solid content of the slurry obtained by mixing and beating in the step 2) is preferably 30-40 wt%.
The spray drying in the above-mentioned method of the present invention is not particularly limited, and may be carried out according to a conventional technique in the art, and the spray drying conditions in the above-mentioned methods may be the same or different. Preferably the spray drying conditions are such that the spray dried particles have an average particle size of from 60 to 80 μm and a particle size distribution predominantly in the range of from 40 to 100. mu.m, and more preferably the spray drying conditions are such that more than 50% of the particles having a particle size of from 60 to 80 μm are present in the spray dried particles.
In the present invention, the calcination conditions may be calcination conditions conventional in the art, and preferably, the calcination conditions in each of the above methods independently include: the roasting atmosphere is air atmosphere, inert atmosphere or steam atmosphere, the roasting temperature is 400-800 ℃, preferably 400-600 ℃, and the roasting time is 0.5-8 hours, preferably 1-5 hours. According to a preferred embodiment of the invention, the calcination is carried out in 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 fourth aspect of the present invention also provides a catalyst for catalytic conversion of gasoline prepared by the above method.
In a fifth aspect, the present invention provides a method for catalytic conversion of gasoline, comprising contacting gasoline, carbon dioxide and a catalyst, and optionally a diluent gas, wherein the catalyst comprises the above-mentioned catalyst for catalytic conversion of gasoline.
According to an embodiment of the present invention, the catalyst may be subjected to hydrothermal aging treatment before being used for catalytic conversion of gasoline. In the present invention, the conditions of the hydrothermal aging treatment are not particularly limited, and the hydrothermal aging treatment can be performed according to a conventional technique in the art. The hydrothermal aging treatment is more favorable for improving the stability of the catalyst. In the examples of the present invention, the aging process is performed for 10 hours at 800 ℃ under 100% steam, but the present invention is not limited thereto.
The conditions for the contact reaction are selected from a wide range, and preferably, the temperature of the contact reaction is not higher than 700 ℃. The catalyst provided by the invention can be suitable for low-temperature gasoline catalytic conversion reaction, the adoption of the preferred embodiment provided by the invention is more favorable for saving energy consumption, and the effective utilization of carbon dioxide can be realized by processing under mild conditions.
In the present invention, preferably, the conditions of the contact reaction include: the temperature is 350-700 ℃, the pressure is 0.1-2MPa, and the weight ratio of the carbon dioxide to the gasoline is 0.22-3: 1, the mass airspeed of the gasoline is 0.3-10h-1(ii) a More preferably, the conditions of the contact reaction include: the temperature is 400-: 1, the mass airspeed of the gasoline is 0.5-5h-1。
In the invention, the gasoline mainly comprises aliphatic hydrocarbons and naphthenic hydrocarbons of C5-C12, and also comprises a certain amount of aromatic hydrocarbons, and specifically comprises one or more of catalytic cracking gasoline, coker gasoline, straight run gasoline, reformed gasoline, laminated gasoline and alkyl gasoline.
In the gasoline catalytic conversion method provided by the invention, dilution gas can be introduced or not introduced in the reaction processThe present invention is not particularly limited thereto, and the diluent gas may be N2、H2O、O2Air, N2O、NO2、NO、H2And SO2One or more of (a).
According to the present invention, it is preferable that the carbon dioxide is contained in an amount of 10 to 100% by volume, based on the total volume of the carbon dioxide and the diluent gas.
The present invention will be described in detail below by way of examples.
In the following examples:
the various parameters of the gasoline used are shown in table 1 below:
TABLE 1
| Parameter(s) | Parameter value |
| Density (20 ℃ C.), g/cm3 | 0.7494 |
| Vapor pressure/kPa | 21.9 |
| Alkane/wt.% | 58.6 |
| Cycloalkane/wt% | 31.1 |
| Aromatic hydrocarbon/wt% | 10.3 |
| C/wt％ | 85.50 |
| H/wt％ | 14.48 |
| S/wt％ | 102 |
| N/wt％ | 0.64 |
Kaolin was purchased from suzhou china kaolin, having a solids content of 75% by weight;
montmorillonite is purchased from red stone bentonite company, Kogyang, Liaoning province, and has a solid content of 75 wt%;
the rectorite is purchased from Zhongxiang rectorite in Hubei province, and the solid content is 75 percent by weight;
the alumina sol was purchased from zilu catalyst division and had an alumina content of 22.5 wt%;
the silica sol is purchased from Qingdao ocean chemical Co., Ltd, the content of silica is 25.5 wt%, and the pH value is 3.0;
WO3/ZrO2the preparation method of the composite solid acid (the molar ratio is 0.2) comprises the following steps: at ZrOCl2Adding ammonia water to the aqueous solution of (1), adjusting the pH to 9.6, continuing stirring for 3h, then filtering, and washing the precipitate with deionized water until no chloride ions can be detected. Then dried in an oven at 110 ℃ overnight to obtain Zr (OH)4. Zr (OH)4Adding into ammonium metatungstate solution to make W/Zr molar ratio 0.2, stirring for 3 hr, heating to evaporate water, and drying in oven at 110 deg.C overnight. The dried sample was calcined in a muffle furnace at 800 ℃ for 3 hours.
MoO3/ZrO2The preparation method of the composite solid acid (the molar ratio is 0.1) is the same as that of WO3/ZrO2The preparation method of the composite solid acid replaces ammonium metatungstate with ammonium paramolybdate, and the molar ratio of Mo/Zr is 0.1.
The contents of the components in the following catalysts are calculated by the feeding amount.
Example 1
This example illustrates the catalyst of the present invention, its preparation and the process for catalytic conversion of gasoline.
Preparing a catalyst:
mixing 71.1g of alumina sol and 72.5g of kaolin, preparing the mixture into slurry by using decationized water, and uniformly stirring; after 1 hour 27.2g of WO were added3/ZrO2Composite solid acid (WO)3And ZrO2In a molar ratio of 0.2: 1) and 4.0g of PdCl2Stirring to form a catalyst slurry (solid content 32 wt%); continuously stirring, and spray drying to obtain microsphere catalyst (average particle diameter is 65 μm, particle with particle diameter of 60-80 μm accounts for 60%, the same below); roasting at 450 deg.c for 1.5 hr to obtain catalyst C-1. The results of the contents of the components in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
aging the prepared catalyst for 10h at 800 ℃ under the condition of 100% of water vapor, and mixing gasoline, carbon dioxide and the catalyst at a temperature of 550 ℃, a pressure of 0.11MPa, a weight ratio of carbon dioxide to gasoline of 0.6: 1, the mass space velocity of the gasoline is 1.0h-1The catalytic conversion product of the gasoline is obtained by the contact reaction under the condition of (1). The yields of each product were tested and the results are shown in table 3.
Example 2
This example illustrates the catalyst of the present invention, its preparation and the process for catalytic conversion of gasoline.
Preparing a catalyst:
1) will contain 2.0g of PdCl2Impregnating 40.0g of WO with the aqueous solution of (2)3/ZrO2Composite solid acid (WO)3And ZrO2In a molar ratio of 0.2: 1) then drying at 100 ℃ for 2h, and roasting at 300 ℃ for 4h to obtain the WO containing noble metal3/ZrO2A composite solid acid;
2) mixing the above-mentioned WO containing noble metal3/ZrO2Preparing composite solid acid, 71.1g of alumina sol and 57.1g of montmorillonite into slurry with the solid content of 32 weight percent by using decationized water; continue to useStirring, and spray drying to obtain microsphere catalyst; roasting the microspherical catalyst for 2 hours at 450 ℃ to obtain the catalyst C-2. The results of the contents of the components in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of each product were tested and the results are shown in table 3.
Example 3
This example illustrates the catalyst of the present invention, its preparation and the process for catalytic conversion of gasoline.
Preparing a catalyst:
mixing 66.7g of alumina sol and 74.7g of kaolin, preparing the mixture into slurry by using decationized water, and uniformly stirring; after 1 hour 25g of WO were added3/ZrO2Composite solid acid (WO)3And ZrO2In a molar ratio of 0.2: 1) and 6.7g of PdCl2Stirring to form a catalyst slurry (solid content 32 wt%); continuously stirring, and then spray-drying to prepare a microspherical catalyst; roasting at 450 deg.c for 1.5 hr to obtain catalyst C-3. The results of the contents of the components in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of each product were tested and the results are shown in table 3.
Example 4
This example illustrates the catalyst of the present invention, its preparation and the process for catalytic conversion of gasoline.
Preparing a catalyst:
mixing 71.1g of alumina sol and 65.5g of montmorillonite, preparing the mixture into slurry by using decationized water, and uniformly stirring; after 1 hour 29.3g of WO were added3/ZrO2Composite solid acid (WO)3And ZrO2In a molar ratio of 0.2: 1) and 5.6g of Rh/Al2O3(Rh content 16% by weight) to form a catalyst slurry (solids content 32% by weight); continuously stirring, and then spray-drying to prepare a microspherical catalyst; the microspherical catalyst was calcined at 450 ℃ for 1.5 hours to obtain catalyst C-4. The results of the contents of the components in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of each product were tested and the results are shown in table 3.
Example 5
This example illustrates the catalyst of the present invention, its preparation and the process for catalytic conversion of gasoline.
Preparing a catalyst:
164.7g of silica sol and 53.2g of rectorite are mixed, and are prepared into slurry by decationized water, and the slurry is stirred uniformly; after 1 hour 16.1g of WO were added3/ZrO2Composite solid acid (WO)3And ZrO2In a molar ratio of 0.2: 1) and 3.3g of AuCl3To form a catalyst slurry (solids content 32 wt%); continuously stirring, and then spray-drying to prepare a microspherical catalyst; the microspherical catalyst was calcined at 450 ℃ for 1.5 hours to obtain catalyst C-5. The results of the contents of the components in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of each product were tested and the results are shown in table 3.
Example 6
This example illustrates the catalyst of the present invention, its preparation and the process for catalytic conversion of gasoline.
Preparing a catalyst:
mixing 71.1g of alumina sol and 63.1g of kaolin, preparing the mixture into slurry by using decationized water, and uniformly stirring; after 2 hours 31.9g of WO were added3/ZrO2Composite solid acid (WO)3And ZrO2In a molar ratio of 0.2: 1) 2.8 g Ga2O3And 3.3g of PdCl2To form a catalyst slurry (35% solids by weight); continuously stirring, and then spray-drying to prepare a microspherical catalyst; roasting the microspherical catalyst for 2 hours at 480 ℃ to obtain the catalyst C-6. The results of the contents of the components in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of each product were tested and the results are shown in table 3.
Example 7
The procedure is as in example 1, except that WO is added3/ZrO2Replacement of composite solid acid by MoO3/ZrO2Composite solid acid (MoO)3And ZrO2In a molar ratio of 0.1: 1). Catalyst C-7 was obtained. The results of the contents of the components in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of each product were tested and the results are shown in table 3.
Example 8
The process of example 1 was followed except that carbon dioxide gas was not introduced during the catalytic conversion of gasoline. The yields of each product were tested and the results are shown in table 3.
Comparative example 1
This comparative example serves to illustrate a comparative catalyst and a method of making the same, as well as a method of catalytic conversion of gasoline.
Catalyst preparation and gasoline catalytic conversion the same as in example 1, except that no PdCl was added2(i.e., no noble metal is added).
The catalyst obtained was designated D-1. The results of the contents of the components in the catalyst are shown in Table 2. The results of yields of the various products obtained from gasoline catalytic conversion are shown in table 3.
Comparative example 2
This comparative example serves to illustrate a comparative catalyst and a method of making the same, as well as a method of catalytic conversion of gasoline.
Catalyst preparation and catalytic conversion of gasoline the same as in example 1, except that no WO was added3/ZrO2Compounding solid acid.
The content of noble metal in the catalyst was calculated from the total weight and the amount of the catalyst to be added, and the results are shown in Table 2. The results of yields of the various products obtained from gasoline catalytic conversion are shown in table 3.
TABLE 2
TABLE 3
As can be seen from the data results in Table 3, the catalyst provided by the invention has high activity, and can realize effective catalytic conversion of gasoline under very mild conditions to produce low-carbon olefins. In addition, the catalyst and CO provided by the invention are adopted2Is used in the catalytic conversion process of gasoline in a matching way, is more favorable for improving the yield of low-carbon olefin, and realizes CO2The effective utilization of the water is realized.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. The catalyst for catalytic conversion of gasoline comprises natural minerals, inorganic oxides, composite oxide solid acids and precious metals, wherein the content of the natural minerals is 15-70 wt%, the content of the inorganic oxides is 5-60 wt%, the content of the composite oxide solid acids is 10-65 wt%, and the content of the precious metals is 0.1-10 wt% calculated by elements.
2. The catalyst of claim 1, wherein the natural mineral content is 20-60 wt%, the inorganic oxide content is 10-55 wt%, the composite oxide solid acid content is 10-55 wt%, and the noble metal content is 0.1-5 wt% calculated by element, based on the total weight of the catalyst;
preferably, the content of the natural mineral matter is 30-55 wt%, the content of the inorganic oxide is 10-43 wt%, the content of the composite oxide solid acid is 25-40 wt%, and the content of the noble metal is 1.2-4 wt% calculated by element based on the total weight of the catalyst.
3. Catalyst according to claim 1 or 2, wherein the noble metal is selected from one or more of Au, Ag, Ru, Rh, Pd, Pt, Ir and Os, preferably from one or more of Au, Pd and Rh.
4. The catalyst according to any one of claims 1 to 3, wherein the complex oxide solid acid is selected from at least two of transition metal oxides;
preferably, the composite oxide solid acid is selected from at least two of tungsten oxide, zirconium oxide, molybdenum oxide, titanium oxide, tin oxide, zinc oxide, copper oxide, nickel oxide, cobalt oxide, vanadium oxide, and niobium oxide;
preferably, the composite oxide solid acid is selected from at least two of tungsten oxide, zirconium oxide, and molybdenum oxide;
further preferably, the composite oxide solid acid comprises tungsten oxide and zirconium oxide, and still further preferably, the molar ratio of tungsten oxide to zirconium oxide is 0.05 to 0.5: 1, more preferably 0.1 to 0.4: 1.
5. the catalyst of any one of claims 1 to 4, wherein the natural mineral is selected from one or more of kaolin, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite;
preferably, the inorganic oxide is selected from one or more of silicon oxide, aluminum oxide, alumina-silicon oxide, zirconium oxide, titanium oxide, boron oxide, amorphous silicon aluminum, aluminum phosphate, tungsten oxide, molybdenum oxide, tin oxide, zinc oxide, copper oxide, nickel oxide, cobalt oxide, vanadium oxide and niobium oxide.
6. The catalyst according to any one of claims 1 to 5, wherein the catalyst further comprises an auxiliary selected from at least one of group IIA, group IIIA, group IVA, group VA, lanthanides, Y, Cr, Mn, Re, Fe and Cd, preferably at least one selected from Ca, Fe, Ga, In, Bi, La and Mn;
preferably, the content of the auxiliary agent is 0.5-9 wt% in terms of oxide based on the total weight of the catalyst.
7. A process for preparing a catalyst for the catalytic conversion of gasoline according to any one of claims 1 to 6, which comprises: mixing noble metal salt and/or supported noble metal, composite oxide solid acid, natural mineral, inorganic oxide and/or inorganic oxide precursor, pulping, spray drying, and roasting;
preferably, the process further comprises introducing a promoter to the catalyst;
preferably, the introduction manner of the auxiliary agent comprises: mixing and pulping an auxiliary agent precursor, a noble metal salt and/or a supported noble metal, a composite oxide solid acid, a natural mineral substance, an inorganic oxide and/or an inorganic oxide precursor, and/or mixing and pulping the supported noble metal containing the auxiliary agent, the composite oxide solid acid, the natural mineral substance, the inorganic oxide and/or the inorganic oxide precursor.
8. The method of claim 7, wherein the supported noble metal comprises a support and a noble metal supported on the support;
preferably, the carrier is selected from one or more of alumina, silica, alumina-silica, zirconia, tungsten oxide-zirconia, molybdenum oxide-zirconia, titania, molybdenum oxide-titania, tungsten oxide-titania, tin oxide, zinc oxide, copper oxide, nickel oxide, cobalt oxide, vanadium oxide and niobium oxide, further preferably alumina;
preferably, the noble metal is present in an amount of 0.5 to 20 wt.% on an elemental basis, based on the total weight of the supported noble metal.
9. A process for preparing a catalyst for the catalytic conversion of gasoline according to any one of claims 1 to 6, which comprises:
1) loading noble metal on the composite oxide solid acid to obtain the composite oxide solid acid containing the noble metal;
2) mixing and pulping the noble metal-containing composite oxide solid acid, natural mineral substances and inorganic oxide and/or inorganic oxide precursor, spray drying, and then roasting;
preferably, the process further comprises introducing a promoter to the catalyst;
preferably, the process further comprises introducing an auxiliary agent to the catalyst in step 1), further preferably step 1) comprises: and loading the noble metal and the auxiliary agent on the composite oxide solid acid to obtain the composite oxide solid acid containing the noble metal and the auxiliary agent.
10. The method of any of claims 7-9, wherein the firing conditions comprise: the roasting atmosphere is air atmosphere, inert atmosphere or steam atmosphere, the roasting temperature is 400-800 ℃, and the roasting time is 0.5-10 hours.
11. A catalyst for the catalytic conversion of gasoline obtainable by the process of any one of claims 7 to 10.
12. A process for the catalytic conversion of gasoline, the process comprising: contacting gasoline, carbon dioxide and a catalyst comprising the catalyst for catalytic conversion of gasoline according to any one of claims 1 to 6 and 11, and optionally a diluent gas;
preferably, the conditions of the contact reaction include: the temperature is 350-700 ℃, the pressure is 0.1-2MPa, and the weight ratio of the carbon dioxide to the gasoline is 0.22-3: 1, the mass airspeed of the gasoline is 0.3-10h-1；
More preferably, the conditions of the contact reaction include: the temperature is 400-: 1, the mass airspeed of the gasoline is 0.5-5h-1。
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| CN101811045A (en) * | 2009-02-25 | 2010-08-25 | 中国科学院大连化学物理研究所 | Catalyst for preparing acetic acid through direct oxidation of ethylene gaseous phase and preparation method thereof |
| CN105498830A (en) * | 2014-10-20 | 2016-04-20 | 中国石油化工股份有限公司 | Desulfurization catalyst, preparation method thereof and method for desulfurizing hydrocarbon oil by employing same |
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