CN108654591B - Supported catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method - Google Patents

Supported catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method Download PDF

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CN108654591B
CN108654591B CN201710194682.8A CN201710194682A CN108654591B CN 108654591 B CN108654591 B CN 108654591B CN 201710194682 A CN201710194682 A CN 201710194682A CN 108654591 B CN108654591 B CN 108654591B
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metal component
metal
component
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CN108654591A (en
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郑仁垟
李明丰
夏国富
李会峰
侯朝鹏
吴玉
晋超
徐润
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

Abstract

The invention discloses a supported catalyst, a preparation method and application thereof, and a Fischer-Tropsch synthesis method1And at least one second metal component M selected from groups VIB and/or VIIB2The catalyst satisfies (M)2/M1)XPS/(M2/M1)XRF2.0-20.0, wherein (M)2/M1)XPS(M) the weight ratio, expressed as the element, of the second metal component to the first metal component of the catalyst, characterized by X-ray photoelectron spectroscopy2/M1)XRFThe weight ratio of the second metal component to the first metal component in elemental form in the catalyst is characterized by X-ray fluorescence spectroscopy. Compared with the catalyst prepared by the prior art, the supported catalyst keeps higher Fischer-Tropsch reaction activity and higher C5+On the premise of selectivity, the isomer selectivity of the product is obviously improved.

Description

Supported catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method
Technical Field
The invention relates to a supported catalyst, a preparation method and application thereof and a Fischer-Tropsch synthesis method.
Background
Under the conditions that the international energy situation is rapidly fluctuated and the energy supply and demand competition is fierce at present, the method has important strategic significance for further efficiently and cleanly utilizing the coal and natural gas resources. The hydrocarbon prepared based on Fischer-Tropsch synthesis technology and other technologies has excellent performance, and can be directly used or mixed with fuel produced by low-quality crude oil for use so as to meet the increasingly rigorous requirements on environmental protection and oil performance indexes. At present, Sasol company in south Africa and Shell company in England/Netherlands master the leading Fischer-Tropsch industrialized synthetic oil technology in the world, and reactors adopted by the technology comprise a tubular fixed bed and a slurry bed. The company Sasol, at the karl's Oryx plant, is the largest slurry bed synthetic oil plant in the world, using a cobalt-based catalyst. The Pearl project which is jointly established by Shell company and Katalun domestic oil company is the natural gas synthetic oil plant with the largest world productivity at present, and the production technology is based on a cobalt-based catalyst and a tubular fixed bed reactor and has good running state.
In addition to the active component Co metal, other metals are often introduced as auxiliary agents to adjust the activity, selectivity and life of the catalyst during the preparation of the catalyst. Studies reported in the literature have shown that these metal promoters, especially noble metal promoters, have a significant effect on the activity of the fischer-tropsch synthesis reaction and on the selectivity of liquid hydrocarbons (ChemCatChem,2010,2, 1030-.
CN102909033B discloses a cobalt-based Fischer-Tropsch synthesis catalyst, which takes platinum modified alumina as a carrier and cobalt as an active component. The preparation process of the catalyst comprises the steps of respectively preparing platinum sol and aluminum sol, fully stirring the platinum sol and the aluminum sol to form gel, then drying and roasting to obtain a platinum modified alumina carrier, and finally loading an active component cobalt by adopting an impregnation method.
CN102441402B discloses a Fischer-Tropsch synthesis catalyst and application thereof, wherein the catalyst comprises a carrier, an active metal component selected from iron and/or cobalt and an auxiliary metal component selected from one or more of noble metals, wherein the active metal component is loaded on the carrier; the preparation method of the catalyst comprises the following steps: (1) carrying out impregnation reaction on the iron-containing compound and/or cobalt-containing compound solution and the carrier; (2) drying and roasting the product obtained in the step (1); (3) carrying out impregnation reaction on a solution containing at least one compound selected from noble metals and the product obtained in the step (2); (4) drying and roasting the product obtained in the step (3); wherein the solution in the step (3) contains alkali, and the molar ratio of the alkali to the noble metal is 20-200. The content of promoter metal is 0.01 to 0.3 wt.%, preferably 0.02 to 0.15 wt.%. Although the method can improve the activity of the catalyst under the condition of low metal content to a certain extent, the activity of the catalyst still needs to be further improved.
Disclosure of Invention
The invention aims to provide a Fischer-Tropsch synthesis catalyst with obviously improved isomer selectivity of a product on the premise of keeping higher Fischer-Tropsch reaction activity and higher C5+ selectivity, and a preparation method and application thereof, and a Fischer-Tropsch synthesis method.
The Fischer-Tropsch synthesis catalyst provided by the invention is a supported catalyst, and comprises a carrier, a carbon component and an active metal component, wherein the carbon component and the active metal component are supported on the carrier, and the active metal component comprises at least one first metal component M selected from non-noble metals in a VIII group1And at least one second metal component M selected from metals of group VIB and/or VIIB2The catalyst satisfies (M)2/M1)XPS/(M2/M1)XRF2.0-20.0, wherein (M)2/M1)XPS(M) the weight ratio, expressed as the element, of the second metal component to the first metal component of the catalyst, characterized by X-ray photoelectron spectroscopy2/M1)XRFThe weight ratio of the second metal component to the first metal component in elemental form in the catalyst is characterized by X-ray fluorescence spectroscopy.
The invention also provides a preparation method of the supported catalyst, which comprises the following steps:
(1) with a first metal component M containing at least one non-noble metal selected from group VIII1The carrier is impregnated by the solution of the compound, and then the impregnated carrier is dried, roasted or not roasted and reduced and activated in sequence;
(2) under a reducing or inert atmosphere, impregnating the product obtained in the step (1) with a solution containing high-boiling point organic matters, and then carrying out heat treatment to obtain a carbon-containing catalyst precursor;
(3) and (3) impregnating the carbon-containing catalyst precursor obtained in the step (2) with a solution containing a compound of a second metal component selected from group VIB and/or VIIB in a reducing atmosphere, and drying and optionally roasting to obtain the supported catalyst.
The invention also provides the supported catalyst prepared by the method and application of the supported catalyst in catalyzing Fischer-Tropsch synthesis reaction.
The invention further provides a Fischer-Tropsch synthesis method, which comprises the step of carrying out contact reaction on carbon monoxide and hydrogen and a catalyst under Fischer-Tropsch synthesis reaction conditions, wherein the catalyst is the supported catalyst.
Compared with the catalyst prepared by the prior art, the catalyst provided by the invention has the advantage that the isomer selectivity of the product is obviously improved on the premise of keeping higher Fischer-Tropsch reaction activity and higher C5+ selectivity. Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an X-ray photoelectron spectrum of W4 f of catalyst R1 obtained in example 1 of the present invention and comparative catalyst D1 obtained in comparative example 1;
FIG. 2 is an X-ray photoelectron spectrum of Co2p of catalyst R1 obtained in example 1 of the present invention and comparative catalyst D1 obtained in comparative example 1.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a supported catalyst, which comprises a carrier and a loadA carbon component and an active metal component on the support, characterized in that the active metal component comprises at least one first metal component M selected from non-noble group VIII metals1And at least one second metal component M selected from groups VIB and/or VIIB2The catalyst satisfies (M)2/M1)XPS/(M2/M1)XRF2.0 to 20.0, preferably, the catalyst satisfies (M)2/M1)XPS/(M2/M1)XRF2.5 to 10, further preferably, the catalyst satisfies (M)2/M1)XPS/(M2/M1)XRF3-5, wherein (M)2/M1)XPS(M) the weight ratio, expressed as the element, of the second metal component to the first metal component of the catalyst, characterized by X-ray photoelectron spectroscopy2/M1)XRFThe weight ratio of the second metal component to the first metal component in elemental form in the catalyst is characterized by X-ray fluorescence spectroscopy.
In the present invention, (M)2/M1)XPSThe catalyst is characterized by X-ray photoelectron spectroscopy, wherein the weight ratio of a second metal component to a first metal component in the catalyst is calculated by metal elements, and the weight ratio is converted by the area of a peak of a characteristic peak of the corresponding metal element, a measuring instrument of the X-ray photoelectron spectroscopy is an ESCALB 250 instrument of Thermo Scientific company, and the measuring condition is that an excitation light source is a monochromator Al K α X-ray of 150kW, and the combination energy is corrected by adopting a C1 s peak (284.8 eV).
In the present invention, (M)2/M1)XRFRefers to the weight ratio of the second metal component to the first metal component in the catalyst characterized by X-ray fluorescence spectrum in terms of metal elements. Wherein the measuring instrument of the X-ray fluorescence spectrum is a 3271 instrument of Nippon science and Motor industry Co., Ltd, and the measuring conditions are as follows: and tabletting and molding the powder sample, wherein the rhodium target is subjected to laser voltage of 50kV and laser current of 50 mA.
Preferably, the content of the first metal component is 5-70 wt%, the content of the second metal component is 0.01-10 wt%, the content of the carbon component is 1-30 wt%, and the balance is a carrier, calculated by element and based on the total weight of the catalyst; further preferably, the content of the first metal component is 8-50 wt%, the content of the second metal component is 0.02-8 wt%, the content of the carbon component is 2-20 wt%, and the balance is the carrier, calculated by element based on the total weight of the catalyst.
According to the present invention, the catalyst preferably further comprises at least one metal promoter selected from the group consisting of Pt, Pd, Ru, Rh, Ir, La, Zr, Ce, Y, and Cu, and the content of the metal promoter in terms of elements is 0.01 to 10 wt%, preferably 0.02 to 8 wt%, and more preferably 0.05 to 5 wt%.
According to the catalyst provided by the invention, preferably, the weight m of carbon component calculated by element in each gram of catalystCThe specific surface area S with the carrier satisfies mC/S＝0.10-4.0mg/(m2(iv)/g); further preferably, the weight m of carbon component calculated as element per gram of catalystCThe specific surface area S with the carrier satisfies mC/S＝0.20-2.5mg/(m2(iv)/g); even more preferably, the weight m of carbon component, calculated as element, per gram of catalystCThe specific surface area S with the carrier satisfies mC/S＝0.50-2.0mg/(m2/g)。
The difference between the supported catalyst of the present invention and the prior art lies in the structural feature that the second metal is directionally supported on the surface of the first metal particle and the carbon-containing component, according to one embodiment of the present invention, the first metal component of the catalyst is at least one of Fe, Co and Ni, preferably Co, and the second metal component is at least one of Mo, W, Re and Mn.
The carrier of the catalyst is not particularly required by the invention, the carrier can be various catalyst carriers which can be used for catalyzing Fischer-Tropsch synthesis reaction, and the carrier is preferably one or more of alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay and molecular sieve, and is preferably one or more of alumina, silica and titania. The carrier can also be one or more of the carriers modified by one or more of phosphorus, silicon, fluorine and boron. The modified carrier can be obtained commercially or modified by the existing method.
According to another aspect of the present invention, there is also provided a method for preparing a supported catalyst, comprising the steps of:
(1) with a first metal component M containing at least one non-noble metal selected from group VIII1The carrier is impregnated by the solution of the compound, and then the impregnated carrier is dried, roasted or not roasted and reduced and activated in sequence;
(2) under a reducing or inert atmosphere, impregnating the product obtained in the step (1) with a solution containing high-boiling point organic matters, and then carrying out heat treatment to obtain a carbon-containing catalyst precursor;
(3) and (3) impregnating the carbon-containing catalyst precursor obtained in the step (2) with a solution containing a compound of a second metal component selected from group VIB and/or VIIB in a reducing atmosphere, and drying and optionally roasting to obtain the supported catalyst.
According to the invention, the first metal component is one or more elements selected from Fe, Co and Ni, preferably, the first metal component is Co; the compound of the first metal component is at least one of nitrate, acetate, sulfate, basic carbonate and chloride containing one or more of Fe, Co and Ni elements; in the solution of the compound containing the first metal active component, the content of the first metal component in terms of the metal element is preferably 50 to 1000 g/l, and more preferably 100 g/l and 700 g/l.
The impregnation method and conditions in steps (1), (2) and (3) are not particularly limited in the present invention and may be the same or different, wherein the impregnation method may be various methods known to those skilled in the art, for example, an equal volume impregnation method, a supersaturated impregnation method, preferably, the steps (1) and (2) employ equal volume impregnation, the volume of the impregnation solution used is calculated by the water absorption rate of the carrier, and the volume of the impregnation solution used in step (3) is 0.5 to 10 times, preferably 1 to 3 times the volume of the impregnation solution used in step (1). The impregnation conditions may be conventional conditions, and the impregnation conditions of step (1) are preferably: the temperature is 10-90 ℃ and the time is 1-10 hours; more preferably: the temperature is 15-40 ℃, and the time is 2-6 hours. The impregnation conditions for steps (2) and (3) are independently preferably: the temperature is 10-90 ℃ and the time is 0.1-10 hours; more preferably: the temperature is 15-40 ℃, and the time is 0.5-2 hours.
According to the invention, the impregnated support obtained in step 1) is first dried and further calcined or not, and then subjected to said reductive activation. The drying and firing are conventional in the art. For example, the drying conditions may be: the temperature is 40-200 ℃, the time is 0.1-24 hours, and the roasting condition can be as follows: the temperature is 200 ℃ and 600 ℃ and the time is 0.1-24 hours.
The reduction activation in step (1) may be carried out in a mixed atmosphere of hydrogen and an inert gas, such as a mixed gas of hydrogen and nitrogen and/or argon, preferably in pure hydrogen. The conditions for the reduction activation are not particularly limited, and the temperature is preferably 200-500 ℃, more preferably 300-500 ℃, more preferably 350-450 ℃, and the time is preferably 1-12 hours, more preferably 1-5 hours, more preferably 2-4 hours. The pressure of the reduction may be normal pressure or increased pressure, and specifically, the partial pressure of hydrogen may be 0.1 to 4MPa, preferably 0.1 to 2 MPa. The pressure in the present invention means an absolute pressure.
According to the present invention, the purpose of the heat treatment in step (2) is to cause the high boiling point organic matter impregnated on the support to be dehydrated and carbonized to form a carbon component supported on the support, and the atmosphere of the heat treatment is not particularly limited, and is preferably performed under oxygen-free conditions. As for the heat treatment conditions, it is preferable that: the temperature is 200-900 ℃ and the time is 0.1-24 hours, and more preferably, the temperature is 300-700 ℃ and the time is 1-12 hours.
The high-boiling-point organic matter in the step (2) is common organic matter with a boiling point higher than 150 ℃, and preferably, the high-boiling-point organic matter is at least one of carbohydrate and polyhydroxy organic matter; wherein, the carbohydrate is at least one of sucrose, glucose, fructose, maltose and starch, the polyhydroxy organic substance is at least one of ethylene glycol, glycerol, 1, 2-propylene glycol, 1, 3-propylene glycol and polyethylene glycol, and the polyethylene glycol can be a commercial reagent, preferably the polyethylene glycol with the number average molecular weight of 190-.
According to the invention, the compound of the second metal component is at least one of soluble compounds containing one or more of Mo, W, Re and Mn elements; the content of the compound of the second metal component in terms of element in the solution containing the compound of the second metal component in the step (3) is preferably 0.1 to 100 g/l, preferably 0.2 to 50 g/l.
Preferably, the solvent used in step (1) and step (2) is water, and the solvent used in step (3) is at least one of water, methanol, ethanol, propanol, ethylene glycol, hexane and cyclohexane.
According to the present invention, the first metal component after reduction in step (1) and the carbon component formed by the heat treatment in step (2) contribute to the promotion of the directional loading of the second metal component in step (3). Therefore, the above method preferably comprises cooling the product after the reduction activation in step (1) to room temperature or the desired temperature in step (2) in a hydrogen and/or inert atmosphere, such as nitrogen and/or argon, and then performing the impregnation in step (2). The method also preferably comprises cooling the product after the heat treatment in the step (2) to room temperature or the temperature required by the step (3) in a hydrogen or inert atmosphere, and then carrying out the impregnation in the step (3).
According to the present invention, the manner and conditions for drying the impregnated product of step (3) are well known to those skilled in the art, and in order to prevent the metal active components in the catalyst from being oxidized, the drying is preferably performed under vacuum conditions or under the protection of inert gas or reducing gas, and the impregnated product is preferably dried by using a gas blow-drying manner of the impregnation atmosphere of step 3). The dried carrier may be further calcined according to the requirement, and the calcination condition may be a conventional calcination condition, for example, under a vacuum condition or under the protection of an inert gas or a reducing gas, at a temperature of 200-600 ℃ for 0.1-24 hours. After completion of step (3), it is preferable to further introduce O2/N2The mixed gas with the volume ratio of 0.05-1.0% is used for 0.5-4 hours to passivate the metal active components in the mixed gas, and the catalyst which can be directly stored in the air is obtained.
According to the present invention, it is preferable that the compound containing the first metal component, the compound containing the second metal component, the high boiling point organic compound are used in an amount and the heat treatment conditions in the step (2) are such that the content of the first metal component is 5 to 70% by weight, the content of the second metal component is 0.01 to 10% by weight, the content of the carbon component is 1 to 30% by weight, and the balance is a carrier, based on the total weight of the catalyst and calculated on elements; further preferably, the content of the first metal component is 8 to 50% by weight, the content of the second metal component is 0.02 to 8% by weight, the content of the carbon component is 2 to 20% by weight, and the balance is a carrier.
According to the invention, under the preferable conditions, the method further comprises the step of introducing a metal auxiliary agent into the carrier, wherein the metal auxiliary agent is at least one selected from Pt, Pd, Ru, Rh, Ir, La, Zr, Ce, Y and Cu. The step of introducing the metal promoter may be carried out once or more at any one period of time before step (2) or after step (2). When the step of introducing the metal promoter is included, it is preferred to introduce it by an impregnation method comprising impregnating the support with a solution containing the metal promoter compound, followed by corresponding drying and optional calcination. If introduced in multiple portions, each impregnation is followed by a corresponding drying and optionally calcination. The impregnation, drying and calcination operations are performed under conventional conditions well known to those skilled in the art and will not be described herein. When the step of introducing the metal promoter is included, the amount of the metal promoter-containing compound solution used is such that the metal promoter content in the final catalyst is 0.01 to 10% by weight, preferably 0.02 to 8% by weight, and more preferably 0.05 to 5% by weight, calculated as the element.
According to the invention, preferably, the selection of the support and the impregnation and heat treatment of step (2) are such that the final content m of the carbon component, expressed as element, per gram of catalyst isCThe specific surface S to the carrier satisfies mC/S＝0.1-4.0mg/(m2/g), more preferably mC/S＝0.20-2.5mg/(m2/g), more preferably mC/S＝0.50-2.0mg/(m2/g)。
As mentioned above, the carrier may be any of various carriers which can be used as a carrier for Fischer-Tropsch synthesis catalysts, such as one or more of alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieves, preferably one or more of alumina, silica, titania. The carrier can also be one or more of the carriers modified by one or more of phosphorus, silicon, fluorine and boron. The modified carrier can be obtained commercially or modified by the existing method.
The invention also provides the supported catalyst prepared by the method and application of the catalyst in Fischer-Tropsch synthesis reaction.
Compared with the prior art, the catalyst provided by the invention maintains higher Fischer-Tropsch reaction activity and higher C5+On the premise of selectivity, the isomer selectivity of the product is obviously improved. The reason for this is probably that the formed second metal is directionally loaded on the surface of the cobalt metal particles and isolated by the surface carbon component, so that the catalyst has relatively proper Fischer-Tropsch synthesis performance and isomerization performance.
The invention also provides a Fischer-Tropsch synthesis method, which comprises the step of carrying out contact reaction on carbon monoxide and hydrogen and a catalyst under the Fischer-Tropsch synthesis reaction condition, wherein the catalyst is the supported catalyst.
The conditions for the contact reaction can be carried out in accordance with the prior art, for example, the molar ratio of hydrogen to carbon monoxide is from 0.5 to 2.6, preferably from 1.5 to 2.4, and more preferably from 1.8 to 2.2, the reaction pressure is from 1 to 10MPa, preferably from 1 to 4MPa, and the reaction temperature is from 150 ℃ to 300 ℃, preferably from 180 ℃ to 250 ℃.
It should be noted that the method of the present invention is suitable for both the fischer-tropsch synthesis reaction of synthesis gas and catalyst, and the fischer-tropsch synthesis reaction of directly contacting hydrogen and carbon monoxide with catalyst.
The means for contacting may be carried out in any reactor sufficient to contact react the feed gas with the catalyst under the reaction conditions, such as one or more of a fixed bed reactor, a slurry bed reactor, a fluidized bed reactor, and a bubble bed reactor.
The following examples are given to facilitate a better understanding of the invention, but do not limit the invention. In the following examples, the percentages stated, unless otherwise specified,are all the mass percentage contents. Wherein the ratio of converted CO to feed CO is defined as CO conversion XCOThe mole percentage of CO converted to methane to CO converted is the methane selectivity SCH4The mole percentage of CO forming C5+ hydrocarbons to converted CO is C5+ selective SC5+The isomer selectivity S is the mass percentage of alkane isomers in the resulting wax (solid at room temperature) to all waxesiso。
The measuring instrument for X-ray photoelectron spectroscopy is an ESCALB 250 type instrument of Thermo Scientific company, the measuring conditions are that an exciting light source is a monochromator Al K α X-ray with 150kW, the combination energy is corrected by a C1 s peak (284.8eV), the measuring instrument for X-ray fluorescence spectroscopy is a 3271 type instrument of Nippon science and electric machinery industry Co., Ltd, and the measuring conditions are that a powder sample is tableted and molded, a rhodium target, the laser voltage is 50kV, and the laser current is 50 mA.
Example 1
(1) Catalyst preparation and characterization
36.1 ml of cobalt nitrate and platinum tetraammine dichloride impregnation solution containing 208 g/l cobalt and 1.38 g/l platinum is prepared according to the content of metal salt required by the equal-volume impregnation method. The impregnation solution was decanted to 42.5 g SiO2The carrier (Nippon Fuji silicon Co., Ltd., average particle size 40-80 μm) was stirred at 20 ℃ and left to stand for 4 hours, then dried at 120 ℃ and calcined at 400 ℃ for 4 hours, and then reduced with hydrogen at 400 ℃ for 4 hours under a hydrogen pressure of 0.1 MPa. Reducing to room temperature after reduction, adding 36.1 ml of 14.5 g/L sucrose aqueous solution under the condition of introducing hydrogen atmosphere, standing for 2 hours, drying at 120 ℃, and heating, dehydrating and carbonizing at 500 ℃. Cooling to room temperature, adding 55.1 ml of ammonium metatungstate aqueous solution containing 9.07 g/L tungsten under hydrogen atmosphere, standing for 2 hours, and blowing with hydrogen. Then pass through O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. The obtained catalyst is marked as R1, and the composition, XPS and XRF characterization results are shown in Table 1, wherein X-ray photoelectron spectra are shown in figures 1 and 2. The atomic ratio (M) of the surface layer was obtained by converting the peak areas corresponding to the electron binding energies of W4 f and Co2p2/M1)XPS. Table 1 also shows the elemental concentrations per gram of catalyst as determined by thermogravimetric analysisCalculated weight m of carbon componentCRatio m to the specific surface S of the supportC/S。
(2) Catalytic Fischer-Tropsch synthesis reaction performance of catalyst
The fischer-tropsch synthesis reaction performance of catalyst R1 was evaluated in a fixed bed reactor. The composition of the raw material gas is H2/CO/N256%/28%/16% (volume percentage), reaction pressure 2.0MPa, reaction temperature 210 ℃. After the reaction had proceeded for 24 hours, a gas sample was taken for chromatography and calculated according to the above definition, and the results are shown in Table 2.
Comparative example 1
(1) Catalyst preparation and characterization
A comparative catalyst D1 which contained no carbon component and the remainder of the same metal component as that of the catalyst R1 was prepared.
36.1 ml of cobalt nitrate and platinum tetraammine dichloride impregnation solution containing 208 g/l cobalt and 1.38 g/l platinum is prepared according to the content of metal salt required by the equal-volume impregnation method. The impregnation solution was decanted to 42.5 g SiO2The carrier (Nippon Fuji silicon Co., Ltd., average particle size 40-80 μm) was stirred at 20 ℃ and left to stand for 4 hours, then dried at 120 ℃ and calcined at 400 ℃ for 4 hours, and then reduced with hydrogen at 400 ℃ for 4 hours under a hydrogen pressure of 0.1 MPa. After reduction, the temperature is reduced to room temperature, 55.1 ml of ammonium metatungstate aqueous solution containing 9.07 g/L of tungsten is added under the atmosphere of hydrogen, the mixture is kept stand for 2 hours, and then the mixture is dried by hydrogen. Then pass through O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. The catalyst obtained was designated as D1 and the characterization results are given in Table 1.
(2) Catalytic Fischer-Tropsch synthesis reaction performance of catalyst
Catalyst D1 was evaluated in the same manner and under the same evaluation conditions as in example 1, and the results are shown in Table 2.
Comparative example 2
(1) Catalyst preparation and characterization
A comparative catalyst D2 was prepared which contained no tungsten component and the remainder contained the same components as those of the catalyst R1.
According to the metal salt content required by the equal-volume impregnation method, 36.1 ml of cobalt nitrate and tetraammineplatinum dichloride containing 208 g/l of cobalt and 1.38 g/l of platinum are preparedThe impregnation solution of (1). The impregnation solution was decanted to 42.5 g SiO2The carrier (Nippon Fuji silicon Co., Ltd., average particle size 40-80 μm) was stirred at 20 ℃ and left to stand for 4 hours, then dried at 120 ℃ and calcined at 400 ℃ for 4 hours, and then reduced with hydrogen at 400 ℃ for 4 hours under a hydrogen pressure of 0.1 MPa. Reducing to room temperature after reduction, adding 36.1 ml of 14.5 g/L sucrose aqueous solution under the condition of introducing hydrogen atmosphere, standing for 2 hours, drying at 120 ℃, and heating, dehydrating and carbonizing at 500 ℃. Cooling to room temperature, and then passing through O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. The catalyst obtained is designated as R1 and the characterization results are given in Table 1.
(2) Catalytic Fischer-Tropsch synthesis reaction performance of catalyst
Catalyst D2 was evaluated in the same manner and under the same evaluation conditions as in example 1, and the results are shown in Table 1.
Comparative example 3
(1) Catalyst preparation and characterization
A comparative catalyst D3 of the same composition as catalyst R1 was prepared using a co-impregnation process.
36.1 ml of impregnation solution containing 208 g/l of cobalt, 1.38 g/l of platinum, 14.5 g/l of sucrose and 13.9 g/l of tungsten, cobalt nitrate, platinum tetraammine dichloride, sucrose and ammonium metatungstate is prepared according to the content of metal salt required by the equal-volume impregnation method. The impregnation solution was decanted to 42.5 g SiO2The carrier (Nippon Fuji silicon Co., Ltd., average particle size 40-80 μm) was stirred at 20 ℃ and left to stand for 4 hours, then dried at 120 ℃ and calcined at 400 ℃ for 4 hours, and then reduced with hydrogen at 400 ℃ for 4 hours under a hydrogen pressure of 0.1 MPa. Reducing to room temperature, and then carrying out O treatment2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. The catalyst obtained was designated as D3 and the characterization results are given in Table 1.
(2) Catalytic Fischer-Tropsch synthesis reaction performance of catalyst
Catalyst D3 was evaluated in the same manner and under the same evaluation conditions as in example 1, and the results are shown in Table 2.
Example 2
(1) Catalyst preparation and characterization
By isovolumetric immersion of the desired metalThe salt content was adjusted to 36.1 ml of a cobalt nitrate and tetraammineplatinum chloride impregnation solution containing 208 g/l cobalt and 1.38 g/l platinum. The impregnation solution was decanted to 42.5 g SiO2The carrier (Nippon Fuji silicon Co., Ltd., average particle size 40-80 μm) was stirred at 20 ℃ and left to stand for 4 hours, then dried at 120 ℃ and calcined at 400 ℃ for 4 hours, and then reduced with hydrogen at 400 ℃ for 4 hours under a hydrogen pressure of 0.1 MPa. Reducing to room temperature after reduction, adding 36.1 ml of 15.3 g/L glucose aqueous solution under the atmosphere of hydrogen, standing for 2 hours, drying at 120 ℃, and heating at 500 ℃ for dehydration and carbonization. Cooling to room temperature, adding 55.1 ml of ammonium molybdate aqueous solution containing 4.54 g/l of molybdenum under the condition of introducing hydrogen atmosphere, standing for 2 hours, and then drying by using hydrogen. Then pass through O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. The catalyst obtained is designated as R2 and the characterization results are given in Table 1.
(2) Catalytic Fischer-Tropsch synthesis reaction performance of catalyst
The fischer-tropsch synthesis reaction performance of catalyst R2 was evaluated in a fixed bed reactor. The composition of the raw material gas is H2/CO/N256%/28%/16% (volume percentage), reaction pressure 2.0MPa, reaction temperature 220 ℃. After the reaction had proceeded for 24 hours, a gas sample was taken for chromatography and calculated according to the above definition, and the results are shown in Table 2.
Example 3
(1) Catalyst preparation and characterization
36.1 ml of cobalt nitrate and ruthenium nitrosyl impregnation solution containing 208 g/l cobalt and 1.38 g/l ruthenium are prepared according to the content of metal salt required by the equal-volume impregnation method. The steep was decanted to 42.5 g of gamma-Al2O3The carrier (Sasol alumina, average grain size 40-80 micron), after stirring and stewing 4 hours at 20 deg.C, drying at 120 deg.C, roasting 4 hours at 500 deg.C, reducing 4 hours with 500 deg.C hydrogen, the pressure of hydrogen is 1.0 MPa. Reducing to room temperature after reduction, adding 36.1 ml of 11.7 g/L aqueous solution of glycerol under the condition of introducing hydrogen atmosphere, standing for 2 hours, drying at 100 ℃, and heating, dehydrating and carbonizing at 400 ℃. Cooling to room temperature, adding 55.1 ml of ammonium metatungstate aqueous solution containing 9.07 g/L tungsten under hydrogen atmosphere, standing for 2 hr, and addingBlow-drying with hydrogen. Then pass through O2/N2And passivating the mixed gas with the volume ratio of 0.5% for 1 hour, and storing the gas in a dryer for standby. The catalyst obtained is designated as R3 and the characterization results are given in Table 1.
(2) Catalytic Fischer-Tropsch synthesis reaction performance of catalyst
The fischer-tropsch synthesis reaction performance of catalyst R3 was evaluated in a fixed bed reactor. The composition of the raw material gas is H2/CO/N256%/28%/16% (volume percentage), reaction pressure 2.5MPa, reaction temperature 210 ℃. After the reaction had proceeded for 24 hours, a gas sample was taken for chromatography and calculated according to the above definition, and the results are shown in Table 2.
Example 4
(1) Catalyst preparation and characterization
36.1 ml of cobalt nitrate and iridium chloride impregnation solution containing 208 g/l cobalt and 0.69 g/l iridium is prepared according to the content of metal salt required by the equal-volume impregnation method. The steep was decanted to 42.5 g of gamma-Al2O3The carrier (Sasol alumina, average particle size 40-80 micron), after stirring and stewing 4 hours at 20 deg.C, drying at 120 deg.C, roasting 4 hours at 350 deg.C, hydrogen reducing 4 hours at 350 deg.C, hydrogen pressure is 0.1 MPa. Reducing to room temperature after reduction, adding 36.1 ml of 7.27 g/L sucrose aqueous solution under the condition of introducing hydrogen atmosphere, standing for 2 hours, drying at 100 ℃, and heating, dehydrating and carbonizing at 500 ℃. Cooling to room temperature, adding 55.1 ml of ammonium molybdate aqueous solution containing 1.81 g/l of molybdenum under the condition of introducing hydrogen atmosphere, standing for 2 hours, and drying by using hydrogen. Then pass through O2/N2And passivating the mixed gas with the volume ratio of 0.5% for 2 hours, and storing the gas in a dryer for standby. The catalyst obtained is designated as R4 and the characterization results are given in Table 1.
(2) Catalytic Fischer-Tropsch synthesis reaction performance of catalyst
The fischer-tropsch synthesis reaction performance of catalyst R4 was evaluated in a fixed bed reactor. The composition of the raw material gas is H2/CO/N256%/28%/16% (volume percentage), reaction pressure 2.5MPa, reaction temperature 210 ℃. After the reaction had proceeded for 24 hours, a gas sample was taken for chromatography and calculated according to the above definition, and the results are shown in Table 2.
TABLE 1
Figure BDA0001257062950000161
TABLE 2
Figure BDA0001257062950000162
Figure BDA0001257062950000171
The results of these examples illustrate that the present invention provides catalysts which maintain higher Fischer-Tropsch activity and higher C than the prior art5+On the premise of selectivity, the isomer selectivity of the product is obviously improved.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.

Claims (41)

1. A method for preparing a supported catalyst, comprising the steps of:
(1) with a first metal component M containing at least one non-noble metal selected from group VIII1The carrier is impregnated by the solution of the compound, and then the impregnated carrier is dried, roasted or not roasted and reduced and activated in sequence;
(2) under a reducing or inert atmosphere, impregnating the product obtained in the step (1) with a solution containing high-boiling point organic matters, and then carrying out heat treatment to obtain a carbon-containing catalyst precursor;
(3) impregnating the carbon-containing catalyst precursor obtained in the step (2) with a solution containing a compound of a second metal component selected from group VIB and/or VIIB in a reducing atmosphere, and drying and optionally roasting to obtain the supported catalyst;
wherein, the compound containing the first metal component, the compound containing the second metal component, the high-boiling point organic matter and the heat treatment condition in the step (2) are used, the content of the first metal component is 5 to 70 weight percent, the content of the second metal component is 0.01 to 10 weight percent, the content of the carbon component is 1 to 30 weight percent and the rest is carrier by taking the total weight of the catalyst as the reference and calculated by elements.
2. The production method according to claim 1, wherein the compound of the first metal component is at least one of nitrate, acetate, sulfate, hydroxycarbonate, and chloride containing at least one non-noble group VIII metal element, and the compound of the second metal component is at least one of soluble compounds containing at least one of Mo, W, Re, and Mn elements.
3. The production method according to claim 1, wherein the high-boiling organic substance is at least one of a carbohydrate and a polyhydroxy organic substance; the carbohydrate is at least one of sucrose, glucose, fructose, maltose and starch, and the polyhydroxy organic matter is at least one of ethylene glycol, glycerol, 1, 2-propylene glycol, 1, 3-propylene glycol and polyethylene glycol.
4. The production method according to any one of claims 1 to 3, wherein the impregnation conditions in the step (1), the step (2) and the step (3) are the same or different and are each independently selected from: the temperature is 10-90 ℃; the time is 0.1-10 hours.
5. The production method according to claim 4, wherein the impregnation conditions in the step (1), the step (2) and the step (3) are each independently selected from: the temperature is 15-40 ℃; the time is 2-6 hours.
6. The production method according to any one of claims 1 to 3 and 5, wherein the drying conditions in step (1) include: the temperature is 40-200 ℃, and the time is 0.1-24 hours; the roasting condition in the step (1) comprises the following steps: the temperature is 200 ℃ and 600 ℃ and the time is 0.1-24 hours.
7. The production method according to claim 4, wherein the drying conditions in step (1) include: the temperature is 40-200 ℃, and the time is 0.1-24 hours; the roasting condition in the step (1) comprises the following steps: the temperature is 200 ℃ and 600 ℃ and the time is 0.1-24 hours.
8. The production method according to any one of claims 1 to 3, 5 and 7, wherein the reductive activation in step (1) is performed under a hydrogen atmosphere, and the conditions of the reductive activation include: the temperature is 200 ℃ and 500 ℃ and the time is 1-12 hours.
9. The production method according to claim 6, wherein the reductive activation of step (1) is performed under a hydrogen atmosphere, and the conditions of the reductive activation include: the temperature is 200 ℃ and 500 ℃ and the time is 1-12 hours.
10. The production method according to any one of claims 1 to 3, 5, 7 and 9, wherein the heat treatment conditions of step (2) include: the temperature is 200 ℃ and 900 ℃ and the time is 0.1-24 hours.
11. The production method according to any one of claim 8, wherein the heat treatment conditions of step (2) include: the temperature is 200 ℃ and 900 ℃ and the time is 0.1-24 hours.
12. The preparation method according to any one of claims 1 to 3, 5, 7, 9 and 11, wherein the method further comprises cooling the product after the reduction activation in the step (1) to room temperature or the temperature required in the step (2) in a hydrogen or inert atmosphere, and then performing the impregnation in the step (2).
13. The method according to claim 10, wherein the method further comprises cooling the product after the reduction activation in step (1) to room temperature or the temperature required in step (2) under hydrogen or inert atmosphere, and then performing the impregnation in step (2).
14. The production method according to any one of claims 1 to 3, 5, 7, 9, 11 and 13, wherein the method further comprises cooling the carbon-containing catalyst precursor after the heat treatment in step (2) to room temperature or the temperature required in step (3) under a hydrogen gas or inert atmosphere, and then performing the impregnation in step (3).
15. The preparation method according to claim 12, wherein the method further comprises cooling the carbon-containing catalyst precursor after the heat treatment in step (2) to room temperature or the temperature required in step (3) under hydrogen or inert atmosphere, and then performing the impregnation in step (3).
16. The production method according to any one of claims 1 to 3, 5, 7, 9, 11, 13 and 15, wherein the method further comprises introducing O into the solid obtained in step (3)2/N2The volume ratio of the mixed gas is 0.05-1.0% for 0.5-4 hours.
17. The production method according to claim 14, further comprising introducing O into the solid obtained in the step (3)2/N2The volume ratio of the mixed gas is 0.05-1.0% for 0.5-4 hours.
18. The method of claim 11, further comprising a step of impregnating with a solution containing a compound of the metal promoter component, the step being performed one or more times before or after step (2).
19. The production method according to claim 18, wherein the metal promoter element comprises at least one selected from the group consisting of Pt, Pd, Ru, Rh, Ir, La, Zr, Ce, Y, Cu, and the solution of the compound containing the metal promoter component is used in an amount such that the metal promoter content in the final catalyst is 0.01 to 10% by weight in terms of element.
20. The process according to claim 19, wherein the solution of the compound containing a metal promoter component is used in an amount such that the metal promoter content in the final catalyst is 0.02 to 8% by weight on an elemental basis.
21. The process according to claim 20, wherein the solution of the compound containing a metal promoter component is used in an amount such that the metal promoter content in the final catalyst is 0.05 to 5% by weight in terms of element.
22. The production method according to claim 1, wherein the selection of the support and the impregnation and heat treatment of step (2) are such that the final content m of the carbon component in terms of element per gram of catalystCThe specific surface S to the carrier satisfies mC/S＝0.1-4.0mg/(m2/g)。
23. The production method according to claim 1, wherein the support is one or more of alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieve.
24. A supported catalyst prepared by the process of any one of claims 1 to 23.
25. A supported catalyst comprising a carrier, a carbon component supported on the carrier and an active metal component, characterized in that the active metal component comprises at least one first metal component M selected from non-noble group VIII metals1And at least one second metal component M selected from metals of group VIB and/or VIIB2The catalyst satisfies (M)2/M1)XPS/(M2/M1)XRF2.0-20.0, wherein (M)2/M1)XPS(M) the weight ratio, expressed as the element, of the second metal component to the first metal component of the catalyst, characterized by X-ray photoelectron spectroscopy2/M1)XRFThe weight ratio of the second metal component to the first metal component in the catalyst is characterized by X-ray fluorescence spectrum; wherein the catalyst is prepared by the preparation method of any one of claims 1 to 23.
26. The catalyst of claim 25, wherein the catalyst satisfies (M)2/M1)XPS/(M2/M1)XRF＝2.5-10。
27. The catalyst of claim 25, wherein the catalyst satisfies (M)2/M1)XPS/(M2/M1)XRF＝3-5。
28. The catalyst of any one of claims 25 to 27, wherein the first metal component is present in an amount of 5 to 70 wt%, the second metal component is present in an amount of 0.01 to 10 wt%, the carbon component is present in an amount of 1 to 30 wt%, and the balance is a support, calculated on an elemental basis and based on the total weight of the catalyst.
29. The catalyst of claim 28, wherein the first metal component is present in an amount of 8 to 50 wt%, the second metal component is present in an amount of 0.02 to 8 wt%, the carbon component is present in an amount of 2 to 20 wt%, and the balance is a support, on an elemental basis, based on the total weight of the catalyst.
30. The catalyst of claim 25, wherein the catalyst comprises at least one metal promoter selected from the group consisting of Pt, Pd, Ru, Rh, Ir, La, Zr, Ce, Y, Cu, in an amount of 0.01 to 10 wt% based on the element and based on the total weight of the catalyst.
31. The catalyst of claim 30 wherein the metal promoter is present in an amount of from 0.02 to 8 wt% on an elemental basis and based on the total weight of the catalyst.
32. The catalyst of claim 31 wherein the metal promoter is present in an amount of from 0.05 to 5 wt% on an elemental basis and based on the total weight of the catalyst.
33. The catalyst of any one of claims 25 to 27, wherein the weight of carbon component, m, in elemental form per gram of catalystCThe specific surface area S with the carrier satisfies mC/S＝0.10-4.0mg/(m2/g)。
34. The catalyst of claim 33, wherein the weight m of carbon component per gram of catalyst, calculated as elementCThe specific surface area S with the carrier satisfies mC/S＝0.20-2.5mg/(m2/g)。
35. The catalyst of claim 34, wherein the weight m of carbon component, calculated as element, per gram of catalystCThe specific surface area S with the carrier satisfies mC/S＝0.50-2.0mg/(m2/g)。
36. The catalyst of any one of claims 25-27, 29-32, 34, 35, wherein the support is one or more of alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieves.
37. The catalyst of claim 33 wherein the support is one or more of alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieves.
38. The catalyst of any one of claims 25-27, 29-32, 34, 35, 37, wherein the X-ray photoelectron spectroscopy is measured by X-ray using a monochromator Al K α with an excitation source of 150kW, and the measurement conditions of the X-ray fluorescence spectroscopy include a rhodium target, a laser voltage of 50kV, and a laser current of 50 mA.
39. The catalyst of claim 36, wherein the X-ray photoelectron spectroscopy is measured by X-ray using a monochromator Al K α having an excitation source of 150kW, and the measurement conditions of the X-ray fluorescence spectroscopy include a rhodium target, a laser voltage of 50kV, and a laser current of 50 mA.
40. Use of a supported catalyst according to any one of claims 24 to 39 in a Fischer-Tropsch synthesis reaction.
41. A Fischer-Tropsch synthesis process comprising contacting carbon monoxide and hydrogen with a catalyst under Fischer-Tropsch synthesis reaction conditions, wherein the catalyst is the supported catalyst of any one of claims 24 to 39, and the Fischer-Tropsch synthesis reaction conditions comprise a molar ratio of hydrogen to carbon monoxide of 0.5 to 2.6, a reaction pressure of 1 to 10MPa, and a reaction temperature of 150 ℃ to 300 ℃.
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