CN111686722A - Ruthenium-based Fischer-Tropsch synthesis catalyst and preparation method and application thereof - Google Patents

Ruthenium-based Fischer-Tropsch synthesis catalyst and preparation method and application thereof Download PDF

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CN111686722A
CN111686722A CN202010542695.1A CN202010542695A CN111686722A CN 111686722 A CN111686722 A CN 111686722A CN 202010542695 A CN202010542695 A CN 202010542695A CN 111686722 A CN111686722 A CN 111686722A
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ruthenium
catalyst
tropsch synthesis
carrier
suspension
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黄礼春
燕来
周建强
索海云
郜文斌
王缠和
李国强
杨勇
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Synfuels China Inner Mongolia Co ltd
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Synfuels China Inner Mongolia Co ltd
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    • 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
    • B01J23/60—Platinum group metals with zinc, cadmium or mercury
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
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    • 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
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • 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
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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
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6562—Manganese
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
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    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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

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Abstract

The invention discloses a ruthenium-based Fischer-Tropsch synthesis catalyst and a preparation method thereof. The ruthenium-based Fischer-Tropsch synthesis catalyst comprises ruthenium, a metal auxiliary agent and a carrier. According to the preparation method of the catalyst, the active component ruthenium of the catalyst is directly reduced on the surface of the carrier through reduction reaction, so that the high-temperature roasting reduction step after ruthenium is loaded in the traditional method is avoided, the sintering phenomenon of ruthenium in the repeated high-temperature roasting reduction process of the catalyst is avoided, and the utilization efficiency of ruthenium in the reaction is ensured. The method can inhibit active ruthenium from sintering and inhibit composite oxide formed between active phase and carrier. The catalyst prepared by the method has the advantages of high activity, low methane selectivity, high heavy hydrocarbon selectivity and the like.

Description

Ruthenium-based Fischer-Tropsch synthesis catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a ruthenium-based Fischer-Tropsch synthesis catalyst, a method for preparing the ruthenium-based Fischer-Tropsch synthesis catalyst through in-situ reduction, and application of the ruthenium-based Fischer-Tropsch synthesis catalyst.
Background
Fischer-Tropsch synthesis (also known as Fischer-Tropsch synthesis) is an important route for converting synthesis gas (with carbon monoxide and hydrogen as the main components) into liquid fuels. The main research targets of F-T synthesis at present are to improve the selectivity of C5+ hydrocarbon and inhibit the generation of by-products such as methane. The key step for realizing the aim is the development and development of the high-activity and high-selectivity F-T synthesis catalyst. How to reasonably match the components (such as active components, auxiliaries and carriers) in the fischer-tropsch synthesis to prepare the fischer-tropsch synthesis catalyst with excellent performance is a hot point of research. The active components of the Fischer-Tropsch synthesis catalyst mainly comprise Fe, Co and Ru, the activity is in the order of Ru > Co > Fe, and the chain growth probability is in the order of Ru > Co > Fe. The ruthenium-based Fischer-Tropsch synthesis catalyst has unique advantages in the aspects of reaction activity, chain growth capability, anti-poisoning capability and the like. Taking catalytic activity as an example, the ruthenium-based Fischer-Tropsch synthesis catalyst can maintain high catalytic activity under high water partial pressure and oxide-containing atmosphere, and the preparation and application costs of the catalyst can be greatly reduced by means of improving the utilization efficiency of ruthenium, prolonging the activity life of ruthenium and the like. Therefore, for the synthesis of the supported ruthenium-based Fischer-Tropsch, the key is to improve the utilization efficiency of ruthenium and add various auxiliary agents to form a high-efficiency ruthenium-based catalyst system.
CN103464147A discloses a preparation method of a ruthenium-containing Fischer-Tropsch synthesis catalyst. The catalyst comprises a carrier and a ruthenium metal component loaded on the carrier, wherein the content of ruthenium calculated by metal is 0.1-15 wt% and the content of the carrier calculated by alumina is 85.0-99.9 wt% based on the catalyst, and the catalyst is prepared by adopting an impregnation method. CN 104437479A and CN 104437480A disclose a ruthenium-based Fischer-Tropsch synthesis catalyst, and preparation and application thereof, which contains an alumina carrier and an active metal component ruthenium, wherein the carrier has a bimodal pore structure. CN 108855058A discloses a ruthenium-based Fischer-Tropsch synthesis catalyst and a preparation method thereof, wherein an alumina precursor is extruded into strips for molding, the molding is dried to obtain a carrier semi-finished product, then the carrier semi-finished product is roasted to obtain an alumina carrier, and then active metal component ruthenium is loaded. CN 109382096A discloses a ruthenium-based Fischer-Tropsch synthesis catalyst and a preparation method thereof, wherein a carrier precursor is extruded and formed to obtain a formed product, the formed product is subjected to water vapor treatment in an atmosphere containing water vapor to obtain a carrier, and then active metal component ruthenium is loaded. The catalyst is prepared by adopting a traditional impregnation method, the active phase of the catalyst is easy to aggregate in the roasting reduction process, the particle size distribution is not uniform, the selectivity of the catalyst C5+ is as high as 93-96%, and the CO conversion rate is lower although the selectivity of C5+ is improved to a certain extent. Therefore, there is a need to develop a highly dispersed ruthenium-based catalyst for fischer-tropsch synthesis.
Disclosure of Invention
The invention aims to provide a ruthenium-based Fischer-Tropsch synthesis catalyst and a method for preparing the ruthenium-based Fischer-Tropsch synthesis catalyst by an in-situ reduction method, the preparation method solves the problem that the sintering phenomenon of ruthenium occurs in the repeated high-temperature roasting reduction process after ruthenium is loaded by the traditional method, and can effectively improve the dispersibility of a catalytic active component ruthenium on the surface of a carrier.
The ruthenium-based Fischer-Tropsch synthesis catalyst provided by the invention comprises ruthenium, a metal auxiliary agent and a carrier, wherein the ruthenium: metal auxiliary agent: the mass ratio of the carrier is (0.5-20): 0.05-10): 100, wherein the ruthenium is calculated by metal, and the metal auxiliary agent is calculated by the metal in the ruthenium.
In a preferred embodiment, in the ruthenium-based fischer-tropsch synthesis catalyst, the ratio of ruthenium: metal auxiliary agent: the mass ratio of the carrier is (2-6): 0.05-10): 100. In a preferred embodiment, in the ruthenium-based fischer-tropsch synthesis catalyst, the ratio of ruthenium: metal auxiliary agent: the mass ratio of the carrier is (0.5-20): 0.1-5): 100.
In a preferred embodiment, in the ruthenium-based fischer-tropsch synthesis catalyst, the ratio of ruthenium: metal auxiliary agent: the mass ratio of the carrier is (2-6): 0.1-5): 100.
For example, in the ruthenium-based fischer-tropsch synthesis catalyst, the ratio of ruthenium: metal auxiliary agent: the mass ratio of the carrier is 2 (0.1-5): 100, 2.5 (0.1-5): 100, 3 (0.1-5): 100, 3.5 (0.1-5): 100, 4 (0.1-5): 100, 4.5 (0.1-5): 100, 5 (0.1-5): 100, 5.5 (0.1-5): 100, 6 (0.1-5): 100.
For example, in the ruthenium-based fischer-tropsch synthesis catalyst, the ratio of ruthenium: metal auxiliary agent: the mass ratio of the carrier is (2-6): 0.1:100, (2-6): 0.5:100, (2-6): 1:100, (2-6): 1.5:100, (2-6): 2:100, (2-6): 2.5:100, (2-6): 3:100, (2-6): 3.5:100, (2-6): 4:100, (2-6): 4.5:100, and (2-6): 5: 100.
For example, in the ruthenium-based fischer-tropsch synthesis catalyst, the ratio of ruthenium: metal auxiliary agent: the mass ratio of the carrier is 2:2: 100.
For example, in the ruthenium-based fischer-tropsch synthesis catalyst, the ratio of ruthenium: metal auxiliary agent: the mass ratio of the carrier is 2:1: 100.
For example, in the ruthenium-based fischer-tropsch synthesis catalyst, the ratio of ruthenium: metal auxiliary agent: the mass ratio of the carrier is 4:0.1: 100.
For example, in the ruthenium-based fischer-tropsch synthesis catalyst, the ratio of ruthenium: metal auxiliary agent: the mass ratio of the carrier is 4:2: 100.
For example, in the ruthenium-based fischer-tropsch synthesis catalyst, the ratio of ruthenium: metal auxiliary agent: the mass ratio of the carrier is 4:5: 100.
For example, in the ruthenium-based fischer-tropsch synthesis catalyst, the ratio of ruthenium: metal auxiliary agent: the mass ratio of the carrier is 6:3: 100.
For example, in the ruthenium-based fischer-tropsch synthesis catalyst, the ratio of ruthenium: metal auxiliary agent: the mass ratio of the carrier is 6:0.2: 100.
The carrier is at least one of alumina, titanium oxide and silicon oxide. In a preferred embodiment, the carrier is in the form of a powder.
As a preferred embodiment, the carrier is characterized by a nitrogen adsorption and desorption curve, and the specific surface area of the alumina powder can be 100-300m2Per g, pore volume of 0.5-1cm3(ii)/g, the average pore diameter may be from 10 to 20 nm; the specific surface area of the titanium oxide powder can be 40-60m2Per g, pore volume of 0.1-0.3cm3(ii)/g, the average pore diameter may be 5-20 nm; the specific surface area of the silicon oxide powder can be 100-300m2Per g, pore volume of 0.7-1.2cm3In terms of/g, the mean pore diameter may be from 10 to 30 nm.
The metal auxiliary agent can be at least one selected from alkali metal, alkaline earth metal, transition metal, rare earth metal and noble metal.
The alkali metals include lithium, sodium and potassium.
The alkaline earth metals include magnesium, calcium, strontium, and barium.
The transition metals include manganese, titanium, vanadium, iron, nickel, copper, zinc, zirconium, niobium, rhenium, thorium and molybdenum.
The rare earth metal comprises scandium, yttrium, lanthanum, cerium, samarium, praseodymium and neodymium.
The noble metal assistant comprises rhodium, palladium, iridium, platinum, gold and silver.
The metal in the metal promoter is preferably selected from at least one of the following: lithium, sodium, magnesium, manganese, titanium, zinc, zirconium, lanthanum, cerium, platinum and silver.
The invention further provides a preparation method of the ruthenium-based Fischer-Tropsch synthesis catalyst, which comprises the following steps:
(1) loading soluble salt of a metal auxiliary agent on the carrier by using an impregnation method, and drying and roasting to obtain a modified carrier A;
(2) preparing a water solution B of soluble ruthenium salt, adding the modified carrier A into the water solution B of the soluble ruthenium salt to obtain a suspension C with a certain solid content, and adjusting the pH value of the suspension C to 4-12 to obtain a suspension D;
(3) adding a reducing agent into the suspension D for reduction in an ice-water bath under continuous stirring, and filtering and drying after the reaction is finished to obtain a material E;
(4) and tabletting, molding and screening the material E to obtain the final catalyst.
The support may be at least one of alumina, titania and silica. In a preferred embodiment, the carrier is in the form of a powder.
In the preparation method, in the step (1), the impregnation method adopts the mode of equal-volume impregnation, over-volume impregnation, one-time impregnation or multiple times of impregnation. The impregnation method is not particularly limited in the present invention, provided that it is sufficient to support the active metal component in the metal assistant on the support. In a preferred embodiment, the impregnation method is an equal volume impregnation.
In a preferred embodiment, the impregnation method comprises: adopting the water solution of the soluble salt of the metal auxiliary agent to impregnate the carrier, wherein the impregnation conditions are as follows: the standing time can be 3-24 h, for example, 3h, 4h, 5h and the like at 20-30 ℃, preferably 25 ℃.
The drying method is a conventional method, for example, a method of heat drying. When the drying method is heating drying, in the step (1), the drying temperature may be 60 to 200 ℃, preferably 100 to 150 ℃, for example 120 ℃, and the time may be 2 to 36 hours, preferably 10 to 24 hours; such as drying at 120 deg.C for 12 h.
When the support impregnated with the metal promoter is calcined, the conditions of the calcination are such as to effect conversion of the compound containing the metal promoter to its oxide. Preferably, in the step (1), the roasting temperature can be 200-800 ℃, preferably 400-600 ℃, and the roasting time can be 2-30 hours, preferably 3-15 hours; for example, the material is roasted at 500 ℃ for 5 h.
In the invention, the soluble salt of the metal auxiliary agent is one or more of water-soluble salt and complex containing the metal auxiliary agent. The soluble salt of the metal promoter may be in the form of a nitrate salt. For example, the soluble salt of the metal promoter is selected from one or more of the following: lithium nitrate, sodium nitrate, magnesium nitrate, manganese nitrate, titanium nitrate, zinc nitrate, zirconium nitrate, lanthanum nitrate, cerium nitrate, platinum nitrate, and silver nitrate. Preferably, the soluble salt of the metal promoter is selected from one or more of the following: one or more of zinc nitrate hexahydrate, manganese nitrate, lanthanum nitrate hexahydrate, lithium nitrate, zirconyl nitrate dihydrate, or silver nitrate.
In the invention, the modified carrier is a carrier containing the oxide of the metal auxiliary agent.
In the step (2), the solid content of the suspension C can be 1-60%, specifically 8-25%, 8-15%, 15-25%, 8%, 15% or 25%. That is, in the suspension C, the content of the modified carrier a may be 1 to 60%, specifically 8 to 25%, 8 to 15%, 15 to 25%, 8%, 15%, or 25%.
In a preferred embodiment, the suspension C is stirred for 0.1 to 6 hours to uniformly mix the soluble ruthenium salt and the modified support, and then the pH of the suspension C is adjusted.
In one embodiment, to enhance the reducibility of the reducing agent, the adjustment of the pH of the suspension C is achieved by adding a nitric acid solution and/or an ethylenediamine solution to the suspension C, thereby obtaining suspension D. Preferably, the pH of the suspension D is 4-12, preferably 7-8. In a preferred embodiment, the concentration of the nitric acid solution or the ethylenediamine solution for adjusting the pH may be 0.01 to 5 mol/L.
The soluble ruthenium salt can be one or more of water-soluble salt and complex containing the ruthenium. Preferably, the soluble ruthenium salt may be at least one of ruthenium nitrosyl nitrate, ruthenium acetylacetonate, ruthenium acetate, and ruthenium trichloride.
In the method, in the step (3), the reducing agent may be potassium borohydride and/or sodium borohydride. The reaction formula is shown as the following formula:
Ru2++2BH4 -+6H2O＝Ru+2H3BO3+7H2
the reduction is carried out for 0.5 to 12 hours, preferably 1 to 5 hours in an ice water bath. In a preferred embodiment, the reduction is carried out under stirring.
In the present invention, the reducing agent is added to the suspension D in the form of an aqueous solution thereof. In the present invention, the reducing agent is added in an excess manner. In a preferred embodiment, the molar ratio of the reducing agent to the ruthenium in the ruthenium-based fischer-tropsch synthesis catalyst may be from 2 to 5:1, as in 3: 1. in a preferred embodiment, the reducing agent is provided in the form of an aqueous solution thereof. For example, in the aqueous solution of the reducing agent, the mass concentration of the reducing agent may be 0.1 to 10 wt%, such as 0.5 wt%.
In the step (3), after the reduction reaction is completed, a washing step may be further included. In a preferred embodiment, in step (3), a reducing agent is added to the suspension D for reduction, and after the reduction is completed, the obtained slurry is filtered, and then washed with deionized water until the filtrate is less than 50ppm, preferably completely free of sodium ions and/or potassium ions, and filtered and dried, thereby obtaining a material E.
In the step (3), it is preferable to suction-filter the slurry after the reduction reaction. With respect to washing, in a preferred embodiment, the resulting filter cake is washed with deionized water.
The drying conditions can be in a wide range, for example, the drying temperature can be 60-200 ℃, and the drying time can be 2-36 h; such as drying at 120 deg.C for 12 h.
And (4) tabletting and forming the material E in powder tabletting, crushing and screening to obtain the final catalyst. In this regard, the parameters used may be selected by those skilled in the art based on the requirements, or may be determined according to the raw material (e.g., carrier) used. In a preferred embodiment, the material E is tabletted at 30MPa, crushed and sieved to 20-40 mesh to obtain the final catalyst.
In the present invention, the drying may be performed in air, an inert atmosphere, or vacuum.
The invention also provides the function of the ruthenium-based Fischer-Tropsch synthesis catalyst in Fischer-Tropsch synthesis. In one embodiment, the invention also provides the application of the ruthenium-based Fischer-Tropsch synthesis catalyst in the preparation of heavy hydrocarbons from synthesis gas.
In one embodiment, the catalytic conditions for the synthesis gas to produce heavy hydrocarbons using the ruthenium-based fischer-tropsch synthesis catalyst of the invention are:
temperature: 180-280 ℃, preferably 200-260 ℃;
pressure: 0.5 to 5.0MPa, preferably 1.0 to 4.0 MPa;
volume space velocity: 300 to 20000h-1Preferably 500 to 10000h-1；
H in synthesis gas2The volume ratio of the carbon to the CO is as follows: 1-3: 1, preferably 1.5 to 2.5: 1.
the carbon number distribution of the heavy hydrocarbon product obtained by preparing the heavy hydrocarbon by the synthesis gas is as follows: 1-80.
The reactor used includes but is not limited to fixed bed reactor, slurry bed reactor.
In the present invention, the heavy hydrocarbon means Fischer-Tropsch wax and has a carbon number of C20-C80.
The invention has the outstanding advantages that:
1) the catalyst prepared by the invention can enable ruthenium nano-particles to directly grow on the carrier, so that the combination of the catalyst particles and the carrier is enhanced, and the catalyst is more stable;
2) the preparation method of the catalyst directly reduces the active component ruthenium of the catalyst on the surface of the carrier through reduction reaction, thereby avoiding the high-temperature roasting reduction step after loading ruthenium by the traditional method, avoiding the sintering phenomenon of ruthenium of the catalyst in the repeated high-temperature roasting reduction process, and effectively improving the dispersibility of the active component ruthenium on the surface of the carrier;
3) according to the preparation method of the catalyst, the active component ruthenium of the catalyst is directly reduced on the surface of the carrier through reduction reaction, so that the reduction of the surface atom migration rate is facilitated, the grain size of an active phase is reduced, and the dispersion degree of the active phase is improved.
4) The preparation method of the catalyst provided by the invention always reacts in a water phase system, a stabilizer or a surfactant is not required to be added, the system is simpler, and the catalyst is green and pollution-free;
5) the catalyst of the invention has the advantages of simple preparation method, strong operability, mild preparation conditions, good reproducibility and larger synthesis application prospect, and is suitable for large-scale industrial production.
In addition, the catalyst prepared by the invention has the advantages of high activity, low methane selectivity, high heavy hydrocarbon selectivity and the like, so the catalyst is suitable for being used as a fixed bed Fischer-Tropsch synthesis catalyst and a slurry bed Fischer-Tropsch synthesis catalyst.
Detailed Description
The invention is further illustrated by the following specific examples.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
In the embodiment of the invention, the specific surface area, the pore volume and the average pore diameter are all characterized by a nitrogen adsorption and desorption curve. The grain size was measured by XRD.
In the present invention, the water used to prepare the aqueous solution is deionized water.
EXAMPLE 1 preparation of catalyst C-1
(1) Weighing 50g of commercial alumina powder, wherein the specific surface area of the alumina powder is 140m2Per g, pore volume of 0.60cm3(ii)/g, average pore diameter 17 nm; weighing 4.55g of zinc nitrate hexahydrate to prepare an aqueous solution according to the content of the metal auxiliary agent zinc of 2 wt% (relative to the carrier), soaking the aqueous solution in the alumina carrier at the temperature of 25 ℃ in an equal volume, and standing for 3 hours; drying at 120 ℃ for 12 h; roasting at 500 ℃ for 5h to obtain a modified carrier A containing metal oxide; the obtained modified carrier A was found to have a specific surface area of 136m2Per g, pore volume of 0.58cm3In g, the mean pore diameter is 17 nm.
(2) Weighing 16g of ruthenium nitrosyl nitrate solution containing 5g of Ru/100g of ruthenium according to the ruthenium content of 2 wt% (relative to the carrier), and adding the solution into 465.5g of water to prepare water solution B; adding 41g of the modified carrier A (containing 40g of alumina) obtained in the step (1) into the aqueous solution B to prepare a suspension C with the solid content of 8%; after stirring for 0.5h, the pH was adjusted to 8 with 1mol/L ethylenediamine, with constant stirring, to form suspension D.
(3) And (3) under the condition of continuously stirring the ice water bath, adding 0.5 wt% of sodium borohydride aqueous solution into the suspension D, wherein the molar ratio of sodium borohydride to ruthenium is 3:1, continuously stirring for 1h, carrying out suction filtration on the slurry, washing the slurry with deionized water until the sodium ion in the filtrate is less than 50ppm, and drying the slurry at 120 ℃ for 12h to obtain a material E.
(4) Pressing the material E under 30MPa for sheet forming, sieving to 20-40 meshes, wherein the specific surface area of the catalyst is 130m2Per g, pore volume of 0.52cm3(iv)/g, average pore diameter 15nm, to obtain the final catalyst C-1.
In catalyst C-1, ruthenium: zinc: alumina 2:2:100 (mass ratio).
The catalyst evaluation test was carried out in a fixed bed reactor under the following reaction conditions: 240 ℃, 3.0MPa and volume space velocity of 4000h-1，H2The volume ratio of CO is 2: 1. The evaluation results of the catalyst are shown in table 1.
The catalyst evaluation test is carried out in a slurry bed reactor under the following reaction conditions: 230 ℃, 3.0MPa and volume space velocity of 6000h-1，H2The volume ratio of CO is 2: 1. The evaluation results of the catalyst are shown in table 1.
EXAMPLE 2 preparation of catalyst C-2
(1) Weighing 50g of commercial alumina powder, wherein the specific surface area of the alumina powder is 140m2Per g, pore volume of 0.60cm3(ii)/g, average pore diameter 17 nm; weighing 3.26g of 50% w/w manganese nitrate aqueous solution (relative to the carrier) according to the manganese content of 1 wt%, soaking the aqueous solution in the alumina powder at the temperature of 25 ℃ in an equal volume, and standing for 3 hours; drying at 120 ℃ for 12 h; roasting at 500 ℃ for 5h to obtain a modified carrier A containing metal oxide; what is needed isThe specific surface area of the obtained modified carrier A was 139m2Per g, pore volume of 0.59cm3In g, the mean pore diameter is 17 nm.
(2) Weighing 16g of ruthenium nitrosyl nitrate solution containing 5g of Ru/100g of ruthenium according to the ruthenium content of 2 wt% (relative to the carrier), and adding the solution into 219.57g of water to prepare water solution B; 40.63g of the modified support A obtained in the step (1) (containing 40g of alumina) was added to the aqueous solution B to prepare a suspension C having a solid content of 15%, and after stirring for 1 hour, the pH was adjusted to 8 with 1mol/L of ethylenediamine with continuous stirring to form a suspension D.
(3) And (3) under the condition of continuously stirring the ice-water bath, adding a 0.5 wt% aqueous solution of sodium borohydride into the suspension D, wherein the molar ratio of the sodium borohydride to the ruthenium is 3:1, continuously stirring for 2h, carrying out suction filtration on the slurry, washing the slurry with deionized water until the sodium ion in the filtrate is less than 50ppm, and drying the slurry for 12h at 120 ℃ to obtain a material E.
(4) Pressing the material E under 30MPa for sheet forming, sieving to 20-40 meshes, wherein the specific surface area of the catalyst is 132m2Per g, pore volume of 0.51cm3(iv)/g, average pore diameter 15nm, to obtain the final catalyst C-2.
In catalyst C-2, ruthenium: manganese: alumina 2:1:100 (mass ratio).
The catalyst evaluation conditions were the same as in example 1. The evaluation results of the catalyst are shown in table 1.
EXAMPLE 3 preparation of catalyst C-3
(1) Weighing 50g of commercial alumina powder, wherein the specific surface area of the alumina powder is 140m2Per g, pore volume of 0.60cm3(ii)/g, average pore diameter 17 nm; weighing 1.56g of lanthanum nitrate hexahydrate to prepare an aqueous solution according to the lanthanum content of 1 wt% (relative to the carrier), soaking the aqueous solution in the alumina powder at the temperature of 25 ℃ in an equal volume, and standing for 3 hours; drying at 120 ℃ for 12 h; roasting at 500 ℃ for 5h to obtain a modified carrier A containing metal oxide; the specific surface area of the obtained modified carrier A was determined to be 137m2Per g, pore volume of 0.59cm3In g, the mean pore diameter is 17 nm.
(2) Weighing 16g of ruthenium nitrosyl nitrate solution containing 5g of Ru/100g of ruthenium according to the ruthenium content of 2 wt% (relative to the carrier), and adding the solution into 108.61g of water to prepare water solution B; 40.47g of the modified carrier A obtained in the step (1) (wherein the modified carrier contains 40g of alumina) is added into the aqueous solution B to prepare a suspension C with a solid content of 25%, and after stirring for 2 hours, the pH is adjusted to 8 by using 1mol/L of ethylenediamine under continuous stirring to form a suspension D.
(3) And (3) under the condition of continuously stirring the ice-water bath, adding a 0.5 wt% aqueous solution of sodium borohydride into the suspension D, wherein the molar ratio of the sodium borohydride to the ruthenium is 3:1, continuously stirring for 4 hours, filtering the slurry, washing the slurry with deionized water until the sodium ion in the filtrate is less than 50ppm, and drying the slurry for 12 hours at 120 ℃ to obtain a material E.
(4) Pressing the material E under 30MPa for sheet forming, sieving to 20-40 meshes, wherein the specific surface area of the catalyst is 133m2Per g, pore volume of 0.53cm3(iv)/g, average pore diameter 15nm, to obtain the final catalyst C-3.
In catalyst C-3, ruthenium: lanthanum: alumina 2:1:100 (mass ratio).
The catalyst evaluation conditions were the same as in example 1. The evaluation results of the catalyst are shown in table 1.
EXAMPLE 4 preparation of catalyst C-4
(1) Weighing 50g of commercial silicon oxide powder with specific surface area of 160m2Per g, pore volume of 0.87cm3(ii)/g, average pore diameter 18 nm; weighing 0.50g of lithium nitrate to prepare an aqueous solution according to the lithium content of 0.1 wt% (relative to the carrier), soaking the aqueous solution in the silicon oxide powder at the temperature of 25 ℃ in an equal volume, and standing for 3 hours; drying at 120 ℃ for 12 h; roasting at 500 ℃ for 5h to obtain a modified carrier A containing metal oxide; the obtained modified carrier A was found to have a specific surface area of 155m2Per g, pore volume of 0.84cm3In g, the mean pore diameter is 17 nm.
(2) Weighing 32g of ruthenium nitrosyl nitrate solution containing 5g of Ru/100g of ruthenium nitrate according to the ruthenium content of 4 wt% (relative to the carrier), and adding the solution into 449.04g of water to prepare water solution B; 40.09g of the modified carrier A obtained in the step (1) (containing 40g of silica) was added to the aqueous solution B to prepare a suspension C having a solid content of 8%, and after stirring for 0.5 hour, the pH was adjusted to 8 with 1mol/L of ethylenediamine under continuous stirring to form a suspension D.
(3) And (3) under the condition of continuously stirring the ice-water bath, adding a 0.5 wt% potassium borohydride aqueous solution into the suspension D, wherein the molar ratio of potassium borohydride to ruthenium is 3:1, continuously stirring for 1h, carrying out suction filtration on the slurry, washing the slurry with deionized water until the potassium ion in the filtrate is less than 50ppm, and drying the slurry for 12h at 120 ℃ to obtain a material E.
(4) Pressing the material E under 30MPa for sheet forming, sieving to 20-40 meshes, wherein the specific surface area of the catalyst is 150m2Per g, pore volume of 0.82cm3The average pore diameter was 17nm, giving the final catalyst C-4.
In catalyst C-4, ruthenium: lithium: silicon oxide ═ 4:0.1:100 (mass ratio).
The catalyst evaluation conditions were the same as in example 1. The evaluation results of the catalyst are shown in table 1.
EXAMPLE 5 preparation of catalyst C-5
(1) Weighing 50g of commercial silicon oxide powder with specific surface area of 160m2Per g, pore volume of 0.87cm3(ii)/g, average pore diameter 18 nm; weighing 3.12g of lanthanum nitrate hexahydrate to prepare an aqueous solution according to the lanthanum content of 2 wt% (relative to the carrier), soaking the aqueous solution in the silicon oxide powder at the temperature of 25 ℃ in an equal volume, and standing for 3 hours; drying at 120 ℃ for 12 h; roasting at 500 ℃ for 5h to obtain a modified carrier A containing metal oxide; the obtained modified carrier A was determined to have a specific surface area of 153m2Per g, pore volume of 0.85cm3In g, the mean pore diameter is 17 nm.
(2) Weighing 32g of ruthenium nitrosyl nitrate solution containing 5g of Ru/100g of ruthenium nitrate according to the ruthenium content of 4 wt% (relative to the carrier), and adding the solution into 210.66g of water to prepare water solution B; 40.94g of the modified carrier A obtained in the step (1) (containing 40g of silica) was added to the aqueous solution B to prepare a suspension C having a solid content of 15%, and after stirring for 1 hour, the pH was adjusted to 8 with 1mol/L of ethylenediamine under continuous stirring to form a suspension D.
(3) And (3) under the condition of continuously stirring the ice-water bath, adding a 0.5 wt% potassium borohydride aqueous solution into the suspension D, wherein the molar ratio of potassium borohydride to ruthenium is 3:1, continuously stirring for 2h, carrying out suction filtration on the slurry, washing the slurry with deionized water until the potassium ion in the filtrate is less than 50ppm, and drying the slurry for 12h at 120 ℃ to obtain a material E.
(4) Pressing the material E under 30MPa for sheet forming, sieving to 20-40 meshes, wherein the specific surface area of the catalyst is 148m2Per g, pore volume of 0.84cm3(iv)/g, average pore diameter 16nm, to obtain the final catalyst C-5.
In catalyst C-5, ruthenium: lanthanum: silicon oxide ═ 4:2:100 (mass ratio).
The catalyst evaluation conditions were the same as in example 1. The evaluation results of the catalyst are shown in table 1.
EXAMPLE 6 preparation of catalyst C-6
(1) Weighing 50g of commercial silicon oxide powder with specific surface area of 160m2Per g, pore volume of 0.87cm3(ii)/g, average pore diameter 18 nm; weighing 7.32g of zirconium oxynitrate dihydrate prepared aqueous solution according to the zirconium content of 5 wt% (relative to the carrier), soaking the solution in the silicon oxide powder at the temperature of 25 ℃ in an equal volume, and standing for 3 hours; drying at 120 ℃ for 12 h; roasting at 500 ℃ for 5h to obtain a modified carrier A containing metal oxide; the obtained modified carrier A was found to have a specific surface area of 150m2Per g, pore volume of 0.84cm3In terms of/g, the mean pore diameter is 19 nm.
(2) Weighing 32g of ruthenium nitrosyl nitrate solution containing 5g of Ru/100g of ruthenium nitrate according to the ruthenium content of 4 wt% (relative to the carrier), and adding the solution into 102.5g of water to prepare water solution B; 42.7g of the modified carrier A obtained in step (1) (containing 40g of silica) was added to the aqueous solution B to prepare a suspension C having a solid content of 25%, and after stirring for 2 hours, the pH was adjusted to 8 with 1mol/L of ethylenediamine under continuous stirring to form a suspension D.
(3) And (3) under the condition of continuously stirring the ice-water bath, adding a 0.5 wt% aqueous solution of sodium borohydride into the suspension D, wherein the molar ratio of the sodium borohydride to the ruthenium is 3:1, continuously stirring for 4 hours, filtering the slurry, washing the slurry with deionized water until the sodium ion in the filtrate is less than 50ppm, and drying the slurry for 12 hours at 120 ℃ to obtain a material E.
(4) Pressing the material E under 30MPa for sheet forming, sieving to 20-40 meshes, wherein the specific surface area of the catalyst is 142m2Per g, pore volume of 0.80cm3The average pore diameter was 16nm, giving the final catalyst C-6.
In catalyst C-6, ruthenium: zirconium: silicon oxide ═ 4:5:100 (mass ratio).
The catalyst evaluation conditions were the same as in example 1. The evaluation results of the catalyst are shown in table 1.
EXAMPLE 7 preparation of catalyst C-7
(1) Weighing 50g of commercial silicon oxide powder with specific surface area of 160m2Per g, pore volume of 0.87cm3(ii)/g, average pore diameter 18 nm; weighing 4.39g of zirconium oxynitrate dihydrate prepared aqueous solution according to the zirconium content of 3 wt% (relative to the carrier), soaking the solution in the silicon oxide powder at the temperature of 25 ℃ in an equal volume, and standing for 3 hours; drying at 120 ℃ for 12 h; roasting at 500 ℃ for 5h to obtain a modified carrier A containing metal oxide; the obtained modified carrier A was found to have a specific surface area of 152m2Per g, pore volume of 0.82cm3In g, the mean pore diameter is 17 nm.
(2) Weighing 48g of ruthenium nitrosyl nitrate solution containing 5g of Ru/100g of ruthenium according to the ruthenium content of 6 wt% (relative to the carrier), and adding the solution into 460.63g of water to prepare water solution B; 41.62g of the modified carrier A obtained in the step (1) (containing 40g of silica) was added to the aqueous solution B to prepare a suspension C having a solid content of 8%, and after stirring for 1 hour, the pH was adjusted to 8 with 1mol/L of ethylenediamine under continuous stirring to form a suspension D.
(3) And (3) under the condition of continuously stirring the ice-water bath, adding a 0.5 wt% aqueous solution of sodium borohydride into the suspension D, wherein the molar ratio of the sodium borohydride to the ruthenium is 3:1, continuously stirring for 1h, carrying out suction filtration on the slurry, washing the slurry with deionized water until the sodium ion in the filtrate is less than 50ppm, and drying the slurry for 12h at 120 ℃ to obtain a material E.
(4) Pressing the material E under 30MPa for sheet forming, sieving to 20-40 meshes, wherein the specific surface area of the catalyst is 143m2Per g, pore volume of 0.76cm3(iv)/g, average pore diameter 15nm, to obtain the final catalyst C-7.
In catalyst C-7, ruthenium: zirconium: silicon oxide ═ 6:3:100 (mass ratio).
The catalyst evaluation conditions were the same as in example 1. The evaluation results of the catalyst are shown in table 1.
EXAMPLE 8 preparation of catalyst C-8
(1) Weighing 50g of commercial alumina powder, wherein the specific surface area of the alumina powder is 140m2Per g, pore volume of 0.60cm3(ii)/g, average pore diameter 17 nm; 0.16g, calculated as 0.2% by weight of silver (relative to the carrier), is weighed outPreparing water solution with silver nitrate, soaking the water solution in the alumina powder at 25 ℃ in an equal volume, and standing for 3 h; drying at 120 ℃ for 12 h; roasting at 500 ℃ for 5h to obtain a modified carrier A containing metal oxide; the obtained modified carrier A was found to have a specific surface area of 132m2Per g, pore volume of 0.58cm3In g, the mean pore diameter is 17 nm.
(2) Weighing 48g of ruthenium nitrosyl nitrate solution containing 5g of Ru/100g of ruthenium according to the ruthenium content of 6 wt% (relative to the carrier), and adding the solution into 195.18g of water to prepare water solution B; 40.09g of the modified carrier A obtained in the step (1) (wherein the modified carrier contains 40g of alumina) is added into the aqueous solution B to prepare a suspension C with a solid content of 15%, and after stirring for 0.5h, the pH is adjusted to 8 by using 1mol/L of ethylenediamine under continuous stirring to form a suspension D.
(3) And (3) under the condition of continuously stirring the ice-water bath, adding a 0.5 wt% potassium borohydride aqueous solution into the suspension D, wherein the molar ratio of potassium borohydride to ruthenium is 3:1, continuously stirring for 1h, carrying out suction filtration on the slurry, washing the slurry with deionized water until the potassium ion in the filtrate is less than 50ppm, and drying the slurry for 12h at 120 ℃ to obtain a material E.
(4) Pressing the material E under 30MPa for sheet forming, sieving to 20-40 meshes, wherein the specific surface area of the catalyst is 128m2Per g, pore volume of 0.52cm3The average pore diameter was 14nm, giving the final catalyst C-8.
In catalyst C-8, ruthenium: silver: alumina ═ 6:0.2:100 (mass ratio).
The catalyst evaluation conditions were the same as in example 1. The evaluation results of the catalyst are shown in table 1.
Comparative examples 1C-1 comparative examples C-db
(1) Weighing 50g of commercial alumina powder, wherein the specific surface area of the alumina powder is 140m2Per g, pore volume of 0.60cm3(ii)/g, average pore diameter 17 nm; weighing 4.55g of zinc nitrate hexahydrate prepared aqueous solution according to the zinc content of 2 wt% (relative to the carrier), soaking the aqueous solution in the alumina powder at the temperature of 25 ℃ in an equal volume, and standing for 3 hours; drying at 120 ℃ for 12 h; roasting at 500 ℃ for 5h to obtain a modified carrier A containing metal oxide; the obtained modified carrier A was found to have a specific surface area of 136m2Per g, pore volume of 0.58cm3Per g, mean pore diameterIs 17 nm.
(2) Based on 2 wt% of ruthenium content (relative to the carrier), 16g of ruthenium nitrosyl nitrate solution containing 5g of Ru/100g of ruthenium is weighed and added into 48g of water, the mixture is immersed in 40g of modified carrier A in equal volume, the mixture is dried at 120 ℃ for 12h, and the mixture is roasted at 350 ℃ for 5h to obtain material B.
(3) Pressing the material B under 30MPa for sheet forming, sieving to 20-40 meshes, wherein the specific surface area of the catalyst is 115m2Per g, pore volume of 0.50cm3The average pore diameter is 15nm, and the final catalyst C-db is obtained.
In comparative example 1, ruthenium: zinc: alumina 2:2:100 (mass ratio).
The catalyst evaluation test was carried out in a fixed bed reactor under the following reduction conditions: h2350 ℃, 1MPa and volume space velocity of 1000h-1Keeping the temperature constant for 5 hours; the reaction conditions are as follows: 240 ℃, 3.0MPa and volume space velocity of 4000h-1，H2The volume ratio of CO is 2: 1. The evaluation results of the catalyst are shown in table 1.
The catalyst evaluation test was carried out in a slurry bed reactor under the following reduction conditions: h2300 ℃, 3MPa and volume space velocity of 3000h-1Keeping the temperature constant for 5 hours; the reaction conditions are as follows: 230 ℃, 3.0MPa and volume space velocity of 6000h-1，H2The volume ratio of CO is 2: 1. The evaluation results of the catalyst are shown in table 1.
As can be seen from the data in Table 1, the catalyst prepared by the method provided by the invention has the advantages of small crystal grain size, good dispersibility and good reaction performance, and the catalyst prepared by the method has high activity, low methane selectivity and heavy hydrocarbon (C)5High (+) selectivity.
Table 1 shows the calculated grain size of the catalyst XRD characterization and the evaluation results of the catalyst.
Figure BDA0002539570030000141

Claims (10)

1. A ruthenium-based Fischer-Tropsch synthesis catalyst comprises ruthenium, a metal auxiliary agent and a carrier;
wherein, ruthenium in terms of metal: metal additives in terms of metal: the mass ratio of the carrier is (0.5-20): (0.05-10): 100, preferably (2-6): (0.1-5): 100.
2. a ruthenium-based fischer-tropsch synthesis catalyst according to claim 1, wherein the support is at least one of alumina, titania and silica.
3. A ruthenium-based fischer-tropsch synthesis catalyst according to claim 2, characterised in that the support is in powder form.
4. A ruthenium-based fischer-tropsch synthesis catalyst according to claim 1 or 2, wherein the metal promoter is selected from at least one of alkali, alkaline earth, transition, rare earth and precious metals.
5. A method for preparing a ruthenium-based Fischer-Tropsch synthesis catalyst according to any one of claims 1 to 4, the method comprising:
(1) loading soluble salt of the metal additive on a carrier by using an impregnation method, and drying and roasting to obtain a modified carrier A;
(2) preparing a water solution B of soluble ruthenium salt, adding the modified carrier A into the water solution B of the soluble ruthenium salt to obtain a suspension C, and adjusting the pH value of the suspension C to 4-12 to obtain a suspension D;
(3) adding a reducing agent into the suspension D for reduction in an ice-water bath under continuous stirring, and filtering and drying after the reaction is finished to obtain a material E;
(4) and tabletting, molding, crushing and screening the material E to obtain the ruthenium-based Fischer-Tropsch synthesis catalyst.
6. The method according to claim 5, wherein in step (1), the impregnation method is selected from one or more of equal volume impregnation, over volume impregnation, one impregnation or multiple impregnations;
preferably, in step (1), the support is impregnated with an aqueous solution of a soluble salt of the metal promoter;
preferably, in the step (1), the drying temperature is 60-200 ℃ and the drying time is 2-36 h;
preferably, in the step (1), the roasting temperature is 200-800 ℃ and the roasting time is 2-30 h;
more preferably, the soluble salt of the metal promoter is a nitrate salt.
7. The method according to claim 5 or 6, wherein in step (2), the solid content of the suspension C is 1% to 60%;
preferably, after the suspension C is stirred for 0.1-6 hours, the pH value of the suspension C is adjusted;
more preferably, the adjustment of the pH of the suspension C is achieved by adding a nitric acid solution and/or an ethylenediamine solution to the suspension C.
8. The process according to any one of claims 5 to 7, wherein in step (2), the soluble ruthenium salt is selected from at least one of ruthenium nitrosyl nitrate, ruthenium acetylacetonate, ruthenium acetate and ruthenium trichloride.
9. The method according to any one of claims 5 to 8, wherein, in step (3), the reducing agent is potassium borohydride or sodium borohydride;
preferably, the reducing agent is added to the suspension D in the form of an aqueous solution thereof;
more preferably, the molar ratio of the reducing agent to the ruthenium is 2-5: 1;
preferably, the method also comprises a step of washing after the reduction is finished;
more preferably, in the step (3), the drying temperature is 60-200 ℃ and the drying time is 2-36 h.
10. Use of the ruthenium-based fischer-tropsch synthesis catalyst of any of claims 1 to 4 in fischer-tropsch synthesis reactions, preferably comprising fixed bed fischer-tropsch synthesis reactions, slurry bed fischer-tropsch synthesis reactions.
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