Cobalt-based Fischer-Tropsch synthesis catalyst and preparation method and application thereof

Abstract

The invention belongs to the technical field of Fischer-Tropsch synthesis catalysts, and particularly relates to a cobalt-based Fischer-Tropsch synthesis catalyst and a preparation method and application thereof.The preparation method comprises the steps that 1, a mixed solution containing an active metal precursor and an auxiliary precursor, a precipitator and dispersion liquid containing a carrier are in contact for a precipitation reaction, and aging treatment is conducted; and (2) filtering, washing, drying and roasting the material obtained in the step (1) to obtain the cobalt-based Fischer-Tropsch synthesis catalyst, the carrier is a titanium dioxide carrier with high chlorine content, and the chlorine content ranges from 0.3 wt% to 5wt%. The cobalt-based Fischer-Tropsch synthesis catalyst obtained in the invention has the advantages of less chlorine loss in the Fischer-Tropsch synthesis reaction process, low catalyst deactivation rate and excellent stability, and is especially suitable for a cobalt-based Fischer-Tropsch synthesis process adopting a fixed bed reactor.

Description

Technical Field

[0001] The present invention belongs to the technical field of Fischer-Tropsch synthesis catalysts, and in particular relates to a cobalt-based Fischer-Tropsch synthesis catalyst and a preparation method and application thereof. Background Art

[0002] Fischer-Tropsch synthesis technology is one of the key technologies for the clean utilization of coal and natural gas. The Fischer-Tropsch synthesis reaction converts synthesis gas into hydrocarbons on a catalyst. Its main products include alkanes and olefins. After deep processing, the Fischer-Tropsch synthesis products can be obtained into high-quality liquid fuels and chemicals.

[0003] Since the advent of Fischer-Tropsch synthesis technology, the active components of the catalysts used are mainly transition metals such as Fe, Co, Ni and Ru. Among them, the catalytic hydrogenation activity of Ni-based catalysts is too strong, and its hydrogenation reaction product is mainly CH4; Ru-based catalysts have high low-temperature hydrogenation activity, and the reaction products are mainly long-chain hydrocarbons, which are more suitable catalysts for Fischer-Tropsch synthesis. However, due to factors such as the small global reserves and high prices of Ru, it cannot be used for large-scale production. Combined with factors such as product distribution, production feasibility and economy, the most suitable active metal components in Fischer-Tropsch synthesis catalysts are Fe and Co.

[0004] Compared with iron-based Fischer-Tropsch synthesis catalysts, Co-based Fischer-Tropsch synthesis catalysts have outstanding advantages such as high activity, weak water-gas shift reaction, heavy hydrocarbon selectivity, high carbon utilization and long life, and have become a research hotspot for FT synthesis catalysts. However, the price of cobalt-based Fischer-Tropsch synthesis catalysts is relatively high, so the requirements for their life are relatively high. The stability of the catalyst has always been a key point and difficulty that needs to be overcome in this field.

[0005] In the Fischer-Tropsch synthesis reaction, in addition to the synthesis of hydrocarbons, a large amount of water vapor is also generated. Therefore, in industrial production, especially when using a tube-in-tube fixed-bed reactor, there are more stringent requirements on the hydrothermal stability of the cobalt-based Fischer-Tropsch synthesis catalyst.

[0006] The hydrothermal stability of TiO2 is significantly better than that of γ-Al2O3 and SiO2, so TiO2 is often used as a carrier for cobalt-based Fischer-Tropsch synthesis catalysts in industry. TiO2 as a catalyst carrier is usually composed of two crystal phases, anatase and rutile. Patent document CN1230164A discloses a cobalt-based Fischer-Tropsch synthesis catalyst with a titanium dioxide carrier, wherein the ratio of rutile to anatase in the titanium dioxide is less than 2:3; the pore volume of the carrier measured by mercury porosimetry is at least 0.45 ml / g. Patent document CN109289864A discloses a high-performance cobalt-based catalyst and its preparation method and application, wherein the cobalt-based catalyst comprises: Co: 10-40%; Mn: 0-5%; TiO2: 55-90%. The catalyst has high activity in the Fischer-Tropsch synthesis reaction, a CO conversion rate of up to 97.1%, high selectivity for heavy hydrocarbons (C5+), extremely low selectivity for the main byproducts methane and carbon dioxide, good stability, and has the advantages of low cost, simple preparation, and easy industrial scale-up.

[0007] Generally speaking, chlorine in the carrier is regarded as an impurity in a cobalt-based Fischer-Tropsch synthesis catalyst. For example, patent document US20100048742A1 points out that when a cobalt-based Fischer-Tropsch catalyst is prepared using alumina obtained by precipitation as a carrier, the alumina needs to be washed to remove the impurity chlorine. The patent also points out that when the catalyst contains chlorine impurities, the catalyst activity and / or C5+ hydrocarbon selectivity may be reduced.

[0008] In the cobalt-based Fischer-Tropsch preparation method, when the active component is loaded on the carrier, it is often necessary to add an exogenous chlorine-containing solution to contact the carrier. For example, patent document US20160175821A1 discloses a chlorine-containing cobalt-based Fischer-Tropsch preparation method and its use; the catalyst is composed of titanium dioxide and at least 5wt% cobalt, 0.1-15wt% of an additive, and the additive includes manganese, rhenium, Group 8-10 noble metals or mixtures thereof; the catalyst is impregnated with a solution containing chloride ions, and the impregnated catalyst is heated at a temperature of 100-500°C for at least 5 minutes to 2 days; the prepared catalyst will contain 0.13-10wt% of chlorine. Patent document CN105392558A discloses a method for preparing a chlorine-containing Fischer-Tropsch catalyst, comprising the following steps: (a) contacting the following substances with titanium dioxide: cobalt and / or cobalt compounds; one or more promoters, wherein the promoters include manganese, rhenium, noble metals of Groups 8-10 or mixtures thereof; one or more metal chloride salts, hydrochloric acid HCl, one or more organic chlorides or combinations thereof; and optionally one or more promoters; after treatment at 70-350°C, the catalyst contains at least 5wt% cobalt, 0.1-15wt% promoter, and 0.15-3wt% elemental chlorine, based on the total weight of the catalyst. The patent confirms through examples that the addition of Cl-containing compounds improves the selectivity of the catalyst to C5+ hydrocarbons.

[0009] The inventors of the present application have discovered that when chlorine is introduced exogenously into the catalyst in the above-mentioned manner, as the Fischer-Tropsch synthesis reaction proceeds, the chlorine in the catalyst will gradually be lost, thereby causing a reduction in catalyst performance and may even cause rapid deactivation of the catalyst. At the same time, the lost chlorine will also cause corrosion to the reaction equipment. Summary of the invention

[0010] In order to solve the problems existing in the existing cobalt-based Fischer-Tropsch synthesis catalysts, the object of the present invention is to provide a highly stable cobalt-based Fischer-Tropsch synthesis catalyst and a preparation method thereof. The obtained cobalt-based Fischer-Tropsch synthesis catalyst has less chlorine loss during the Fischer-Tropsch synthesis reaction, low catalyst deactivation rate and excellent stability, and is particularly suitable for a cobalt-based Fischer-Tropsch synthesis process using a fixed bed reactor.

[0011] In order to achieve the above object, the present invention provides the following technical solutions:

[0012] In a first aspect, a method for preparing a cobalt-based Fischer-Tropsch synthesis catalyst is provided, comprising the following steps:

[0013] (1) contacting a mixed solution containing an active metal precursor and an auxiliary agent precursor, a precipitant and a dispersion containing a carrier to perform a deposition precipitation reaction, and performing an aging treatment on the obtained precipitate;

[0014] (2) filtering, washing, drying and calcining the material obtained in step (1) to obtain a cobalt-based Fischer-Tropsch synthesis catalyst.

[0015] According to the preparation method provided by the present invention, in some embodiments, the carrier is a titanium dioxide carrier with a high chlorine content.

[0016] In some embodiments, the chloride (ion) content ranges from 0.3 to 5wt%, based on the weight of the titanium dioxide carrier, for example, 0.35wt%, 0.4wt%, 0.5wt%, 0.8wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.2wt%, 2.5wt%, 2.8wt%, 3.0wt%, 3.2wt%, 3.5wt%, 4.0wt%, 4.5wt%; preferably 0.3-3wt%.

[0017] In the present invention, the Co source is selected from soluble salts of Co. In some embodiments, the active metal precursor (ie, the Co source) is selected from at least one of cobalt nitrate, cobalt carbonate, cobalt acetate, and cobalt chloride.

[0018] In the present invention, the additive source is selected from the soluble salts corresponding to each additive. In some embodiments, the additive precursor (i.e., the additive source) is selected from at least one of the soluble salts of Mn, V, Ce, Re, Ru, Hf, Zr, Ti, and Cr.

[0019] In some embodiments, the precipitant is selected from at least one of sodium hydroxide solution, sodium carbonate solution, aqueous ammonia, ammonium carbonate solution, ammonium bicarbonate solution and potassium carbonate solution.

[0020] In some embodiments, the molar ratio of active metal precursor: auxiliary agent precursor: carrier is (0.10-2.0): (0.002-0.2): 1. For example, based on 1 mol of carrier, the molar amount of active metal precursor can be 0.1 mol, 0.15 mol, 0.2 mol, 0.3 mol, 0.4 mol, 0.5 mol, 0.8 mol, 1.0 mol, 1.5 mol, and the molar amount of auxiliary agent precursor can be 0.002 mol, 0.005 mol, 0.01 mol, 0.02 mol, 0.04 mol, 0.05 mol, 0.09 mol, 0.1 mol, 0.15 mol.

[0021] In step (1), a solution containing an active metal precursor and a solution containing an auxiliary agent precursor can be prepared in advance (when preparing each solution, the sum of the concentrations of the two solutions is 0.5-3 mol / L), and then the two can be mixed; alternatively, a mixed solution containing an active metal precursor and an auxiliary agent precursor can be prepared in advance; and a dispersion containing a carrier can also be prepared in advance, and a precipitant can be prepared in advance.

[0022] In some embodiments, the concentration of the mixed solution containing the active metal precursor and the auxiliary agent precursor is 0.5-3 mol / L, for example, 0.6 mol / L, 0.8 mol / L, 1.0 mol / L, 1.5 mol / L, 2.0 mol / L, 2.5 mol / L.

[0023] In some embodiments, the concentration of the precipitant is 1.0-4.0 mol / L, for example, 1.2 mol / L, 1.5 mol / L, 2.0 mol / L, 2.5 mol / L, 3.0 mol / L, 3.5 mol / L.

[0024] In some embodiments, the amount of the precipitant is determined according to the required pH value of the precipitation environment in the reaction, the pH of the control system in the deposition precipitation reaction is 7.0-10.0 (for example, 7.5, 8.0, 8.5, 9.0, 9.5), and the temperature of the deposition precipitation reaction is 40-90°C (for example, 50°C, 60°C, 80°C, 85°C).

[0025] After the precipitation reaction is completed, the precipitate obtained in the system is contacted with the solution for a period of time under certain conditions for aging treatment. In some embodiments, the process conditions of the aging treatment include: an aging time of 1-5 hours (e.g., 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours), an aging temperature of 40-90°C (e.g., 50°C, 60°C, 80°C, 85°C), and a control system pH of 7.0-10.0 (e.g., 7.5, 8.0, 8.5, 9.0, 9.5).

[0026] In some embodiments, the drying process conditions include: a drying temperature of 60-150°C (e.g., 70°C, 80°C, 90°C, 100°C, 120°C, 130°C, 140°C), and a drying time of 2-48h (e.g., 4h, 5h, 8h, 10h, 15h, 20h, 30h, 40h, 45h).

[0027] In some embodiments, the calcination process conditions include: a calcination temperature of 350-700°C (e.g., 360°C, 380°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C), and a calcination time of 2-48h (e.g., 4h, 5h, 8h, 10h, 15h, 20h, 30h, 40h, 45h).

[0028] In the present invention, the catalyst is prepared according to the above method. After precipitation and deposition operation, the components in the catalyst are mixed more evenly, the cobalt species have higher dispersion, and the catalytic activity and stability are further improved.

[0029] In a second aspect, a cobalt-based Fischer-Tropsch synthesis catalyst is provided, wherein the cobalt-based Fischer-Tropsch synthesis catalyst comprises the following components, based on the total weight of the catalyst:

[0030] 10%-40% (e.g., 12wt%, 14wt%, 15wt%, 16wt%, 20wt%, 25wt%, 30wt%, 34wt%, 35wt%, 38wt%) of active ingredient cobalt (e.g., calculated as element),

[0031] 0.1-5wt% (e.g., 0.15wt%, 0.3wt%, 0.5wt%, 0.8wt%, 1wt%, 1.2wt%, 1.5wt%, 1.8wt%, 2wt%, 2.2wt%, 2.5wt%, 3wt%, 3.2wt%, 3.5wt%, 3.8wt%, 4.0wt%, 4.2wt%, 4.5wt%, 4.8wt%) of an auxiliary component (e.g., calculated as an element), wherein the auxiliary component is selected from one or more of Mn, V, Ce, Re, Ru, Hf, Zr, Ti and Cr,

[0032] 0.2-3 wt% (e.g., 0.22 wt%, 0.25 wt%, 0.28 wt%, 0.3 wt%, 0.32 wt%, 0.35 wt%, 0.38 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.8 wt%, 1.0 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2.0 wt%, 2.5 wt%) of chlorine;

[0033] The balance is titanium dioxide support.

[0034] According to the catalyst provided by the present invention, in some embodiments, the cobalt-based Fischer-Tropsch synthesis catalyst is prepared by the preparation method as described above. In some embodiments, in the catalyst preparation method, the amount of each raw material component can be calculated based on the content range of each component in the catalyst product.

[0035] In a third aspect, there is provided a cobalt-based Fischer-Tropsch synthesis catalyst prepared by the preparation method described above or use of the cobalt-based Fischer-Tropsch synthesis catalyst described above in a Fischer-Tropsch synthesis reaction.

[0036] The operating steps, process conditions and reaction apparatus of the Fischer-Tropsch synthesis reaction may be conventional choices in the art and will not be described in detail here.

[0037] The present invention selects titanium dioxide with a high chlorine content as a carrier, adopts a deposition precipitation method, and controls the precipitation reaction and aging treatment process parameters in this process. The obtained cobalt-based Fischer-Tropsch synthesis catalyst has high stability, less chlorine loss when applied to the Fischer-Tropsch synthesis reaction, low catalyst deactivation rate, and excellent catalytic performance.

[0038] The preparation process of the catalyst of the present invention is simple. When the catalyst is applied to the Fischer-Tropsch synthesis reaction, less chlorine is lost during the reaction, which can overcome the defect of serious chlorine loss when the catalyst with exogenously introduced chlorine element is applied to the Fischer-Tropsch synthesis reaction. The catalyst has a low deactivation rate and excellent stability, and is particularly suitable for a fixed-bed cobalt-based Fischer-Tropsch synthesis process. DETAILED DESCRIPTION

[0039] In order to understand the technical features and content of the present invention in detail, the preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described in the embodiments, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments described herein. For those who do not specify specific conditions in the embodiments, they are carried out according to normal conditions or the conditions recommended by the manufacturer.

[0040] <Source of raw materials>

[0041] In the following examples and comparative examples, the sources of some reagents or raw materials used, without specifying the manufacturer, are all conventional products that can be purchased commercially.

[0042] Embodiment 1:

[0043] (1) Weigh 50 g of titanium dioxide (the chlorine content is 0.6 wt % based on the weight of titanium dioxide) and disperse it in deionized water. Stir for 1 h to obtain a suspension, and prepare a dispersion containing a carrier; dissolve 52.6 g of cobalt nitrate (hexahydrate) and 20 g of a 50 wt % manganese nitrate solution in 150 g of water to prepare a mixed solution containing cobalt nitrate and manganese nitrate; prepare ammonia water with a concentration of 2.8 mol / L;

[0044] Ammonia water and a mixed solution containing cobalt nitrate and manganese nitrate are added dropwise to the prepared suspension to perform a precipitation reaction, the pH value of the system is adjusted to 8.0 by the amount of ammonia water added, the temperature is controlled to 60° C., and then aged for 4 hours under this condition to obtain a precipitate;

[0045] (2) The material obtained in step (1) was filtered and washed, and the filter cake was dried at 120° C. for 10 h and then calcined at 500° C. for 3 h to obtain a cobalt-based Fischer-Tropsch synthesis catalyst A.

[0046] According to XRF testing, based on the total weight of catalyst A, the Cl content is 0.39 wt%.

[0047] Example 2

[0048] The preparation steps of the cobalt-based Fischer-Tropsch synthesis catalyst refer to Example 1, except that the chlorine content in the titanium dioxide used in step (1) is 0.3 wt %; the remaining steps are the same as Comparative Example 1.

[0049] Finally, a cobalt-based Fischer-Tropsch synthesis catalyst B is obtained.

[0050] According to XRF testing, based on the total weight of Catalyst B, the Cl content was 0.20 wt%.

[0051] Example 3

[0052] The preparation steps of the cobalt-based Fischer-Tropsch synthesis catalyst refer to Example 1, except that the chlorine content in the titanium dioxide used in step (1) is 3 wt %; the remaining steps are the same as Comparative Example 1.

[0053] Finally, a cobalt-based Fischer-Tropsch synthesis catalyst C is obtained.

[0054] According to XRF testing, based on the total weight of the catalyst C, the Cl content is 1.78 wt%.

[0055] Example 4

[0056] The preparation steps of the cobalt-based Fischer-Tropsch synthesis catalyst refer to Example 1, except that the precipitant in step (1) is replaced by a sodium carbonate solution with a concentration of 1.0 mol / L; the remaining steps are the same as those in Comparative Example 1.

[0057] Finally, a cobalt-based Fischer-Tropsch synthesis catalyst D was obtained.

[0058] According to XRF testing, based on the total weight of the catalyst D, the Cl content is 0.34 wt%.

[0059] Example 5

[0060] The preparation steps of the cobalt-based Fischer-Tropsch synthesis catalyst refer to Example 1, except that the amount of the 50 wt % manganese nitrate solution in step (1) is changed to 7.0 g; the remaining steps are the same as those in Comparative Example 1.

[0061] Finally, the cobalt-based Fischer-Tropsch synthesis catalyst E is obtained.

[0062] According to XRF testing, based on the total weight of the catalyst E, the Cl content was 0.41 wt%.

[0063] Example 6

[0064] The preparation steps of the cobalt-based Fischer-Tropsch synthesis catalyst refer to Example 1, except that the amount of cobalt nitrate (hexahydrate) in step (1) is changed to 180 g; the remaining steps are the same as Comparative Example 1.

[0065] Finally, a cobalt-based Fischer-Tropsch synthesis catalyst F is obtained.

[0066] According to XRF testing, based on the total weight of Catalyst F, the Cl content is 0.26 wt%.

[0067] Example 7

[0068] The preparation steps of the cobalt-based Fischer-Tropsch synthesis catalyst refer to Example 1, except that the amount of cobalt nitrate (hexahydrate) in step (1) is changed to 38 g, and the amount of 50 wt% manganese nitrate solution is changed to 4.0 g; the remaining steps are the same as those in Comparative Example 1.

[0069] Finally, the cobalt-based Fischer-Tropsch synthesis catalyst G is obtained.

[0070] According to XRF testing, based on the total weight of the catalyst G, the Cl content was 0.43 wt%.

[0071] Comparative Example 1:

[0072] Weigh 50g of titanium dioxide (the chlorine content is 0.03wt% based on the weight of titanium dioxide), dissolve 52.6g of cobalt nitrate (hexahydrate) and 1.689g of cobalt chloride (hexahydrate) in 30g of water to prepare a salt solution, directly add the salt solution dropwise to the carrier, stir evenly, and soak for 6 hours; then dry the obtained material at 120°C for 10h, and then calcine at 500°C for 3h to obtain a cobalt-based catalyst A'.

[0073] According to XRF testing, the Cl content is 0.36 wt % based on the total weight of the catalyst A'.

[0074] Comparative Example 2

[0075] The preparation process of the catalyst refers to the impregnation method in Comparative Example 1, except that 50g of titanium dioxide (based on the weight of titanium dioxide, the chlorine content is 0.5wt%) is weighed; the remaining steps are the same as Comparative Example 1.

[0076] Finally, a cobalt-based Fischer-Tropsch synthesis catalyst B' is obtained.

[0077] According to XRF testing, the Cl content was 0.29 wt % based on the total weight of the catalyst B'.

[0078] Test Example 1: Catalytic Performance Evaluation of Catalyst

[0079] Evaluation method: 0.5 g of the catalyst prepared as above was loaded into a fixed bed reactor, and first reduced for 12 h in a H2 atmosphere at a space velocity of 8000 ml / g / h, normal pressure, and a temperature of 300°C, and then the reducing gas was switched to the reaction gas to carry out the reaction. The reaction conditions were:

[0080] The reaction raw gas composition is H2 / CO / N2=66 / 33 / 1, the space velocity is 3200ml / g / h, the pressure is 2MPa, the temperature is 215-220℃, the reaction time is 102 hours, and the CO conversion rate is measured after 10h and 110h of reaction, and the deactivation rate D is calculated:

[0081] D = (CO conversion rate (10h) - CO conversion rate (110h)) / 100h.

[0082] Table 1 Composition of catalysts obtained in various embodiments and comparative examples

[0083]

[0084]

[0085] Table 2 Performance evaluation results of the catalysts obtained in each embodiment and comparative example

[0086]

[0087] Note: The “fresh” in Table 1 refers to the state of the prepared catalyst before it is applied to the Fischer-Tropsch synthesis reaction.

[0088] Table 3 Performance evaluation results of the catalysts obtained in each embodiment and comparative example

[0089]

[0090]

[0091] The composition of the catalysts prepared in each embodiment and comparative example is shown in Table 1. It can be seen from the data in Tables 2-3 that the present invention adopts a precipitation method to prepare the catalyst, and at the same time, titanium dioxide with a high chlorine content is selected as a carrier during the precipitation reaction, and the process conditions of the precipitation reaction and aging treatment are reasonably controlled. The obtained catalyst has excellent catalytic performance and high stability; the obtained catalyst is applied to the Fischer-Tropsch synthesis reaction, and the chlorine loss during the reaction is small, the catalyst deactivation rate is low, and the stability is excellent, which is particularly suitable for a fixed-bed cobalt-based Fischer-Tropsch synthesis process. Comparative Examples 1-2 exogenously introduce chlorine elements in the form of cobalt chloride by an impregnation method. The obtained catalyst has a high chlorine loss rate during the Fischer-Tropsch synthesis reaction, a high catalyst deactivation rate, and poor stability, and is not suitable for a fixed-bed cobalt-based Fischer-Tropsch synthesis process.

[0092] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the spirit of the present invention.

Claims

1. A method for preparing a cobalt-based Fischer-Tropsch synthesis catalyst, characterized in that: The steps include: (1) contacting a mixed solution containing an active metal precursor and an auxiliary agent precursor, a precipitant and a dispersion containing a carrier to perform a deposition precipitation reaction, and performing an aging treatment; (2) filtering, washing, drying and calcining the material obtained in step (1) to obtain a cobalt-based Fischer-Tropsch synthesis catalyst.

2. The preparation method according to claim 1, characterized in that: The carrier is a titanium dioxide carrier with a high chlorine content; Preferably, the chlorine content is in the range of 0.3-5 wt % based on the weight of the titanium dioxide carrier.

3. The preparation method according to any one of claims 1-2, characterized in that The active metal precursor is selected from at least one of cobalt nitrate, cobalt carbonate, cobalt acetate and cobalt chloride; and / or The auxiliary agent precursor is selected from at least one of a soluble salt of Mn, a soluble salt of V, a soluble salt of Ce, a soluble salt of Re, a soluble salt of Ru, a soluble salt of Hf, a soluble salt of Zr, a soluble salt of Ti and a soluble salt of Cr; and / or The precipitant is selected from at least one of sodium hydroxide solution, sodium carbonate solution, aqueous ammonia, ammonium carbonate solution, ammonium bicarbonate solution and potassium carbonate solution.

4. The preparation method according to any one of claims 1 to 3, characterized in that The molar ratio of active metal precursor: auxiliary agent precursor: carrier is (0.10-2.0): (0.002-0.2):

1.

5. The preparation method according to any one of claims 1 to 4, characterized in that: The concentration of the mixed solution containing the active metal precursor and the auxiliary agent precursor is 0.5-3 mol / L.

6. The preparation method according to any one of claims 1 to 5, characterized in that: The concentration of the precipitant is 1.0-4.0 mol / L.

7. The preparation method according to any one of claims 1 to 6, characterized in that The amount of the precipitant is determined according to the pH value required for the precipitation environment in the reaction. The pH of the control system in the sedimentation reaction is 7.0-10.0, and the temperature of the sedimentation reaction is 40-90°C; and / or The process conditions of the aging treatment include: an aging time of 1-5 hours, an aging temperature of 40-90° C., and a control system pH of 7.0-10.

0.

8. The preparation method according to any one of claims 1 to 7, characterized in that: The drying process conditions include: drying temperature of 60-150° C., drying time of 2-48 h; and / or The calcination process conditions include: a calcination temperature of 350-700° C. and a calcination time of 2-48 hours.

9. A cobalt-based Fischer-Tropsch synthesis catalyst, characterized in that: Based on the total weight of the catalyst, the cobalt-based Fischer-Tropsch synthesis catalyst comprises the following components: 10%-40% active ingredient cobalt, 0.1-5wt% of an auxiliary component, wherein the auxiliary component is selected from one or more of Mn, V, Ce, Re, Ru, Hf, Zr, Ti and Cr, 0.2-3wt% chlorine, The balance is titanium dioxide support; Preferably, the cobalt-based Fischer-Tropsch synthesis catalyst is prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the cobalt-based Fischer-Tropsch synthesis catalyst prepared by the preparation method according to any one of claims 1 to 8 or the cobalt-based Fischer-Tropsch synthesis catalyst according to claim 9 in a Fischer-Tropsch synthesis reaction.

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