Fischer-tropsch synthesis catalyst, process for its preparation and use

Abstract

The application relates to the field of Fischer-Tropsch synthesis catalysts, and discloses a Fischer-Tropsch synthesis catalyst, a preparation method and application thereof. The Fischer-Tropsch synthesis catalyst contains 10-40 wt% of Co, 0.5-7 wt% of B and 53-89.5 wt% of a carrier, with the total weight of the catalyst as the basis. The carrier is TiO2, Co exists in the form of an oxide, and B exists in the form of boron oxide and titanium diboride. The boron element of the Fischer-Tropsch synthesis catalyst exists in the form of boron oxide and titanium diboride, the boron oxide in the catalyst system can reduce the grain size of cobalt oxide, and the boron oxide and titanium diboride can adjust the SMSI effect between cobalt and the carrier, so that the catalyst activity and stability are improved.

Description

Technical Field

[0001] This invention relates to the field of Fischer-Tropsch synthesis catalysts, specifically to a Fischer-Tropsch synthesis catalyst, its preparation method, and its application. Background Technology

[0002] The Fischer-Tropsch synthesis reaction refers to the reaction in which syngas (H₂ + CO) is converted into hydrocarbons and other chemicals under the action of a catalyst and at certain temperature and pressure. In recent years, due to the increasing scarcity of petroleum resources, Fischer-Tropsch synthesis has received widespread attention from researchers worldwide. Typically, the reaction for the formation of hydrocarbons through Fischer-Tropsch synthesis can be represented by the following reaction equation:

[0003] mCO + (2m + 1)H₂ → C m H 2m+2 +mH2O (1)

[0004] mCO + 2mH2 → CmH 2m +mH2O (2)

[0005] 2mCO + (m+1)H2 → C m H 2m+2 +mCO2 (3)

[0006] In the Fischer-Tropsch synthesis reaction and its process, catalysts are one of the most crucial core technologies. Iron (Fe), cobalt (Co), nickel (Ni), and ruthenium (Ru) are the main metallic elements that can serve as active components in Fischer-Tropsch synthesis catalysts. Long-term theoretical research and practical experience have shown that Fe and Co are the two metallic elements with the greatest industrial application value as active components of catalysts. Currently, the most commonly used Fischer-Tropsch synthesis catalysts worldwide are mainly iron (Fe)-based catalysts and cobalt (Co)-based catalysts. Compared with iron-based Fischer-Tropsch catalysts, cobalt-based Fischer-Tropsch catalysts have the characteristics of high catalytic activity, high selectivity for straight-chain saturated heavy hydrocarbons, and low water-gas shift reaction.

[0007] Activity is a crucial performance parameter for cobalt catalysts in the Fischer-Tropsch synthesis. High catalyst activity allows for operation at lower temperatures to achieve the same conversion rate under the same conditions. Conversely, if catalyst activity decreases as the reaction proceeds, the activity can be maintained by slowly increasing the reaction temperature, thus extending the catalyst's lifespan. Furthermore, due to the high cost of cobalt catalysts, stability is also a critical performance parameter. The main causes of deactivation in cobalt-based catalysts include particle sintering, oxidation, carbon deposition, the formation of recalcitrant substances between cobalt and the support, and strong metal-support interaction (SMSI) between cobalt and the support.

[0008] US6130184A discloses a Fischer-Tropsch synthesis catalyst and its preparation method, which is prepared by a kneading method. The catalyst is a Co / promoter / TiO2 system, and the promoter includes one or more of Mn, V, Re, Ru, Zr, Ti, and Cr. Because the support in the prior art is commonly titanium dioxide, there is an SMSI effect between it and the cobalt phase. This effect easily leads to the coating of cobalt surface active sites during high-temperature reduction and the reaction, resulting in low catalyst activity and poor stability.

[0009] Therefore, there is an urgent need to synthesize a Fischer-Tropsch synthesis catalyst that is simple to process, highly active, and stable by adjusting the composition of the catalyst. Summary of the Invention

[0010] The purpose of this invention is to overcome the problems of low catalyst activity and poor stability in the prior art, and to provide a Fischer-Tropsch synthesis catalyst, its preparation method and application. This catalyst has the characteristics of simple preparation, high catalytic activity and good stability.

[0011] To achieve the above objectives, the first aspect of the present invention provides a Fischer-Tropsch synthesis catalyst, characterized in that, based on the total weight of the catalyst, the Fischer-Tropsch synthesis catalyst comprises: 10-40 wt% Co, 0.5-7 wt% B, and 53-89.5 wt% support.

[0012] The support is TiO2, Co exists in the form of oxide, and B exists in the form of boron oxide and titanium diboride.

[0013] A second aspect of the present invention provides a method for preparing a Fischer-Tropsch synthesis catalyst, characterized in that the method comprises the following steps:

[0014] S1. Mix the Co source, the support, and the B source to obtain a first mixture;

[0015] S2. Add the adhesive solvent to the first mixture and perform a second kneading to obtain a second mixture;

[0016] S3. The second mixture is shaped, dried, and calcined to obtain the Fischer-Tropsch synthesis catalyst;

[0017] The amounts of the Co source, the B source, and the support are such that the content of Co in the catalyst is 10-40 wt%, the content of B is 0.5-7 wt%, and the content of the support is 53-89.5 wt%.

[0018] The support is TiO2, Co exists in the form of oxide, and B exists in the form of boron oxide and titanium diboride.

[0019] A third aspect of the present invention provides a Fischer-Tropsch synthesis catalyst prepared by the above method.

[0020] The fourth aspect of this invention provides the application of the above-mentioned Fischer-Tropsch synthesis catalyst in the Fischer-Tropsch synthesis reaction.

[0021] Through the above technical solutions, the Fischer-Tropsch synthesis catalyst, its preparation method, and its application provided by the present invention achieve the following beneficial effects: the boron element in the Fischer-Tropsch synthesis catalyst exists in the form of boron oxide and titanium diboride. The boron oxide in the catalyst system can reduce the grain size of cobalt oxide, while the boron oxide and titanium diboride can regulate the SMSI interaction between cobalt and the support, thereby improving the catalyst activity and stability. Attached Figure Description

[0022] Figure 1 These are the XRD patterns of the Fischer-Tropsch catalysts prepared in Example 1 and Comparative Example 1. Detailed Implementation

[0023] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0024] The first aspect of the present invention provides a Fischer-Tropsch synthesis catalyst, characterized in that, based on the total weight of the catalyst, the Fischer-Tropsch synthesis catalyst comprises: 10-40 wt% Co, 0.5-7 wt% B and 53-89.5 wt% support;

[0025] The support is TiO2, Co exists in the form of oxide, and B exists in the form of boron oxide and titanium diboride.

[0026] In this invention, the catalyst contains a specific amount of B, which exists in the form of boron oxide and titanium diboride. Boron oxide can reduce the grain size of cobalt oxide, while boron oxide and titanium diboride can regulate the SMSI interaction between cobalt and the support, thereby improving the catalyst activity and stability.

[0027] In this invention, the sum of the contents of Co, B, and the carrier is 100 wt%.

[0028] According to the present invention, the Fischer-Tropsch synthesis catalyst comprises, based on the total weight of the catalyst, 20-30 wt% Co, 1-5 wt% B and 65-79 wt% support.

[0029] The support is TiO2, Co exists in the form of oxide, preferably in the form of cobalt tetroxide, and B exists in the form of boron oxide and titanium diboride.

[0030] In this invention, when the components in the catalyst meet the above-mentioned ranges, the catalytic activity of the catalyst is further improved.

[0031] According to the present invention, the molar ratio of boron oxide to titanium diboride is 0.05-0.25:1.

[0032] Furthermore, when the molar ratio of boron oxide to titanium diboride is 0.05-0.25:1, the grain size of Co oxide can be reduced, further reducing the SMSI effect between cobalt and the support, thereby further improving the catalytic activity and stability of the catalyst.

[0033] Furthermore, the molar ratio of boron oxide to titanium diboride is 0.1-0.2:1.

[0034] According to the present invention, the catalyst has a specific surface area of ​​80-180 m². 2 / g.

[0035] Furthermore, the catalyst has a specific surface area of ​​100-160 m². 2 / g.

[0036] According to the present invention, the grain size of the oxide of Co in the catalyst is 8-20 nm.

[0037] Furthermore, when the grain size of the Co oxide is 8-20 nm, the addition of boron oxide and titanium diboride can reduce the SMSI effect between cobalt and the support, thereby further improving the catalytic activity of the catalyst.

[0038] Furthermore, the grain size of the cobalt oxide in the catalyst is 10-16 nm.

[0039] A second aspect of the present invention provides a method for preparing a Fischer-Tropsch synthesis catalyst, characterized in that the method comprises the following steps:

[0040] S1. Mix the Co source, the support, and the B source to obtain a first mixture;

[0041] S2. Add the adhesive solvent to the first mixture and perform a second kneading to obtain a second mixture;

[0042] S3. The second mixture is shaped, dried, and calcined to obtain the Fischer-Tropsch synthesis catalyst;

[0043] The amounts of the Co source, the B source, and the support are such that the content of Co in the catalyst is 10-40 wt%, the content of B is 0.5-7 wt%, and the content of the support is 53-89.5 wt%.

[0044] The support is TiO2, Co exists in the form of oxide, and B exists in the form of boron oxide and titanium diboride.

[0045] In this invention, the preparation method is simple, the components are mixed more evenly, and the prepared catalyst has high catalytic activity.

[0046] According to the present invention, the amounts of the Co source, the B source and the support are such that the catalyst contains 20-30 wt% Co, 1-5 wt% B and 65-79 wt% support.

[0047] According to the present invention, the Co source is selected from at least one of cobalt nitrate, cobalt hydroxide, cobalt chloride, and cobalt acetate.

[0048] Furthermore, the B source is a first B source, titanium diboride, and at least one second B source selected from boric acid, ammonium borate, and monoethanolamine borate.

[0049] Furthermore, the adhesive solvent is selected from at least one of water, nitric acid, hydrochloric acid, citric acid, and ammonia.

[0050] According to the present invention, the amounts of the first B source and the second B source are such that the molar ratio of boron oxide to titanium diboride in the catalyst is (0.05-0.25):1.

[0051] In this invention, when the ratio of the first B source to the second B source meets the above-mentioned range, the molar ratio of boron oxide to titanium diboride in the prepared Fischer-Tropsch synthesis catalyst meets the requirements. Furthermore, the activity of the catalyst is improved by adjusting the grain size of the cobalt oxide.

[0052] Furthermore, the amounts of the first B source and the second B source are such that the molar ratio of boron oxide to titanium diboride in the catalyst is (0.1-0.2):1.

[0053] According to the present invention, the first kneading time is 20-120 min, and the second kneading time is 20-120 min.

[0054] Furthermore, the drying conditions include drying at 100-150°C for 0.5-10 hours.

[0055] Furthermore, the calcination conditions include calcination at 400-650℃ for 1-8 hours.

[0056] In this invention, when the mixing, drying, and calcination conditions meet the above-mentioned ranges, the components are mixed more uniformly, resulting in a more uniform grain size of the Co oxide in the prepared catalyst and further improving the catalytic activity.

[0057] A third aspect of the present invention provides a Fischer-Tropsch catalyst prepared by the above method.

[0058] A fourth aspect of the present invention provides the application of the above-described Fischer-Tropsch synthesis catalyst in the Fischer-Tropsch synthesis reaction.

[0059] According to one embodiment of the present invention, the Fischer-Tropsch synthesis catalyst is reduced before use, and the reduction conditions include: firstly, under an H2 atmosphere and a space velocity of 1000-8000 mL / g·h. -1 Under conditions of pressure of 0.1-1 MPa and temperature of 300-450℃, the sample is reduced in a fixed bed for 10-30 hours, and then cooled to 120-160℃.

[0060] The Fischer-Tropsch synthesis reaction conditions include: a feed gas composition of H2:CO:N2 (molar ratio) of 52-78:20-40:2-8, and a space velocity of 1000-6000 mL / g·h. -1 The pressure is 2-4 MPa and the temperature is 205-235℃.

[0061] The present invention will be described in detail below through embodiments. In the following embodiments,

[0062] The content of each component in the catalyst was determined by XRF.

[0063] The grain size of Co oxide was calculated using the XRD Scherrer formula;

[0064] The specific surface area of ​​the catalyst was measured by BET.

[0065] The catalyst deactivation rate was calculated using the formula (CO conversion rate (2h) - CO conversion rate (102h) / 100h).

[0066] Preparation Example 1

[0067] S1. Add 2.47g of cobalt nitrate hexahydrate, 7.1g of cobalt hydroxide, 14.4g of titanium dioxide, 0.89g of boric acid and 1.68g of titanium diboride to a kneader and knead for 30 minutes to obtain the first mixture.

[0068] S2. Add 10g of water and 2g of citric acid to the first mixture, and knead for 30 minutes to obtain the second mixture;

[0069] S3. The second mixture is shaped into a 3 mm cylindrical shape, dried at 100 °C for 5 h and then calcined at 600 °C for 3 h to obtain Fischer-Tropsch synthesis catalyst A1.

[0070] XRF analysis revealed that, based on the total weight of catalyst A1, the content of Co was 24.9 wt%, TiO2 was 72.1 wt%, and B was 3 wt%. The molar ratio of boron oxide to titanium diboride was 0.15:1, and the specific surface area of ​​A1 was 125 m². 2 / g, the grain size of Co3O4 is 13.5nm.

[0071] Preparation Example 2

[0072] The method is consistent with that of Example 1, except that in step S1, the amounts of each component are: 1.98 g cobalt nitrate hexahydrate, 5.68 g cobalt hydroxide, 15.8 g titanium dioxide, 0.21 g boric acid and 0.58 g titanium diboride, and finally Fischer-Tropsch synthesis catalyst A2 is prepared.

[0073] XRF analysis revealed that, based on the total weight of catalyst A2, the content of Co was 20.1 wt%, TiO2 was 78.9 wt%, and B was 1 wt%. The molar ratio of boron oxide to titanium diboride was 0.1:1, and the specific surface area of ​​A2 was 132 m². 2 / g, the grain size of Co3O4 is 15.5nm.

[0074] Preparation Example 3

[0075] The method is consistent with that of Example 1, except that in step S1, the amounts of each component are: 2.96g cobalt nitrate hexahydrate, 8.5g cobalt hydroxide, 13g titanium dioxide, 1.91g boric acid and 2.68g titanium diboride, and the Fischer-Tropsch synthesis catalyst A3 is finally prepared.

[0076] XRF analysis revealed that, based on the total weight of catalyst A3, the content of Co was 30 wt%, TiO2 was 65 wt%, and B was 5 wt%. The molar ratio of boron oxide to titanium diboride was 0.2:1, and the specific surface area of ​​A3 was 110 m². 2 / g, the grain size of Co3O4 is 12.2nm.

[0077] Preparation Example 4

[0078] The method is consistent with that of Example 1, except that in step S1, the amounts of each component are: 3.95g cobalt nitrate hexahydrate, 11.36g cobalt hydroxide, 10.6g titanium dioxide, 3.2g boric acid and 3.6g titanium diboride, and finally the Fischer-Tropsch synthesis catalyst A4 is prepared.

[0079] XRF analysis revealed that, based on the total weight of catalyst A4, the content of Co was 40 wt%, TiO2 was 53 wt%, and B was 7 wt%. The molar ratio of boron oxide to titanium diboride was 0.25:1, and the specific surface area of ​​A4 was 95 m². 2 / g, the grain size of Co3O4 is 10.6nm.

[0080] Preparation Example 5

[0081] The method is consistent with that of Example 1, except that in step S1, the amounts of each component are: 0.98g cobalt nitrate hexahydrate, 2.84g cobalt hydroxide, 17.8g titanium dioxide, 0.54g boric acid and 0.31g titanium diboride, and finally the Fischer-Tropsch synthesis catalyst A5 is prepared.

[0082] XRF analysis revealed that, based on the total weight of catalyst A5, the content of Co was 10 wt%, TiO2 was 89.5 wt%, and B was 0.5 wt%. The molar ratio of boron oxide to titanium diboride was 0.05:1, and the specific surface area of ​​A5 was 152 m². 2 / g, the grain size of Co3O4 is 15.5nm.

[0083] Preparation Example 6

[0084] The method was the same as that used in Example 1, except that the amount of boric acid was 1.96 g and the amount of titanium diboride was 1.38 g, and Fischer-Tropsch synthesis catalyst A6 was prepared.

[0085] XRF analysis revealed that, based on the total weight of catalyst A6, the content of Co was 25 wt%, TiO2 was 72 wt%, and B was 3 wt%. The molar ratio of boron oxide to titanium diboride was 0.4:1, and the specific surface area of ​​A6 was 121 m². 2 / g, the grain size of Co3O4 is 8.5nm.

[0086] Preparation Example 7

[0087] The method is the same as that used in Example 1, except that in step S3, the catalyst A7 for Fischer-Tropsch synthesis is obtained by calcination at 500°C for 6 hours.

[0088] XRF analysis revealed that, based on the total weight of catalyst A7, the content of Co was 27.5 wt%, TiO2 was 68.5 wt%, and B was 3 wt%. The molar ratio of boron oxide to titanium diboride was 0.15:1, and the specific surface area of ​​A7 was 116 m². 2 / g, the grain size of Co3O4 is 12.5nm.

[0089] Preparation Example 8

[0090] The method is consistent with that of Example 1, except that in step S1, the amounts of each component are: 2.22 g cobalt nitrate hexahydrate, 6.38 g cobalt hydroxide, 15.1 g titanium dioxide, 0.09 g boric acid and 1.26 g titanium diboride, and finally the Fischer-Tropsch synthesis catalyst A8 is prepared.

[0091] XRF analysis revealed that, based on the total weight of catalyst A8, the content of Co was 22.5 wt%, TiO2 was 75.5 wt%, and B was 2 wt%. The molar ratio of boron oxide to titanium diboride was 0.02:1, and the specific surface area of ​​A8 was 125 m². 2 / g, the grain size of Co3O4 is 20.5nm.

[0092] Preparation Example 9

[0093] The method is the same as that used in Example 1, except that in step S3, the catalyst A9 is obtained by calcination at 700°C for 5 hours.

[0094] XRF analysis revealed that, based on the total weight of catalyst A9, the content of Co was 25 wt%, TiO2 was 72 wt%, and B was 3 wt%. The molar ratio of boron oxide to titanium diboride was 0.15:1, and the specific surface area of ​​A9 was 121 m². 2 / g, the grain size of Co3O4 is 18.1nm.

[0095] Comparative Preparation Example 1

[0096] The method is the same as that used in Example 1, except that in step S1, 2.47 g of cobalt nitrate hexahydrate, 7.09 kg of cobalt hydroxide, and 15 g of titanium dioxide were weighed to prepare Fischer-Tropsch synthesis catalyst D1.

[0097] XRF testing showed that, based on the total weight of catalyst D1, the Co content was 25 wt% and the TiO2 content was 75 wt%. The specific surface area of ​​D1 was 130 m². 2 / g, the grain size of Co3O4 is 22.7nm.

[0098] Comparative Preparation Example 2

[0099] The method is the same as that used in Example 1, except that boric acid is not added in step S1, and 1.93 g of titanium diboride is added to prepare Fischer-Tropsch synthesis catalyst D2.

[0100] XRF analysis revealed that, based on the total weight of catalyst D2, the content of Co was 25 wt%, TiO2 was 72 wt%, and B was 3 wt%. The molar ratio of boron oxide to titanium diboride was 0:1.15, and the specific surface area of ​​D2 was 124 m².2 / g, the grain size of Co3O4 is 22.6nm.

[0101] Comparative preparation example 3

[0102] The method is the same as that used in Example 1, except that titanium diboride is not added in step S1, but 3.43 g of boric acid is added to prepare Fischer-Tropsch synthesis catalyst D3.

[0103] XRF analysis revealed that, based on the total weight of catalyst D3, the content of Co was 25 wt%, TiO2 was 72 wt%, and B was 3 wt%. The molar ratio of boron oxide to titanium diboride was 1.15:0, and the specific surface area of ​​D3 was 125 m². 2 / g, the grain size of Co3O4 is 5.5nm.

[0104] Comparative preparation example 4

[0105] The method is consistent with that of Example 1, except that in step S1, the amount of cobalt nitrate hexahydrate is 4.94 g, the amount of cobalt hydroxide is 14.2 g, the amount of boric acid is 0.9 g, and the amount of titanium diboride is 1.68 g, so as to prepare Fischer-Tropsch synthesis catalyst D4.

[0106] XRF analysis revealed that, based on the total weight of catalyst D4, the content of Co was 50 wt%, TiO2 was 47 wt%, and B was 3 wt%. The molar ratio of boron oxide to titanium diboride was 0.15:1, and the specific surface area of ​​D4 was 80 m². 2 / g, the grain size of Co3O4 is 19.5nm.

[0107] Comparative preparation example 5

[0108] The method is consistent with that of Example 1, except that in step S1, titanium diboride and boric acid are not added, but silicon dioxide is added to obtain Fischer-Tropsch synthesis catalyst D5;

[0109] XRF testing revealed that, based on the total weight of catalyst D5, the content of Co was 25 wt%, TiO2 was 72 wt%, SiO2 was 3 wt%, and the specific surface area of ​​D5 was 130 m². 2 / g, the grain size of Co3O4 is 22.6nm.

[0110] Example 1

[0111] The activity of the Fischer-Tropsch synthesis catalyst A1 prepared in Preparation Example 1 was evaluated by the following method: the catalyst was ground to obtain 40-60 mesh particles, 1 gram of catalyst was packed into a fixed bed, and first reduced for 20 h at H2 atmosphere, space velocity 20000 ml / g / h, atmospheric pressure and temperature 400℃, and then cooled to 150℃.

[0112] The reducing gas was switched to the reactant gas, and the reaction was carried out under the following conditions: feed gas ratio H2 / CO / N2 = 66 / 33 / 1, space velocity 3000 ml / g / h, pressure 2.5 MPa, and temperature 220℃. The deactivation rate was calculated based on the CO conversion rates after 2 h and 102 h of reaction, as shown in Table 2.

[0113] Examples 2-9

[0114] The procedure was carried out in a similar manner to Example 1, except that the catalysts prepared in Preparation Examples 2-9 were used instead of the catalysts prepared in Preparation Example 1, and everything else was the same as in Example 1.

[0115] The deactivation rate was calculated based on the CO conversion rates at 2h and 102h, as shown in Table 2.

[0116] Comparative Examples 1-5

[0117] The procedure was carried out in a similar manner to Example 1, except that the catalysts prepared in Comparative Preparation Examples 1-5 were used instead of the catalysts prepared in Preparation Example 1, and everything else was the same as in Example 1.

[0118] The deactivation rate was calculated based on the CO conversion rates at 2h and 102h, as shown in Table 2.

[0119] Table 1

[0120]

[0121]

[0122] Table 2

[0123] catalyst CO conversion rate / % CO conversion rate / % Inactivation rate / % / h Example 1 61.2 60.6 0.004 Example 2 52.3 51.8 0.005 Example 3 72 71.5 0.005 Example 4 76.9 76 0.009 Example 5 45.5 44.5 0.01 Example 6 56.5 55.3 0.012 Example 7 64.7 64.2 0.005 Example 8 52.5 51.1 0.014 Example 9 53.5 52.3 0.012 Comparative Example 1 45.5 40.4 0.051 Comparative Example 2 49.7 47.9 0.018 Comparative Example 3 40.6 34.8 0.058 Comparative Example 4 68.8 67 0.018 Comparative Example 5 45.6 40.7 0.049

[0124] Note: t1 is the conversion rate after 2 hours of reaction, and t2 is the conversion rate after 102 hours of reaction.

[0125] As can be seen from the results in Table 2, the methods used in Examples 1-9 of this invention exhibit good results and excellent catalytic activity. Figure 1The XRD patterns of the Fischer-Tropsch catalysts prepared in Comparative Example 1 and Example 1 show that the Co3O4 peak near 59° is smaller in Example 1, indicating that the crystallite size of the Fischer-Tropsch catalyst prepared in Example 1 is smaller. This confirms that the addition of boron can effectively reduce the crystallite size of Co3O4, thereby improving the conversion rate and stability of CO.

[0126] The embodiments 1-3 and 7, which conform to the preferred technical solutions of the present invention, have achieved significantly better technical effects. Specifically, the CO conversion rate has reached more than 52%, and at the same time, they have good catalytic stability, with a deactivation rate of no more than 0.005% / h.

[0127] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A Fischer-Tropsch synthesis catalyst, characterized in that, Based on the total weight of the catalyst, the Fischer-Tropsch synthesis catalyst comprises: 10-40 wt% Co, 0.5-7 wt% B and 53-89.5 wt% support; The support is TiO2, Co exists in the form of cobalt tetroxide, and B exists in the form of boron oxide and titanium diboride, with the molar ratio of boron oxide to titanium diboride being (0.05-0.25):

1.

2. The catalyst according to claim 1, wherein, Based on the total weight of the catalyst, the Fischer-Tropsch synthesis catalyst comprises: 20-30 wt% Co, 1-5 wt% B and 65-79 wt% support.

3. The catalyst according to claim 1, wherein, The molar ratio of boron oxide to titanium diboride is (0.1-0.2):

1.

4. The catalyst according to claim 1, wherein, The catalyst has a specific surface area of ​​80-180 m². 2 / g.

5. The catalyst according to claim 1, wherein, The crystallite size of the Co oxide in the catalyst is 8-20 nm.

6. A method for preparing a Fischer-Tropsch synthesis catalyst, characterized in that, The method includes the following steps: S1. Mix the Co source, the support, and the B source to obtain a first mixture; S2. Add the adhesive solvent to the first mixture and perform a second kneading to obtain a second mixture; S3. The second mixture is shaped, dried, and calcined to obtain the Fischer-Tropsch synthesis catalyst; The amounts of the Co source, the B source, and the support are such that the catalyst contains 10-40 wt% Co, 0.5-7 wt% B, and 53-89.5 wt% support. The support is TiO2, Co exists in the form of cobalt tetroxide, and B exists in the form of boron oxide and titanium diboride. The B source is a first B source titanium diboride and at least one second B source selected from boric acid, ammonium borate and monoethanolamine borate. The amount of the first B source and the second B source is such that the molar ratio of boron oxide to titanium diboride in the catalyst is (0.05-0.25):

1.

7. The method according to claim 6, wherein, The amounts of the Co source, the B source, and the support used in the catalyst are such that the content of Co in the catalyst is 20-30 wt%, B is 1-5 wt%, and support is 65-79 wt%.

8. The method according to claim 6, wherein, The Co source is selected from at least one of cobalt nitrate, cobalt hydroxide, cobalt chloride, and cobalt acetate.

9. The method according to claim 6, wherein, The adhesive solvent is selected from at least one of water, nitric acid, hydrochloric acid, citric acid, and ammonia.

10. The method according to claim 6, wherein, The amounts of the first B source and the second B source are such that the molar ratio of boron oxide to titanium diboride in the catalyst is (0.1-0.2):

1.

11. The method according to claim 6, wherein, The first kneading time is 20-120 min, and the second kneading time is 20-120 min.

12. The method according to claim 6, wherein, The drying conditions include drying at 100-150℃ for 0.5-10 hours.

13. The method according to claim 6, wherein, The calcination conditions include calcination at 400-650℃ for 1-8 hours.

14. The Fischer-Tropsch synthesis catalyst prepared by the method according to any one of claims 6-13.

15. The use of the Fischer-Tropsch synthesis catalyst according to any one of claims 1-5 and 14 in the Fischer-Tropsch synthesis reaction.

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