Preparation and application of Al2O3 auxiliary-assisted carbon-supported cobalt catalyst

Abstract

The invention discloses a preparation method and application of a Co-based Fischer-Tropsch synthesis catalyst derived from a metal organic framework containing an Al2O3 auxiliary agent. According to the catalyst, Co is used as an active component, Al2O3 is used as an auxiliary agent, carbon is used as a carrier, and the molar ratio of Al to Co is 0.129-0.996. The Co metal organic framework parent material and the aluminum isopropoxide are mixed through a simple grinding method, then the carbon-supported Co catalyst containing the Al2O3 auxiliary agent is obtained through pyrolysis, the dispersity of Co is reasonably improved, meanwhile, the formation of inert CoAl2O4 is avoided, and when the catalyst is used for the Fischer-Tropsch synthesis reaction, good C < 5 + > selectivity is achieved on the basis that high activity is kept.

Description

Technical Field

[0001] The present invention relates to a preparation method and application of a cobalt (Co) catalyst derived from a metal organic framework (MOFs) containing an Al2O3 additive by simple physical mixing (grinding method), belonging to the technical field of nanocatalysis, nanomaterials and metal organic framework materials. Background Art

[0002] Energy is the foundation of social progress and technological development. However, the continuous reduction of crude oil reserves and the serious environmental problems caused by fossil fuels have prompted humans to turn their attention to the use of more abundant or renewable and clean resources, such as biomass, shale gas, CO2, etc. One strategy to achieve high value of these resources is to first convert them into synthesis gas (a mixture of CO and H2) through gasification or reforming, and then carry out Fischer-Tropsch synthesis (FTS) reaction, and finally convert them into long-chain hydrocarbons (gasoline, diesel, aviation kerosene) or chemicals such as alcohols. Although all Group VIII metals are catalytically active in FTS, Co-based catalysts have received widespread attention in the industry because of their lower cost than precious metals, excellent chain growth ability, higher selectivity for valuable long-chain hydrocarbons, and relatively low tendency of water gas shift side reaction (producing useless CO2).

[0003] The concepts used in FTS catalyst design mainly focus on improving the reducibility of metallic Co, maximizing the number of exposed Co active sites by adjusting the interaction between metallic Co and the support, and the Co particle size distribution. Recently, researchers have found that carbon-supported Co materials (Co@C) can be produced by pyrolysis of Co metal-organic frameworks (MOFs), which are highly active for FTS and have a high affinity for C. 5+ Hydrocarbons have good selectivity. It was found that during the pyrolysis process, the organic ligand not only acts as a reducing agent to reduce Co(II) 100% to metallic Co nanoparticles, but also forms a porous carbon network, which not only plays the role of loading Co nanoparticles but also has the effect of inhibiting the aggregation of Co nanoparticles. Moreover, this type of Co@C material has a very high Co content (usually greater than 30% by mass). In order to further improve the FTS reaction performance of Co@C materials, a common strategy is to add one or more auxiliary elements to promote the reduction and dispersion of Co, or to change the basic electronic structure of the Co active site. Specifically, the introduction of auxiliary agents in MOFs-derived Co@C materials can be divided into two strategies: introducing auxiliary agents outside the MOFs framework and introducing auxiliary agents into the MOFs framework. For example, Chinese patent [201610300820.1] reported that Co-MOF-71 (a Co metal organic framework) precursor was impregnated with tetraethyl orthosilicate or methyl orthosilicate dissolved in ethanol, and then pyrolyzed to obtain SiO2-assisted Co@C material, which improved the FTS reaction activity and C5+ Hydrocarbon selectivity. However, the impregnation liquid of this method uses a non-aqueous organic reagent, which increases the manufacturing cost of the catalyst. The literature [Chem.Eng.J.2023,463,142359.] prepares a MOFs precursor with a bimetallic center, and then prepares a Co@C material containing a Mn additive after pyrolysis. When used in the FTS reaction, it promotes the formation of alcohols. However, this method is limited to metal elements that can be coordinated with organic ligands, resulting in a limited number of additives that can be used, and some of these limited types of additives do not even have an auxiliary effect. The prior art shows that there is still a need to improve the method of introducing additives and expand the types of additives used, in order to improve the performance of FTS catalysts through the introduction of high-efficiency additives and reduce the cost of catalyst manufacturing. Summary of the invention

[0004] The purpose of the present invention is to provide a simple method for introducing Co@C material into Al2O3 additive and a catalyst obtained by the method.

[0005] In order to experiment the above-mentioned purpose of the present invention, the present invention provides the following technical scheme: a catalyst for FTS reaction, using Co-MON reported in the document [Ultrason.Sonochem.2019,59,104714.] as a parent material and Al2O3 as an auxiliary agent, wherein the amount of the Al2O3 auxiliary agent added is calculated according to the molar ratio of the Al element to the Co element in the catalyst, and its value is between 0.129 and 0.996.

[0006] The preparation method of the catalyst comprises the following steps:

[0007] 1) A Co metal organic framework (Co-MON) reported in the literature [Ultrason.Sonochem.2019,59,104714.] was used as a matrix material, and it was ground and mixed with an appropriate amount of aluminum isopropoxide in a mortar for a certain period of time to obtain a catalyst precursor.

[0008] 2) Subsequently, the catalyst precursor was pyrolyzed at a certain pyrolysis temperature (heating rate of 10°C / min) for a certain time under flowing N2 (30 mL / min) to obtain a Co@C catalyst containing an Al2O3 promoter.

[0009] Preferably, the grinding time in step 1) is between 15 min and 30 min;

[0010] Preferably, the certain pyrolysis temperature in step 2) is between 500 and 510°C;

[0011] Preferably, the certain pyrolysis time in step 2) is between 4 and 8 hours;

[0012] When the Co@C catalyst containing Al2O3 additive provided by the present invention is used for FTS reaction, it is preferred to control the volume ratio of H2 to CO feed to 1-2, the reaction temperature to 290-310°C, the reaction pressure to 2.9-3.1MPa, and the total reaction space velocity to 12-18L / h / g-catalyst.

[0013] Compared with the prior art, the present invention has the following advantages:

[0014] The method of introducing the Al2O3 additive into the Co@C material is simple and can be achieved by simple grinding and subsequent pyrolysis without using an organic solvent. The catalyst preparation process is simple and low in cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 The XRD (X-ray diffraction) diagrams of the catalysts obtained in Examples 1-5 and Comparative Examples 1-2 of the present invention are shown.

[0016] Figure 2 The XPS characterization results of Al species of different catalysts in Examples 1-5 of the present invention and Comparative Example 2 are shown in FIG. In the figure, (a) is the 2p orbital characteristic XPS peak of Al in the form of Al2O3 on the catalyst surface in Example 1; (b) is the 2p orbital characteristic XPS peak of Al in the form of Al2O3 on the catalyst surface in Example 2; (c) is the 2p orbital characteristic XPS peak of Al in the form of Al2O3 on the catalyst surface in Example 3; (d) is the 2p orbital characteristic XPS peak of Al in the form of Al2O3 on the catalyst surface in Example 4; (e) is the 2p orbital characteristic XPS peak of Al in the form of Al2O3 on the catalyst surface in Example 5; (f) is the 2p orbital characteristic XPS peak of Al in the form of CoAl2O4 on the catalyst surface in Comparative Example 2. DETAILED DESCRIPTION

[0017] In order to more clearly understand the present invention, the present invention is further described below in conjunction with embodiments and drawings, but the embodiments of the present invention are not limited thereto.

[0018] Example 1

[0019] The Co-MOFs parent material (Co-MON) was synthesized according to the method reported in the literature [Ultrason.Sonochem.2019,59,104714.]: Co(NO3)2·6H2O (1.31 g) and H2BDC (0.5 g) were dispersed in a mixed solution of 60 mL N, N-dimethylformamide (DMF) and water (the volume ratio of DMF / H2O was 1:1) and stirred at 25°C for 45 min. The mixture was then transferred to an 80 mL hydrothermal kettle, sealed and maintained at 120°C for 8 h, then cooled to 30°C, filtered, and washed three times with ethanol and distilled water respectively. Finally, the obtained solid sample was ultrasonically vibrated in a room temperature aqueous solution for 25 min, filtered again and dried at 70°C for 6 h to obtain Co-MON.

[0020] Using Co-MON as a sacrificial template, the Al source was added by grinding and mixing method, and then the Co@C catalyst containing Al2O3 additive was synthesized by pyrolysis: 0.40g Co-MON and an appropriate amount of aluminum isopropoxide (the molar ratio of Al to Co = 1 / 8) were ground in a mortar for 15 minutes to obtain a precursor containing the Al2O3 additive source. Subsequently, this precursor was pyrolyzed at 510℃ (heating rate of 10℃ / min) for 4h under flowing N2 (30mL / min) to obtain a Co@C catalyst containing Al2O3 additive, which was recorded as Co-1 / 8Al@C. The XRD characterization results of the catalyst are shown in Figure 1 (b), obvious metal Co characteristic peaks (JCPDS 01-1259) can be seen at 44.3 and 51.5°. The mass fractions of Co and Al measured by ICP-OES, the molar ratio of Co and Al calculated from the total mass of the catalyst and the mass fractions of Co and Al, the molar ratio of Al to Co set in the catalyst, the Co particle size calculated by the Scherrer formula, and the Co dispersion D are listed in Table 1. The XPS characterization results of Al2O3 species on the catalyst surface are shown in Figure 2 (a) As can be seen from the figure, the binding energy of Al's 2p orbital is 74.4 eV, which can be qualitatively identified as Al2O3 species.

[0021] The prepared catalyst was directly subjected to Fischer-Tropsch synthesis reaction, wherein the reaction temperature was 290°C, the H2 to CO feed volume ratio was 2, the flow rate was 12 L / h / g-catalyst, and the reaction pressure was 3.1 MPa. Under the above conditions, the evaluation results of the catalyst are shown in Table 2 below.

[0022] Example 2

[0023] The Co-MOFs parent material (Co-MON) was synthesized according to the method reported in the literature [Ultrason.Sonochem.2019,59,104714.]: Co(NO3)2·6H2O (1.31 g) and H2BDC (0.5 g) were dispersed in a mixed solution of 60 mL N, N-dimethylformamide (DMF) and water (the volume ratio of DMF / H2O was 1:1) and stirred at 25°C for 45 min. The mixture was then transferred to an 80 mL hydrothermal kettle, sealed and maintained at 120°C for 8 h, then cooled to 30°C, filtered, and washed three times with ethanol and distilled water respectively. Finally, the obtained solid sample was ultrasonically vibrated in a room temperature aqueous solution for 25 min, filtered again and dried at 70°C for 6 h to obtain Co-MON.

[0024] Using Co-MON as a sacrificial template, the Al source was added by grinding and mixing method, and then the Co@C catalyst containing Al2O3 additive was synthesized by pyrolysis: 0.40g Co-MON and an appropriate amount of aluminum isopropoxide (the molar ratio of Al to Co = 1 / 6) were ground in a mortar for 30 minutes to obtain a precursor containing the Al2O3 additive source. Subsequently, this precursor was pyrolyzed at 500℃ (heating rate of 10℃ / min) for 8h under flowing N2 (30mL / min) to obtain a Co@C catalyst containing Al2O3 additive, which was recorded as Co-1 / 6Al@C. The XRD characterization results of the catalyst are shown in Figure 1 (c), obvious characteristic peaks of metal Co can be seen at 44.3 and 51.5° (JCPDS 01-1259). The mass fractions of Co and Al measured by ICP-OES, the molar ratio of Co and Al calculated from the total mass of the catalyst and the mass fractions of Co and Al, the molar ratio of Al to Co set in the catalyst, the Co particle size calculated by the Scherrer formula, and the Co dispersion D are listed in Table 1. The XPS characterization results of Al2O3 species on the catalyst surface are shown in Figure 2 (b) As can be seen from the figure, the binding energy of Al's 2p orbital is 74.4 eV, which can be qualitatively identified as Al2O3 species.

[0025] The prepared catalyst was directly subjected to Fischer-Tropsch synthesis reaction, wherein the reaction temperature was 310°C, the volume ratio of H2 to CO feed was 2, the flow rate was 18 L / h / g-catalyst, and the reaction pressure was 3.1 MPa. Under the above conditions, the evaluation results of the catalyst are shown in Table 2 below.

[0026] Example 3

[0027] The Co-MOFs parent material (Co-MON) was synthesized according to the method reported in the literature [Ultrason.Sonochem.2019,59,104714.]: Co(NO3)2·6H2O (1.31 g) and H2BDC (0.5 g) were dispersed in a mixed solution of 60 mL N, N-dimethylformamide (DMF) and water (the volume ratio of DMF / H2O was 1:1) and stirred at 25°C for 45 min. The mixture was then transferred to an 80 mL hydrothermal kettle, sealed and maintained at 120°C for 8 h, then cooled to 30°C, filtered, and washed three times with ethanol and distilled water respectively. Finally, the obtained solid sample was ultrasonically vibrated in a room temperature aqueous solution for 25 min, filtered again and dried at 70°C for 6 h to obtain Co-MON.

[0028] Using Co-MON as a sacrificial template, the Al source was added by grinding and mixing method, and then the Co@C catalyst containing Al2O3 additive was synthesized by pyrolysis: 0.40g Co-MON and an appropriate amount of aluminum isopropoxide (the molar ratio of Al to Co = 1 / 4) were ground in a mortar for 20 minutes to obtain a precursor containing the Al2O3 additive source. Subsequently, this precursor was pyrolyzed at 500℃ (heating rate of 10℃ / min) for 6h under flowing N2 (30mL / min) to obtain a Co@C catalyst containing Al2O3 additive, which was recorded as Co-1 / 4Al@C. The XRD characterization results of the catalyst are shown in Figure 1 (d), obvious characteristic peaks of metal Co can be seen at 44.3 and 51.5° (JCPDS 01-1259). The mass fractions of Co and Al measured by ICP-OES, the molar ratio of Co and Al calculated from the total mass of the catalyst and the mass fractions of Co and Al, the molar ratio of Al to Co set in the catalyst, the Co particle size calculated by the Scherrer formula, and the Co dispersion D are listed in Table 1. The XPS characterization results of Al2O3 species on the catalyst surface are shown in Figure 2 (c) As can be seen from the figure, the binding energy of Al's 2p orbital is 74.4 eV, which can be qualitatively identified as Al2O3 species.

[0029] The prepared catalyst was directly subjected to Fischer-Tropsch synthesis reaction, wherein the reaction temperature was 300°C, the volume ratio of H2 to CO feed was 2, the flow rate was 18 L / h / g-catalyst, and the reaction pressure was 3.0 MPa. Under the above conditions, the evaluation results of the catalyst are shown in Table 2 below.

[0030] Example 4

[0031] The Co-MOFs parent material (Co-MON) was synthesized according to the method reported in the literature [Ultrason.Sonochem.2019,59,104714.]: Co(NO3)2·6H2O (1.31 g) and H2BDC (0.5 g) were dispersed in a mixed solution of 60 mL N, N-dimethylformamide (DMF) and water (the volume ratio of DMF / H2O was 1:1) and stirred at 25°C for 45 min. The mixture was then transferred to an 80 mL hydrothermal kettle, sealed and maintained at 120°C for 8 h, then cooled to 30°C, filtered, and washed three times with ethanol and distilled water respectively. Finally, the obtained solid sample was ultrasonically vibrated in a room temperature aqueous solution for 25 min, filtered again and dried at 70°C for 6 h to obtain Co-MON.

[0032] Using Co-MON as a sacrificial template, the Al source was added by grinding and mixing method, and then the Co@C catalyst containing Al2O3 additive was synthesized by pyrolysis: 0.40g Co-MON and an appropriate amount of aluminum isopropoxide (the molar ratio of Al to Co = 1 / 2) were ground in a mortar for 30 minutes to obtain a precursor containing the Al2O3 additive source. Subsequently, this precursor was pyrolyzed at 500℃ (heating rate of 10℃ / min) for 8h under flowing N2 (30mL / min) to obtain a Co@C catalyst containing Al2O3 additive, which was recorded as Co-1 / 2Al@C. The XRD characterization results of the catalyst are shown in Figure 1 (e), obvious metal Co characteristic peaks (JCPDS 01-1259) can be seen at 44.3 and 51.5°. The mass fractions of Co and Al measured by ICP-OES, the molar ratio of Co and Al calculated from the total mass of the catalyst and the mass fractions of Co and Al, the molar ratio of Al to Co set in the catalyst, the Co particle size calculated by the Scherrer formula, and the Co dispersion D are listed in Table 1. The XPS characterization results of Al2O3 species on the catalyst surface are shown in Figure 2 (d) As can be seen from the figure, the binding energy of Al's 2p orbital is 74.4 eV, which can be qualitatively identified as Al2O3 species.

[0033] The prepared catalyst was directly subjected to Fischer-Tropsch synthesis reaction, wherein the reaction temperature was 300°C, the volume ratio of H2 to CO feed was 2, the flow rate was 18 L / h / g-catalyst, and the reaction pressure was 3.0 MPa. Under the above conditions, the evaluation results of the catalyst are shown in Table 2 below.

[0034] Example 5

[0035] The Co-MOFs parent material (Co-MON) was synthesized according to the method reported in the literature [Ultrason.Sonochem.2019,59,104714.]: Co(NO3)2·6H2O (1.31 g) and H2BDC (0.5 g) were dispersed in a mixed solution of 60 mL N, N-dimethylformamide (DMF) and water (the volume ratio of DMF / H2O was 1:1) and stirred at 25°C for 45 min. The mixture was then transferred to an 80 mL hydrothermal kettle, sealed and maintained at 120°C for 8 h, then cooled to 30°C, filtered, and washed three times with ethanol and distilled water respectively. Finally, the obtained solid sample was ultrasonically vibrated in a room temperature aqueous solution for 25 min, filtered again and dried at 70°C for 6 h to obtain Co-MON.

[0036] Using Co-MON as a sacrificial template, the Al source was added by grinding and mixing method, and then the Co@C catalyst containing Al2O3 additive was synthesized by pyrolysis: 0.40g Co-MON and an appropriate amount of aluminum isopropoxide (the molar ratio of Al to Co = 1 / 1) were ground in a mortar for 30 minutes to obtain a precursor containing the Al2O3 additive source. Subsequently, this precursor was pyrolyzed at 500℃ (heating rate of 10℃ / min) for 8h under flowing N2 (30mL / min) to obtain a Co@C catalyst containing Al2O3 additive, which was recorded as Co-1 / 1Al@C. The XRD characterization results of the catalyst are shown in Figure 1 (f), obvious metal Co characteristic peaks (JCPDS 01-1259) can be seen at 44.3 and 51.5°. The mass fractions of Co and Al measured by ICP-OES, the molar ratio of Co and Al calculated from the total mass of the catalyst and the mass fractions of Co and Al, the molar ratio of Al to Co set in the catalyst, the Co particle size calculated by the Scherrer formula, and the Co dispersion D are listed in Table 1. The XPS characterization results of Al2O3 species on the catalyst surface are shown in Figure 2 (e) As can be seen from the figure, the binding energy of Al's 2p orbital is 74.4 eV, which can be qualitatively identified as Al2O3 species.

[0037] The prepared catalyst was directly subjected to Fischer-Tropsch synthesis reaction, wherein the reaction temperature was 300°C, the volume ratio of H2 to CO feed was 2, the flow rate was 18 L / h / g-catalyst, and the reaction pressure was 3.0 MPa. Under the above conditions, the evaluation results of the catalyst are shown in Table 2 below.

[0038] Comparative Example 1

[0039] The Co-MOFs parent material (Co-MON) was synthesized according to the method reported in the literature [Ultrason.Sonochem.2019,59,104714.]: Co(NO3)2·6H2O (1.31 g) and H2BDC (0.5 g) were dispersed in a mixed solution of 60 mL N, N-dimethylformamide (DMF) and water (the volume ratio of DMF / H2O was 1:1) and stirred at 25°C for 45 min. The mixture was then transferred to an 80 mL hydrothermal kettle, sealed and maintained at 120°C for 8 h, then cooled to 30°C, filtered, and washed three times with ethanol and distilled water respectively. Finally, the obtained solid sample was ultrasonically vibrated in a room temperature aqueous solution for 25 min, filtered again and dried at 70°C for 6 h to obtain Co-MON.

[0040] Co-MON was used as a sacrificial template to synthesize a Co@C catalyst without an additive by pyrolysis: 0.40 g of Co-MON was pyrolyzed at 500 °C for 8 h at a rate of 10 °C / min under flowing N2 (30 mL / min) to obtain a catalyst without an Al additive, which was recorded as Co@C. The XRD characterization results of the catalyst are shown in Figure 1 (a), obvious characteristic peaks of metallic Co can be seen at 44.3 and 51.5° (JCPDS 01-1259). The Co mass fraction measured by ICP-OES, the Co particle size calculated by Scherrer equation, and the Co dispersion D are listed in Table 1.

[0041] The prepared catalyst was directly subjected to Fischer-Tropsch synthesis reaction, wherein the reaction temperature was 300°C, the volume ratio of H2 to CO feed was 2, the flow rate was 18 L / h / g-catalyst, and the reaction pressure was 3.0 MPa. Under the above conditions, the evaluation results of the catalyst are shown in Table 2 below.

[0042] Comparative Example 2

[0043] Co-MOFs parent material (Co-MON) was synthesized according to the method reported in the literature [Ultrason.Sonochem.2019,59,104714.]: Co(NO3)2·6H2O (1.31 g) and H2BDC (0.5 g) were dispersed in a mixed solution of 60 mL N, N-dimethylformamide (DMF) and water (the volume ratio of DMF / H2O was 1:1) and stirred at 25°C for 45 min. The mixture was then transferred to an 80 mL hydrothermal kettle, sealed and maintained at 120°C for 8 h, then cooled to 30°C, filtered, and washed three times with ethanol and distilled water respectively. Finally, the obtained solid sample was ultrasonically vibrated in a room temperature aqueous solution for 25 min, filtered and dried at 70°C for 6 h to obtain Co-MON.

[0044] Using Co-MON as a sacrificial template, an Al source was added by impregnation method, and then a Co@C catalyst containing an Al2O3 additive was synthesized by thermal decomposition: 0.40g Co-MON was impregnated in an ethanol solution containing Al(NO3)3·9H2O (the solution contained 2mL of ethanol, and the molar ratio of Al to Co = 1 / 2), and dried at 70℃ for 6h to obtain a precursor containing an Al2O3 additive source. Subsequently, this precursor was thermally decomposed at 500℃ (heating rate of 10℃ / min) for 8h under flowing N2 (30mL / min) to obtain a Co@C catalyst containing an Al2O3 additive, which was recorded as Co-1 / 2Al@C′. The XRD characterization results of the catalyst are shown in Figure 1 (g), no characteristic peak of metal Co appeared. The mass fractions of Co and Al measured by ICP-OES, the molar ratio of Co and Al calculated from the total mass of the catalyst and the mass fractions of Co and Al, and the molar ratio of Al to Co set in the catalyst are listed in Table 1. The XPS characterization results of Al2O3 species on the catalyst surface are shown in Figure 2 (f) As can be seen from the figure, the binding energy of Al's 2p orbital is 73.2 eV, which can be qualitatively identified as the CoAl2O4 species. It can be seen that Al and Co on the catalyst exist in the form of CoAl2O4.

[0045] The prepared catalyst was directly subjected to Fischer-Tropsch synthesis reaction, wherein the reaction temperature was 300°C, the volume ratio of H2 to CO feed was 2, the flow rate was 18 L / h / g-catalyst, and the reaction pressure was 3.0 MPa. Under the above conditions, the evaluation results of the catalyst are shown in Table 2 below.

[0046] Table 1 Basic parameters of catalysts in Examples and Comparative Examples

[0047]

[0048] Table 2 Results of Fischer-Tropsch synthesis using the catalysts of the present invention and the comparative examples

[0049]

[0050] Table 1 is the basic information of the catalysts in the examples of the present invention and the catalysts in the comparative examples. It can be seen from Table 1 that the molar ratio of Al to Co set in the present invention is close to the actual measured result, indicating that the molar ratio of Al to Co on the Co@C catalyst containing Al additive in the present invention is in line with expectations. From the basic information of the catalysts and the reaction results in Tables 1 and 2, it can be seen that the Al-assisted Co@C catalyst prepared by the method of the present invention has a reasonably improved Co dispersion compared to the Co@C catalyst without Al additive, which makes the CO conversion rate, reaction rate and C 5+ Selectivity increases; Figure 2The results show that in the Co@C catalyst containing Al additive prepared by the impregnation method, Al and Co are converted into inert CoAl2O4 species, thereby making the catalyst inactive, indicating that the grinding method provided by the present invention can prevent Al from converting into inactive CoAl2O4 and maintain the function of the additive to improve the reaction performance of the catalyst. Therefore, compared with the unmodulated Co@C catalyst, the reaction performance of the Co@C catalyst containing Al additive provided by the present invention is improved, and the preparation method of the Co@C catalyst containing Al additive provided by the present invention is not only simpler than the impregnation process, the catalyst cost is low, and the efficacy of the Al additive is maintained.

Claims

1. A Co-based Fischer-Tropsch synthesis catalyst derived from a metal organic framework containing an Al2O3 promoter, characterized in that: The catalyst uses Co as an active component, Al2O3 as a promoter, and carbon as a carrier, wherein the molar ratio of Al to Co is between 0.129 and 0.

996.

2. The method for preparing the Co-based Fischer-Tropsch synthesis catalyst derived from a metal organic framework containing an Al2O3 additive according to claim 1, characterized in that The steps include: 1) Co-MON reported in the literature [Ultrason.Sonochem.2019,59,104714.] was used as the parent material, and it was ground with an appropriate amount of aluminum isopropoxide in a mortar to obtain a catalyst precursor. 2) The catalyst precursor obtained in step 1) is placed in a fixed bed reactor, heated to 500 to 510° C. at a rate of 10° C. / min under flowing N2 (30 mL / min), and pyrolyzed for 4 to 8 h to obtain a Fischer-Tropsch synthesis Co catalyst containing an Al2O3 additive.

3. The method for preparing a Co-based Fischer-Tropsch synthesis catalyst derived from a metal organic framework containing an Al2O3 additive according to claim 2, characterized in that: The grinding time is 15 minutes to 30 minutes.

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