METHOD FOR PRODUCING LIQUID HYDROCARBONS AND METHOD FOR PRODUCING Co-SUPPORTED CATALYST

Abstract

A method for producing liquid hydrocarbons and a method for producing a Co-supported catalyst are provided, which are capable of efficiently producing liquid hydrocarbons suitable for aircraft fuels such as kerosene and preferably containing a large amount of iso-forms. The method for producing liquid hydrocarbons comprises: using a Co-supported catalyst in which Co is supported on a carrier that is at least one selected from the group consisting of aluminum oxide (alumina), silicon oxide (silica), silica-alumina composite oxide, and titanium oxide, and that has a pore size distribution in the range of 3 nm to 100 nm; and bringing a reaction gas comprising carbon monoxide, hydrogen, and at least one hydrocarbon gas selected from the group consisting of ethylene and 1-hexene into contact with the Co-supported catalyst to react at 220°C to 240°C, thereby producing C7 to C25 liquid hydrocarbons CxH2(x+1) and CyH2y (where x and y are each an integer of 7 to 25).

Description

Method for producing liquid hydrocarbons and method for producing a Co-supported catalyst

[0001] The present invention relates to a method for producing liquid hydrocarbons that can efficiently produce liquid hydrocarbons suitable for aircraft fuels such as kerosene, and to a method for producing a Co-supported catalyst.

[0002] From an environmental perspective, the arrival of a net-zero carbon society is eagerly awaited, and the concept of carbon recycling has been proposed as one method to achieve this. The effective utilization of waste is one of the themes in this concept, but there are many problems. For example, waste plastics are burned, and electricity is generated using the thermal energy obtained during combustion. However, the proportion of energy that can be recovered is limited, and there is also the problem of large amounts of carbon dioxide (CO2) being emitted. As one method to solve this problem, a technology has been developed to obtain an energy source with a low environmental impact by gasifying waste such as waste plastics and using the resulting gas as a raw material to produce useful liquid hydrocarbons such as liquid fuels. Patent document 1 discloses a technology for producing liquid hydrocarbons from waste.

[0003] To address these challenges, a liquid hydrocarbon production method and apparatus have been proposed for producing liquid hydrocarbons with high efficiency by suppressing the bonding of oxygen to carbon (see Patent Document 1).

[0004] In commercial plant-scale applications, catalysts using cobalt supported on a porous support are commonly used for Fischer-Tropsch synthesis in the production of liquid hydrocarbons, and catalysts containing various co-catalysts have also been developed (see Non-Patent Literature 1).

[0005] Special table 2018-525510 publication

[0006] R.Oukaci et al.,Applied Catalysis A:General,186(1999)129-144

[0007] However, while the technology disclosed in Patent Document 1 is said to be able to produce kerosene, a problem is that the yield of effective liquid hydrocarbons such as kerosene is not sufficiently high. Another problem is that the proportion of iso-iso compounds necessary for reducing the viscosity of aviation fuel is not sufficiently high in the synthetic oil.

[0008] Furthermore, among the catalysts disclosed in Non-Patent Document 1, high-performance catalysts are those containing precious metals such as Pt and Ru, which have very high manufacturing costs. Moreover, there is still much room for improvement in the physical and chemical properties of elements and chemical substances added other than cobalt. Therefore, there is a need for a catalyst that is relatively inexpensive, suitable for aviation fuel, and preferably suitable for the production of liquid hydrocarbons containing a large amount of iso-isomers.

[0009] In view of these challenges, the objective is to provide a liquid hydrocarbon production method and a method for producing a Co-supported catalyst that can efficiently produce liquid hydrocarbons suitable for aircraft fuels such as kerosene, preferably containing a large amount of iso-isomers.

[0010] In order to solve the above problems, the inventors of the present invention investigated how to produce liquid hydrocarbons with a favorable carbon distribution and high iso-isomer ratio for aviation fuel in a single fixed-bed reactor using an approach different from the conventional Fischer-Tropsch synthesis reaction. As a result, they found that by adding predetermined amounts of ethylene and 1-hexene to a conventional Fischer-Tropsch reaction system using carbon monoxide and hydrogen, and carrying out the synthesis reaction using a Co-supported catalyst with physical and chemical properties suitable for these conditions, it is possible to efficiently produce liquid hydrocarbons with properties and carbon distribution favorable for the production of aviation fuel.

[0011] The first aspect of the present invention is at least one selected from the group consisting of aluminum oxide (alumina), silicon oxide (silica), silica-alumina composite oxide, and titanium oxide, and a Co-supported catalyst in which Co is supported on a carrier having a pore size distribution in the range of 3 nm to 100 nm is used. By contacting a reaction gas containing at least one hydrocarbon gas selected from the group consisting of ethylene and 1-hexene, carbon monoxide, and hydrogen with the Co-supported catalyst and reacting at 220°C to 240°C, liquid hydrocarbons C7 to C25 are produced. ｘ H ２（ｘ＋１） and C ｙ H ２ｙ (where x and y are integers from 7 to 25). The second aspect of the present invention is the method for producing liquid hydrocarbons according to the above aspect, wherein the ratio of the hydrocarbon gas, the carbon monoxide, and the hydrogen is (0.4 to 0.8):1:(2.0 to 2.2). The third aspect of the present invention is the method for producing liquid hydrocarbons according to the above aspect, wherein the Co-supported catalyst is produced by impregnating the carrier with a cobalt nitrate solution. The fourth aspect of the present invention is the method for producing liquid hydrocarbons according to the above aspect, wherein the Co-supported catalyst supports a zirconia sol having a particle size distribution in the range of 2 nm to 8 nm and supports manganese in addition to Co. The fifth aspect of the present invention is the method for producing liquid hydrocarbons according to the above aspect, wherein the Co-supported catalyst is filled in a fixed-bed reactor and contacted with the reaction gas. The sixth aspect of the present invention is the method for producing liquid hydrocarbons according to the above aspect, wherein zeolite powder is filled in the fixed-bed reactor and used together with the Co-supported catalyst. The seventh aspect of the present invention is the method for producing liquid hydrocarbons according to the above aspect, wherein the liquid hydrocarbons C7 to C25 are obtained by the following reaction. ２ +C ｍ H ２ｍ →C ｘ H ２（ｘ＋１） +C ｙ H ２ｙ +nH ２O (In the formula, m is 2 or 6. x and y are integers from 7 to 25.) The eighth aspect of the present invention is a method for producing a Co-supported catalyst, comprising the steps of: impregnating a dry powder of a carrier selected from the group consisting of aluminum oxide (alumina), silicon oxide (silica), silica-alumina composite oxide and titanium oxide, having a pore size distribution in the range of 3 nm to 100 nm, then drying and calcining the carrier; impregnating the dry powder of the carrier with a zirconia sol having an average particle size of 2 nm to 8 nm, then drying and calcining the carrier; and impregnating the dry powder of the carrier with a manganese nitrate solution, then drying, or drying and calcining the carrier. The ninth aspect of the present invention is a method for producing a Co-supported catalyst, wherein the Co-supported catalyst has an average pore size of 3 nm to 100 nm. ２ The present invention relates to a method for producing a Co-supported catalyst according to the above embodiment, wherein the Co-supported catalyst contains 50 to 60 wt% of the catalyst weight. The tenth embodiment of the present invention relates to a method for producing a Co-supported catalyst according to the above embodiment, wherein the Co-supported catalyst contains 10 to 30 wt% of cobalt by the total amount of catalyst. The eleventh embodiment of the present invention relates to a method for producing a Co-supported catalyst according to the above embodiment, wherein the Co-supported catalyst contains 10 to 30 wt% of zirconia by the total amount of catalyst. The twelfth embodiment of the present invention relates to a method for producing a Co-supported catalyst according to the above embodiment, wherein the Co-supported catalyst contains 5 wt% or less of manganese by the total amount of catalyst. The thirteenth embodiment of the present invention relates to a method for producing a Co-supported catalyst according to the above embodiment, wherein the drying of the Co-supported catalyst is carried out at 100°C to 140°C for 3 to 7 hours.

[0012] The present invention provides a liquid hydrocarbon production method that can efficiently produce liquid hydrocarbons suitable for aircraft fuels such as kerosene, preferably containing a large amount of iso-isomers, and further provides a method for producing a Co-supported catalyst suitable for liquid hydrocarbon production.

[0013] This figure shows the carbon number distribution of the products obtained in Liquid Hydrocarbon Production Examples 1-3. This figure shows the carbon number distribution of the products obtained in Liquid Hydrocarbon Production Examples 4-5. This figure shows the carbon number distribution of the products obtained in Liquid Hydrocarbon Production Examples 6-8. This figure shows the carbon number distribution of the products obtained in Liquid Hydrocarbon Production Examples 9-10.

[0014] The present invention will be described in further detail below. The liquid hydrocarbon production method of the present invention uses a Co-supported catalyst, which is at least one selected from the group consisting of aluminum oxide (alumina), silicon oxide (silica), silica-alumina composite oxide and titanium oxide, and has a pore size distribution in the range of 3 nm to 100 nm, on which Co is supported. A reaction gas containing at least one hydrocarbon gas selected from the group consisting of ethylene and 1-hexene, carbon monoxide and hydrogen is brought into contact with the Co-supported catalyst and reacted at 220°C to 240°C to produce C7 to C25 liquid hydrocarbons. ｘ H ２（ｘ＋１） and C ｙ H ２ｙ This manufactures (where x and y are integers between 7 and 25).

[0015] This liquid hydrocarbon production method involves adding predetermined amounts of ethylene and 1-hexene to a conventional Fischer-Tropsch reaction system using carbon monoxide and hydrogen, and carrying out the synthesis reaction using a Co-supported catalyst with physical and chemical properties suitable for those conditions. This allows for the efficient production of C7-C25 liquid hydrocarbons with desirable properties and carbon distribution for the production of aviation fuel.

[0016] Here, C7-C15 liquid hydrocarbons can be used directly as jet fuel, but C16-C25 liquid hydrocarbons can be converted into jet fuel consisting of C7-C15 liquid hydrocarbons through a general upgrading process, that is, by hydrocracking the C16-C25 liquid hydrocarbons.

[0017] The liquid hydrocarbon production method in this invention produces liquid hydrocarbons through the following reaction: (Reaction equation) nCO + 2nH ２ +C ｍ H ２ｍ →CC ｘ H ２（ｘ＋１） +C ｙ H ２ｙ +nH ２ O (In the formula, m is 2 or 6. x and y are integers between 7 and 25.)

[0018] Such a reaction is carried out using a reaction gas containing at least one hydrocarbon gas selected from the group consisting of ethylene and 1-hexene, carbon monoxide, and hydrogen, and a predetermined Co-supported catalyst.

[0019] Details of the reaction conditions will be described later. The catalyst central layer is set at 220°C to 240°C, and the total gas flow rate is set at 30 to 40 ml / min. The reaction is carried out under conditions such that the ratio of catalyst weight to gas flow rate W / F = 5 to 10.

[0020] The reaction is preferably carried out using a reaction tube for a fixed-bed reactor as described later, but it may also be a reaction using a slurry bed, a fluidized bed, etc. In any case, a reaction system that efficiently contacts the Co-supported catalyst and the reaction gas in a predetermined temperature environment may be used.

[0021] In particular, when using a fixed-bed reaction tube and filling the Co-supported catalyst in the reaction tube for reaction, by mixing and filling zeolite powder with the Co-supported catalyst, the isomerization reaction of the product is promoted, and the content of the Iso body tends to increase, which is preferable.

[0022] The composition of the reaction gas is selected from the range of ethylene and 1-hexene:CO:hydrogen = (0.2 to 0.8):1:(1.8 to 2.2), preferably (0.4 to 0.8):1:(2.0 to 2.2).

[0023] The predetermined Co-supported catalyst used in the present invention is obtained by impregnating a carrier composed of at least one selected from the group consisting of aluminum oxide (alumina), silicon oxide (silica), silica-alumina composite oxide, and titanium oxide with a cobalt nitrate solution to support Co.

[0024] The Co-supported catalyst supports Co as an active metal and is finally manufactured by sintering. Although nitric acid evaporates, it was confirmed that using cobalt acetate or cobalt oxide instead of cobalt nitrate changes the characteristics of the catalyst and is inappropriate for the use of the present invention.

[0025] Further, a predetermined Co-supported catalyst is one supporting a zirconia sol having a particle size distribution in the range of 2 nm to 8 nm in addition to Co. This zirconia (zirconium dioxide) sol is a colloid of zirconia particles having a particle size distribution in the range of 2 nm to 8 nm, preferably 2 nm to 4 nm, and more preferably 3 nm. The dispersion medium is not particularly limited, but examples include H ２ O, methanol, and the like. It is also necessary to use a zirconia sol for supporting zirconia. It has been confirmed that when zirconia powder itself or its dispersion is used, the characteristics of the Co-supported catalyst change.

[0026] Further, a predetermined Co-supported catalyst supports manganese. Manganese has a function as a promoter. The support of manganese may be carried out by a general method and is not particularly limited, but it is preferable to support it using manganese nitrate.

[0027] The Co-supported catalyst of the present invention contains cobalt at 10 to 30 wt%, preferably 10 to 25 wt%, and more preferably around 20 wt% of the total amount of the catalyst. Further, the Co-supported catalyst contains zirconia at 10 to 30 wt%, preferably 10 to 25 wt%, and more preferably around 20 wt% of the total amount of the catalyst. Further, the Co-supported catalyst contains manganese at 5 wt% or less, preferably around 2 wt% of the total amount of the catalyst. The supported amount of manganese is less than the general supported amount, but the production method of liquid hydrocarbons of the present invention cannot be realized without supporting this amount.

[0028] As the carrier of the catalyst composed of at least one selected from the group consisting of aluminum oxide (alumina), silicon oxide (silica), silica-alumina composite oxide, and titanium oxide, it is preferable to use a carrier having a pore size distribution in the range of 3 nm to 100 nm, preferably 5 nm to 15 nm, and particularly preferably around 10 nm, that is, in the range of 9 to 11 nm. Further, as the carrier, it is preferable to mainly use silica in terms of heat resistance and selectivity for hydrocarbon generation.

[0029] As the promoter, an aqueous solution of manganese nitrate is used, and as the active metal, cobalt nitrate is used. Further, the weight of the carrier with respect to the total weight of the Co-supported catalyst is 50 to 60 wt%.

[0030] The Co-supported catalyst used in this invention is as described above, but will be explained in more detail below with an example of its manufacturing method.

[0031] The Co-supported catalyst is obtained by using a support selected from the group consisting of aluminum oxide (alumina), silicon oxide (silica), silica-alumina composite oxide, and titanium oxide, having a pore size distribution in the range of 3 nm to 100 nm, and performing the following steps: impregnating the dried powder of the support with a cobalt nitrate solution, then drying and calcining; impregnating the dried powder of the support with a zirconia sol having an average particle size of 2 nm to 8 nm, then drying and calcining; and impregnating the dried powder of the support with a manganese nitrate solution, then drying, or drying and calcining. Each step can be performed sequentially, and the order of execution is not particularly limited, but it is preferable to perform the steps in the order of zirconia support, Mn support, and Co support.

[0032] The process of supporting Co, zirconia, and Mn on a support involves impregnating and supporting cobalt at a concentration of 10 to 30 wt% of the total catalyst weight, followed by drying and calcination. Similarly, zirconia is impregnated and supported at a concentration of 10 to 30 wt% of the total catalyst weight, followed by drying and calcination. Manganese is impregnated and supported at a concentration of 5 wt% or less of the total catalyst weight, followed by drying, or drying and calcination. In each of these steps, drying is carried out at 100°C to 140°C for 3 to 7 hours, preferably at 115°C to 125°C, and particularly at around 120°C for 5 hours. Calcination is carried out at 350°C to 500°C for 3 to 7 hours, preferably at 380°C to 420°C, and particularly at around 400°C for 5 hours.

[0033] A preferred embodiment of the catalyst manufacturing method in the present invention is a catalyst having an average pore size of 3 nm to 200 nm, preferably around 10 nm, i.e., 9 to 11 nm. ２The catalyst is impregnated with zirconia sol having an average particle size of 2 nm to 8 nm, preferably around 3 nm, i.e., 2 to 4 nm, in an amount of 50 to 60 wt% of the total weight of the catalyst, so that it makes up 10 to 30 wt% of the total amount of the catalyst. The catalyst is dried at around 120°C for 5 hours and then calcined at around 400°C for 5 hours. This dried powder is then impregnated with manganese nitrate so that the amount of manganese is 5% or less of the total amount of the catalyst, dried at around 120°C for 5 hours, and then further impregnated and supported with cobalt nitrate so that the amount of cobalt is 10 to 30 wt% of the total amount of the catalyst. The catalyst is dried at around 120°C for 5 hours and then calcined at around 400°C for 5 hours to obtain a Co-supported catalyst powder.

[0034] When carrying out the liquid hydrocarbon production method using this Co-supported catalyst, the Co-supported catalyst produced as described above is thoroughly physically mixed with quartz sand in an amount 2 to 3 times the weight of the catalyst, the mixture is packed into a fixed-bed reactor, and the liquid hydrocarbon production method of the present invention is carried out under the reaction conditions described above.

[0035] The catalyst design conditions for a Co-supported catalyst in a preferred embodiment are as follows: The specific surface area, average pore diameter, and pore volume, as measured by BET analysis and BJH method, are each 65 m³. ２ / g, 55nm, 0.86cm ３ A silica support of 1 / g is used, and a zirconia sol with an average particle size of 3 nm is used. Manganese is supported using an aqueous manganese nitrate solution as a co-catalyst, and cobalt is supported using cobalt nitrate as the active metal.

[0036] Regarding the above materials, a slurry is prepared by adding cobalt (20 wt%), manganese (2 wt%), zirconia (20 wt%), and silica (58 wt%) to a heat-resistant dish relative to the total weight of the catalyst. This slurry is then dried at 120°C for 5 hours and calcined at 400°C for 5 hours to produce the catalyst.

[0037] [Catalyst Manufacturing Example 1] Catalyst Manufacturing and Performance Evaluation Using silica (CARiACT, Q-50) manufactured by Fuji Silysia Chemical as a support, a zirconia sol aqueous solution was prepared so that the zirconia content was 20 wt% of the final catalyst weight. The silica material was placed in a heat-resistant dish and thoroughly impregnated with the zirconia sol aqueous solution by impregnation method, dried at 120°C for 5 hours, and calcined at 400°C for 5 hours. Next, a manganese nitrate hexahydrate aqueous solution was prepared and thoroughly impregnated so that the manganese load was 2 wt% of the final catalyst weight, and dried at 120°C for 5 hours. Subsequently, a cobalt nitrate hexahydrate aqueous solution was prepared for the obtained powder so that the cobalt load was 20 wt% of the final catalyst weight, and the powder was thoroughly impregnated with the cobalt nitrate hexahydrate aqueous solution, dried at 120°C for 5 hours, and calcined at 400°C for 5 hours to obtain the target catalyst.

[0038] [Liquid Hydrocarbon Production Example 1-2] 1.0 g of catalyst obtained from ethylene additive catalyst sample 1 was mixed with quartz sand in an amount equal to twice the catalyst weight, packed into a Φ1 / 2 inch fixed-bed reactor reaction tube, and subjected to a reduction treatment using hydrogen at 400°C for 10 hours. After replacing with nitrogen and cooling to 50°C, the mixture was converted to ethylene:CO:H ２ = 0.8:1:2.2 (Liquid hydrocarbon production example 1) and ethylene:CO:H ２ Two reactions were carried out with a ratio of 0.4:1:2.2 (Liquid hydrocarbon production example 2).

[0039] [Liquid hydrocarbon production example 3] Without adding ethylene, ethylene:CO:H ２ The ratio was set to 0:1:2.2, and the reaction was carried out in the same manner as in Liquid Hydrocarbon Production Example 1.

[0040] (Summary of Liquid Hydrocarbon Production Examples 1-3) The reaction results for Liquid Hydrocarbon Production Examples 1-3 are shown in Table 1. As shown in Table 1, the CO conversion rate and CH for Liquid Hydrocarbon Production Example 1-2 are shown. ４ Compared to the reaction without ethylene addition shown in Liquid Hydrocarbon Production Example 3, the (C1) selectivity, C7-C25 selectivity, and isoparaffin selectivity were higher, resulting in a higher CO conversion rate, higher C7-C25 selectivity, and higher iso-isomer content. Figure 1 shows the carbon number distribution of the products obtained in Liquid Hydrocarbon Production Examples 1-3.

[0041]

[0042] [Liquid Hydrocarbon Production Example 4] 0.5 g of the catalyst obtained in Production Example 1 of 1-hexene addition catalyst was mixed with quartz sand in an amount equal to twice the catalyst weight, packed into a Φ1 / 2 inch fixed-bed reactor reaction tube, and reduced using hydrogen at 400°C for 10 hours. After replacing with nitrogen and cooling to 50°C, the mixture was converted to 1-hexene:CO:H ２ A reaction with a ratio of 0.8:1:2.2 was performed.

[0043] [Liquid hydrocarbon production example 5] Without adding 1-hexene, 1-hexene:CO:H ２ The ratio was set to 0:1:2.2, and the reaction was carried out in the same manner as in Liquid Hydrocarbon Production Example 4.

[0044] (Summary of Liquid Hydrocarbon Production Examples 4-5) The reaction results for Liquid Hydrocarbon Production Examples 4-5 are shown in Table 2. As shown in Table 2, the CO conversion rate and CH for Liquid Hydrocarbon Production Example 4 are shown. ４ Compared to the reaction in Liquid Hydrocarbon Production Example 5 without the addition of 1-hexene, the (C1) selectivity, C7-C25 selectivity, and isoparaffin content were higher, resulting in a higher CO conversion rate, higher C7-C25 selectivity, and higher iso-isomer content. Figure 2 shows the carbon number distribution of the products in Liquid Hydrocarbon Production Examples 4-5.

[0045]

[0046] [Catalyst Production Example 2-3] Using silica (CARiACT, Q-50) manufactured by Fuji Silysia Chemical as a support, a zirconia sol aqueous solution was prepared with an average particle size of 3 nm in the constituent sol so that zirconia accounted for 20 wt% of the final catalyst weight. The silica material as a support was placed in a heat-resistant dish and thoroughly impregnated with the zirconia sol aqueous solution by impregnation method, dried at 120°C for 5 hours, and calcined at 400°C for 5 hours. Next, a manganese nitrate hexahydrate aqueous solution was prepared and thoroughly impregnated so that the manganese load amounted to 2 wt% of the final catalyst weight, and dried at 120°C for 5 hours. Subsequently, a cobalt nitrate hexahydrate aqueous solution was prepared for the obtained powder so that the cobalt load amounted to 20 wt% of the final catalyst weight, and the powder was thoroughly impregnated with the cobalt nitrate hexahydrate aqueous solution, dried at 120°C for 5 hours, and calcined at 400°C for 5 hours to obtain the target catalyst (Catalyst Production Example 2). Furthermore, the target catalyst was obtained in the same manner as in Catalyst Production Example 2, except that a zirconia sol with an average particle size of 8 nm was used (Catalyst Production Example 3).

[0047] (Liquid hydrocarbon production example 6-7) 0.25 g of catalyst obtained in catalyst production examples 3 and 2 was mixed with quartz sand in an amount equal to twice the catalyst weight, packed into a Φ1 / 2 inch fixed-bed reactor reaction tube, and subjected to a reduction treatment using hydrogen at 400°C for 10 hours. After replacing with nitrogen and cooling to 50°C, 1-hexene:CO:H ２ A reaction was carried out with a ratio of 0.8:1:2.2 (Liquid hydrocarbon production example 6-7).

[0048] [Catalyst Production Example 4] The catalyst was produced in the same manner as in Catalyst Production Example 2, except that a zirconia sol with an average particle size of 100 nm was used, and the target catalyst was obtained (Catalyst Production Example 4).

[0049] (Liquid hydrocarbon production example 8) The reaction was carried out in the same manner as in liquid hydrocarbon production example 6, except that 0.25 g of the catalyst obtained in catalyst production example 4 was used.

[0050] (Summary of Liquid Hydrocarbon Production Example 6-8) The reaction results for Liquid Hydrocarbon Production Example 6-8 are shown in Table 3. As shown in Table 3, the CO conversion rate and CH for Liquid Hydrocarbon Production Example 6-7 are shown. ４The (C1) selectivity, C7-C25 selectivity, and isoparaffin selectivity were higher compared to the reaction in Liquid Hydrocarbon Production Example 8 using the catalyst from Catalyst Production Example 4, where the average particle size of zirconia was 100 nm, resulting in a higher CO conversion rate, higher C7-C25 selectivity, and higher iso-isomer content. Figure 3 shows the carbon number distribution of the products in the reactions of Liquid Hydrocarbon Production Examples 6-8.

[0051]

[0052] [Catalyst Production Example 5] Average pore size of silica A catalyst was prepared using a silica product (Q-100: average pore size = 100 nm) manufactured by Fuji Silicia Chemical as a support. The procedure was as follows: an aqueous zirconia sol solution was prepared so that zirconia accounted for 20 wt% of the final catalyst weight. The silica material was placed in a heat-resistant dish and thoroughly impregnated with the aqueous zirconia sol solution by impregnation. The material was then dried at 120°C for 5 hours and calcined at 400°C for 5 hours. Next, an aqueous manganese nitrate hexahydrate solution was prepared and impregnated so that the manganese load amounted to 2 wt% of the final catalyst weight. The material was then dried at 120°C for 5 hours. Subsequently, an aqueous cobalt nitrate hexahydrate solution was prepared for the obtained powder so that the cobalt load amounted to 20 wt% of the final catalyst weight. The material was then thoroughly impregnated with the aqueous cobalt nitrate hexahydrate solution, dried at 120°C for 5 hours, and calcined at 400°C for 5 hours to obtain the desired catalyst.

[0053] (Liquid hydrocarbon production example 9) 0.5 g of the catalyst obtained in catalyst production example 5 was mixed with quartz sand in an amount equal to twice the weight of the catalyst, packed into a Φ1 / 2 inch fixed-bed reactor reaction tube, and reduced using hydrogen at 400°C for 10 hours. After replacing with nitrogen and cooling to 50°C, ethylene:CO:H ２ A reaction with a ratio of 0.8:1:2.2 was performed.

[0054] [Catalyst Production Example 6] The procedure was carried out in the same manner as in Catalyst Production Example 5, except that a catalyst prepared using silica (CARiACT, Q-50) manufactured by Fuji Silysia Chemical Co., Ltd. with an average pore size of 50 nm was used, and the target catalyst was obtained.

[0055] (Liquid hydrocarbon production example 10) The reaction was carried out in the same manner as in liquid hydrocarbon production example 9, except that 0.5 g of the catalyst obtained in catalyst production example 6 was used.

[0056] (Summary of Liquid Hydrocarbon Production Examples 9-10) The reaction results for Liquid Hydrocarbon Production Examples 9-10 are shown in Table 4. As shown in Table 4, the CO conversion rate and CH for Liquid Hydrocarbon Production Example 9 are shown. ４ The (C1) selectivity, C7-C25 selectivity, and isoparaffin selectivity were higher compared to the reaction in Liquid Hydrocarbon Production Example 10 using the catalyst obtained in Catalyst Production Example 6, where the average pore size of silica was 50 nm, resulting in a higher CO conversion rate, a higher C7-C25 selectivity, and a higher iso-isomer content. Figure 4 shows the carbon number distribution of the products in the reactions of Liquid Hydrocarbon Production Examples 9-10.

[0057]

Claims

1. Using a Co-supported catalyst, Co is supported on a support selected from the group consisting of aluminum oxide (alumina), silicon oxide (silica), silica-alumina composite oxide, and titanium oxide, and the pore size distribution is in the range of 3 nm to 100 nm. A reaction gas containing at least one hydrocarbon gas selected from the group consisting of ethylene and 1-hexene, carbon monoxide, and hydrogen is brought into contact with the Co-supported catalyst and reacted at 220°C to 240°C to produce C7 to C25 liquid hydrocarbon C ｘ H ２（ｘ＋１） and C ｙ H ２ｙ A method for producing liquid hydrocarbons, characterized by producing (where x and y are integers from 7 to 25).

2. The liquid hydrocarbon production method according to claim 1, wherein the ratio of the hydrocarbon gas, carbon monoxide, and hydrogen is (0.4 to 0.8):1:(2.0 to 2.2).

3. The liquid hydrocarbon production method according to claim 1, wherein the Co-supported catalyst is produced by impregnating the carrier with a cobalt nitrate solution.

4. The liquid hydrocarbon production method according to claim 1, wherein the Co-supported catalyst is supported with zirconia sol having a particle size distribution in the range of 2 nm to 8 nm in addition to Co, and is also supported with manganese.

5. The liquid hydrocarbon production method according to claim 1, wherein the Co-supported catalyst is packed into a fixed-bed reactor and brought into contact with the reaction gas.

6. The liquid hydrocarbon production method according to claim 5, wherein zeolite powder is packed into the fixed-bed reactor together with the Co-supported catalyst.

7. The liquid hydrocarbon of C7-C25 is obtained by the following reaction, and the method for producing a liquid hydrocarbon according to claim 1. nCO + 2nH ２ + C ｍ H ２ｍ → C ｘ H ２（ｘ＋１） + C ｙ H ２ｙ + nH ２ O (In the formula, m is 2 or 6. x and y are integers from 7 to 25.) 8. A method for producing a Co-supported catalyst, comprising the steps of: impregnating a dry powder of a carrier selected from the group consisting of aluminum oxide (alumina), silicon oxide (silica), silica-alumina composite oxide, and titanium oxide, having a pore size distribution in the range of 3 nm to 100 nm, with a cobalt nitrate solution, followed by drying and calcination; impregnating the dry powder of the carrier with a zirconia sol having an average particle size of 2 nm to 8 nm, followed by drying and calcination; and impregnating the dry powder of the carrier with a manganese nitrate solution, followed by drying, or drying and calcination.

9. The Co-supported catalyst is SiO having an average pore size of 3 nm to 100 nm. ２ A method for producing a Co-supported catalyst according to claim 8, comprising 50 to 60 wt% of the catalyst weight.

10. The method for producing a Co-supported catalyst according to claim 9, wherein the Co-supported catalyst contains 10 to 30 wt% cobalt of the total amount of the catalyst.

11. The method for producing a Co-supported catalyst according to claim 9, wherein the Co-supported catalyst contains 10 to 30 wt% of zirconia in total amount of the catalyst.

12. The method for producing a Co-supported catalyst according to claim 9, wherein the Co-supported catalyst contains manganese in an amount of 5 wt% or less of the total amount of catalyst.

13. The method for producing a Co-supported catalyst according to claim 9, wherein the drying of the Co-supported catalyst is carried out at 100°C to 140°C for 3 to 7 hours.

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