JP2018187556A - Manufacturing method of catalyst for manufacturing hydrocarbon from synthetic gas and manufacturing method of hydrocarbon for manufacturing hydrocarbon from synthetic gas - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a catalyst for manufacturing hydrocarbon from a synthetic gas exhibiting high activity, and a manufacturing method of hydrocarbon using the catalyst manufactured by the manufacturing method.SOLUTION: There is provided a manufacturing method of a catalyst for manufacturing hydrocarbon from a synthetic gas, manufactured by carrying a cobalt component and a noble metal component on a catalyst carrier mainly containing silica, the carrying includes a process for impregnating and carrying the cobalt component into/on a catalyst carrier mainly containing the silica with total content of sodium, potassium, magnesium, calcium of 1,000 ppm or less in terms of metals by using a precursor solution of cobalt acetate, a process for impregnating and carrying the noble metal component by using a precursor of the noble metal compound after the process, and a process for reducing the catalyst after the process with a gas containing hydrogen.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a catalyst for producing hydrocarbons from so-called synthesis gas mainly composed of carbon monoxide and hydrogen, and to produce hydrocarbons from synthesis gas using the catalyst produced by the production method. The present invention relates to a method for producing hydrocarbons.

  In recent years, environmental problems such as global warming have become apparent, and hydrocarbon fuels other than oil and coal have been reviewed. Among them, the importance of natural gas, which has a higher H / C than coal and the like, can suppress carbon dioxide emissions that are a cause of global warming, and has abundant reserves, has been reviewed. The demand for natural gas is expected to increase in the future. Under such circumstances, in Southeast Asia and Oceania, natural gas has been discovered in remote areas where infrastructure such as pipelines and LNG plants has not been developed. However, there are many small and medium-sized gas fields that remain undeveloped because natural gas recoverable reserves are not suitable for infrastructure construction that requires huge investments. The development of these undeveloped small and medium-sized gas fields is desired. As one of the effective development means, after natural gas is converted into synthesis gas, the synthesis gas represented by the following formula (1) is subjected to a Fischer-Tropsch synthesis reaction (FT synthesis reaction). Development of technology to convert to liquid hydrocarbon fuels such as kerosene and light oil, which are excellent in transportability and handling properties, has been vigorously carried out in various places.

  This FT synthesis reaction is an exothermic reaction in which synthesis gas is converted into hydrocarbon using a catalyst. In the FT synthesis reaction, cobalt, ruthenium, iron or the like is used as a catalyst, but a cobalt catalyst is mainly used from the viewpoint of performance and cost. Effective removal of heat of reaction is extremely important for stable operation of a plant using such a catalyst. The reaction modes that have been proven to date include gas phase synthesis processes (fixed bed, spouted bed, fluidized bed) and liquid phase synthesis processes (slurry bed). Each of these reaction modes has its characteristics. Above all, the heat removal efficiency is high, and the high boiling point hydrocarbons produced do not accumulate on the catalyst and the resulting reaction tube clogging does not occur. It is being advanced.

  Needless to say, the higher the activity of the catalyst, the better. Particularly in the slurry bed, there is a limitation that the slurry concentration needs to be a certain value or less in order to maintain a good slurry flow state. Therefore, high activation of the catalyst is a very important factor in expanding the degree of freedom in process design.

  In plants that produce hydrocarbons, it is desirable to set the conversion rate high. As shown in the above formula (1), water is by-produced in the FT synthesis reaction, so that the water pressure in the reactor increases as the conversion rate increases. Under conditions where the moisture pressure is high, the activity of the cobalt catalyst generally tends to decrease. For this reason, an operation is often performed in which the one-pass conversion rate is set to about 60% and the total conversion rate is increased by tail gas recycling. Therefore, the one-pass conversion rate is set to a constant value by changing the reaction temperature and other conditions according to the activity of the catalyst. When the reaction temperature is increased and the reaction temperature is increased, the one-pass conversion rate is maintained at a constant value and the operation is terminated when a specific reaction temperature is reached. The temperature becomes lower. Therefore, the catalyst can be used for a long time.

  Effect of impurities such as alkali metals and alkaline earth metals on the activity of a catalyst in which cobalt is supported on a catalyst carrier mainly composed of silica for the purpose of high activation, using a precursor solution of cobalt nitrate Has been studied in detail. As a result, there has been known an example in which the activity is greatly improved as compared with a conventional catalyst by setting the impurity concentration within a certain range (see, for example, Patent Document 1).

  In addition, for a catalyst in which cobalt is supported on a catalyst carrier mainly composed of silica using a cobalt nitrate precursor solution and the impurity concentration of alkali metal, alkaline earth metal or the like is lowered, noble metal is further provided. An example is known in which the activity is improved by adding as a promoter (see, for example, Patent Document 2).

Japanese Patent Laid-Open No. 2004-322085 JP 2007-260669 A

  Patent Documents 1 and 2 describe a method for producing a catalyst in which cobalt is supported on a catalyst carrier using a precursor solution of cobalt nitrate. The catalyst produced by this production method shows relatively good activity. From the viewpoint of improving the activity, a method of adding a noble metal to a catalyst carrier is conventionally known. However, a catalyst manufactured by a manufacturing method described in Patent Document 2 using a cobalt nitrate precursor solution, in which cobalt is supported on a catalyst carrier and noble metal is added thereto, does not necessarily have a large activity improvement effect. Therefore, further improvement in activity has been desired.

  Therefore, in the present invention, a method for producing a catalyst carrying both cobalt and a noble metal, wherein the produced catalyst can be more improved in activity than a catalyst produced by a conventional method. It is an object of the present invention to provide a method for producing a catalyst for producing hydrocarbons, and a method for producing hydrocarbons for producing hydrocarbons from synthesis gas using the catalyst produced by the production method.

  The present invention relates to a catalyst for FT synthesis having high activity, a method for producing the catalyst, and a method for producing hydrocarbons using the catalyst. As a result of intensive studies, the present inventors have found that noble metal is supported after cobalt is supported on a catalyst carrier mainly composed of silica having an alkali metal or alkaline earth metal content of 1,000 ppm or less, with cobalt acetate as a precursor. Or by simultaneously carrying using a mixed solution of cobalt acetate and a noble metal precursor, followed by a calcination treatment to reduce the small particle size cobalt that is highly dispersed and difficult to reduce. The present inventors have found that a catalyst exhibiting extremely high activity can be obtained in which cobalt metal particles exhibiting activity are formed in a highly dispersed state.

  Further, it was also found that a catalyst exhibiting extremely high activity can be obtained even when a cobalt component and a noble metal component are supported by the above method after zirconium is first supported on the catalyst carrier mainly composed of silica. . These findings have led to the present invention.

  As a result of the study by the present inventors, the case where cobalt nitrate is used as a precursor and the case where cobalt acetate is used as a precursor differ greatly in the degree of dispersion of cobalt particles, and the case where cobalt acetate is used as a precursor is dispersed. Although the degree of reduction is not sufficiently advanced by the activation treatment, it has been found that the activity when cobalt acetate is used as a precursor is equivalent to that when cobalt nitrate is used as a precursor. Further, in Patent Document 2, the activity is improved by further adding a noble metal as a cocatalyst. However, when cobalt nitrate is used as a precursor, reduction is relatively easy even if the noble metal does not coexist. It has been found that the activity improvement effect by addition is not necessarily great.

  On the other hand, in the present invention, when cobalt acetate is used as a precursor, it can be seen that, if noble metal is not added, small particle size cobalt which is in an unreduced state can be reduced by addition of noble metal, It was found that it exhibits extremely high activity. The gist of the present invention is as described below.

(1) A method for producing a catalyst for producing hydrocarbons from synthesis gas, which is produced by supporting a cobalt component and a noble metal component on a catalyst carrier mainly composed of silica,
The support is obtained by using a precursor solution of cobalt acetate on a catalyst support mainly composed of silica having a total content of sodium, potassium, magnesium and calcium of 1,000 ppm or less in terms of metal, Impregnating and supporting, using a noble metal compound precursor solution on the silica-based catalyst carrier on which the cobalt component is supported, impregnating and supporting the noble metal component, the cobalt component and the noble metal And a step of reducing the catalyst carrier mainly composed of silica on which a component is supported with a gas containing hydrogen, and a method for producing a catalyst for producing hydrocarbons from synthesis gas.
(2) A method for producing a catalyst for producing hydrocarbons from synthesis gas, which is produced by carrying a cobalt component, a zirconium component and a noble metal component on a catalyst carrier mainly composed of silica,
The support is obtained by using a precursor solution of a zirconium compound on a catalyst carrier mainly composed of silica having a total content of sodium, potassium, magnesium, and calcium of 1,000 ppm or less in terms of metal, and using the zirconium compound precursor solution. A step of impregnating and supporting, a step of impregnating and supporting the cobalt component using a precursor solution of cobalt acetate on a catalyst support mainly composed of silica on which the zirconium component is supported, the zirconium component and the cobalt A step of impregnating and supporting the noble metal component using a precursor solution of a noble metal compound on the catalyst carrier mainly composed of silica on which the component is supported, and supporting the zirconium component, the cobalt component, and the noble metal component Reducing the silica-based catalyst carrier as a main component with a gas containing hydrogen. Process for preparing a catalyst for producing a hydrocarbon from a syngas, wherein.
(3) A method for producing a catalyst for producing hydrocarbons from synthesis gas, which is produced by carrying a cobalt component and a noble metal component on a catalyst carrier mainly composed of silica,
The support is prepared by adding a cobalt acetate precursor solution and a noble metal compound precursor solution to a catalyst carrier mainly composed of silica having a total content of sodium, potassium, magnesium and calcium of 1,000 ppm or less in terms of metal. Using the mixed solution, simultaneously impregnating and supporting the cobalt component and the noble metal component, firing the catalyst support mainly composed of silica on which the cobalt component and the noble metal component are supported, And a step of reducing with a gas containing hydrogen after calcination, a method for producing a catalyst for producing hydrocarbons from synthesis gas.
(4) A method for producing a catalyst for producing hydrocarbons from synthesis gas, which is produced by carrying a cobalt component, a zirconium component and a noble metal component on a catalyst carrier mainly composed of silica,
The support is obtained by using a precursor solution of a zirconium compound on a catalyst carrier mainly composed of silica having a total content of sodium, potassium, magnesium, and calcium of 1,000 ppm or less in terms of metal, and using the zirconium compound precursor solution. A step of impregnating and using a solution in which a precursor solution of cobalt acetate and a precursor solution of a noble metal compound are mixed in a catalyst support mainly composed of silica on which the zirconium component is supported; A step of impregnating and supporting a noble metal component at the same time; a step of calcining the silica-based catalyst carrier on which the zirconium component, the cobalt component and the noble metal component are supported; and reduction with a gas containing hydrogen after the calcining A method for producing a catalyst for producing hydrocarbons from synthesis gas.
(5) The method for producing a catalyst for producing a hydrocarbon from a synthesis gas according to any one of (1) to (4), wherein the noble metal is at least one of platinum and ruthenium.
(6) Any of (1) to (5), wherein the content of sodium, potassium, calcium and magnesium contained in the catalyst carrier mainly composed of silica is 300 ppm or less in terms of metal. A method for producing a catalyst for producing hydrocarbons from the synthesis gas according to claim 1.
(7) The method of supporting the cobalt component and the noble metal component on the catalyst carrier containing silica as a main component is impregnation support using an incipient wetness method, respectively (1), (3) A method for producing a catalyst for producing hydrocarbons from the synthesis gas according to any one of (5) and (6).
(8) The method of loading the cobalt component, the zirconium component, and the noble metal component on the catalyst carrier mainly composed of silica is impregnation loading using an incipient wetness method. (2), (4), (5) or a method for producing a catalyst for producing a hydrocarbon from the synthesis gas according to any one of (6).
(9) In the step of reducing with the gas containing hydrogen,
The hydrogen flow rate per 1 g of the catalyst support mainly composed of the silica on which the cobalt component and the noble metal component are supported is reduced in the range of 0.1 mL / min to 60 mL / min (1), (3) A method for producing a catalyst for producing a hydrocarbon from a synthesis gas according to any one of (5), (6) and (7).
(10) In the step of reducing with the gas containing hydrogen,
The hydrogen flow rate per 1 g of the catalyst carrier mainly composed of the silica on which the zirconium component, the cobalt component, and the noble metal component are supported is reduced within a range of 0.1 mL / min to 60 mL / min. (2), (4), (5), (6) or a method for producing a catalyst for producing a hydrocarbon from a synthesis gas according to any one of (8).
(11) Using the catalyst produced by the production method according to any one of (1) to (10), a hydrocarbon is produced from synthesis gas by a Fischer-Tropsch synthesis reaction in a slurry bed. A hydrocarbon production method for producing hydrocarbons from synthesis gas.

  According to the present invention, cobalt metal particles exhibiting activity can be formed in a highly dispersed state, and therefore an extremely high activity FT synthesis catalyst can be provided.

  The present invention is described in further detail below.

[Method for producing a catalyst for producing hydrocarbons from synthesis gas]
As a result of intensive studies, the present inventors have determined that a cobalt component supported by cobalt acetate as a precursor is supported on a catalyst support mainly composed of silica with a small particle size and high dispersibility. Since cobalt of this type is difficult to be reduced, the amount of cobalt metal as an active species is small compared to the case where it is supported by a precursor such as cobalt nitrate, and it has been found that high activity cannot be obtained. By carrying a trace amount of the noble metal component, when the noble metal component is not present, the cobalt having a small particle diameter, which has not been reduced, is converted into cobalt metal, thereby obtaining extremely high activity.

The catalyst (catalyst used in the FT synthesis reaction) according to the method for producing a catalyst for producing hydrocarbons from the synthesis gas of the present invention (hereinafter sometimes abbreviated as “catalyst production method”) is an active species of cobalt. It is what. In addition, as a catalyst carrier, one having silica as a main component (hereinafter sometimes referred to as “silica carrier”) is selected and used.
As used herein, the catalyst carrier mainly composed of silica refers to a catalyst carrier composed of 50% by mass or more of silica and the balance of inevitable impurities. The catalyst carrier mainly composed of silica may further contain alumina. The catalyst carrier mainly composed of silica preferably has a silica content of 50% by mass or more and less than 100% by mass.
The inevitable impurities referred to here are based on the impurity species contained in the washing water used in the production process of the silica carrier and the elements contained in the starting material, and are not limited. For example, sodium, calcium, Magnesium, iron and the like.

  Even if iron contains a trace amount of about several hundred ppm, there is almost no influence on catalyst activity. On the other hand, the alkali metals sodium and potassium, and the alkaline earth metals magnesium and calcium affect the catalytic activity. Therefore, controlling their contents is important for improving the catalytic activity. Alkaline metals other than sodium and potassium, and alkaline earth metals other than magnesium and calcium are also considered to affect the catalytic activity, but are hardly mixed in the production process of the silica support. Therefore, what is necessary is just to control content of sodium, potassium, magnesium, and calcium. In addition, mixing of sodium, potassium, magnesium, and calcium can occur in any of the manufacturing processes of the silica carrier, the catalyst manufacturing processes such as loading, firing, and reduction. For example, in a process for producing a catalyst carrier mainly composed of silica, sodium is contained in the raw material and calcium is often contained in the washing water, which is easily mixed into the silica carrier.

As a method for supporting a cobalt component, a zirconium component, and a noble metal component on a catalyst carrier containing silica as a main component, a normal impregnation method, an incipient wetness method, a precipitation method, an ion exchange method, or the like is used. . As a raw material (precursor) used for loading, in the case of a zirconium compound or a noble metal compound, a counter ion (for example, ZrO (NO in the case of a zirconium nitrate oxide salt) is used in the reduction treatment or the firing treatment and the reduction treatment after the loading. ₃₎ in _{2 (nO} 3) ^-) is intended to volatilization is not particularly limited as long as it dissolves in the solvent. As the zirconium compound and the noble metal compound, nitrates, carbonates, acetates, chlorides, acetylacetonates and the like can be used. Among these, it is preferable to use a water-soluble compound that can be used as an aqueous solution during the carrying operation in order to reduce manufacturing costs and secure a safe manufacturing work environment. Specifically, zirconium nitrate oxide, chlorinated noble metal acid, and the like are preferable because they easily change to zirconium oxide, noble metal oxide, or noble metal during firing. The concentration of the precursor aqueous solution when impregnating the precursor aqueous solution composed of the zirconium compound is not particularly limited, but is preferably 0.5 mol / L to 4.0 mol / L, and particularly preferably 1.0 mol / L to 3.0 mol / L. . Further, the precursor aqueous solution concentration when impregnating the precursor aqueous solution composed of the noble metal compound is not particularly limited, but is preferably 0.001 mol / L to 0.5 mol / L, and is preferably 0.003 mol / L to 0.05 mol / L. Particularly preferred.

  The precursor of cobalt is cobalt acetate. The concentration of the precursor aqueous solution when impregnating the precursor aqueous solution of cobalt acetate is not particularly limited, but is preferably 0.53 mol / L to 3 mol / L, and particularly preferably 1.03 mol / L to 2.0 mol / L. When the zirconium component is not included as a co-catalyst, the cobalt component is first supported on a catalyst carrier mainly composed of silica using an aqueous cobalt acetate solution, and then a sequential loading method is employed in which a noble metal component is supported. Can do.

  Further, a co-supporting method in which a cobalt component and a noble metal component are simultaneously supported using a solution obtained by mixing a precursor aqueous solution of cobalt acetate and a precursor aqueous solution of a noble metal compound may be employed. From the viewpoint of production cost, co-supporting is more advantageous. In the co-supporting method, it is necessary to carry out the firing step after the support (even in the sequential support method, it is preferable to carry out the firing step after the support). In the co-supporting, there is a concern that the noble metal component is taken into the cobalt component and the function of promoting the reduction of the cobalt component is deteriorated. Therefore, by carrying out the calcination treatment, it is possible to obtain a catalytic activity equivalent to that in the case where sequential loading is performed. This is because the crystal structure of the cobalt component and the noble metal component are different, so that even when the noble metal component is incorporated into the cobalt component in the co-supporting, the noble metal component is easily formed on the cobalt surface by the firing treatment. .

  When a zirconium component is contained as a cocatalyst, a zirconium component is first supported on a catalyst carrier mainly composed of silica, and then a cobalt acetate component and a noble metal component are supported. As in the case of not containing a zirconium component as a promoter, the cobalt component and the noble metal component may be sequentially supported or co-supported. The zirconium component not only prevents the formation of cobalt silicate formed at the interface between the cobalt component and the catalyst carrier mainly composed of silica, but also adds the zirconium component to the catalyst carrier mainly composed of silica. Improves water resistance. Therefore, the zirconium component and the catalyst carrier mainly composed of silica are preferably brought into contact with each other, and the zirconium component is preferably first supported on the catalyst carrier mainly composed of silica. In addition, when the zirconium component is supported after the cobalt component or the noble metal component, the surface of the cobalt component or the noble metal component is covered with the zirconium component, so that the active surface area of cobalt is reduced or the effect of promoting the reduction of the noble metal is not sufficiently exhibited. It is possible. Further, the noble metal component is intended to promote the reduction of the cobalt component, and it is effective to come into contact with hydrogen during the reduction treatment. For this reason, it is not preferable that the noble metal component is incorporated into the cobalt component. In the case of sequential loading, the loss of the noble metal component is reduced by a final firing or co-supporting firing process.

  When the zirconium component, the cobalt component, and the noble metal component are sequentially supported, the firing treatment or the drying and firing treatment is performed after the zirconium component is supported. Then, after supporting each compound of the cobalt component and the noble metal component, firing treatment, or drying and firing treatment may be performed. After both compounds are supported, without performing drying or drying and firing treatment, hydrogen It is also possible to perform a reduction treatment with a gas containing. The drying and firing treatment can be performed after supporting any compound in the step of sequentially supporting the cobalt component and the noble metal component. About both compounds, it is preferable to carry out a drying and baking process after carrying | supporting respectively. When the noble metal component is supported without firing after the cobalt component is supported, the cobalt component may be eluted in the precursor solution of the noble metal component. Then, since a precious metal component that is preferably formed on the outer surface of the catalyst is taken into the cobalt component and performance may be lowered, it is preferable to carry out drying and firing treatment after loading. Moreover, it is preferable to carry out drying and baking treatment after the noble metal component is supported. However, in the step of reducing with a gas containing hydrogen, if the counter ions of the noble metal component precursor are volatilized, the firing treatment may not be performed.

  In the case where the cobalt component and the noble metal component are co-supported after the zirconium component is supported, a firing treatment or a drying and firing treatment is performed after the zirconium component is supported. Then, after simultaneously carrying a cobalt component and a noble metal component, a calcination process or a drying and calcination process is performed, and a reduction process is performed with a gas containing hydrogen.

The loading ratio of the cobalt component is not less than the minimum amount for exhibiting the activity and may be equal to or less than the loading amount at which the degree of dispersion of the supported cobalt is extremely lowered and the reaction contribution efficiency of cobalt is reduced. The loading ratio of the cobalt component is preferably 5% by mass to 50% by mass, and more preferably 10% by mass to 40% by mass.
When the loading ratio of the cobalt component is below the above range, the activity may not be sufficiently exhibited. On the other hand, when the loading ratio of the cobalt component exceeds the above range, the degree of dispersion is lowered, and the utilization efficiency of the loaded cobalt may be lowered, which is uneconomical.

  The loading ratio of the cobalt component here is not necessarily that the loaded cobalt is finally reduced by 100%, so that the mass of cobalt when converted to metal considering that it is reduced by 100% occupies the entire catalyst mass. Refers to the percentage. In the production process, it is preferable to adjust the amount of cobalt acetate in the starting material so as to achieve the proper loading rate. The total catalyst mass is the catalyst mass after reduction treatment after supporting a cobalt component and a noble metal component, or after supporting a zirconium component, a cobalt component and a noble metal component.

The loading ratio of the zirconium component is preferably 0.2% by mass to 30% by mass as the zirconium oxide among the total weight of the zirconium oxide before supporting cobalt and the catalyst support mainly composed of silica, More preferably, it is 0.5 mass%-20 mass%, More preferably, it is 1 mass%-15 mass%.
If the loading ratio of the zirconium component is below the above range, the water resistance obtained by loading the zirconium component may not be sufficiently exhibited. On the other hand, if the loading ratio of the zirconium component exceeds the above range, the utilization efficiency of the zirconium component may be lowered, which is uneconomical.

The supporting rate of zirconium oxide here is the supporting rate of zirconium dioxide formed by supporting zirconium and then performing a firing treatment. When not firing process is converted into ZrO _2. In the production process, it is preferable to adjust the amount of the zirconium precursor in the starting material so that the above-mentioned proper loading ratio is obtained. Moreover, when measuring the supporting rate of a zirconium oxide, it measures in the state by which the zirconium oxide was carry | supported by the catalyst support | carrier which has a silica as a main component after carrying | supporting a zirconium nitrate oxide and baking processing.

  As the noble metal component to be supported, Ru, Rh, Pt, Pd, Ir, and Os can be used. These noble metals may be used alone or in combination of two or more. The noble metals having a large effect are Ru, Rh, Pt, and Pd, and it is preferable to select them.

The proper range of the loading ratio of these noble metal components is at least the minimum amount for exhibiting the effect of promoting the reduction of the cobalt compound, and the dispersibility of the loaded noble metal is extremely lowered, and the effect is manifested among the added noble metals. It is sufficient that the ratio of the precious metal not contributing to the increase is not higher than the supporting rate, which is uneconomical. Specifically, the precious metal component in terms of metal in the catalyst is 0.01% by mass to 2.00% by mass, preferably 0.02% by mass to 1.00% by mass, and more preferably 0.05% by mass. % To 0.20 mass%. The catalyst as a denominator is the total amount of a catalyst carrier mainly composed of silica, a zirconium component converted to ZrO ₂ , a cobalt component converted to metal, and a noble metal converted to metal.
When the loading ratio of the noble metal component is below the above range, the effect of promoting the reduction of the cobalt compound cannot be sufficiently exhibited. On the other hand, if the loading ratio of the noble metal component exceeds the above range, the utilization efficiency of the loaded noble metal component is reduced, which is not preferable.

  The amount of zirconium oxide, cobalt and noble metal supported in the produced catalyst is determined by ICP-AES (Inductively Coupled Plasma Atomic Emission Spectroscopy, ICP (Inductively Coupled Plasma) emission spectroscopy) after pretreatment such as acid decomposition and alkali melting. Can be measured.

  It is necessary that the cobalt component and the noble metal component be supported on the catalyst carrier containing silica as a main component. If supported simultaneously, a part of the noble metal component may be taken into the cobalt component, so from the viewpoint of catalyst performance, it is necessary to sequentially support the zirconium component, the cobalt component, and the noble metal component in this order.

  The amount of zirconium component or noble metal component necessary for exhibiting a sufficient effect is extremely large in a catalyst with many impurities. It is uneconomical to add a large amount of a zirconium component or a noble metal component. Conventionally, even when a zirconium component or a noble metal component is added, the effect cannot be sufficiently obtained. According to the catalyst obtained by the method for producing a catalyst of the present invention, it has been found that a sufficient and advanced effect can be obtained even if the amount of zirconium component or noble metal component is relatively small. This is particularly noticeable when a carrier with few impurities is used. Zirconium oxide and noble metals are easily formed in a highly dispersed and homogeneous manner on the silica surface due to the small amount of impurities. For this reason, it is presumed that the characteristics of the catalyst surface could be changed efficiently with a small amount.

Below, an example of the method of obtaining the catalyst which carries a cobalt component and a noble metal component is shown.
First, after impregnating an aqueous cobalt acetate solution into a catalyst carrier containing silica as a main component and having a small amount of impurities, drying and firing are performed. As a result, the cobalt carrier is impregnated and supported on the catalyst carrier mainly composed of silica.
Next, a precursor solution made of a noble metal compound is impregnated and supported on a catalyst carrier mainly composed of silica on which a cobalt component is supported.
Next, the catalyst carrier mainly composed of silica on which the cobalt component and the noble metal component are supported is dried, calcined, and reduced to obtain an FT synthesis catalyst.

  After the cobalt compound is supported, a drying process (for example, 100 ° C.-1 h in the air) is performed, and even if a subsequent baking process (for example, 450 ° C.-5 h in the air) is performed, the precious metal that is the next step is simply the drying process. The component may be impregnated and supported. In order to prevent the addition effect of the noble metal by taking the noble metal during the impregnation of the noble metal component, the cobalt component is preferably converted into cobalt oxide by performing a baking treatment.

  After impregnating and supporting the noble metal component, drying treatment is performed as necessary, and the cobalt compound on the surface of the catalyst support is subsequently reduced to cobalt metal (for example, 350 ° C.-15 h in a normal pressure hydrogen stream, the hydrogen flow rate per gram of catalyst. FT synthesis catalyst is obtained by carrying out 60 mL / min). Here, the reduction treatment may be performed after firing and converting to an oxide, or the reduction treatment may be performed directly without firing. If the reduction conditions are made stricter by increasing the temperature of the reduction treatment or lengthening the time, the ratio of cobalt being reduced from the oxide state to the metal state after the reduction treatment increases. In general reducing conditions, the cobalt metal often contains a part of the cobalt metal oxide. The catalyst after the reduction treatment needs to be handled so as not to be oxidized and deactivated by contact with the atmosphere. It is preferable to perform a stabilization treatment in which the surface of the cobalt metal on the catalyst support is shielded from the atmosphere because it can be handled in the atmosphere. This stabilization treatment involves so-called passivation (surface decontamination) in which only the extreme surface of cobalt metal on the catalyst carrier is oxidized by bringing the catalyst into contact with nitrogen, carbon dioxide, or an inert gas containing a low concentration of oxygen. Treatment) or when the FT synthesis reaction is carried out in a liquid phase, a method of immersing in a reaction solvent, molten FT wax or the like and blocking from the atmosphere is used. These stabilization processes may be appropriately selected according to the situation.

In addition, an example of a method for obtaining a catalyst supporting a cobalt component, a zirconium component, and a noble metal component will be described below.
First, after impregnating a catalyst carrier containing silica as a main component with few impurities with an aqueous precursor solution composed of a zirconium compound, drying and firing are performed. Thus, the zirconium carrier is impregnated and supported on the catalyst carrier mainly composed of silica.
Next, after impregnating and supporting a cobalt acetate aqueous solution on a catalyst carrier mainly composed of silica on which a zirconium component is supported, drying and firing are performed. As a result, the cobalt carrier is impregnated and supported on the catalyst carrier mainly composed of silica.
Next, a precursor solution made of a noble metal compound is impregnated and supported on a catalyst carrier mainly composed of silica on which a zirconium component and a cobalt component are supported.
Next, the catalyst carrier mainly composed of silica on which a zirconium component, a cobalt component, and a noble metal component are supported is dried, calcined, and reduced to obtain an FT synthesis catalyst.

  After supporting the zirconium compound, the cobalt compound, and the noble metal compound, a drying process (for example, 100 ° C.-1 h in the air) is performed, and a subsequent baking process (for example, 450 ° C.-5 h in the air) is performed. The impregnation support in the next step may be performed. In order for the zirconium compound to incorporate cobalt during the impregnation support of the cobalt compound, and to prevent the addition effect from being reduced by the cobalt compound or zirconium compound incorporating the precious metal during the impregnation support of the noble metal compound, each support It is preferable to carry out a firing treatment later to convert into zirconium oxide and cobalt oxide. About a reduction process and a stabilization process, it can implement similarly to the catalyst which carry | supports the above-mentioned cobalt component and a noble metal component.

  In an example of the method for obtaining the above catalyst, hydrogen is used as a reducing gas when reducing the cobalt compound to cobalt metal, and the hydrogen flow rate is a large excess flow rate of 60 mL / min per 1 g of the catalyst. In such a large excess of hydrogen flow rate, depending on the temperature and holding time, after supporting a cobalt component with cobalt acetate as a precursor, after supporting a catalyst that supports a noble metal component, or a zirconium compound, A cobalt component is supported using cobalt acetate as a precursor, and then a catalyst that supports a noble metal component, a catalyst that does not support a noble metal component, cobalt is supported using cobalt acetate as a precursor, or a zirconium compound is supported. Thereafter, the activity difference from the catalyst supporting cobalt component with cobalt acetate as a precursor is smaller than that when the hydrogen flow rate is small. Depending on the catalyst composition such as precious metal species and amount added, production conditions such as reduction temperature and holding time, when the hydrogen flow rate is reduced to about 10 mL / min to 20 mL / min, the difference in catalytic activity and cobalt reduction degree depends on whether or not noble metal is contained. Becomes larger. The normal reducing gas flow rate range employed in mass production on a commercial scale is often 20 mL / min or less per gram of catalyst.

After a cobalt component is supported using cobalt acetate as a precursor, a catalyst that supports a noble metal component, or a zirconium compound, a cobalt component is supported using cobalt acetate as a precursor, and then a noble metal component is supported. The range of the preferable hydrogen flow rate in the reduction treatment for the catalyst is appropriately adjusted according to the temperature and holding time. The range of the hydrogen flow rate is preferably 0.1 mL / min to 60 mL / min per gram of catalyst, more preferably 0.1 mL / min to 40 mL / min per gram of catalyst, and still more preferably 0.2 mL / min per gram of catalyst. It is min-20mL / min, Most preferably, it is 0.5mL / min-10mL / min.
If the hydrogen flow rate is less than 0.1 mL / min per gram of catalyst, it is necessary to increase the amount of noble metal in the catalyst in order to increase the reduction promotion effect by the noble metal, which is uneconomical, and the temperature is significantly reduced in the reduction operation. As a result of the sintering of cobalt metal or noble metal during reduction at high temperature, the performance is lowered, and the processing time is increased due to time extension. On the other hand, when the hydrogen flow rate exceeds 60 mL / min per gram of catalyst, when a large excess of reducing gas can be secured, a constant catalytic activity can be obtained even if there is no reduction promoting effect by noble metals, but the amount of reducing gas per catalyst amount. As the amount of catalyst that can be treated at one time is relatively reduced, the production cost increases and becomes uneconomical.

  In addition, it is extremely effective for improving the activity to reduce the alkali metal and alkaline earth metal in the catalyst carrier and control them within a predetermined range. When silica is used as a catalyst support, alkali metal sodium, potassium, alkaline earth metal magnesium, calcium, Fe, and the like are often contained in silica as impurities, as described above. The influence of magnesium and calcium is strong, and the presence of sodium is the strongest. Potassium, magnesium, and calcium are less affected than sodium, but the greater the content, the greater the effect.

  In order to develop good catalytic activity, the total amount of sodium, potassium, magnesium and calcium in the catalyst carrier is suppressed to 1,000 ppm or less. If this amount is exceeded, the activity is greatly reduced, which is a disadvantage. However, reducing the amount of impurities more than necessary increases the cost of purity and is uneconomical, so the total amount of sodium, potassium, magnesium, and calcium in the catalyst support is 100 ppm or less. Although it is difficult to limit because it depends on the loading rate and the type of precursor, in order to reduce the total amount of sodium, potassium, magnesium and calcium in the catalyst support, the active metal precursor as described above is used. It is effective to suppress the total amount of impurities therein to 5% by mass or less. As impurities in the precursor, the contents of sodium, potassium, magnesium, and calcium are not usually large as compared with the catalyst carrier, but when they are large, it is preferable to reduce these contents. In addition, the total amount of said sodium, potassium, magnesium, and calcium is a metal conversion amount with respect to the catalyst weight after converting from cobalt oxide to cobalt metal by an activation process. The total amount of sodium, potassium, magnesium, and calcium is 100% when the content of sodium, potassium, magnesium, and calcium in the catalyst in which cobalt is an oxide without measuring the activation is measured. It is an amount converted based on the assumption that the product has been reduced.

  Among the impurities in the catalyst carrier, the elements that have the worst effect on the effect of suppressing the decrease in activity are sodium, potassium, magnesium and calcium. When the content of these metals in the catalyst support is less than 30 ppm, the influence of sodium, potassium, magnesium, and calcium is hardly observed, but when it exceeds 100 ppm, the activity decreases. Therefore, the total amount of sodium, potassium, magnesium and calcium in the catalyst support is 1,000 ppm, preferably 30 ppm to 700 ppm, more preferably 30 ppm to 400 ppm. The content of each element of alkali metal and alkaline earth metal is preferably 300 ppm or less, more preferably 200 ppm or less. The lower limit of the content of each element is the detection limit in the measurement.

  When the total amount of sodium, potassium, magnesium and calcium in the catalyst support exceeds 1,000 ppm as described above, the activity of the catalyst is greatly reduced. Here again, as described above, it is uneconomical to reduce the contents of sodium, potassium, magnesium and calcium in the catalyst carrier more than necessary. Therefore, sodium, potassium, magnesium, and calcium in the catalyst carrier may be contained in a range that does not adversely affect the catalyst activity. As described above, if the total amount of sodium, potassium, magnesium and calcium in the catalyst support is reduced to about 100 ppm, a sufficient effect can be obtained. Therefore, it is preferable from the viewpoint of cost that the content of sodium, potassium, magnesium and calcium in the catalyst carrier is 100 ppm or more.

  The total amount of sodium, potassium, magnesium, and calcium impurities in the catalyst carrier thus produced is 30 ppm to 1,000 ppm. Beyond this range, the decrease in activity under conditions of high moisture pressure increases. The determination method of sodium, potassium, magnesium and calcium in the catalyst carrier is the same as the method in the catalyst carrier, and can be measured by, for example, ICP-AES method after pretreatment such as acid decomposition or alkali melting. .

  If the catalyst carrier can be devised so that impurities such as sodium, potassium, magnesium and calcium do not enter during the production process, it is preferable to take measures to prevent impurities from being mixed during production. In general, silica production methods are roughly classified into a dry method and a wet method. Examples of the dry method include a combustion method and an arc method. Examples of the wet method include a sedimentation method and a gel method. Although any production method can produce a catalyst carrier, it is technically and economically difficult to form the catalyst carrier into a spherical shape by the above method except the gel method. Therefore, it is preferable to manufacture by a gel method in which silica sol can be easily formed into a spherical shape by spraying in a gaseous medium or a liquid medium. Sodium, potassium, magnesium, and calcium are often mixed from raw materials and washing water. Sodium is often mainly derived from raw materials, and calcium is often mainly derived from washing water.

  When producing a catalyst carrier mainly composed of silica by the gel method described above, a large amount of washing water is usually used. When washing water containing a large amount of impurities such as industrial water is used, a large amount of impurities remain in the carrier, and the activity of the catalyst is greatly reduced. However, it is possible to obtain a good silica carrier having a low impurity content by using a cleaning water having a low impurity content or no impurities such as ion-exchanged water. In this case, the content of sodium, potassium, magnesium and calcium in the washing water is preferably 600 ppm or less. If it exceeds this, the impurity content in the catalyst carrier containing silica as a main component will increase, and the activity of the catalyst after preparation will be greatly reduced. Even when an acidic aqueous solution is used as the washing water, the content of sodium, potassium, magnesium, and calcium in the acidic aqueous solution is preferably 600 ppm or less for the same reason. From the viewpoint of reducing the amount of impurities, ideally ion-exchanged water is preferably used. In order to obtain ion-exchanged water, ion-exchange resin or the like may be used, but ion-exchanged water can also be produced by performing ion exchange using silica gel generated as a non-standard product on the silica production line. It is. In principle, silica supplements impurities in the wash water by ion exchange between hydrogen in silanol on the silica surface and impurity ions such as sodium ion, potassium ion, magnesium ion and calcium ion. Therefore, even if the cleaning water contains a little impurities, it is possible to prevent impurities from being captured to some extent by adjusting the pH of the cleaning water to be low. Further, the amount of ion exchange (amount of impurities mixed) is proportional to the amount of cleaning water used. Therefore, it is possible to reduce the amount of impurities in silica by reducing the amount of washing water, in other words, by increasing the efficiency of use of water until the end of washing.

  Improve impurities in the catalyst carrier mainly composed of silica by pretreatment such as washing with water, washing with acid, washing with alkali, etc. without greatly changing the physical and chemical properties of the catalyst carrier. These pretreatments are extremely effective in improving the activity of the catalyst.

  For example, for washing a catalyst carrier mainly composed of silica, washing with an acidic aqueous solution such as nitric acid, hydrochloric acid or acetic acid, or washing with ion exchange water is particularly effective. If it becomes an obstacle that a part of the acid remains in the carrier after the washing treatment with these acids, it is effective to further wash with clean water such as ion-exchanged water.

  Further, in the production of a catalyst carrier mainly composed of silica, a calcination treatment for the purpose of improving particle strength, surface silanol group activity and the like is often performed. However, if firing is performed in a state where there are relatively many impurities, the impurity element is incorporated into the silica skeleton when the catalyst carrier mainly composed of silica is washed to reduce the impurity concentration, and the impurity content Is difficult to reduce. Therefore, when it is desired to reduce the impurity concentration by washing the catalyst carrier mainly composed of silica, it is preferable to use unfired silica gel.

From the viewpoint of the activity of the FT synthesis catalyst, it is preferable to use a catalyst carrier having a large specific surface area in order to keep the dispersibility of cobalt high and improve the efficiency of contributing to the reaction of the supported active cobalt. In order to increase the specific surface area of the catalyst support, it is necessary to reduce the pore diameter and increase the pore volume. However, if these two factors are increased too much, the wear resistance and strength will decrease. Therefore, the physical properties of the catalyst support, as the pore size is 8Nm～50nm, the specific surface area of ^{80m 2} / ^g~450m 2 / g, pore volume satisfies 0.2mL / g~1.2mL / g simultaneously Is suitable as a support for the catalyst. Pore size 8Nm～30nm, a specific surface area of 100m ² / g~400m ² / g, a pore volume of more preferable as long as it simultaneously satisfies 0.2mL / g~0.9mL / g, pore size 8nm to 20 nm, a specific surface area of 150m ² / g~350m ² / g, a pore volume of more preferable as long as it simultaneously satisfies 0.3mL / g~0.8mL / g. In particular, since the strength of the catalyst is required in the slurry bed, the pore volume is particularly preferably from 0.3 mL / g to 0.6 mL / g.

  The specific surface area can be measured by the BET method, and the pore volume can be measured by the mercury intrusion method or the water titration method. The pore diameter can be measured by a mercury adsorption method using a gas adsorption method or a mercury porosimeter, but can also be calculated from the specific surface area and pore volume.

In order to obtain a catalyst that exhibits sufficient activity for the FT synthesis reaction, the specific surface area of the catalyst carrier is preferably 80 m ² / g or more. Below this specific surface area, the degree of dispersion of the supported metal may decrease, and the contribution efficiency to the reaction of active cobalt may decrease. On the other hand, if the specific surface area of the catalyst support exceeds 450 m ² / g, it may be difficult for the pore volume and the pore diameter to satisfy the above ranges at the same time. Therefore, the specific surface area of the catalyst support is 450 m ² / g or less. Preferably there is.

  Although the specific surface area can be increased as the pore size of the catalyst carrier is reduced, the pore size is preferably 8 nm or more. When the pore diameter is less than 8 nm, the gas diffusion rate in the pore is different between hydrogen and carbon monoxide, and the hydrogen partial pressure increases as it goes deeper into the pore. A large amount of light hydrocarbons such as methane can be produced. In addition, the diffusion rate of the produced hydrocarbons in the pores is reduced, and as a result, the apparent reaction rate may be reduced. Further, when the comparison is made with a constant pore volume, the specific surface area of the catalyst carrier decreases as the pore diameter increases, so the pore diameter is preferably 50 nm or less. When the pore diameter exceeds 50 nm, it is difficult to increase the specific surface area of the catalyst support, and the dispersity of the active cobalt is lowered.

  The pore volume of the catalyst support is preferably 0.2 mL / g to 1.2 mL / g. When the pore volume is less than 0.2 mL / g, it is difficult for the pore diameter and the specific surface area to satisfy the above ranges at the same time. On the other hand, when the pore volume exceeds 1.2 mL / g, the strength of the catalyst carrier may be reduced.

The FT synthesis catalyst for slurry bed reaction is required to have wear resistance and strength. In addition, since a large amount of water is produced as a by-product in the FT synthesis reaction, the use of a catalyst or catalyst carrier that is destroyed or pulverized in the presence of water causes the disadvantages described above. Attention is required. Therefore, a catalyst using a spherical catalyst carrier is preferable instead of a crushed catalyst carrier which has a high possibility of being cracked in advance and whose sharp corners are easily broken and peeled off.
The particle size of the catalyst carrier is preferably about 10 μm to 250 μm. The average particle size of the catalyst carrier is preferably 20 μm to 150 μm, more preferably 30 μm to 120 μm, and even more preferably 40 μm to 100 μm. When producing a spherical catalyst carrier, a spraying method such as a general spray drying method is used. In particular, when producing a spherical silica carrier having a particle size of about 10 μm to 250 μm, a spray method is suitably used, and a spherical silica carrier excellent in wear resistance, strength and water resistance can be obtained.

A method for producing such a catalyst carrier containing silica as a main component is exemplified below.
A silica silicate aqueous solution and an acid aqueous solution are mixed, and the produced silica sol is sprayed into a gaseous medium such as air or into an organic solvent insoluble in the silica sol, followed by acid treatment, water washing and drying.
Here, as the silicate alkali, a sodium silicate aqueous solution is preferably used. The molar ratio of Na ₂ O: SiO ₂ is preferably 1: 1 to 1: 5, and the concentration of silica is preferably 5% by mass to 30% by mass.

Examples of the acid used in the production method of the catalyst carrier mainly composed of silica include nitric acid, hydrochloric acid, sulfuric acid, and organic acid. Among these, sulfuric acid is preferable from the viewpoint of preventing corrosion of the container during production and leaving no organic matter.
The acid concentration is preferably 1 mol / L to 10 mol / L. When the acid concentration is less than 1 mol / L, the progress of gelation is remarkably slowed. On the other hand, when the acid concentration exceeds 10 mol / L, the gelation rate is too fast and it is difficult to control the gel, and it is difficult to obtain desired physical property values.

Moreover, when employ | adopting the method sprayed in an organic solvent, kerosene, paraffin, xylene, toluene etc. can be used as an organic solvent.
In addition, when aluminum is contained, a method of doping after mixing an aluminum source with a raw material or manufacturing silica is used.

  By using a catalyst obtained by using the catalyst carrier mainly composed of silica as described above and a method for producing the catalyst, an FT synthesis reaction catalyst having extremely high activity can be obtained. . It is difficult to obtain a very high activity with a catalyst that uses cobalt acetate as a precursor but does not contain a noble metal, although the reduction of cobalt does not proceed sufficiently and the cobalt particle size is small and the cobalt specific surface area is large. . On the other hand, the catalyst according to the present invention exhibits extremely high activity due to the effect of promoting the reduction of cobalt particles by a noble metal.

  Since the activity according to the present invention is extremely high, the hydrocarbon productivity per unit catalyst weight / unit time is 2 kg / g-cat. It is also possible to manufacture with a productivity of / h or more. Thereby, since the amount of catalyst to be used can be reduced under the same conditions for the amount of hydrocarbon production in the plant, the slurry concentration during operation can be set low, or the reactor can be made small.

[Hydrocarbon production method for producing hydrocarbons from synthesis gas]
The hydrocarbon production method for producing hydrocarbons from the synthesis gas of the present invention comprises the above-described Fischer-Tropsch synthesis reaction in a slurry bed using the catalyst produced by the catalyst production method of the present invention. In (FT synthesis reaction), hydrocarbons are produced from synthesis gas.

  As the synthesis gas used in the present invention, a gas in which the total of hydrogen and carbon monoxide is 50% by volume or more is preferable from the viewpoint of productivity, and in particular, the molar ratio of hydrogen to carbon monoxide (hydrogen / monoxide) Carbon) is preferably in the range of 0.5 to 4.0. This is because when the molar ratio of hydrogen to carbon monoxide is less than 0.5, the amount of hydrogen in the raw material gas is too small, so that the carbon monoxide hydrogenation reaction (FT synthesis reaction) is difficult to proceed. This is because the productivity of liquid hydrocarbons does not increase. On the other hand, when the molar ratio of hydrogen to carbon monoxide exceeds 4.0, the amount of carbon monoxide present in the raw material gas is too small, and the productivity of liquid hydrocarbons does not increase regardless of the catalyst activity. It is.

  Hereinafter, although an example and a comparative example explain the present invention still in detail, the present invention is not limited to these examples.

[Catalyst synthesis]
A noble metal-Co / SiO ₂ catalyst or a noble metal-Co / ZrO ₂ / SiO ₂ catalyst was produced by one of the following two production methods.
(First manufacturing method)
A catalyst support based on silica (silica with few impurities with controlled washing process (washing time, washing water purity) when producing by the above-mentioned silica production method), precursor of cobalt acetate by the incipient wetness method. A cobalt compound is supported as a body, dried and fired, and then a noble metal compound is supported and dried, fired, reduced (15 h), and passivated to prepare a noble metal-Co / SiO ₂ catalyst. Obtained. The concentration of the cobalt acetate tetrahydrate aqueous solution was 1.7 mol / L.

(Second manufacturing method)
After a zirconium compound is supported on a catalyst carrier mainly composed of silica by an incipient wetness method and dried and fired, the cobalt compound is supported using cobalt acetate as a precursor and dried and fired. Next, a noble metal compound is supported, dried, calcined, reduced (15 h), and passivated to prepare a noble metal-Co / ZrO ₂ / SiO ₂ catalyst (silica-based catalyst carrier has an average particle size) A spherical shape having a diameter of 100 μm). Zirconium nitrate oxide was used as the precursor of the zirconium compound, the concentration of the zirconium oxide nitrate dihydrate aqueous solution was 1.8 mol / L, and the concentration of the noble metal compound was in the range of 0.005 mol / L to 0.02 mol / L. It was. The precursor of the noble metal compound is hexachloroplatinic acid hexahydrate when carrying Pt, ruthenium chloride n-hydrate when carrying Ru, and rhodium chloride hydrate when carrying Rh. used.

[Hydrocarbon synthesis]
After charging 1 g of noble metal-Co / SiO ₂ catalyst or 1 g of noble metal-Co / ZrO ₂ / SiO ₂ catalyst and 50 mL of n-C ₁₆ (n-hexadecane) in an autoclave having an internal volume of 300 mL, While rotating the stir bar at 800 min ⁻¹ under the condition of 2 MPa-G, W (catalyst mass) / F (synthesis gas flow rate); (g · h / mol) = 1.5 F (syngas (H ₂ / CO = 2) flow rate) is adjusted, and the composition of the supply gas and autoclave outlet gas is obtained by gas chromatography, CO conversion, CH ₄ selectivity, CO ₂ selectivity, hydrocarbon production Got sex.

(Example 1)
Using a catalyst carrier as shown in Table 1 A, a Pt—Co / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of the catalyst. The Pt—Co / SiO ₂ catalyst was activated.
Thereafter, using this Pt—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 1.
CO conversion is 82.3%, CH ₄ selectivity is 4.5%, CO ₂ selectivity is 1.4%, and hydrocarbon productivity of 5 or more carbon atoms is 2.5 (kg-hydrocarbon / kg -Catalyst / hour).

(Example 2)
Using a catalyst carrier as shown in Table 1 B, a Pt—Co / ZrO ₂ / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of catalyst. This Pt—Co / ZrO ₂ / SiO ₂ catalyst was activated.
Thereafter, using this Pt—Co / ZrO ₂ / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 1.
CO conversion is 79.8%, CH ₄ selectivity is 6.0%, CO ₂ selectivity is 1.6%, hydrocarbon productivity with 5 or more carbon atoms is 2.4 (kg-hydrocarbon / kg -Catalyst / hour).

Example 3
Using a catalyst carrier as shown in Table 1 C, a Pt—Co / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of catalyst, The Pt—Co / SiO ₂ catalyst was activated.
Thereafter, using this Pt—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 1.
CO conversion is 78.7%, CH ₄ selectivity is 5.0%, CO ₂ selectivity is 1.2%, and hydrocarbon productivity of 5 or more carbon atoms is 2.4 (kg-hydrocarbon / kg -Catalyst / hour).

(Example 4)
Using a catalyst carrier as shown in Table 1 C, cobalt acetate is mixed as a cobalt precursor with a Pt precursor to prepare a Pt-Co / SiO ₂ catalyst by co-impregnation, and the hydrogen flow rate during the reduction treatment is adjusted. The Pt—Co / SiO ₂ catalyst was activated by setting to 40 mL / min per gram of catalyst.
Thereafter, using this Pt—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 1.
CO conversion is 76.2%, CH ₄ selectivity is 5.4%, CO ₂ selectivity is 0.8%, hydrocarbon productivity with 5 or more carbon atoms is 2.3 (kg-hydrocarbon / kg -Catalyst / hour).

(Example 5)
Using a catalyst support as shown in Table 1 C, a Ru-Co / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of catalyst, The Ru—Co / SiO ₂ catalyst was activated.
Thereafter, using this Ru—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 1.
CO conversion is 78.0%, CH ₄ selectivity is 4.9%, CO ₂ selectivity is 1.0%, and hydrocarbon productivity of 5 or more carbon atoms is 2.4 (kg-hydrocarbon / kg -Catalyst / hour).

(Example 6)
Using a catalyst carrier as shown in Table 1 C, Rh—Co / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of catalyst, The Rh—Co / SiO ₂ catalyst was activated.
Thereafter, using this Rh—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 1.
CO conversion is 73.6%, CH ₄ selectivity is 5.7%, CO ₂ selectivity is 0.7%, and hydrocarbon productivity of 5 or more carbon atoms is 2.2 (kg-hydrocarbon / kg -Catalyst / hour).

(Example 7)
Using a catalyst carrier as shown in Table 1 C, a Pt—Co / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, the hydrogen flow rate during the reduction treatment was set to 10 mL / min per gram of catalyst, The Pt—Co / SiO ₂ catalyst was activated.
Thereafter, using this Pt—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 1.
CO conversion is 78.7%, CH ₄ selectivity is 4.4%, CO ₂ selectivity is 1.0%, and hydrocarbon productivity of 5 or more carbon atoms is 2.4 (kg-hydrocarbon / kg -Catalyst / hour).

(Example 8)
Using a catalyst carrier as shown in Table 2C, a Pt-Co / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 1 mL / min per gram of catalyst. The Pt—Co / SiO ₂ catalyst was activated.
Thereafter, using this Pt—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 2.
CO conversion is 69.8%, CH ₄ selectivity is 5.0%, CO ₂ selectivity is 0.5%, and hydrocarbon productivity of 5 or more carbon atoms is 2.1 (kg-hydrocarbon / kg). -Catalyst / hour).

Example 9
Using a catalyst carrier as shown in Table 2C, a Pt-Co / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 0.5 mL / min per gram of catalyst. This Pt—Co / SiO ₂ catalyst was activated.
Thereafter, using this Pt—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 2.
CO conversion is 66.4%, CH ₄ selectivity is 5.4%, CO ₂ selectivity is 0.4%, and hydrocarbon productivity with 5 or more carbon atoms is 2.0 (kg-hydrocarbon / kg -Catalyst / hour).

(Example 10)
Using a catalyst carrier as shown in Table 2D, a Pt—Co / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of catalyst. The Pt—Co / SiO ₂ catalyst was activated.
Thereafter, using this Pt—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 2.
CO conversion is 78.2%, CH ₄ selectivity is 4.6%, CO ₂ selectivity is 1.4%, and hydrocarbon productivity of 5 or more carbon atoms is 2.3 (kg-hydrocarbon / kg -Catalyst / hour).

(Example 11)
Using a catalyst carrier as shown in Table 2 E, a Pt—Co / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of catalyst. The Pt—Co / SiO ₂ catalyst was activated.
Thereafter, using this Pt—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 2.
CO conversion is 68.3%, CH ₄ selectivity is 5.9%, CO ₂ selectivity is 1.4%, and hydrocarbon productivity of 5 or more carbon atoms is 2.0 (kg-hydrocarbon / kg -Catalyst / hour).

(Example 12)
Using a catalyst carrier as shown in Table 2 F, a Pt—Co / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of the catalyst. The Pt—Co / SiO ₂ catalyst was activated.
Thereafter, using this Pt—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 2.
CO conversion is 73.1%, CH ₄ selectivity is 4.8%, CO ₂ selectivity is 0.9%, and hydrocarbon productivity of 5 or more carbon atoms is 2.3 (kg-hydrocarbon / kg -Catalyst / hour).

(Example 13)
Using a catalyst carrier as shown in G of Table 2, a Pt-Co / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of catalyst. The Pt—Co / SiO ₂ catalyst was activated.
Thereafter, using this Pt—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 2.
The CO conversion is 59.2%, the CH ₄ selectivity is 7.0%, the CO ₂ selectivity is 0.7%, and the hydrocarbon productivity of 5 or more carbon atoms is 1.7 (kg-hydrocarbon / kg -Catalyst / hour).

(Comparative Example 1)
Using a catalyst carrier as shown in Table 3A, a Co / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of the catalyst. The / SiO ₂ catalyst was activated.
Thereafter, using this Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-described method. The results are shown in Table 3.
CO conversion is 69.8%, CH ₄ selectivity is 4.9%, CO ₂ selectivity is 0.4%, and hydrocarbon productivity of 5 or more carbon atoms is 2.2 (kg-hydrocarbon / kg -Catalyst / hour).

(Comparative Example 2)
Using a catalyst carrier as shown in Table 3B, a Co / ZrO ₂ / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of catalyst. The Co / ZrO ₂ / SiO ₂ catalyst was activated.
Thereafter, using this Co / ZrO ₂ / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 3.
CO conversion is 71.2%, CH ₄ selectivity is 5.3%, CO ₂ selectivity is 0.9%, hydrocarbon productivity with 5 or more carbon atoms is 2.2 (kg-hydrocarbon / kg -Catalyst / hour).

(Comparative Example 3)
Using a catalyst carrier as shown in Table 3C, a Co / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of the catalyst. The / SiO ₂ catalyst was activated.
Thereafter, using this Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-described method. The results are shown in Table 3.
CO conversion is 58.8%, CH ₄ selectivity is 6.3%, CO ₂ selectivity is 0.3%, and hydrocarbon productivity with 5 or more carbon atoms is 1.8 (kg-hydrocarbon / kg -Catalyst / hour).

(Comparative Example 4)
Using a catalyst carrier as shown in Table 3C, a Co / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 10 mL / min per gram of the catalyst. The / SiO ₂ catalyst was activated.
Thereafter, using this Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-described method. The results are shown in Table 3.
The CO conversion is 22.9%, the CH ₄ selectivity is 9.5%, the CO ₂ selectivity is 0.2%, and the hydrocarbon productivity of 5 or more carbon atoms is 0.7 (kg-hydrocarbon / kg -Catalyst / hour).

(Comparative Example 5)
Using a catalyst carrier as shown in Table 3C, a Co / SiO ₂ catalyst was prepared using cobalt nitrate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of the catalyst. The / SiO ₂ catalyst was activated.
Thereafter, using this Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-described method. The results are shown in Table 3.
CO conversion is 72.3%, CH ₄ selectivity is 3.9%, CO ₂ selectivity is 0.5%, and hydrocarbon productivity of 5 or more carbon atoms is 2.3 (kg-hydrocarbon / kg -Catalyst / hour).

(Comparative Example 6)
Using a catalyst carrier as shown in Table 3C, a Co / SiO ₂ catalyst was prepared using cobalt nitrate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 10 mL / min per gram of the catalyst. The / SiO ₂ catalyst was activated.
Thereafter, using this Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-described method. The results are shown in Table 3.
CO conversion is 65.1%, CH ₄ selectivity is 4.5%, CO ₂ selectivity is 0.4%, and hydrocarbon productivity of 5 or more carbon atoms is 2.0 (kg-hydrocarbon / kg -Catalyst / hour).

(Comparative Example 7)
Using a catalyst carrier as shown in Table 3C, a Pt—Co / SiO ₂ catalyst was prepared using cobalt nitrate as a cobalt precursor, the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of catalyst, The Pt—Co / SiO ₂ catalyst was activated.
Thereafter, using this Pt—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 3.
CO conversion is 74.0%, CH ₄ selectivity is 3.8%, CO ₂ selectivity is 0.5%, and hydrocarbon productivity of 5 or more carbon atoms is 2.3 (kg-hydrocarbon / kg -Catalyst / hour).

(Comparative Example 8)
Using a catalyst carrier as shown in Table 3C, a Pt—Co / SiO ₂ catalyst was prepared using cobalt nitrate as a cobalt precursor, the hydrogen flow rate during the reduction treatment was set to 10 mL / min per gram of catalyst, The Pt—Co / SiO ₂ catalyst was activated.
Thereafter, using this Pt—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 3.
CO conversion is 72.5%, CH ₄ selectivity is 3.9%, CO ₂ selectivity is 0.5%, and hydrocarbon productivity of 5 or more carbon atoms is 2.3 (kg-hydrocarbon / kg -Catalyst / hour).

(Comparative Example 9)
Using a catalyst carrier as shown in Table 3C, cobalt acetate as a cobalt precursor is mixed with a Pt precursor to prepare a Pt—Co / SiO ₂ catalyst by co-impregnation, and reduced without firing. The Pt—Co / SiO ₂ catalyst was activated by setting the hydrogen flow rate during the treatment to 40 mL / min per gram of catalyst.
Thereafter, using this Pt—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 3.
CO conversion is 62.8%, CH ₄ selectivity is 4.0%, CO ₂ selectivity is 0.5%, and hydrocarbon productivity of 5 or more carbon atoms is 2.0 (kg-hydrocarbon / kg). -Catalyst / hour).

(Comparative Example 10)
Using a catalyst carrier as shown in Table 3D, a Co / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of the catalyst. The / SiO ₂ catalyst was activated.
Thereafter, using this Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-described method. The results are shown in Table 3.
CO conversion is 66.5%, CH ₄ selectivity is 5.2%, CO ₂ selectivity is 0.4%, and hydrocarbon productivity of 5 or more carbon atoms is 2.0 (kg-hydrocarbon / kg -Catalyst / hour).

(Comparative Example 11)
Using a catalyst carrier as shown in Table 4H, a Co / SiO ₂ catalyst was prepared using cobalt nitrate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of the catalyst. The / SiO ₂ catalyst was activated.
Thereafter, using this Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-described method. The results are shown in Table 4.
The CO conversion is 73.2%, the CH ₄ selectivity is 4.6%, the CO ₂ selectivity is 0.6%, and the hydrocarbon productivity of 5 or more carbon atoms is 2.3 (kg-hydrocarbon / kg -Catalyst / hour).

(Comparative Example 12)
Using a catalyst carrier as shown in H of Table 4, a Pt-Co / SiO ₂ catalyst was prepared using cobalt nitrate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of catalyst. The Pt—Co / SiO ₂ catalyst was activated.
Thereafter, using this Pt—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 4.
CO conversion is 76.8%, CH ₄ selectivity is 4.2%, CO ₂ selectivity is 1.0%, and hydrocarbon productivity with 5 or more carbon atoms is 2.4 (kg-hydrocarbon / kg -Catalyst / hour).

(Comparative Example 13)
Using a catalyst carrier as shown in Table 4 H, a Ru—Co / SiO ₂ catalyst was prepared using cobalt nitrate as a cobalt precursor, the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of catalyst, The Ru—Co / SiO ₂ catalyst was activated.
Thereafter, using this Ru—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 4.
The CO conversion is 75.5%, the CH ₄ selectivity is 4.2%, the CO ₂ selectivity is 0.7%, and the hydrocarbon productivity of 5 or more carbon atoms is 2.4 (kg-hydrocarbon / kg -Catalyst / hour).

(Comparative Example 14)
Using a catalyst carrier as shown in Table 4 I, a Co / ZrO ₂ / SiO ₂ catalyst was prepared using cobalt nitrate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of catalyst. The Co / ZrO ₂ / SiO ₂ catalyst was activated.
Thereafter, using this Co / ZrO ₂ / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 4.
The CO conversion is 66.5%, the CH ₄ selectivity is 5.1%, the CO ₂ selectivity is 0.4%, and the hydrocarbon productivity of 5 or more carbon atoms is 2.0 (kg-hydrocarbon / kg). -Catalyst / hour).

(Comparative Example 15)
Using a catalyst support as shown in Table 4 I, a Pt—Co / ZrO ₂ / SiO ₂ catalyst was prepared using cobalt nitrate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of catalyst. This Pt—Co / ZrO ₂ / SiO ₂ catalyst was activated.
Thereafter, using this Pt—Co / ZrO ₂ / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 4.
CO conversion is 69.5%, CH ₄ selectivity is 4.9%, CO ₂ selectivity is 0.5%, and hydrocarbon productivity of 5 or more carbon atoms is 2.1 (kg-hydrocarbon / kg). -Catalyst / hour).

(Comparative Example 16)
Using a catalyst carrier as shown in Table 4B, a Pt / Co—ZrO ₂ / SiO ₂ catalyst in which a zirconium component and a cobalt acetate precursor are co-supported and platinum is further supported is prepared. The Pt / Co—ZrO ₂ / SiO ₂ catalyst was activated by setting the hydrogen flow rate at 40 mL / min per gram of catalyst.
Thereafter, using this Pt / Co—ZrO ₂ / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-described method. The results are shown in Table 4.
CO conversion is 61.5%, CH ₄ selectivity is 5.9%, CO ₂ selectivity is 0.4%, and hydrocarbon productivity of 5 or more carbon atoms is 1.9 (kg-hydrocarbon / kg -Catalyst / hour).

(Comparative Example 17)
Using a catalyst carrier as shown in Table 4 F, a Pt—Co / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of the catalyst. The Pt—Co / SiO ₂ catalyst was activated.
Thereafter, using this Pt—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 4.
The CO conversion is 46.2%, the CH ₄ selectivity is 7.4%, the CO ₂ selectivity is 0.2%, and the hydrocarbon productivity of 5 or more carbon atoms is 1.4 (kg-hydrocarbon / kg -Catalyst / hour).

(Comparative Example 18)
Using a catalyst carrier as shown in Table 4 G, a Pt-Co / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, and the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of catalyst. The Pt—Co / SiO ₂ catalyst was activated.
Thereafter, using this Pt—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 4.
CO conversion is 12.4%, CH ₄ selectivity is 12.1%, CO ₂ selectivity is 0.4%, and hydrocarbon productivity of 5 or more carbon atoms is 0.3 (kg-hydrocarbon / kg -Catalyst / hour).

(Comparative Example 19)
Using a catalyst carrier as shown in Table 4 J, a Pt—Co / SiO ₂ catalyst was prepared using cobalt acetate as a cobalt precursor, the hydrogen flow rate during the reduction treatment was set to 40 mL / min per gram of catalyst, The Pt—Co / SiO ₂ catalyst was activated.
Thereafter, using this Pt—Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the method described above. The results are shown in Table 4.
CO conversion is 32.9%, CH ₄ selectivity is 8.8%, CO ₂ selectivity is 1.5%, and hydrocarbon productivity with 5 or more carbon atoms is 0.9 (kg-hydrocarbon / kg -Catalyst / hour).

Claims (11)

A method for producing a catalyst for producing hydrocarbons from synthesis gas, which is produced by carrying a cobalt component and a noble metal component on a catalyst carrier mainly composed of silica,
The support is obtained by using a precursor solution of cobalt acetate on a catalyst support mainly composed of silica having a total content of sodium, potassium, magnesium and calcium of 1,000 ppm or less in terms of metal, Impregnating and supporting, using a noble metal compound precursor solution on the silica-based catalyst carrier on which the cobalt component is supported, impregnating and supporting the noble metal component, the cobalt component and the noble metal And a step of reducing the catalyst carrier mainly composed of silica on which a component is supported with a gas containing hydrogen, and a method for producing a catalyst for producing hydrocarbons from synthesis gas. A method for producing a catalyst for producing hydrocarbons from synthesis gas, which is produced by carrying a cobalt component, a zirconium component and a noble metal component on a catalyst carrier mainly composed of silica,
The support is obtained by using a precursor solution of a zirconium compound on a catalyst carrier mainly composed of silica having a total content of sodium, potassium, magnesium, and calcium of 1,000 ppm or less in terms of metal, and using the zirconium compound precursor solution. A step of impregnating and supporting, a step of impregnating and supporting the cobalt component using a precursor solution of cobalt acetate on a catalyst support mainly composed of silica on which the zirconium component is supported, the zirconium component and the cobalt A step of impregnating and supporting the noble metal component using a precursor solution of a noble metal compound on the catalyst carrier mainly composed of silica on which the component is supported, and supporting the zirconium component, the cobalt component, and the noble metal component Reducing the silica-based catalyst carrier as a main component with a gas containing hydrogen. Process for preparing a catalyst for producing a hydrocarbon from a syngas, wherein. A method for producing a catalyst for producing hydrocarbons from synthesis gas, which is produced by carrying a cobalt component and a noble metal component on a catalyst carrier mainly composed of silica,
The support is prepared by adding a cobalt acetate precursor solution and a noble metal compound precursor solution to a catalyst carrier mainly composed of silica having a total content of sodium, potassium, magnesium and calcium of 1,000 ppm or less in terms of metal. Using the mixed solution, simultaneously impregnating and supporting the cobalt component and the noble metal component, firing the catalyst support mainly composed of silica on which the cobalt component and the noble metal component are supported, And a step of reducing with a gas containing hydrogen after calcination, a method for producing a catalyst for producing hydrocarbons from synthesis gas. A method for producing a catalyst for producing hydrocarbons from synthesis gas, which is produced by carrying a cobalt component, a zirconium component and a noble metal component on a catalyst carrier mainly composed of silica,
The support is obtained by using a precursor solution of a zirconium compound on a catalyst carrier mainly composed of silica having a total content of sodium, potassium, magnesium, and calcium of 1,000 ppm or less in terms of metal, and using the zirconium compound precursor solution. A step of impregnating and using a solution in which a precursor solution of cobalt acetate and a precursor solution of a noble metal compound are mixed in a catalyst support mainly composed of silica on which the zirconium component is supported; A step of impregnating and supporting a noble metal component at the same time; a step of calcining the silica-based catalyst carrier on which the zirconium component, the cobalt component and the noble metal component are supported; and reduction with a gas containing hydrogen after the calcining A method for producing a catalyst for producing hydrocarbons from synthesis gas.   The method for producing a catalyst for producing hydrocarbons from synthesis gas according to any one of claims 1 to 4, wherein the noble metal is at least one of platinum and ruthenium.   The content of sodium, potassium, calcium, and magnesium contained in the catalyst carrier mainly composed of silica is 300 ppm or less in terms of metal, respectively. A method for producing a catalyst for producing hydrocarbons from synthesis gas.   6. The method for supporting the cobalt component and the noble metal component on the catalyst carrier mainly composed of silica is impregnation support using an incipient wetness method, respectively. 7. A method for producing a catalyst for producing hydrocarbons from the synthesis gas according to any one of 6 above.   3. The method for supporting the cobalt component, the zirconium component, and the noble metal component on the catalyst support mainly composed of silica is impregnation support using an incipient wetness method, respectively. A method for producing a catalyst for producing hydrocarbons from the synthesis gas according to any one of 4, 5, and 6.   In the step of reducing with the gas containing hydrogen, the hydrogen flow rate per 1 g of the catalyst carrier mainly composed of the silica on which the cobalt component and the noble metal component are supported is in the range of 0.1 mL / min to 60 mL / min. The method for producing a catalyst for producing hydrocarbons from synthesis gas according to any one of claims 1, 3, 5, 6, and 7, wherein reduction is performed.   In the step of reducing with the hydrogen-containing gas, the hydrogen flow rate per 1 g of the catalyst carrier mainly composed of the silica on which the zirconium component, the cobalt component, and the noble metal component are supported is 0.1 mL / min to 60 mL / The method for producing a catalyst for producing hydrocarbons from synthesis gas according to any one of claims 2, 4, 5, 6, or 8, wherein the reduction is performed in a range of min.   A synthesis gas comprising producing a hydrocarbon from synthesis gas by a Fischer-Tropsch synthesis reaction in a slurry bed using the catalyst produced by the production method according to any one of claims 1 to 10. A method for producing hydrocarbons from hydrocarbons.