JP6839602B2 - A method for producing a catalyst for producing a hydrocarbon from a synthetic gas, and a method for producing a hydrocarbon for producing a hydrocarbon from a synthetic gas. - Google Patents

Description

The present invention uses a method for producing a catalyst for producing a hydrocarbon from a so-called synthetic gas containing carbon monoxide and hydrogen as main components, and a catalyst produced by the production method to produce a hydrocarbon from the synthetic gas. The present invention relates to a method for producing a hydrocarbon.

In recent years, environmental problems such as global warming have become apparent, and hydrocarbon fuels other than petroleum and coal are being reviewed. In particular, the importance of natural gas, which has a higher H / C than coal and the like, can suppress carbon dioxide emissions, which are a causative substance of global warming, and has abundant reserves, has been reviewed. It is expected that the demand for natural gas will increase in the future. Under such circumstances, natural gas has been discovered in remote areas such as Southeast Asia and Oceania, 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 the recoverable reserves of natural gas are not worth the construction of infrastructure that requires huge investment. Development promotion is desired for these undeveloped small and medium-sized gas fields. As one of the effective development means, after converting natural gas into synthetic gas, Fischer-Tropsch synthesis reaction (FT synthesis reaction) from synthetic gas represented by the following formula (1). The development of technology for converting to liquid hydrocarbon fuels such as kerosene and light oil, which have excellent transportability and handleability, is being vigorously carried out in various places.

This FT synthesis reaction is an exothermic reaction in which a synthetic gas is converted into hydrocarbons using a catalyst. In the FT synthesis reaction, cobalt, ruthenium, iron and the like are used as catalysts, but from the viewpoint of performance and cost, cobalt catalysts are mainly used. Effective removal of heat of reaction is extremely important for stable operation of plants using such catalysts. Examples of reaction types that have been proven to date include a gas phase synthesis process (fixed bed, jet bed, fluidized bed) and a liquid phase synthesis process (slurry bed). Each of these reaction formats has its own characteristics. In particular, the slurry bed liquid phase synthesis process has attracted attention and is being vigorously developed because it has high heat removal efficiency and does not accumulate the generated high boiling point hydrocarbons on the catalyst and cause blockage of the reaction tube. It is being advanced.

Needless to say, in general, the higher the activity of the catalyst, the more preferable it is. In particular, in a slurry bed, there is a limitation that the slurry concentration must be kept below a certain value 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 a high conversion rate. As shown in the above formula (1), since water is by-produced in the FT synthesis reaction, the water pressure in the reactor increases as the conversion rate increases. Under conditions of high water pressure, cobalt catalysts generally tend to lose activity. Therefore, the one-pass conversion rate is set to about 60%, and the tail gas recycling is often performed to increase the total conversion rate. Therefore, the one-pass conversion rate is set to a constant value by changing the conditions such as the reaction temperature according to the activity of the catalyst. In the case of a method in which the one-pass conversion rate is maintained at a constant value while increasing the reaction temperature as the activity of the catalyst decreases and the operation is terminated when a specific reaction temperature is reached, the reaction is started by using a catalyst having high activity. The temperature of the Therefore, the catalyst can be used for a long time.

Effect of impurities such as alkali metal and alkaline earth metal on the activity of the catalyst in a catalyst in which cobalt is supported by using a precursor solution of cobalt nitrate on a catalyst carrier containing silica as a main component for the purpose of high activation. Is being examined in detail. As a result, there is known an example in which the activity is greatly improved as compared with the conventional catalyst by setting the impurity concentration to a catalyst in a certain range (see, for example, Patent Document 1).

Further, for a catalyst in which cobalt is supported on a catalyst carrier containing silica as a main component by using a precursor solution of cobalt nitrate and the concentration of impurities such as alkali metal and alkaline earth metal is lowered, a noble metal is further added. Is known as an example in which the activity is improved by adding the above as a co-catalyst (see, for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 2004-322805 JP-A-2007-260669

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

Therefore, in the present invention, there is a method for producing a catalyst in which both cobalt and a noble metal are supported, and the produced catalyst is made from synthetic gas, which can further improve the activity as compared with the catalyst produced by the conventional method. It is an object of the present invention to provide a method for producing a catalyst for producing a hydrocarbon, and a method for producing a hydrocarbon for producing a hydrocarbon from syngas by 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 a catalyst, and a method for producing a hydrocarbon using the catalyst. As a result of diligent studies, the present inventors supported cobalt with cobalt acetate as a precursor on a catalyst carrier containing silica having an alkali metal or alkaline earth metal content of 1,000 ppm or less as a main component, and then the noble metal. Is further supported, or by simultaneously supporting a mixture of cobalt acetate and a precursor of a noble metal and then carrying out a calcining treatment, the reduction of small-particle cobalt that is highly dispersed and difficult to be reduced can be achieved. It has been found that a catalyst showing extremely high activity can be obtained, in which cobalt metal particles showing activity are formed in a highly dispersed manner.

It was also found that a catalyst showing extremely high activity can be obtained even when zirconium is first supported on the catalyst carrier containing silica as a main component and then the cobalt component and the noble metal component are supported by the above method. .. These findings led to the present invention.

As a result of the study by the present inventors, the degree of dispersion of cobalt particles differs greatly between the case where cobalt nitrate is used as a precursor and the case where cobalt acetate is used as a precursor, and the degree of dispersion is significantly different when cobalt acetate is used as a precursor. Although the degree is high, the reduction does not proceed sufficiently by the activation treatment, so 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, although the activity is further improved by adding a noble metal as a co-catalyst, when cobalt nitrate is used as a precursor, reduction is relatively easy to proceed even if the noble metal does not coexist, so that the noble metal It has been found that the effect of improving activity by addition is not necessarily large.

On the other hand, in the present invention, it was found that when cobalt acetate is used as a precursor, small particle size cobalt, which is mostly in an unreduced state, can be reduced by adding a noble metal without adding a noble metal. They found that they showed extremely high activity. The gist of the present invention is as described below.

(1) A method for producing a hydrocarbon from synthetic gas, which is produced by supporting a cobalt component and a noble metal component on a catalyst carrier containing silica as a main component.
In the support, the cobalt component is supported by using a precursor solution of cobalt acetate on a catalyst carrier containing the silica as a main component and having a total content of sodium, potassium, magnesium and calcium of 1,000 ppm or less in terms of metal. The step of impregnating and supporting, the step of impregnating and supporting the noble metal component by using a precursor solution of the noble metal compound on the catalyst carrier containing the silica as the main component, and the cobalt component and the noble metal. A method for producing a catalyst for producing a hydrocarbon from a synthetic gas, which comprises a step of reducing a catalyst carrier containing the silica as a main component on which a component is supported with a gas containing hydrogen.
(2) A method for producing a hydrocarbon from synthetic gas, which is produced by supporting a cobalt component, a zirconium component, and a noble metal component on a catalyst carrier containing silica as a main component.
In the support, the zirconium component is supported by using a precursor solution of a zirconium compound on a catalyst carrier containing the silica as a main component and having a total content of sodium, potassium, magnesium and calcium of 1,000 ppm or less in terms of metal. The step of impregnating and supporting the cobalt component, the step of impregnating and supporting the cobalt component by using a precursor solution of cobalt acetate on the silica-based catalyst carrier on which the zirconium component is supported, and the zirconium component and the cobalt. A step of impregnating and supporting the noble metal component by using a precursor solution of a noble metal compound on the silica-based catalyst carrier on which the component is supported, and supporting the zirconium component, the cobalt component, and the noble metal component. A method for producing a catalyst for producing a hydrocarbon from a synthetic gas, which comprises a step of reducing the prepared catalyst carrier containing silica as a main component with a gas containing hydrogen.
(3) A method for producing a hydrocarbon from synthetic gas, which is produced by supporting a cobalt component and a noble metal component on a catalyst carrier containing silica as a main component.
The carrier is a catalyst carrier containing silica as a main component having a total content of sodium, potassium, magnesium, and calcium of 1,000 ppm or less in terms of metal, and a precursor solution of cobalt acetate and a precursor solution of a noble metal compound. A step of simultaneously impregnating and supporting the cobalt component and the noble metal component using the mixed solution, a step of calcining the silica-based catalyst carrier on which the cobalt component and the noble metal component are supported, and the above. A method for producing a catalyst for producing a hydrocarbon from a synthetic gas, which comprises a step of reducing with a gas containing hydrogen after firing.
(4) A method for producing a hydrocarbon from synthetic gas, which is produced by supporting a cobalt component, a zirconium component, and a noble metal component on a catalyst carrier containing silica as a main component.
In the support, the zirconium component is supported by using a precursor solution of a zirconium compound on a catalyst carrier containing the silica as a main component and having a total content of sodium, potassium, magnesium and calcium of 1,000 ppm or less in terms of metal. Using a solution in which a precursor solution of cobalt acetate and a precursor solution of a noble metal compound are mixed with the silica-based catalyst carrier on which the zirconium component is supported, the cobalt component and the above. A step of simultaneously impregnating and supporting the noble metal component, a step of firing the silica-based catalyst carrier on which the zirconium component, the cobalt component and the noble metal component are supported, and a step of reducing with a gas containing hydrogen after the firing. A method for producing a catalyst for producing a hydrocarbon from a synthetic gas, which comprises.
(5) The method for producing a catalyst for producing a hydrocarbon from the synthetic 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 containing silica as a main component is 300 ppm or less in terms of metal, respectively. A method for producing a catalyst for producing a hydrocarbon from the synthetic gas described in.
(7) The method of supporting the cobalt component and the noble metal component on the catalyst carrier containing silica as a main component is characterized by impregnation and support using the insiient wetness method, respectively (1). The method for producing a catalyst for producing a hydrocarbon from the synthetic gas according to any one of (3), (5) or (6).
(8) The method of supporting the cobalt component, the zirconium component, and the noble metal component on the catalyst carrier containing silica as a main component is characterized by impregnation and support using the insiient wetness method, respectively. (2), one process for preparing a catalyst for producing a hydrocarbon from a syngas described in (4).
(9) In the step of reducing with the gas containing hydrogen,
The hydrogen flow rate per 1 g of the silica-based catalyst carrier 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). The method for producing a catalyst for producing a hydrocarbon from the synthetic gas according to any one of (3), (5), (6) or (7).
(10) In the step of reducing with the gas containing hydrogen,
The hydrogen flow rate per 1 g of the silica-based catalyst carrier on which the zirconium component, the cobalt component and the noble metal component are supported is reduced in the range of 0.1 mL / min to 60 mL / min. (2), (4) or process for preparing a catalyst for producing a hydrocarbon from a syngas according to any one of (8).
(11) Using the catalyst produced by the production method according to any one of (1) to (10), hydrocarbons are produced from syngas by a Fischer-Tropsch synthesis reaction on a slurry bed. A method for producing a hydrocarbon, which produces a hydrocarbon from a synthetic gas.

According to the present invention, since the cobalt metal particles exhibiting activity can be formed in a highly dispersed manner, it is possible to provide a catalyst for FT synthesis having extremely high activity.

Hereinafter, the present invention will be described in more detail.

[Manufacturing method of catalyst for producing hydrocarbon from syngas]
As a result of diligent studies by the present inventors, the cobalt component supporting cobalt acetate as a precursor is supported on a catalyst carrier containing silica as a main component with a small particle size and high dispersibility. Such a small particle size Since cobalt is not easily reduced, the amount of cobalt metal, which is an active species, is smaller than that when supported by a precursor such as cobalt nitrate, and it has been found that high activity cannot be obtained. By supporting a small amount of the noble metal component, cobalt having a small particle size, which was unreduced in the absence of the noble metal component, is converted into a cobalt metal, so that extremely high activity can be obtained.

The catalyst (catalyst used in the FT synthesis reaction) according to the method for producing a hydrocarbon from the synthetic gas of the present invention (hereinafter, may be abbreviated as "catalyst production method") uses cobalt as an active species. Is to be. Further, as the catalyst carrier, one containing silica as a main component (hereinafter, also referred to as "silica carrier") is selected and used.
The catalyst carrier containing silica as a main component here means a carrier composed of 50% by mass or more of silica and unavoidable impurities in the balance. The silica-based catalyst carrier may further contain alumina. The silica-based catalyst carrier preferably has a silica content of 50% by mass or more and less than 100% by mass.
The unavoidable impurities referred to here depend on the impurity species contained in the washing water used in the manufacturing process of the silica carrier and the elements contained in the starting material, and are not limited, but for example, sodium, calcium, and the like. Magnesium, iron, etc.

Even if iron contains a trace amount of about several hundred ppm, there is almost no effect on the catalytic activity. On the other hand, alkali metals sodium and potassium and alkaline earth metals magnesium and calcium affect the catalytic activity, and it is important to control their contents in order to improve 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 they are difficult to be mixed in the silica carrier manufacturing process. Therefore, the contents of sodium, potassium, magnesium, and calcium may be controlled. The mixing of sodium, potassium, magnesium, and calcium can occur in any of the catalyst manufacturing steps such as the manufacturing step of the silica carrier, the support, the firing, and the reduction. For example, in the process of manufacturing a catalyst carrier containing silica as a main component, sodium is often contained in the raw material and calcium is often contained in the washing water, and the catalyst carrier is easily mixed with 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 usual impregnation method, an incident wetness method, a precipitation method, an ion exchange method, or the like is used. .. As the raw material (precursor) used in the carrying, in the case of a zirconium compound or a noble metal compound, when the reduction treatment, the calcination treatment and the reduction treatment are carried out after the support, a counter ion (for example, ZrO (NO) for a zirconium oxide salt 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, acetylacetonate and the like can be used. Among them, it is preferable to use a water-soluble compound that can use an aqueous solution during the supporting operation in order to reduce the manufacturing cost and secure a safe manufacturing working environment. Specifically, zirconium nitrate oxide, noble metal chloride acid and the like are preferable because they easily change to zirconium oxide, noble metal oxide or noble metal at the time of 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, particularly preferably 1.0 mol / L to 3.0 mol / L. .. Further, the concentration of the precursor aqueous solution 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, preferably 0.003 mol / L to 0.05 mol / L. Especially preferable.

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 contained as a co-catalyst, a method of sequentially supporting the cobalt component on a catalyst carrier containing silica as a main component using an aqueous solution of cobalt acetate and then supporting the noble metal component is adopted. Can be done.

Further, a co-supporting method in which a cobalt component and a noble metal component are simultaneously supported by 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 adopted. From the viewpoint of manufacturing 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, the noble metal component is taken into the inside of the cobalt component, and there is a concern that the function of promoting the reduction of the cobalt component is deteriorated. Therefore, by carrying out the firing treatment, it is possible to obtain the same catalytic activity as in the case of sequential support. It is considered that this is because the crystal structures of the cobalt component and the noble metal component are different, so that the noble metal component is easily formed on the cobalt surface by the firing treatment even when the noble metal component is incorporated inside the cobalt component in co-supporting. ..

When the zirconium component is contained as a co-catalyst, the zirconium component is first supported on a catalyst carrier containing silica as a main component, and then the cobalt acetate component and the noble metal component are supported. Similar to the case where the zirconium component is not contained as a co-catalyst, the cobalt component and the noble metal component may be sequentially supported or co-supported, but in the case of co-supporting, a firing treatment after co-supporting is required. The zirconium component not only prevents the formation of cobalt silicate formed at the interface between the cobalt component and the catalyst carrier containing silica as the main component, but also silica by adding the zirconium component to the catalyst carrier containing silica as the main component. Improves resistance to water. From this, it is preferable that the zirconium component and the catalyst carrier containing silica as the main component come into contact with each other, and it is preferable that the zirconium component is first supported on the catalyst carrier containing silica as the main component. Further, if the zirconium component is supported after the cobalt component or the noble metal component, the zirconium component covers the surface of the cobalt component or the noble metal component, the active surface area of the cobalt is lowered, or the reduction promoting effect of the noble metal is not sufficiently exhibited. Can be considered. 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, and in the case of sequential support, the noble metal component is reduced by carrying it last, and in the case of co-supporting, performing a firing treatment.

When the zirconium component, the cobalt component, and the noble metal component are sequentially supported, the zirconium component is supported and then calcined, or dried and fired. Then, after supporting each compound of the cobalt component and the noble metal component, a firing treatment or a drying and firing treatment may be performed, and after carrying both compounds, hydrogen is not carried out without drying, drying and firing treatment. It is also possible to carry out reduction treatment with a gas containing. The drying and firing treatment can be carried out after supporting any of the compounds in the step of sequentially supporting the cobalt component and the noble metal component. It is preferable that both compounds are supported and then dried and fired. When the noble metal component is supported without the firing treatment after supporting the cobalt component, the cobalt component may elute into the precursor solution of the noble metal component. Then, the noble metal component preferably formed on the outer surface of the catalyst is incorporated into the cobalt component, which may deteriorate the performance. Therefore, it is preferable to carry out the drying and firing treatment after the support. Further, it is preferable to carry out the drying and firing treatment even 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, it is not necessary to carry out the firing treatment.

When the cobalt component and the noble metal component are co-supported after supporting the zirconium component, a firing treatment or a drying and firing treatment is performed after the zirconium component is supported. Then, after supporting the cobalt component and the noble metal component at the same time, the calcination treatment or the drying and calcination treatment is performed, and the reduction treatment is performed with a gas containing hydrogen.

The loading ratio of the cobalt component may be at least the minimum amount for exhibiting the activity, and may be less than or equal to the loading amount at which the dispersity of the carried cobalt is extremely lowered and the reaction contribution efficiency of cobalt is lowered. The carrying ratio of the cobalt component is preferably 5% by mass to 50% by mass, and more preferably 10% by mass to 40% by mass.
If the carrying ratio of the cobalt component is less than the above range, the activity may not be sufficiently expressed. On the other hand, if the carrying ratio of the cobalt component exceeds the above range, the dispersity may decrease and the utilization efficiency of the carried cobalt may decrease, which is uneconomical.

The support ratio of the cobalt component referred to here does not mean that the carried cobalt is finally reduced to 100%, so the mass of cobalt when converted to metal assuming that it has been reduced to 100% occupies the entire catalyst mass. Refers to the ratio. In the manufacturing process, it is preferable to adjust the amount of cobalt acetate in the starting material so as to obtain the above-mentioned appropriate loading ratio. The total catalyst mass is the mass of the catalyst after the cobalt component and the noble metal component are supported, or after the zirconium component, the cobalt component and the noble metal component are supported and the reduction treatment is performed.

The carrying ratio of the zirconium component is preferably 0.2% by mass to 30% by mass as the zirconium oxide, out of the total weight of the zirconium oxide before supporting cobalt and the catalyst carrier containing silica as a main component. It is more preferably 0.5% by mass to 20% by mass, and further preferably 1% by mass to 15% by mass.
If the carrying ratio of the zirconium component is less than the above range, the water resistance obtained by supporting the zirconium component may not be sufficiently exhibited. On the other hand, if the carrying ratio of the zirconium component exceeds the above range, the utilization efficiency of the zirconium component may decrease, which is uneconomical.

The support rate of zirconium oxide referred to here is the support rate of zirconium dioxide formed by supporting zirconium and then firing it. If it is not fired, it is converted to _{ZrO 2.} In the manufacturing process, it is preferable to adjust the amount of the zirconium precursor in the starting material so as to obtain the above-mentioned appropriate loading ratio. Further, when measuring the carrying ratio of the zirconium oxide, the zirconium oxide is supported on a catalyst carrier containing silica as a main component after the zirconium oxide is supported and calcined.

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

The appropriate range of the carrying ratio of these noble metal components is equal to or more than the minimum amount for exhibiting the effect of promoting the reduction of the cobalt compound, and the dispersibility of the carried noble metal is extremely lowered, so that the effect is exhibited among the added noble metals. It suffices as long as the proportion of the noble metal that does not contribute to Specifically, the metal-equivalent noble metal component 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% by mass. The catalyst serving as the denominator is _{a total amount of a catalyst carrier containing silica as a main component, a zirconium component converted to ZrO 2} , a cobalt component converted to metal, and a noble metal converted to metal.
If the loading ratio of the noble metal component is less than 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 supported noble metal component is lowered, which is uneconomical, which is not preferable.

The amount of zirconium oxide, cobalt and noble metal carried 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 at.

It is necessary to sequentially support the cobalt component and the noble metal component on the catalyst carrier containing silica as the main component. If they are supported at the same time, a part of the noble metal component may be incorporated into the cobalt component. Therefore, from the viewpoint of catalytic performance, it is necessary to sequentially support the zirconium component, the cobalt component, and the noble metal component in this order.

The amount of the zirconium component and the noble metal component added in order to exhibit a sufficient effect is extremely large in a catalyst containing a large amount of impurities. It is uneconomical to add a large amount of zirconium component or precious metal component. Further, conventionally, even if 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 highly effective effect can be obtained even if the amount of the zirconium component or the noble metal component added is relatively small. This is particularly noticeable when a carrier with few impurities is used. Since there are few impurities, zirconium oxides and precious metals are easily formed on the silica surface in a highly dispersed and homogeneous manner. Therefore, it is presumed that the characteristics of the catalyst surface could be changed efficiently with a small amount.

The following is an example of a method for obtaining a catalyst supporting a cobalt component and a noble metal component.
First, a catalyst carrier containing silica as a main component and having few impurities is impregnated with an aqueous solution of cobalt acetate, and then dried and fired. As a result, the cobalt component is impregnated and supported on the catalyst carrier containing silica as the main component.
Next, a precursor solution composed of a noble metal compound is impregnated and supported on a silica-based catalyst carrier on which a cobalt component is supported.
Next, a catalyst carrier containing silica as a main component, which carries a cobalt component and a noble metal component, is dried, calcined, and reduced to obtain an FT synthesis catalyst.

Even if a drying treatment (for example, 100 ° C-1h in air) is performed after the support of the cobalt compound and then a firing treatment (for example, 450 ° C-5h in air) is performed, only the drying treatment is performed, which is the next step of the precious metal. The component may be impregnated and supported. In order to prevent the effect of adding the noble metal from being reduced by incorporating the noble metal while the cobalt component is impregnated with the noble metal component, it is preferable to perform a firing treatment to convert it into cobalt oxide.

After impregnating and supporting the noble metal component, if necessary, a drying treatment is performed, and then the cobalt compound on the surface of the catalyst carrier is reduced to a cobalt metal (for example, 350 ° C.-15 h in a normal pressure hydrogen stream, the hydrogen flow rate is per 1 g of the catalyst. 60 mL / min) to obtain an FT synthesis catalyst. Here, the reduction treatment may be performed after firing to convert into an oxide, or the reduction treatment may be performed directly without firing. If the reduction conditions are made stricter by raising the temperature of the reduction treatment or lengthening the time, the ratio of cobalt being reduced from the oxide state to the metallic state after the reduction treatment increases. Under general reduction conditions, the cobalt metal often contains a part of the oxide of the cobalt metal. The catalyst after the reduction treatment must be handled so as not to be oxidatively deactivated by contact with the atmosphere. It is preferable to perform a stabilization treatment that shields the surface of the cobalt metal on the catalyst carrier from the atmosphere because it can be handled in the atmosphere. As this stabilization treatment, nitrogen, carbon dioxide, and an inert gas containing low-concentration oxygen are brought into contact with the catalyst to oxidize only the polar surface of the cobalt metal on the catalyst carrier, so-called passivation (surface non-conductor). 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 to shut off from the atmosphere is used. These stabilization processes may be appropriately selected according to the situation.

Further, an example of a method for obtaining a catalyst supporting a cobalt component, a zirconium component, and a noble metal component is shown below.
First, a catalyst carrier containing silica as a main component and having few impurities is impregnated with an aqueous precursor solution composed of a zirconium compound, and then dried and fired. As a result, the zirconium component is impregnated and supported on the catalyst carrier containing silica as the main component.
Next, a catalyst carrier containing silica as a main component on which a zirconium component is supported is impregnated with an aqueous solution of cobalt acetate and supported, and then dried and fired. As a result, the cobalt component is impregnated and supported on the catalyst carrier containing silica as the main component.
Next, a precursor solution composed of a noble metal compound is impregnated and supported on a silica-based catalyst carrier on which a zirconium component and a cobalt component are supported.
Next, a catalyst carrier containing silica as a main component, which carries a zirconium component, a cobalt component, and a noble metal component, is dried, calcined, and reduced to obtain an FT synthesis catalyst.

After the zirconium compound, cobalt compound, and noble metal compound are supported, a drying treatment (for example, 100 ° C-1h in air) is performed, and then a firing treatment (for example, 450 ° C-5h in air) is performed, but only the drying treatment is performed. In the next step, impregnation may be carried out. In order to prevent the addition effect from being reduced by incorporating cobalt during the impregnation and carrying of the cobalt compound by the zirconium compound and by incorporating the noble metal during the impregnation and carrying of the noble metal compound by the cobalt compound and the zirconium compound, each support is performed. It is preferable to carry out a firing treatment afterwards to convert it into zirconium oxide and cobalt oxide. The reduction treatment and the stabilization treatment can be carried out in the same manner as the catalyst supporting the cobalt component and the noble metal component described above.

In an example of the method for obtaining the catalyst, hydrogen is used as the reducing gas when the cobalt compound is reduced to the 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 hydrogen flow rate, although it depends on the temperature and the holding time, after supporting the cobalt component with cobalt acetate as a precursor, and then supporting the catalyst or the zirconium compound supporting the noble metal component, A catalyst having a cobalt component as a precursor and then supporting a noble metal component, and a catalyst having no noble metal component and carrying cobalt as a precursor of cobalt acetate, or a zirconium compound was supported. After that, the difference in activity from the catalyst supporting the cobalt component with cobalt acetate as a precursor is smaller than that in the case where the hydrogen flow rate is small. It depends on the catalyst composition such as the noble metal type and the amount added, and the production conditions such as the reduction temperature and the holding time, but when the hydrogen flow rate is reduced to about 10 mL / min to 20 mL / min, the difference in catalytic activity and the degree of reduction of cobalt depends on the presence or absence of the noble metal. Becomes larger. The normal reduction gas flow rate range adopted in mass production on a commercial scale is often 20 mL / min or less per gram of catalyst.

After supporting the cobalt component using cobalt acetate as a precursor, the catalyst or the zirconium compound supporting the noble metal component is supported, then the cobalt component is supported using cobalt acetate as the precursor, and then the 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 the holding time. The hydrogen flow rate range 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 even more preferably 0.2 mL / min per gram of catalyst. It is min to 20 mL / min, most preferably 0.5 mL / min to 10 mL / min.
If the hydrogen flow rate is less than 0.1 mL / min per 1 g of the catalyst, it becomes uneconomical because it is necessary to increase the amount of the noble metal in the catalyst in order to increase the reduction promoting effect of the noble metal, and the temperature is significantly increased in the reduction operation. It becomes necessary to improve the performance, and the catalysting of cobalt metal and noble metal occurs during the reduction at a high temperature, which deteriorates the performance and requires an extension of time, which increases the processing cost. On the other hand, when the hydrogen flow rate exceeds 60 mL / min per 1 g of catalyst, a certain amount of catalytic activity can be obtained even if there is no reduction promoting effect by the noble metal when a large excess of reduced gas can be secured, but the amount of reduced gas per amount of catalyst. As the amount of catalyst that can be processed at one time becomes relatively small, the manufacturing cost increases and it becomes uneconomical.

Further, reducing alkali metals and alkaline earth metals in the catalyst carrier and controlling them within a predetermined range is extremely effective for improving the activity. When silica is used as a catalyst carrier, as described above, alkali metals sodium and potassium, alkaline earth metals magnesium and calcium, Fe and the like are often contained in silica as impurities, and sodium, potassium, etc. The influence of magnesium and calcium is strong, and the influence of the presence of sodium is the strongest. Potassium, magnesium, and calcium have a smaller effect than sodium, but the higher 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 it exceeds this amount, the activity is greatly reduced, which is a significant disadvantage. However, reducing the amount of impurities more than necessary is costly and uneconomical in improving purity, so the total amount of sodium, potassium, magnesium, and calcium in the catalyst carrier is 100 ppm or less. Although it is difficult to limit because it depends on the loading ratio and the type of precursor, in order to reduce the total amount of sodium, potassium, magnesium and calcium in the catalyst carrier, the precursor of the active metal as described above is used. It is effective to keep the total amount of impurities in the mixture to 5% by mass or less. The contents of sodium, potassium, magnesium, and calcium as impurities in the precursor are usually not high as compared with the catalyst carrier, but when they are high, it is preferable to reduce these contents. The total amount of sodium, potassium, magnesium, and calcium described above is a metal-equivalent amount with respect to the catalyst weight after conversion from cobalt oxide to cobalt metal by the activation treatment. The total amount of sodium, potassium, magnesium, and calcium described above is 100 when the content of sodium, potassium, magnesium, and calcium in the catalyst in which cobalt is an oxide is measured without performing the activation treatment. It is the converted amount assuming that it has been reduced by%.

Among the impurities in the catalyst carrier, the elements that most adversely affect the effect of suppressing the decrease in activity are sodium, potassium, magnesium, and calcium. When the content of these metals in the catalyst carrier 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 carrier is 1,000 ppm, preferably 30 ppm to 700 ppm, more preferably 30 ppm to 400 ppm. The content of each element of the alkali metal and the 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 carrier exceeds 1,000 ppm as described above, the activity of the catalyst is greatly reduced. Again, similarly to the above, it is uneconomical to reduce the content 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 within a range that does not adversely affect the catalytic activity. As described above, if the total amount of sodium, potassium, magnesium and calcium in the catalyst carrier is reduced to about 100 ppm, a sufficient effect can be obtained. Therefore, it is preferable that the content of sodium, potassium, magnesium, and calcium in the catalyst carrier is 100 ppm or more from the viewpoint of cost.

The total amount of impurities of sodium, potassium, magnesium and calcium in the catalyst carrier produced in this manner is 30 ppm to 1,000 ppm. If it exceeds this range, the decrease in activity under the condition of high water pressure becomes large. The method for quantifying sodium, potassium, magnesium, and calcium in the catalyst carrier is the same as the method in the catalyst carrier, and for example, it can be measured by the ICP-AES method after pretreatment such as acid decomposition and alkali melting. ..

If the catalyst carrier can be devised so that impurities such as sodium, potassium, magnesium, and calcium do not enter in the manufacturing process, it is preferable to take measures to prevent impurities from entering during the manufacturing process. Generally, the method for producing silica is 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 it is possible to produce a catalyst carrier by any of the production methods, it is technically and economically difficult to form the catalyst carrier into a spherical shape by the above methods except the gel method. Therefore, it is preferable to produce the silica sol by a gel method that can be easily formed into a spherical shape by spraying it in a gas medium or a liquid medium. Sodium, potassium, magnesium and calcium are often mixed from raw materials and washing water. Sodium is often derived mainly from raw materials, and calcium is often derived mainly from wash water.

When producing a catalyst carrier containing silica as a main component by the above gel method, a large amount of washing water is usually used. If wash water containing a large amount of impurities such as industrial water is used, a large amount of impurities will remain in the carrier, and the activity of the catalyst will be significantly reduced. However, by using a washing water having a low impurity content or containing no impurities such as ion-exchanged water, it is possible to obtain a good silica carrier having a low impurity content. 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 increases, and the activity of the catalyst after preparation is greatly reduced. 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. Ideally, the use of ion-exchanged water is preferable from the viewpoint of reducing the amount of impurities. In order to obtain ion-exchanged water, an ion-exchange resin or the like may be used, but it is also possible to produce ion-exchanged water by performing ion exchange using silica gel generated as a nonstandard product on the silica production line. Is. In principle, silica supplements impurities in the washing water by ion exchange between hydrogen in silanol on the surface of silica and impurity ions such as sodium ion, potassium ion, magnesium ion and calcium ion. Therefore, even if the washing water contains a small amount of impurities, it is possible to prevent the supplementation of impurities to some extent by adjusting the pH of the washing water to be low. The amount of ion exchange (the amount of impurities mixed in) is proportional to the amount of wash water used. Therefore, it is possible to reduce the amount of impurities in silica by reducing the amount of washing water, in other words, increasing the efficiency of water use until the end of washing with water.

Impurities in the catalyst carrier containing silica as the main component are reduced by performing pretreatment such as washing with water, washing with acid, and washing with alkali without significantly changing the physical and chemical properties of the catalyst carrier. If this is possible, these pretreatments are extremely effective in improving the activity of the catalyst.

For example, for cleaning the catalyst carrier containing silica as a main component, it is particularly effective to clean it with an acidic aqueous solution such as nitrate, hydrochloric acid or acetic acid, or with ion-exchanged water. When 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 containing silica as a main component, a firing treatment for the purpose of improving particle strength, surface silanol group activity, and the like is often performed. However, if the firing treatment is performed in a state where the amount of impurities is relatively large, when the catalyst carrier containing silica as a main component is washed to reduce the impurity concentration, the impurity element is taken into the silica skeleton and the impurity content is contained. It becomes difficult to reduce. Therefore, when it is desired to wash the catalyst carrier containing silica as a main component to reduce the impurity concentration, it is preferable to use uncalcined 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 maintain a high dispersity of cobalt and improve the efficiency of contributing to the reaction of the carried active cobalt. In order to increase the specific surface area of the catalyst carrier, 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 However, it is suitable as a carrier for a 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 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 droplet determination method. The pore diameter can be measured by a gas adsorption method, a mercury intrusion method using a mercury porosimeter, or the like, but it can also be calculated from the specific surface area and the pore volume.

In order to obtain a catalyst exhibiting sufficient activity for the FT synthesis reaction, the specific surface area of the catalyst carrier ^{is preferably 80 m 2} / g or more. If it is less than this specific surface area, the dispersity of the supported metal may decrease, and the efficiency of contribution of active cobalt to the reaction may decrease. On the other hand, if the specific surface area of the catalyst carrier ^{exceeds 450 m 2} / g, it may be difficult for the pore volume and the pore diameter to simultaneously satisfy the above ranges. Therefore, the specific surface area of the catalyst carrier is 450 m ² / g or less. It is preferable to have.

The smaller the pore size of the catalyst carrier, the larger the specific surface area can be, but the pore size is preferably 8 nm or more. When the pore diameter is less than 8 nm, the gas diffusion rate in the pores differs between hydrogen and carbon monoxide, resulting in a higher partial pressure of hydrogen toward the depths of the pores, which is a by-product in the FT synthesis reaction. A large amount of light hydrocarbons such as methane, which can be said to be a substance, may be produced. In addition, the rate of intrapore diffusion of the produced hydrocarbons is also reduced, and as a result, the apparent reaction rate may be reduced. Further, when comparison is performed with a constant pore volume, the specific surface area of the catalyst carrier decreases as the pore diameter increases, so that the pore diameter is preferably 50 nm or less. If the pore diameter exceeds 50 nm, it becomes difficult to increase the specific surface area of the catalyst carrier, and the dispersity of active cobalt decreases.

The pore volume of the catalyst carrier 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 simultaneously satisfy the above ranges. On the other hand, if the pore volume exceeds 1.2 mL / g, the strength of the catalyst carrier may decrease.

Abrasion resistance and strength are required for the FT synthesis catalyst for the slurry bed reaction. Further, in the FT synthesis reaction, since a large amount of water is by-produced, if a catalyst or a catalyst carrier that is destroyed or pulverized in the presence of water is used, the above-mentioned inconvenience will occur. Be careful. Therefore, a catalyst using a spherical catalyst carrier is preferable to 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, the spray method is preferably used, and a spherical silica carrier having excellent wear resistance, strength, and water resistance can be obtained.

A method for producing such a catalyst carrier containing silica as a main component is illustrated below.
The alkali silicate aqueous solution and the acid aqueous solution are mixed, and the generated silica sol is sprayed into a gas medium such as air or an organic solvent insoluble in the silica sol to gel, and then acid treatment, washing with water, and drying are performed.
Here, as the alkali silicate, an aqueous solution of sodium silicate 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 method for producing a catalyst carrier containing silica as a main component include nitric acid, hydrochloric acid, sulfuric acid, and organic acids. Among these, sulfuric acid is preferable from the viewpoint of preventing corrosion to 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 significantly slowed down. On the other hand, when the acid concentration exceeds 10 mol / L, the gelation rate is too fast and its control becomes difficult, and it becomes difficult to obtain a desired physical property value.

When the method of spraying into an organic solvent is adopted, kerosene, paraffin, xylene, toluene and the like can be used as the organic solvent.
When aluminum is contained, a method of mixing an aluminum source with a raw material or doping after producing silica is used.

By using a catalyst carrier containing silica as a main component as described above and a catalyst obtained by using the method for producing a catalyst, it is possible to obtain an FT synthesis reaction catalyst showing extremely high activity. .. Although cobalt acetate is used as a precursor, it is difficult to obtain extremely high activity with a catalyst that does not contain a noble metal, despite the fact that the reduction of cobalt does not proceed sufficiently and the cobalt particle size is small and the specific surface area of cobalt 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 the noble metal.

When the catalyst according to the present invention is used, the activity is extremely high, and therefore, depending on the reaction conditions, 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. As a result, the amount of catalyst used can be small under the same conditions of hydrocarbon production in the plant, so that the slurry concentration during operation can be set low and the reactor can be made small.

[Method for producing hydrocarbons from synthetic gas]
The method for producing a hydrocarbon from the synthetic gas of the present invention is a Fischer-Tropsch synthesis reaction described above on a slurry bed using the catalyst produced by the method for producing a catalyst of the present invention. (FT synthesis reaction) produces hydrocarbons from syngas.

As the synthetic gas used in the present invention, a gas in which the total of hydrogen and carbon monoxide is 50% by volume or more of the total is preferable from the viewpoint of productivity, and in particular, the molar ratio of hydrogen to carbon monoxide (hydrogen / carbon 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 abundance of hydrogen in the raw material gas is too small, so that the hydrogenation reaction of carbon monoxide (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 abundance of carbon monoxide in the raw material gas is too small, and the productivity of liquid hydrocarbons does not increase regardless of the catalytic activity. Is.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but 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 carrier containing silica as a main component (silica with few impurities whose washing process is controlled (washing time, washing water purity) when manufactured by the above-mentioned silica manufacturing method) is preceded by cobalt acetate by the insiient wetness method. After the cobalt compound is supported as a body and dried and fired, the noble metal compound is supported and prepared by drying, firing, reducing (15h) and passing 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)
A zirconium compound is supported on a catalyst carrier containing silica as a main component by an incision wetness method and dried and fired, and then a cobalt compound is supported using cobalt acetate as a precursor and dried and fired. Then, a noble metal compound is supported and prepared by drying treatment, firing treatment, reduction treatment (15h), and passivation to prepare a noble metal-Co / ZrO ₂ / SiO ₂ catalyst (the catalyst carrier containing silica as a main component is an average grain. A spherical shape with a diameter of 100 μm) was obtained. Zirconium nitrate was used as the precursor of the zirconium compound, the concentration of the aqueous solution of zirconium nitrate dihydrate 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 n-hydrate chloride when supporting Ru, and rhodium chloride hydrate when supporting Rh. used.

[Synthesis of hydrocarbons]
_{After charging 1 g of the noble metal-Co / SiO 2} catalyst or 1 g of the noble metal-Co / ZrO ₂ / SiO ₂ catalyst and 50 mL of n-C ₁₆ (n-hexadecane) into an autoclave having an internal volume of 300 mL, the temperature was 230 ° C. Under the condition of 2 MPa-G, ^{while rotating the stirrer at 800 min -1} , W / F (catalyst mass) / F (synthetic gas flow rate); (g · h / mol) = 1.5. Adjust F (synthetic gas (H ₂ / CO = 2) flow rate), determine the composition of the supply gas and autoclave outlet gas by gas chromatography, and determine the CO conversion rate, CH ₄ selectivity, CO ₂ selectivity, and hydrocarbon production. I got sex.

(Example 1)
Using a catalyst carrier as shown in Table 1A, 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 1 g of the catalyst. This Pt-Co / SiO ₂ catalyst was activated.
Then, using this Pt-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 1.
The CO conversion rate is 82.3%, the CH ₄ selectivity is 4.5%, the CO ₂ selectivity is 1.4%, and the hydrocarbon productivity with 5 or more carbon atoms is 2.5 (kg-hydrocarbon / kg). -Catalyst / hour).

(Example 2)
Using a catalyst carrier as shown in Table 1B, 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 1 g of the catalyst. Then, this Pt-Co / ZrO ₂ / SiO ₂ catalyst was activated.
Then, using this Pt-Co / ZrO ₂ / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 1.
The CO conversion rate is 79.8%, the CH ₄ selectivity is 6.0%, the CO ₂ selectivity is 1.6%, and the 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 1C, 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 1 g of the catalyst. This Pt-Co / SiO ₂ catalyst was activated.
Then, using this Pt-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 1.
The CO conversion rate is 78.7%, the CH ₄ selectivity is 5.0%, the CO ₂ selectivity is 1.2%, and the hydrocarbon productivity with 5 or more carbon atoms is 2.4 (kg-hydrocarbon / kg). -Catalyst / hour).

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

(Example 5)
Using a catalyst carrier as shown in Table 1C, a Ru-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 1 g of the catalyst. This Ru-Co / SiO ₂ catalyst was activated.
Then, using this Ru-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 1.
The CO conversion rate is 78.0%, the CH ₄ selectivity is 4.9%, the CO ₂ selectivity is 1.0%, and the hydrocarbon productivity with 5 or more carbon atoms is 2.4 (kg-hydrocarbon / kg). -Catalyst / hour).

(Example 6)
Using a catalyst carrier as shown in Table 1C, a Rh-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 1 g of the catalyst. This Rh-Co / SiO ₂ catalyst was activated.
Then, using this Rh-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 1.
The CO conversion rate is 73.6%, the CH ₄ selectivity is 5.7%, the CO ₂ selectivity is 0.7%, and the hydrocarbon productivity with 5 or more carbon atoms is 2.2 (kg-hydrocarbon / kg). -Catalyst / hour).

(Example 7)
Using a catalyst carrier as shown in Table 1C, 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 10 mL / min per 1 g of the catalyst. This Pt-Co / SiO ₂ catalyst was activated.
Then, using this Pt-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 1.
The CO conversion rate is 78.7%, the CH ₄ selectivity is 4.4%, the CO ₂ selectivity is 1.0%, and the hydrocarbon productivity with 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 1 g of the catalyst. This Pt-Co / SiO ₂ catalyst was activated.
Then, using this Pt-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 2.
The CO conversion rate is 69.8%, the CH ₄ selectivity is 5.0%, the CO ₂ selectivity is 0.5%, and the hydrocarbon productivity with 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 1 g of the catalyst. The Pt-Co / SiO ₂ catalyst was activated.
Then, using this Pt-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 2.
The CO conversion rate is 66.4%, the CH ₄ selectivity is 5.4%, the CO ₂ selectivity is 0.4%, and the 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 1 g of the catalyst. This Pt-Co / SiO ₂ catalyst was activated.
Then, using this Pt-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 2.
The CO conversion rate is 78.2%, the CH ₄ selectivity is 4.6%, the CO ₂ selectivity is 1.4%, and the hydrocarbon productivity with 5 or more carbon atoms is 2.3 (kg-hydrocarbon / kg). -Catalyst / hour).

(Example 11)
Using a catalyst carrier as shown in E in 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 1 g of the catalyst. This Pt-Co / SiO ₂ catalyst was activated.
Then, using this Pt-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 2.
The CO conversion rate is 68.3%, the CH ₄ selectivity is 5.9%, the CO ₂ selectivity is 1.4%, and the hydrocarbon productivity with 5 or more carbon atoms is 2.0 (kg-hydrocarbon / kg). -Catalyst / hour).

(Example 12)
Using a catalyst carrier as shown in F 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 1 g of the catalyst. This Pt-Co / SiO ₂ catalyst was activated.
Then, using this Pt-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 2.
The CO conversion rate is 73.1%, the CH ₄ selectivity is 4.8%, the CO ₂ selectivity is 0.9%, and the hydrocarbon productivity with 5 or more carbon atoms is 2.3 (kg-hydrocarbon / kg). -Catalyst / hour).

(Example 13)
Using a catalyst carrier as shown in G in 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 1 g of the catalyst. This Pt-Co / SiO ₂ catalyst was activated.
Then, using this Pt-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 2.
The CO conversion rate is 59.2%, the CH ₄ selectivity is 7.0%, the CO ₂ selectivity is 0.7%, and the hydrocarbon productivity with 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 1 g of the catalyst, and this Co. The / SiO ₂ catalyst was activated.
Then, using this Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 3.
The CO conversion rate is 69.8%, the CH ₄ selectivity is 4.9%, the CO ₂ selectivity is 0.4%, and the hydrocarbon productivity with 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 1 g of the catalyst. , This Co / ZrO ₂ / SiO ₂ catalyst was activated.
Then, using this Co / ZrO ₂ / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 3.
The CO conversion rate is 71.2%, the CH ₄ selectivity is 5.3%, the CO ₂ selectivity is 0.9%, and the 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 1 g of the catalyst, and this Co. The / SiO ₂ catalyst was activated.
Then, using this Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 3.
The CO conversion rate is 58.8%, the CH ₄ selectivity is 6.3%, the CO ₂ selectivity is 0.3%, and the 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 1 g of the catalyst, and this Co. The / SiO ₂ catalyst was activated.
Then, using this Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 3.
The CO conversion rate is 22.9%, the CH ₄ selectivity is 9.5%, the CO ₂ selectivity is 0.2%, and the hydrocarbon productivity with 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 1 g of the catalyst, and this Co. The / SiO ₂ catalyst was activated.
Then, using this Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 3.
The CO conversion rate is 72.3%, the CH ₄ selectivity is 3.9%, the CO ₂ selectivity is 0.5%, and the hydrocarbon productivity with 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 1 g of the catalyst, and this Co. The / SiO ₂ catalyst was activated.
Then, using this Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 3.
The CO conversion rate is 65.1%, the CH ₄ selectivity is 4.5%, the CO ₂ selectivity is 0.4%, and the hydrocarbon productivity with 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, and the hydrogen flow rate during the reduction treatment was set to 40 mL / min per 1 g of the catalyst. This Pt-Co / SiO ₂ catalyst was activated.
Then, using this Pt-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 3.
The CO conversion rate is 74.0%, the CH ₄ selectivity is 3.8%, the CO ₂ selectivity is 0.5%, and the hydrocarbon productivity with 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, and the hydrogen flow rate during the reduction treatment was set to 10 mL / min per 1 g of the catalyst. This Pt-Co / SiO ₂ catalyst was activated.
Then, using this Pt-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 3.
The CO conversion rate is 72.5%, the CH ₄ selectivity is 3.9%, the CO ₂ selectivity is 0.5%, and the hydrocarbon productivity with 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 is mixed with a Pt precursor as a cobalt precursor _{to prepare a Pt-Co / SiO 2} catalyst by co-impregnation, and the catalyst is 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 1 g of the catalyst.
Then, using this Pt-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 3.
The CO conversion rate is 62.8%, the CH ₄ selectivity is 4.0%, the CO ₂ selectivity is 0.5%, and the hydrocarbon productivity with 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 1 g of the catalyst, and this Co. The / SiO ₂ catalyst was activated.
Then, using this Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 3.
The CO conversion rate is 66.5%, the CH ₄ selectivity is 5.2%, the CO ₂ selectivity is 0.4%, and the hydrocarbon productivity with 5 or more carbon atoms is 2.0 (kg-hydrocarbon / kg). -Catalyst / hour).

(Comparative Example 11)
Using a catalyst carrier as shown in H in Table 4, 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 1 g of the catalyst, and this Co. The / SiO ₂ catalyst was activated.
Then, using this Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 4.
The CO conversion rate is 73.2%, the CH ₄ selectivity is 4.6%, the CO ₂ selectivity is 0.6%, and the hydrocarbon productivity with 5 or more carbon atoms is 2.3 (kg-hydrocarbon / kg). -Catalyst / hour).

(Comparative Example 12)
Using a catalyst carrier as shown in H in 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 1 g of the catalyst. This Pt-Co / SiO ₂ catalyst was activated.
Then, using this Pt-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 4.
The CO conversion rate is 76.8%, the CH ₄ selectivity is 4.2%, the CO ₂ selectivity is 1.0%, and the 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 H in Table 4, a Ru-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 1 g of the catalyst. This Ru-Co / SiO ₂ catalyst was activated.
Then, using this Ru-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 4.
The CO conversion rate is 75.5%, the CH ₄ selectivity is 4.2%, the CO ₂ selectivity is 0.7%, and the hydrocarbon productivity with 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 1 g of the catalyst. , This Co / ZrO ₂ / SiO ₂ catalyst was activated.
Then, using this Co / ZrO ₂ / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 4.
The CO conversion rate is 66.5%, the CH ₄ selectivity is 5.1%, the CO ₂ selectivity is 0.4%, and the hydrocarbon productivity with 5 or more carbon atoms is 2.0 (kg-hydrocarbon / kg). -Catalyst / hour).

(Comparative Example 15)
Using a catalyst carrier 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 1 g of the catalyst. Then, this Pt-Co / ZrO ₂ / SiO ₂ catalyst was activated.
Then, using this Pt-Co / ZrO ₂ / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 4.
The CO conversion rate is 69.5%, the CH ₄ selectivity is 4.9%, the CO ₂ selectivity is 0.5%, and the hydrocarbon productivity with 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 were co-supported and platinum was further supported was prepared, and during the reduction treatment. The hydrogen flow rate was set to 40 mL / min per 1 g of the catalyst to activate the _{Pt / Co-ZrO 2} / SiO _{2 catalyst.}
Then, using this Pt / Co-ZrO ₂ / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 4.
The CO conversion rate is 61.5%, the CH ₄ selectivity is 5.9%, the CO ₂ selectivity is 0.4%, and the hydrocarbon productivity with 5 or more carbon atoms is 1.9 (kg-hydrocarbon / kg). -Catalyst / hour).

(Comparative Example 17)
Using a catalyst carrier as shown in F of Table 4, 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 1 g of the catalyst. This Pt-Co / SiO ₂ catalyst was activated.
Then, using this Pt-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 4.
The CO conversion rate is 46.2%, the CH ₄ selectivity is 7.4%, the CO ₂ selectivity is 0.2%, and the hydrocarbon productivity with 5 or more carbon atoms is 1.4 (kg-hydrocarbon / kg). -Catalyst / hour).

(Comparative Example 18)
Using a catalyst carrier as shown in G in Table 4, 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 1 g of the catalyst. This Pt-Co / SiO ₂ catalyst was activated.
Then, using this Pt-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. The results are shown in Table 4.
The CO conversion rate is 12.4%, the CH ₄ selectivity is 12.1%, the CO ₂ selectivity is 0.4%, and the hydrocarbon productivity with 5 or more carbon atoms is 0.3 (kg-hydrocarbon / kg). -Catalyst / hour).

(Comparative Example 19)
Using a catalyst carrier as shown in J in Table 4, 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 1 g of the catalyst. This Pt-Co / SiO ₂ catalyst was activated.
Then, using this Pt-Co / SiO ₂ catalyst, hydrocarbons were synthesized according to the above-mentioned method. 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 hydrocarbon from synthetic gas, which is produced by supporting a cobalt component and a noble metal component on a catalyst carrier containing silica as a main component.
In the support, the cobalt component is supported by using a precursor solution of cobalt acetate on a catalyst carrier containing the silica as a main component and having a total content of sodium, potassium, magnesium and calcium of 1,000 ppm or less in terms of metal. The step of impregnating and supporting, the step of impregnating and supporting the noble metal component by using a precursor solution of the noble metal compound on the catalyst carrier containing the silica as the main component, and the cobalt component and the noble metal. A method for producing a catalyst for producing a hydrocarbon from a synthetic gas, which comprises a step of reducing a catalyst carrier containing the silica as a main component on which a component is supported with a gas containing hydrogen. A method for producing a hydrocarbon from synthetic gas, which is produced by supporting a cobalt component, a zirconium component, and a noble metal component on a catalyst carrier containing silica as a main component.
In the support, the zirconium component is supported by using a precursor solution of a zirconium compound on a catalyst carrier containing the silica as a main component and having a total content of sodium, potassium, magnesium and calcium of 1,000 ppm or less in terms of metal. The step of impregnating and supporting the cobalt component, the step of impregnating and supporting the cobalt component by using a precursor solution of cobalt acetate on the silica-based catalyst carrier on which the zirconium component is supported, and the zirconium component and the cobalt. A step of impregnating and supporting the noble metal component by using a precursor solution of a noble metal compound on the silica-based catalyst carrier on which the component is supported, and supporting the zirconium component, the cobalt component, and the noble metal component. A method for producing a catalyst for producing a hydrocarbon from a synthetic gas, which comprises a step of reducing the prepared catalyst carrier containing silica as a main component with a gas containing hydrogen. A method for producing a hydrocarbon from synthetic gas, which is produced by supporting a cobalt component and a noble metal component on a catalyst carrier containing silica as a main component.
The carrier is a catalyst carrier containing silica as a main component having a total content of sodium, potassium, magnesium, and calcium of 1,000 ppm or less in terms of metal, and a precursor solution of cobalt acetate and a precursor solution of a noble metal compound. A step of simultaneously impregnating and supporting the cobalt component and the noble metal component using the mixed solution, a step of calcining the silica-based catalyst carrier on which the cobalt component and the noble metal component are supported, and the above. A method for producing a catalyst for producing a hydrocarbon from a synthetic gas, which comprises a step of reducing with a gas containing hydrogen after firing. A method for producing a hydrocarbon from synthetic gas, which is produced by supporting a cobalt component, a zirconium component, and a noble metal component on a catalyst carrier containing silica as a main component.
In the support, the zirconium component is supported by using a precursor solution of a zirconium compound on a catalyst carrier containing the silica as a main component and having a total content of sodium, potassium, magnesium and calcium of 1,000 ppm or less in terms of metal. Using a solution in which a precursor solution of cobalt acetate and a precursor solution of a noble metal compound are mixed with the silica-based catalyst carrier on which the zirconium component is supported, the cobalt component and the above. A step of simultaneously impregnating and supporting the noble metal component, a step of firing the silica-based catalyst carrier on which the zirconium component, the cobalt component and the noble metal component are supported, and a step of reducing with a gas containing hydrogen after the firing. A method for producing a catalyst for producing a hydrocarbon from a synthetic gas, which comprises. The method for producing a catalyst for producing a hydrocarbon from a synthetic gas according to any one of claims 1 to 4, wherein the noble metal is at least one of platinum and ruthenium. The invention according to any one of claims 1 to 5, wherein the content of sodium, potassium, calcium and magnesium contained in the catalyst carrier containing silica as a main component is 300 ppm or less in terms of metal, respectively. A method for producing a catalyst for producing a hydrocarbon from the synthetic gas of. Claims 1, 3, and 5 are characterized in that the method of supporting the cobalt component and the noble metal component on the catalyst carrier containing silica as a main component is impregnated and supported by using the instant wetness method, respectively. Alternatively, a method for producing a catalyst for producing a hydrocarbon from the synthetic gas according to any one of 6. 2. The method of supporting the cobalt component, the zirconium component, and the noble metal component on the catalyst carrier containing silica as a main component is impregnated and supported by using the insiient wetness method, respectively. 4. A method for producing a catalyst for producing a hydrocarbon from a synthetic gas according to any one of 4. In the step of reducing with the gas containing hydrogen, the hydrogen flow rate per 1 g of the catalyst carrier containing the silica as the main component 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 a hydrocarbon from a synthetic gas according to any one of claims 1, 3, 5, 6 or 7, which comprises reducing. In the step of reducing with the gas containing hydrogen, the hydrogen flow rate per 1 g of the catalyst carrier containing the silica as the main component, in which the zirconium component, the cobalt component and the noble metal component are supported, is 0.1 mL / min to 60 mL /. claim 2, 4 or the process for preparing a catalyst for producing a hydrocarbon from a syngas described in any one of 8, characterized in that the reduction in the range of min. A synthetic gas characterized in that a hydrocarbon is produced from a synthetic gas by a Fischer-Tropsch synthesis reaction on a slurry bed using a catalyst produced by the production method according to any one of claims 1 to 10. A method for producing a hydrocarbon, which produces a hydrocarbon from.