JP7018754B2 - A catalyst for producing a hydrocarbon from syngas, a method for producing the catalyst, a method for producing a hydrocarbon from syngas, and a catalyst carrier. - Google Patents

Description

The present invention relates to a catalyst for producing a hydrocarbon from a so-called synthetic gas containing carbon monoxide and hydrogen as main components, a method for producing the same, a method for producing a hydrocarbon using the catalyst, and a catalyst carrier.

In recent years, environmental problems such as global warming have become apparent, and the H / C is higher than other hydrocarbon fuels, coal, etc., and it is possible to suppress carbon dioxide emissions, which are the causative agents of global warming, and reserves. The importance of abundant natural gas is being reassessed, and its demand is expected to increase in the future. Under such circumstances, infrastructure such as pipelines and LNG plants was found in remote areas such as Southeast Asia and Oceania, but the recoverable reserves required huge investment. There are many small and medium-sized gas fields that are left undeveloped, and it is hoped that their development will be promoted. As one of the effective development means, after converting natural gas into synthetic gas, a lamp with excellent transportability and handleability is used by using the Fischer-Tropsch (FT, Fischer-Tropsch) synthetic reaction from the synthetic gas. The development of technology for converting to liquid hydrocarbon fuels such as light oil is being vigorously carried out in various places.

This FT synthesis reaction is an exothermic reaction that converts synthetic gas into hydrocarbons using a catalyst, but it is extremely important to effectively remove the reaction heat for stable operation of the plant. Reaction types that have been proven to date include a gas phase synthesis process (fixed bed, jet bed, fluid bed) and a liquid phase synthesis process (slurry bed), each of which has its own characteristics. The slurry bed liquid phase synthesis process, which has high removal efficiency and does not cause accumulation of the generated high boiling point hydrocarbon on the catalyst and the accompanying blockage of the reaction tube, has attracted attention and is being energetically developed.

In general, it goes without saying that the higher the activity of the catalyst, the more preferable it is, but especially in the slurry bed, there is a limitation that the slurry concentration needs to be kept below a certain value in order to maintain a good slurry flow state. Due to its existence, high catalyst activation is a very important factor in expanding the degree of freedom in process design.

As a result of detailed examination of the effect of impurities such as alkali metal and alkaline earth metal on the activity of the catalyst for the purpose of high activation, by setting the impurity concentration to a certain range of catalyst, it is compared with the conventional catalyst. An example in which the activity is greatly improved has been reported (see Patent Document 1).

Further, in general, the smaller the particle size of the FT synthesis reaction catalyst is, the more preferable it is from the viewpoint of reducing the possibility that heat or diffusion of a substance becomes rate-determining. However, in the FT synthesis reaction using a slurry bed, high-boiling hydrocarbons are accumulated in the reaction vessel among the generated hydrocarbons, so that a solid-liquid separation operation between the catalyst and the product is absolutely necessary. If the particle size of the catalyst is too small, there arises a problem that the efficiency of the separation operation is greatly reduced. Therefore, the catalyst for the FT synthesis reaction in the slurry bed has an optimum particle size range, and it is generally said that the particle size is preferably about 20 to 250 μm and the average particle size is about 40 to 150 μm. However, as shown below, care must be taken as the catalyst may be destroyed or pulverized during the reaction, resulting in a smaller particle size.

That is, in the FT synthesis reaction on the slurry bed, the catalyst particles are often operated at a considerably high raw material gas empty tower speed (0.1 m / sec or more), and the catalyst particles collide violently during the reaction. If the strength and abrasion resistance (powder resistance) are insufficient, the catalyst particle size may decrease during the reaction, which may cause inconvenience in the separation operation. Further, in the slurry bed, an organic substance is used as a liquid medium, but in the FT synthesis reaction, a large amount of water is produced as a by-product. May cause the catalyst particle size to become finer during the reaction, which causes inconvenience in the separation operation as described above.

Further, in general, the catalyst for the FT synthesis reaction in the slurry bed is often pulverized to have the optimum particle size as described above, the particle size is adjusted, and the catalyst is put into practical use. However, such a crushed catalyst often has pre-cracks or sharp protrusions, and is inferior in mechanical strength and wear resistance. Therefore, when a crushed catalyst is used for the FT synthesis reaction in the slurry bed, the catalyst is destroyed and fine powder is generated, and it is extremely difficult to separate the generated high boiling point hydrocarbon from the catalyst. It had the drawback of becoming. Further, it is widely known that a catalyst having relatively high activity can be obtained by using porous silica as a catalyst carrier for the FT synthesis reaction. However, when the particle size is adjusted by crushing, it is described above. For these reasons, not only the strength of the catalyst decreases, but also the catalyst carrier mainly composed of silica has low water resistance and is often destroyed or pulverized by the presence of water, which may cause a problem especially in a slurry bed. There were many.

Further, under a reaction atmosphere in which a large amount of water produced by the FT reaction is present (particularly in an atmosphere having a high CO conversion rate), at the interface between the supported cobalt, which is an active metal, and the catalyst carrier mainly composed of silica. In addition to the phenomenon that the catalytic activity decreases, which is thought to be due to the formation of cobalt silicate or the oxidation of the supported cobalt itself, when a carrier with insufficient water resistance is used, the specific surface area and pores of the carrier There is a problem that the catalytic activity is lowered due to the structural change such as the volume, or the strength is lowered and the catalytic pulverization is likely to occur. This phenomenon leads to a reduction in the usable time of the catalyst, which has been a factor in raising the operating cost. Therefore, from the viewpoint of extending the usable time of the catalyst, it is important to apply a catalyst manufactured by using a carrier having high water resistance.

Japanese Unexamined Patent Publication No. 2004-322085 U.S. Pat. No. 4,568,663

E.Iglesia, Applied Catalysis A: Genaral, 161 (1997) 59-78

The catalyst carrier mainly composed of silica has a certain solubility in water, and structural changes such as specific surface area and pore volume change especially in an atmosphere where a large amount of water produced as a by-product due to the FT reaction is present. There is a problem that the catalytic activity is lowered by the occurrence. Therefore, it has been desired to improve the water resistance of the catalyst carrier mainly composed of silica.

INDUSTRIAL APPLICABILITY The present invention improves the durability of a catalyst for producing a hydrocarbon from syngas, and in particular, enhances the water resistance of a catalyst carrier mainly composed of silica, so that a high CO conversion rate in which a large amount of by-product water is generated is generated. Provided are a catalyst for producing a hydrocarbon from syngas, a method for producing the catalyst, a method for producing a hydrocarbon using the catalyst, and a catalyst carrier used for the catalyst, which can be stably used even under conditions. The purpose is to do.

According to the catalyst containing a vanadium, particularly a catalyst in which a metal compound is supported using a catalyst carrier mainly composed of silica containing vanadium, the present inventors have a condition that the partial pressure of water produced as a by-product is relatively high. We have found that the catalyst has high water resistance even under the above conditions, and have reached the present invention.
The present invention relates to a catalyst having high water resistance, a method for producing the catalyst, a method for producing a hydrocarbon using the catalyst, and a catalyst carrier used for the catalyst. More details are as described below.

(1) A catalyst in which cobalt is supported on a catalyst carrier containing silica as a main component, and the content of vanadium in the catalyst is 0.1 to 10.0% by mass, and sodium, potassium, and calcium. , And a catalyst for producing a hydrocarbon from a synthetic gas, characterized in that the total impurity content of magnesium is 0.01-0.15% by mass.
(2) The catalyst for producing a hydrocarbon from the synthetic gas according to (1), wherein the carrying ratio of cobalt is 5 to 50% by mass in terms of metal.
(3) The catalyst for producing a hydrocarbon from the synthetic gas according to (1) or (2), wherein the content of vanadium is 0.2 to 2.0% by mass.
(4) A catalyst for producing a hydrocarbon from the synthetic gas according to any one of (1) to (3), wherein the catalyst carrier is spherical.

(5) The silica sol produced by mixing an alkaline silicate aqueous solution and an acid aqueous solution is gelled and further dried to obtain silica, and the silica is contained with vanadium in an amount of 0.1 to 10.0% by mass , and then dried and dried. A catalyst carrier is prepared by firing and further adjusted so that the impurity content of sodium, potassium, calcium, and magnesium is 0.01 to 0.15% by mass, and the catalyst carrier is supported by cobalt. A method for producing a catalyst for producing a hydrocarbon from a synthetic gas.
(6) The method for producing a hydrocarbon from the synthetic gas according to (5), wherein the content of sodium in the catalyst carrier is 0.01 to 0.10% by mass.
(7) The method according to (5) or (6), wherein the catalyst is produced so that the impurity content of sodium, potassium, calcium, and magnesium is 0.01 to 0.15% by mass. A method for producing a catalyst for producing a hydrocarbon from syngas.
(8) When the silica is impregnated with vanadium to prepare a catalyst carrier, the silica is impregnated with vanadium by an impregnation method, an infant wetness method, a precipitation method, or an ion exchange method. , A method for producing a catalyst for producing a hydrocarbon from a synthetic gas according to any one of (5) to (7), which comprises performing a drying treatment, or a drying treatment and a firing treatment to produce a catalyst carrier. ..

(9) Syngas using the catalyst according to any one of (1) to (4) or the catalyst produced by the production method according to any one of (5) to (8). A method for producing a hydrocarbon from a synthetic gas, which comprises producing a hydrocarbon from a synthetic gas.
(10) The method for producing a hydrocarbon from the synthetic gas according to (9), which is produced by a liquid phase reaction on a slurry bed.
(11) In the liquid phase reaction, the one-pass CO conversion rate, which is the CO conversion rate in a state where the catalyst amount, the synthetic gas supply amount, the reaction temperature, and the reaction pressure are adjusted and the synthetic gas is passed through the reactor only once, is 40. The method for producing a hydrocarbon from the synthetic gas according to ( 10), wherein the content is ~ 95%.

(12) A catalyst carrier used for a catalyst for producing a hydrocarbon from syngas, which contains silica as a main component, a vanadium content of 0.1 to 10.0% by mass, and sodium, potassium, calcium, and. A catalyst carrier characterized in that the total impurity content of magnesium is 0.01 to 0.15% by mass.
(13) The catalyst carrier according to (12), wherein the sodium content is 0.01 to 0.10% by mass.
(14) The catalyst carrier according to (12) or (13), wherein the content of vanadium is 0.2 to 2.0% by mass.

According to the present invention, a hydrocarbon is produced from a catalyst having high stability, a method for producing the same, and a synthetic gas using the catalyst, even under conditions where a large amount of by-product water is generated, especially under a high CO conversion rate condition. And the catalyst carrier used for the catalyst can be provided.

Hereinafter, an embodiment of the present invention for producing a hydrocarbon from a synthetic gas, a method for producing the catalyst, a method for producing a hydrocarbon from the synthetic gas, and a catalyst carrier used for the catalyst will be described in detail.
First, a catalyst for producing a hydrocarbon from the synthetic gas according to the present embodiment will be described.

The catalyst according to this embodiment contains cobalt as a metal having activity in the FT synthesis reaction, and further contains vanadium from the viewpoint of water resistance. Specifically, the vanadium content of the catalyst is 0.1 to 10% by mass in terms of vanadium metal with respect to the total mass of the entire catalyst, more preferably 0.1 to 6% by mass, and further preferably 0. .2 to 2% by mass. Below this range, the effect of improving water resistance by vanadium is not sufficiently exhibited, while above this range, the catalytic activity in the reaction decreases, which is not preferable.

Further, the catalyst carrier to be used is a catalyst carrier containing silica as a main component (hereinafter, also simply referred to as a silica carrier or a carrier). The carrier containing silica as a main component as used herein has a silica content of 50% by mass or more and less than 100% by mass, and is a silica-alumina carrier containing alumina in addition to silica, or in a manufacturing process of a silica carrier. It may contain a small amount of unavoidable impurities.
Examples of the method for measuring the silica content in the catalyst and the catalyst carrier include a method of measuring by the ICP-AES method after pretreatment such as acid decomposition and alkali melting.
Here, as described above, the catalyst according to the present embodiment contains cobalt and vanadium, but this vanadium may be contained in the silica carrier itself used. Details of the silica carrier will be described later.

The impurities in the catalyst according to the present embodiment are impurities that inevitably enter in the catalyst manufacturing process, and are, for example, raw materials and raw materials when the catalyst carrier is manufactured or when a metal-based compound such as a cobalt compound is supported on the catalyst carrier. It is an impurity contained in the wash water that inevitably enters the catalyst.

Impurities that may be mixed in during the production of the catalyst carrier of the present embodiment are contained in the impurity species and the starting material contained in the washing water used in the manufacturing process of the carrier containing silica containing vanadium as a main component. For example, in the case of a vanadium-containing silica carrier, metals other than vanadium and silica are impurities. Further, for example, in the case of a silica-alumina carrier containing vanadium-containing silica as a main component, metals and metal compounds other than vanadium, silicon, and aluminum are impurities.

In addition, impurities that may be mixed when the metal-based compound is supported on the catalyst carrier are found in the precursor of the metal-based compound to be supported, the treated water and washing water for the support, and the drying step and the baking step after the support. Metals that inevitably enter and affect the catalytic performance become impurities.
When the cobalt compound is supported on the catalyst carrier, the use of high-purity cobalt precursor, high-purity treated water, and washing water, the supporting step, and the drying step are performed rather than reducing the amount of impurities in the catalyst carrier. In many cases, it is easier to reduce the amount of impurities in the firing step. That is, impurities in the catalyst carrier are often the main cause of impurities in the entire catalyst.
These impurities are usually alkali metals such as sodium, potassium, calcium and magnesium, alkaline earth metals, and iron as the main impurities. The effect of the type of impurities on the catalytic performance is small for iron, with the greatest effect being the alkali metals sodium and potassium, followed by the alkaline earth metals calcium and magnesium. be.

Therefore, in this embodiment, it is necessary to reduce the total content of sodium, potassium, calcium, and magnesium in the catalyst and the catalyst carrier. Of these, potassium is often contained in a very small amount in a catalyst produced from a carrier containing silica as a main component, and in reality, sodium, calcium, magnesium and iron are the main impurities. Many of these metals exist as compounds such as oxides, but the content is calculated based on the amount converted to metal. In the present invention, the total content of these metals contained in the catalyst is defined as the impurity content.

The total content of sodium, calcium, and magnesium in the vanadium-containing catalyst is 0.01 to 0.15% by mass, which makes it possible to suppress the decrease in activity and improve the water resistance at the same time.
In the present embodiment, it is preferable that the total content of sodium, potassium, calcium, and magnesium obtained by adding potassium to these impurities is 0.01 to 0.15% by mass. It should be noted that the content of these impurities is the total content, and any of them may not be contained, but even in that case, the total content of these impurities should be 0.01 to 0.15% by mass. Just do it.

Next, a catalyst carrier that can be suitably used for the catalyst of the present embodiment will be described.
The catalyst carrier according to the present embodiment contains silica as a main component, has a vanadium content of 0.1 to 10% by mass, and has a total impurity content of sodium, potassium, calcium, and magnesium of 0.01 to 0. It is 15% by mass.
Each requirement will be described below.

The vanadium content of the silica-based carrier is 0.1 to 10% by mass, more preferably 0.1 to 10% by mass in terms of vanadium metal, based on the total mass of the vanadium and the silica-based carrier. It is 6% by mass, more preferably 0.2 to 2% by mass. Below this range, the effect of improving water resistance by vanadium is not sufficiently exhibited, while above this range, the catalytic activity in the reaction decreases, which is not preferable.

Further, the amount of impurities in the carrier containing silica as a main component is controlled as follows.
As described above, controlling impurities in the catalyst other than cobalt metal and carrier constituent elements within a certain range is extremely effective for activity, water resistance, and catalyst cost. Further, in the silica carrier of the present embodiment, as described above, Na, K, Ca, Mg, Fe and the like are often contained in the carrier as impurities. When the effects of these impurities were investigated in detail, it was found that the water resistance of the silica carrier was improved by supporting vanadium even in the presence of relatively large amounts of Na, K, Ca, and Mg. As impurities, the influence on the activity of sodium and potassium is strong, and the influence of the presence of sodium is the strongest. Although potassium has a strong influence, it is often not present in the carrier depending on the production method and the type of the carrier.

Of the amount of impurities in the catalyst carrier containing silica as the main component, the influence of alkali metal and alkaline earth metal is large, and the influence of the total amount of sodium, potassium, calcium and magnesium is particularly large. Therefore, the total amount of sodium, potassium, calcium, and magnesium to the carrier is preferably 0.01 to 0.15% by mass in total. This range is a range that can be manufactured without adopting a cleaning treatment such as an acid treatment for extremely reducing the content of impurities, and an increase in carrier manufacturing cost can be avoided. On the other hand, even if vanadium is supported on a catalyst carrier in which the amount of impurities is less than this range, the effect of improving water resistance can be obtained in the same manner, but it is disadvantageous because the cost required for the cleaning treatment increases. The total amount of impurities in the catalyst carrier is preferably 0.01 to 0.15% by mass. Further, impurities may be mixed in a certain amount during the cobalt supporting operation, and it is not necessary to use an extremely pure cobalt precursor, which is preferable from the viewpoint of catalyst cost.
Here, as a method for quantifying the amount of impurities in the catalyst carrier, for example, a method of measuring by the ICP-AES method after pretreatment such as acid decomposition or alkali melting can be mentioned.

Among the impurities in the catalyst carrier, the elements that most affect the reactivity and water resistance are alkali metals and alkaline earth metals. In particular, when the total content of sodium, potassium, calcium and magnesium in the carrier exceeds 0.15% by mass, the water resistance is not significantly reduced, but the reaction activity is significantly reduced, which is not preferable. Therefore, the content of sodium, potassium, calcium and magnesium in the catalyst carrier is preferably 0.03 to 0.15% by mass, more preferably 0.02 to 0.1% by mass, and even more preferably 0. It is 03 to 0.08% by mass.
Further, as described above, since sodium has the strongest effect on the catalytic activity, the sodium content in the carrier is preferably 0.01 to 0.10% by mass.

Next, a method for producing the catalyst will be described.
In the method for producing a catalyst according to the present embodiment, first, a silica sol produced by mixing an alkaline silicate aqueous solution and an acid aqueous solution is gelled, and the silica obtained by drying contains vanadium, and then dried and fired. Then, the catalyst carrier is further adjusted so that the impurity content of sodium, potassium, calcium, and magnesium is 0.01 to 0.15% by mass, and the catalyst carrier is supported with cobalt.

The method for incorporating vanadium into the carrier containing silica as a main component may be an ordinary impregnation method, an Incipient Wetness method, a precipitation method, an ion exchange method or the like. The vanadium compound, which is a raw material (precursor) used for inclusion, is oxidized in the silica network or on the silica surface by further drying treatment, drying treatment, and firing treatment after the above-mentioned inclusion treatment. Any substance that forms a stable compound of vanadium such as a substance may be used, and there is no particular limitation as long as it is soluble in a solvent. Specifically, vanadium oxide and ammonium vanadate are preferable because they are soluble in water.

Next, the method of supporting the metal-based compound on the vanadium-containing silica carrier may be an ordinary impregnation method, an Incipient Wetness method, a precipitation method, an ion exchange method, or the like. As the metal-based compound which is a raw material (precursor) used in the carrier, a counter ion (for example, Cobalt nitrate is Co (NO ₃ ) There is no particular limitation as long as (NO ₃ ) ^- ) in ₂ is volatilized and is soluble in a solvent. For example, nitrates, carbonates, acetates, chlorides, acetylacetonates, etc. can be used, but it is safer to use a water-soluble compound that can use an aqueous solution when carrying out the carrying operation. It is preferable for ensuring a stable manufacturing work environment. The drying process after loading can be omitted. When the metallic compound is cobalt, cobalt nitrate or the like is preferable because it easily changes to cobalt oxide at the time of firing and the subsequent reduction treatment of the cobalt oxide is easy.

The loading ratio of cobalt on the catalyst carrier may be at least the minimum amount for exhibiting activity, and the supporting amount may be such that the dispersity of the carried cobalt is extremely lowered and the reaction contribution efficiency of cobalt is lowered. ..
Specifically, the carrying ratio of cobalt is 5 to 50% by mass in terms of metal (however, the mass of the entire catalyst including the silica carrier is 100% (mass not converted to metal)), preferably 10 to 50% by mass. It is 40% by mass. If it is below this range, the activity may not be sufficiently expressed, and if it exceeds this range, the dispersity may be lowered and the utilization efficiency of the carried cobalt may be lowered, which is uneconomical and is not preferable. The cobalt support rate here refers to the ratio of the mass of metallic cobalt to the total catalyst mass when it is considered that the supported cobalt is 100% reduced because it is not always 100% reduced. ..
Examples of the method for quantifying cobalt in the catalyst include a method of measuring by the ICP-AES method after pretreatment such as acid decomposition and alkali melting.

When vanadium is contained in a carrier containing silica as a main component and cobalt is further supported, it is important to sequentially treat them in this order. That is, by supporting cobalt on a silica carrier containing vanadium, it is possible to effectively exhibit the effect of vanadium on improving the water resistance of the silica carrier and the catalyst. The details of the mechanism of water resistance improvement by vanadium are unknown, but it is presumed as follows.
Silica carriers have low resistance to water vapor coexistence, but vanadium content improves this, according to our research. In this way, in order for vanadium to act directly on the silica carrier and contribute to improving water resistance, it is presumed that it is better to support vanadium in a state where cobalt is not supported than to support vanadium after cobalt is supported. do. From this point of view, it is desirable to support vanadium and cobalt in this order, but it is considered that the above-mentioned effects can be obtained even if vanadium and cobalt are supported at the same time. As described above, the vanadium-containing state when vanadium is contained in the carrier containing silica as the main component may be such that the stable compound of vanadium is contained in the silica network, or the silica. It may be in a state of being supported on the surface.
Examples of the method for measuring the vanadium content in the catalyst carrier in the catalyst thus produced include SEM-EDS, TEM-EDS and the like. The vanadium content can be measured by selecting a field of view in which cobalt particles existing on the surface of the catalyst carrier containing vanadium do not exist and performing composition analysis with EDS.

As a method for evaluating the water resistance of the catalyst and the catalyst carrier obtained as described above, the catalyst or the carrier is charged into an autoclave together with water, and the temperature is raised to maintain a high water pressure for a certain period of time. A steaming test for measuring changes (surface area, pore volume, etc.) can be mentioned. In the steaming test, a general method may be used as a method for measuring the surface area, pore volume, etc. of the carrier before and after the test, and examples thereof include a BET surface area measurement method in which gas is adsorbed and calculated by the BET formula. The conditions of the steaming test are, for example, 225 ° C., 2.55 Mpa, 20 h.

The following is an example of a method for obtaining the catalyst of the present embodiment.
First, an aqueous solution of a vanadium precursor is impregnated with a carrier containing silica as a main component and treated, and then dried or dried and fired to prepare a vanadium-containing catalyst carrier. Next, the vanadium-containing catalyst carrier is impregnated with an aqueous cobalt precursor solution and, if necessary, subjected to drying and reduction treatment, or drying, calcination and reduction treatment to obtain a cobalt-supported catalyst.
The aqueous solution of the vanadium precursor is not particularly limited, but ammonium vanadate or the like can be used.

After the silica carrier contains vanadium, a drying treatment (for example, 100 ° C.-1h in air, usually in the range of about 50 to 150 ° C., but not particularly limited) is performed, followed by a firing treatment (for example, 450 in air). ℃ -5h, usually in the range of about 300 to 600 ° C., but is not particularly limited), or impregnation with cobalt, which is the next step, may be performed only by performing a drying treatment, but vanadium. In order to increase the water resistance effect due to the addition, it is advisable to carry out the above-mentioned firing treatment.

After impregnating the cobalt precursor solution with the carrier containing vanadium, a drying treatment is performed as necessary, and then the cobalt compound on the surface of the carrier is subsequently reduced to an active metal (for example, 450 ° C-15h in a normal pressure hydrogen stream, usually The temperature is in the range of about 250 to 600 ° C., but is not particularly limited). A reduction treatment may be performed. The aqueous solution of the cobalt precursor is not particularly limited, but cobalt nitrate, cobalt acetate and the like can be used.

If the reduction conditions are made stricter by raising the temperature of the reduction treatment or lengthening the time, the ratio of the metal-based compound being reduced from the oxide state to the metallic state after the reduction treatment increases, and the reduction is extremely severe. By performing the treatment, it is possible to make only the active metal. However, under general reduction conditions, it is often in a chemical state containing a part of cobalt oxide.

The catalyst after the reduction treatment must be handled so that it will not be oxidatively deactivated by contact with the atmosphere. However, if the surface of the cobalt metal on the carrier is stabilized from the atmosphere, it will be handled in the atmosphere. It is possible and suitable. In this stabilization treatment, a so-called passivation (passivation treatment) is performed in which nitrogen, carbon dioxide, or an inert gas containing a low concentration of oxygen is brought into contact with the catalyst to oxidize only the extreme surface layer of the active metal on the carrier. When the FT synthesis reaction is carried out in a liquid phase, there is a method of immersing it in a reaction solvent, molten FT wax, etc. to shut it off from the atmosphere. good.

The total amount of sodium, potassium, calcium and magnesium in the catalyst produced in this manner is 0.01 to 0.15% by mass. The method for quantifying the amount of impurities in the catalyst is the same as the method in the catalyst carrier, and can be measured by the ICP-AES method after pretreatment such as acid decomposition or alkali melting.

Here, the method for producing a silica carrier is generally roughly classified into a dry method and a wet method. The dry method includes a combustion method, an arc method, and the like, and the wet method includes a sedimentation method, a gel method, and the like, and it is possible to produce a catalyst carrier by any of the production methods. However, since it is technically and economically difficult to form the catalyst carrier into a spherical shape by the above methods other than the gel method, the silica sol is sprayed in a gas medium or a liquid medium to easily form the gel into a spherical shape. The gel method, which is possible, is preferred.
The gel is formed into a spherical shape by spraying a silica sol produced by mixing an aqueous acid aqueous solution of silicate and an aqueous acid solution in a gas medium or a liquid medium, and then at least one of acid treatment and water washing treatment. Can be obtained as a silica carrier by firing after performing the above. Details will be described later.

When producing a silica carrier by the above gel method, a large amount of washing water is usually used, but if washing water containing a large amount of impurities such as industrial water is used, a large amount of impurities will remain in the carrier. , The catalytic activity is significantly reduced, which is not preferable. On the other hand, 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, but the cost is high. It will increase. From the viewpoint of both catalyst performance and cost, it is preferable to control the amount of impurities in the catalyst carrier within a certain range, and when vanadium is contained as a catalyst, the water resistance effect is exhibited even if the amount of impurities is relatively large. The amount of impurities in the catalyst carrier is preferably 0.01 to 0.15% by mass. In this case, the total content of sodium, potassium, calcium and magnesium in the washing water used is preferably 0.1% by mass or less. When an acidic aqueous solution is used for the washing water, the total content of sodium, potassium, calcium and magnesium in the acidic aqueous solution is preferably 0.1% by mass or less for the same reason. Although the use of ion-exchanged water can be considered from the viewpoint of reducing the amount of impurities, it is better to avoid using it from the viewpoint of cost.

Further, in the production of the silica carrier, a firing treatment for the purpose of improving the particle strength and the surface silanol group activity is often performed. However, when firing is performed in a range where the impurities in the carrier exceed 0.15% by mass, the impurity elements are incorporated into the silica skeleton when the silica carrier is washed to reduce the impurity concentration, and the impurity content is contained. It becomes difficult to reduce. Therefore, when it is desired to wash the silica carrier to reduce the impurity concentration, it is preferable to use uncalcined silica gel.

By using the carrier as described above, it is possible to obtain a catalyst having high water resistance in the FT synthesis reaction. In the FT synthesis reaction, water is by-produced, and the higher the one-pass conversion rate, the higher the water pressure of the reaction system. It is presumed that if a catalyst produced with a catalyst carrier having low water resistance is used under high water pressure conditions, the catalyst structure in which activity is likely to be exhibited is destroyed and the activity is reduced. On the other hand, if a catalyst produced by the catalyst carrier having high water resistance according to the present embodiment is used, it is considered that the catalyst structure destruction can be suppressed and the activity decrease can be suppressed.

The physical properties of the carrier are not particularly limited, but from the viewpoint of the activity of the FT synthesis catalyst, in order to maintain a high dispersity of the metal and further improve the efficiency of contributing to the reaction of the carried active metal, it is necessary to improve the efficiency. It is preferable to use a carrier having a high specific surface area. However, in order to increase the specific surface area of the carrier, it is necessary to reduce the pore diameter and increase the pore volume, but if these two factors are increased, the wear resistance and strength will decrease. Therefore, the range shown below is preferable from the viewpoint of both activity and strength. A carrier having a pore diameter of 8 to 50 nm, a specific surface area of 80 to 450 m ² / g, and a pore volume of 0.2 to 1.2 mL / g is suitable as a catalyst carrier. It is more preferable if the pore diameter is 8 to 30 nm, the specific surface area is 100 to 400 m ² / g, and the pore volume is 0.2 to 0.9 mL / g at the same time. It is more preferable if the amount is 150 to 350 m ² / g and the pore volume is 0.3 to 0.8 mL / g at the same time. The above specific surface area is measured by the BET method, and the pore volume is measured by the mercury intrusion method. The pore diameter is measured by a gas adsorption method.

In order to obtain a catalyst exhibiting sufficient activity for the FT synthesis reaction, the specific surface area of the catalyst carrier needs to be 80 m ² / g or more. If it is less than this specific surface area, the dispersity of the supported metal is lowered, and the efficiency of contribution of the active metal to the reaction is lowered, which is not preferable. Further, when the specific surface area of the catalyst carrier is more than 450 m ² / g, it is difficult for the pore volume and the pore diameter to simultaneously satisfy the above ranges, which is not preferable. Therefore, the specific surface area of the catalyst carrier is preferably 80 to 450 m ² / g.

The smaller the pore diameter of the catalyst carrier, the larger the specific surface area, but if it is less than 8 nm, the gas diffusion rate in the pores differs between hydrogen and carbon monoxide, and hydrogen goes deeper into the pores. This is not preferable because a large amount of light hydrocarbons such as methane, which can be said to be a by-product, is produced in the FT synthesis reaction, which results in an increase in the partial pressure. In addition, the diffusion rate of the produced hydrocarbon in the pores also decreases, and as a result, the apparent reaction rate decreases, which is not preferable. Further, when comparison is performed with a constant pore volume, the specific surface area decreases as the pore diameter increases. Therefore, when the pore diameter exceeds 50 nm, it becomes difficult to increase the specific surface area and the dispersity of the active metal decreases. It is not preferable because it will be done. Therefore, the pore diameter of the catalyst carrier is preferably 8 to 50 nm.

The pore volume of the catalyst carrier is preferably in the range of 0.2 to 1.2 mL / g. If 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, which is not preferable, and if the pore volume is more than 1.2 mL / g, it is not preferable. It is not preferable because it reduces the strength.

As described above, the catalyst for the FT synthesis reaction on the slurry bed (FT synthesis catalyst) is required to have abrasion resistance and strength. Further, in the FT synthesis reaction, since a large amount of water is by-produced, if a catalyst or 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 carrier is preferable, rather than a crushed carrier having a high possibility of pre-cracking and having sharp corners that are easily broken and peeled off. For example, a circularity, which is an index for measuring the complexity of a shape, which is expressed numerically based on the area and the peripheral length of a two-dimensional image when an image of a particle is analyzed, can be used, and the circularity is 0. 7 or more is preferable. When producing the spherical carrier, a spraying method such as a general spray-drying method may be used. In particular, when producing a spherical silica carrier having a particle size of about 20 to 250 μm, the spraying method is suitable, and a spherical silica carrier having excellent wear resistance, strength, and water resistance can be obtained.

A method for producing such a silica carrier is illustrated below.
A silica sol generated by mixing an aqueous alkali silicate solution and an aqueous acid solution and having a pH of 2 to 10.5 is sprayed into a gas medium such as air or an organic solvent insoluble in the sol to gel. Then, acid treatment, washing with water, and drying. Here, as the alkali silicate, an aqueous solution of sodium silicate is preferable, the molar ratio of Na ₂ O: SiO ₂ is 1: 1 to 1: 5, and the concentration of silica is preferably 5 to 30% by mass. As the acid to be used, nitric acid, hydrochloric acid, sulfuric acid, organic acid and the like can be used, but 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 to 10 mol / L, and if it is below this range, the progress of gelation is significantly slowed down, and if it is above this range, the gelation rate is too fast and its control becomes difficult, and the desired physical property value. It is not preferable because it becomes difficult to obtain. When a method of spraying into an organic solvent at the time of gelation is adopted, kerosene, paraffin, xylene, toluene or the like can be used as the organic solvent.

The catalyst according to the present embodiment, the method for producing the catalyst, and the catalyst carrier that can be suitably used for the catalyst have been described above. However, if the catalyst carrier obtained by the above configuration or production method is used, the strength and wear resistance It is possible to provide a catalyst that exhibits high water resistance by containing vanadium without impairing the above, and is particularly suitable as a catalyst for FT synthesis.

Further, if a hydrocarbon is produced from a synthetic gas using the catalyst according to the present embodiment, the decrease in activity due to by-product water is very small, and high catalytic activity can be exhibited for a long period of time. A good FT synthesis reaction can be stably carried out under the condition that the partial pressure of the above is very high, particularly under the condition that the one-pass CO conversion rate is 60 to 95%. The one-pass CO conversion rate referred to here is different from the one in which the gas containing the unreacted raw material gas discharged from the reactor is supplied to the reactor again, and the CO conversion rate is determined by passing the raw material gas through the reactor only once. It is what I asked for. Even when the one-pass CO conversion rate is relatively low at 40 to 60%, the decrease in activity due to by-product water is very small, so that the catalyst life is extended and the catalyst cost can be reduced. If the one-pass CO conversion rate is less than 40%, the equipment cost of the tail gas recycling equipment will increase, so it is common to operate at 40% or more.

In addition, the slurry bed is an operation method in which the inside of the reactor is flowed and circulated by blowing the raw material gas, but in a large reactor of the actual scale, there may be a flow retention area in the reactor. In the retention area, the stirring of products such as raw material gas and by-product water near the catalyst is insufficient. That is, a region having a high water pressure is locally formed, and a catalyst using a carrier having a low water resistance is liable to cause structural destruction.

On the other hand, by producing a hydrocarbon from a synthetic gas using the catalyst according to the present embodiment, the activity is unlikely to decrease due to the structural destruction of the catalyst even in the retention region of the flow generated in the slurry bed as described above, so that the efficiency is high. Moreover, the FT synthesis reaction can be carried out at low cost, and hydrocarbons can be stably produced.

When the activity decreases due to factors such as a remarkably high CO conversion rate or a long reaction time, the catalyst can be regenerated by supplying a gas containing hydrogen instead of the synthetic gas. As a method for regenerating the catalyst, there are an in-situ (in-situ) method in which the regenerated gas is supplied to the reactor to bring the regenerated gas into contact with the reactor, and after the catalyst is extracted, the catalyst is filled in another container called a regenerating tower. There is a method of supplying regenerated gas.

The in-situ method has the advantage that the equipment of the regeneration tower is not required, but has the disadvantage that the production is stopped during the regeneration operation, and the equipment cost of the regeneration tower, the time required for regeneration (production stop time), etc. are taken into consideration. It is necessary to determine the method of regenerating the catalyst. The hydrogen content of the regenerated gas is preferably 5% or more, and may be 100%. In addition, an inert gas such as nitrogen or argon may be contained. The regeneration conditions may be any conditions as long as the catalyst regeneration proceeds, and are not particularly limited. It is presumed that the catalyst regeneration mechanism by contacting the regenerated gas containing hydrogen with the catalyst is due to the re-reduction of cobalt oxidized by by-product water and the removal of precipitated carbon by hydrogen. Further, in in-situ regeneration in a slurry bed in which a catalyst is dispersed in a liquid hydrocarbon of a solvent, the solvent is not eliminated by conversion of the liquid hydrocarbon into a gas component by hydrocracking from the viewpoint of restart operation after regeneration. It is preferable to do so, and care must be taken in setting conditions such as temperature, pressure, time, and gas flow rate. For example, the regeneration temperature is 100 to 400 ° C., the regeneration pressure is normal pressure to reaction pressure, the regeneration time is 1 hour or more, and the regeneration gas flow rate is that the hydrogen flow rate in the regeneration gas is about the same as the hydrogen flow rate in the synthetic gas in the reaction. Suitable. When the regeneration pressure is lower than the reaction pressure, it becomes possible to use a compressor for boosting the reaction pressure in the reaction, and it is not necessary to install a new compressor for regeneration, which is advantageous in terms of equipment cost. ..

In the method of supplying the regenerated gas by filling the regenerating tower after extracting the catalyst, it is possible to select a fluidized bed, a fixed bed, etc. in addition to the slurry bed, but the air of the fluidized bed, the fixed bed, etc. Since it is not necessary to consider the hydrocracking of the solvent in the solid reaction, the regeneration temperature may be determined in consideration of the regeneration rate and the syntering of the catalyst metal such as cobalt. In addition, the regeneration pressure can be selected according to the capacity of the compressor of the regeneration equipment regardless of the reaction pressure, but the equipment cost of the compressor increases as the boosting capacity increases, so the pressure dependence of the regeneration speed is taken into consideration. It is necessary to decide.

As the synthetic gas used for the reaction in the method for producing a hydrocarbon of the present embodiment, a gas in which the total amount of hydrogen and carbon monoxide is 50% by volume or more of the total is preferable from the viewpoint of productivity, and particularly hydrogen. It is desirable that the molar ratio of carbon monoxide (hydrogen / carbon monoxide) is 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 hydrocarbon reaction of carbon monoxide (FT synthesis reaction) is difficult to proceed. This is because the productivity of liquid hydrocarbons does not increase, while 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 catalytic activity. This is because the productivity of liquid hydrocarbons does not increase regardless.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Spherical silica carrier prepared by spraying silica sol using an autoclave with an internal volume of 1200 mL (VO _x / SiO ₂ (x is chemical) prepared by supporting V by the impingient wetness method, drying treatment, and firing treatment. The carrier containing silica as a main component was charged with 4 g))) and 30 g of water, and then the temperature was raised to 225 ° C. As the aqueous solution of the vanadium precursor, ammonium vanadate was used. When the temperature reached 225 ° C., the pressure became about 2.55 MPa, and the steaming test was carried out by holding the pressure in this state for 20 hours. After the steaming test, the mixture was cooled to room temperature, VO _x / SiO ₂ was recovered, and a drying treatment was performed. The specific surface area and pore volume were analyzed by BET measurement, and the rate of change in specific surface area and pore volume before and after this steaming test was calculated.

The specific surface area change rate and the pore volume change rate described in the following examples were calculated by the following formulas, respectively.

In addition, the following tests were conducted to evaluate the reactivity of the catalyst.
First, cobalt nitrate was adopted as a cobalt precursor solution on a catalyst carrier containing V-containing silica as a main component, which was produced by the above method, and Co was supported by an incision wetness method, and after drying and firing treatment. , Reduction treatment and passivation were applied to prepare a catalyst (Co / VO _x / SiO ₂ (x is a chemically acceptable value, Co carrying ratio is 20 to 30% by mass)).
Next, using an autoclave with an internal volume of 300 mL, 1 g of the adjusted catalyst (Co / VO _x / SiO ₂ ) and 50 mL of n-C ₁₆ (n-hexadecane) were charged, and then 230 ° C., 2.0 MPa-G. Under the above conditions, while rotating the stirrer at 800 min ^-1 , F (synthetic gas (H ₂ ) so that W (catalyst mass) / F (synthetic gas flow rate); (g · h / mol) = 1.5. / CO = 2) Flow rate) was adjusted, and the compositions of the supply gas and the autoclave outlet gas were determined by gas chromatography to obtain CO conversion rate, CH ₄ selectivity, CO ₂ selectivity, and hydrocarbon productivity.

The CO conversion rate, CH ₄ selectivity, and CO ₂ selectivity described in the following examples were calculated by the following formulas, respectively.

Tables 1 to 3 summarize the impurity concentrations in the carriers and the steaming test results in Examples and Comparative Examples. In the catalyst carriers shown in Comparative Examples 1 to 5, the additive element was not V but "-(no additive)", "Al", "Mn", and "Ce".

(Example 1)
When a steaming test was performed using a catalyst carrier as shown in Table 1A, the specific surface area change rate was -41.5% and the pore volume change rate was 5.3%.
(Example 2)
When a steaming test was performed using a catalyst carrier as shown in Table 1B, the specific surface area change rate was -35.2% and the pore volume change rate was 3.3%.
(Example 3)
When a steaming test was performed using a catalyst carrier as shown in Table 1C, the specific surface area change rate was -35.2% and the pore volume change rate was 3.4%.
(Example 4)
When a steaming test was performed using a catalyst carrier as shown in Table 1D, the specific surface area change rate was -32.2% and the pore volume change rate was 1.4%.
(Example 5)
When a steaming test was performed using a catalyst carrier as shown in Table 1E, the specific surface area change rate was −29.4% and the pore volume change rate was 6.7%.
(Example 6)
When a steaming test was performed using a catalyst carrier as shown in Table 1F, the specific surface area change rate was −29.8% and the pore volume change rate was 5.8%.

(Example 7)
FT synthesis catalyst carrying 5 wt% Co using a catalyst carrier as shown in C in Table 1 (Na content: 137.1 ppm, K content: 0.1 ppm, Ca content: 9.5 ppm, Mg concentration: 0 .7 ppm, total Na, K, Ca, Mg content: 147.3 ppm) was prepared, and the FT synthesis reaction was carried out. As a result, the CO conversion rate was 11.6%, the CH ₄ selectivity was 9.8%, and the CO ₂ was selected. The hydrocarbon productivity with a rate of 0.3% and 5 or more carbon atoms was 0.3 (kg-hydrocarbon / kg-catalyst / hour).

(Example 8)
FT synthesis catalyst carrying 20 wt% Co using a catalyst carrier as shown in C in Table 1 (Na content: 115.5 ppm, K content: 0.1 ppm, Ca content: 8 ppm, Mg concentration: 0.6 ppm) , Na, K, Ca, Mg content total: 124.1 ppm) was prepared and the FT synthesis reaction was carried out. As a result, the CO conversion rate was 40.6%, the CH ₄ selectivity was 7.8%, and the CO ₂ selectivity was 0. The hydrocarbon productivity of .2% and 5 or more carbon atoms was 1.2 (kg-hydrocarbon / kg-catalyst / hour).

(Example 9)
FT synthesis catalyst carrying 50 wt% Co using a catalyst carrier as shown in C in Table 1 (Na content: 72.3 ppm, K content: 0 ppm, Ca content: 5 ppm, Mg concentration: 0.3 ppm, Na , K, Ca, Mg content total: 77.7 ppm) was prepared and the FT synthesis reaction was carried out. As a result, the CO conversion rate was 75.1%, the CH ₄ selectivity was 6.2%, and the CO ₂ selectivity was 1.3. %, The hydrocarbon productivity of 5 or more carbon atoms was 2.3 (kg-hydrocarbon / kg-catalyst / hour).

(Example 10)
FT synthesis catalyst carrying 20 wt% Co using a catalyst carrier as shown in C in Table 1 (Na content: 115.5 ppm, K content: 0.1 ppm, Ca content: 8 ppm, Mg concentration: 0.6 ppm) , Na, K, Ca, Mg content total: 124.1 ppm) was prepared and a steaming test was performed. As a result, the specific surface area change rate was -36.6% and the pore volume change rate was -4.0%. rice field.

(Example 11)
After the steaming test shown in Example 10, reduction treatment and passage were performed to carry out an FT synthesis reaction. As a result, after the steaming test shown in Comparative Example 2 (no V content, described later), reduction treatment and passage were performed. , FT synthesis reaction, and catalyst supporting 20 wt% of Co on the catalyst carrier shown in K in Table 3 (Na content: 115.5 ppm, K content: 0.1 ppm, Ca content: 8 ppm, Mg concentration. : 0.6 ppm), the CO conversion rate was doubled as compared with the case where the FT synthesis reaction was carried out by performing the reduction treatment and the passivation after the steaming test. A catalyst in which Co was carried on a catalyst carrier containing V-containing silica as a main component showed relatively high activity even after a steaming test because it had high resistance to steam even with the same composition.

(Example 12)
After the steaming test shown in Example 10, 1 g of the catalyst was dispersed in 100 ml of ion-exchanged water, and the slurry was irradiated with ultrasonic waves for 30 minutes with an ultrasonic oscillator. The particle size distribution before and after ultrasonic irradiation was measured with a Coulter counter, and the amount of increase in fine powder of 30 μm or less due to ultrasonic irradiation was confirmed. The amount was 20% less. The catalyst in which Co was carried on a catalyst carrier containing V-containing silica as a main component showed relatively high strength even after the steaming test because of its high resistance to steam.

(Example 13)
When a steaming test was performed using a catalyst carrier as shown in G in Table 2, the specific surface area change rate was -32.0% and the pore volume change rate was 3.2%.

(Example 14)
FT synthesis catalyst carrying 20 wt% Co using a catalyst carrier as shown in G in Table 2 (Na content: 195.2 ppm, K content: 0.1 ppm, Ca content: 8 ppm, Mg concentration: 0.6 ppm , Na, K, Ca, Mg content total: 203.8 ppm) was prepared and the FT synthesis reaction was carried out. As a result, the CO conversion rate was 32.0%, the CH ₄ selectivity was 8.3%, and the CO ₂ selectivity was 0. The hydrocarbon productivity of 3.3% and 5 or more carbon atoms was 0.9 (kg-hydrocarbon / kg-catalyst / hour).

(Example 15)
When a steaming test was performed using a catalyst carrier as shown in Table 2H, the specific surface area change rate was -32.6% and the pore volume change rate was 4.0%.
(Example 16)
FT synthesis catalyst carrying 20 wt% Co using a catalyst carrier as shown in H in Table 2 (Na content: 434.3 ppm, K content: 0.1 ppm, Ca content: 8 ppm, Mg concentration: 0.6 ppm) , Na, K, Ca, Mg content total: 442.9 ppm) was prepared and the FT synthesis reaction was carried out. As a result, the CO conversion rate was 34.2%, the CH ₄ selectivity was 7.9%, and the CO ₂ selectivity was 0. The hydrocarbon productivity of 3.3% and 5 or more carbon atoms was 1.0 (kg-hydrocarbon / kg-catalyst / hour).

(Example 17)
When a steaming test was performed using a catalyst carrier as shown in Table 2I, the specific surface area change rate was -32.3% and the pore volume change rate was 5.5%.
(Example 18)
FT synthesis catalyst carrying 20 wt% Co using a catalyst carrier as shown in Table 2 I (Na content: 796.8 ppm, K content: 0.1 ppm, Ca content: 8 ppm, Mg concentration: 0.6 ppm) , Na, K, Ca, Mg content total: 805.4 ppm) was prepared and the FT synthesis reaction was carried out. As a result, the CO conversion rate was 14.2%, the CH ₄ selectivity was 8.1%, and the CO ₂ selectivity was 0. The hydrocarbon productivity of 0.4% and 5 or more carbon atoms was 0.4 (kg-hydrocarbon / kg-catalyst / hour).

(Example 14)
When a steaming test was performed using a catalyst carrier as shown in Table 2J, the specific surface area change rate was -33.4% and the pore volume change rate was 8.8%.

(Comparative Example 1)
When a steaming test was performed using a catalyst carrier as shown in Table 3 K, the specific surface area change rate was -89.5% and the pore volume change rate was -25.6%.

(Comparative Example 2)
Using a catalyst carrier as shown in K in Table 3, the FT synthesis catalyst (Na content: 116 ppm, K content: 0.1 ppm, Ca content: 8 ppm, Mg concentration so that the Co-supported amount is 20 wt%). : 0.6 ppm, total Na, K, Ca, Mg content: 124.6 ppm) was prepared and a steaming test was performed. As a result, the specific surface area change rate was 51.5% and the pore volume change rate was -13.1. %Met.

(Comparative Example 3)
When a steaming test was performed using a catalyst carrier as shown in L in Table 3, the specific surface area change rate was -64.8% and the pore volume change rate was -42.1%.

(Comparative Example 4)
When a steaming test was performed using a catalyst carrier as shown in M in Table 3, the specific surface area change rate was -84.7% and the pore volume change rate was -80.1%.

(Comparative Example 5)
When a steaming test was performed using a catalyst carrier as shown in Table 3 N, the specific surface area change rate was -83.2% and the pore volume change rate was -81.9%.

(Comparative Example 6)
When a steaming test was performed using a catalyst carrier as shown in O in Table 3, the specific surface area change rate was -37.9% and the pore volume change rate was 1.7%.
(Comparative Example 7)
FT synthesis catalyst carrying 20 wt% Co using a catalyst carrier as shown in O in Table 3 (Na content: 2,390 ppm, K content: 0.1 ppm, Ca content: 8 ppm, Mg concentration: 0.6 ppm) , Na, K, Ca, Mg content total: 2,399 ppm), and the FT synthesis reaction was carried out. As a result, the CO conversion rate was 5.1%, the CH ₄ selectivity was 14.4%, and the CO ₂ selectivity was 0. The hydrocarbon productivity of 0.1% and 5 or more carbon atoms was 0.1 (kg-hydrocarbon / kg-catalyst / hour), resulting in inferior reaction activity.

Claims (14)

It is a catalyst in which cobalt is supported on a catalyst carrier containing silica as a main component, and the content of vanadium in the catalyst is 0.1 to 10.0% by mass, and sodium, potassium, calcium, and magnesium. A catalyst for producing a hydrocarbon from a synthetic gas, characterized in that the total impurity content of the above is 0.01 to 0.15% by mass. The catalyst for producing a hydrocarbon from the synthetic gas according to claim 1, wherein the carrying ratio of cobalt is 5 to 50% by mass in terms of metal. The catalyst for producing a hydrocarbon from the synthetic gas according to claim 1 or 2, wherein the content of vanadium is 0.2 to 2.0% by mass. The catalyst for producing a hydrocarbon from the synthetic gas according to any one of claims 1 to 3, wherein the catalyst carrier is spherical. The silica sol produced by mixing an aqueous alkali silicate solution and an aqueous acid solution is gelled and further dried to obtain silica.
The silica contains 0.1 to 10.0% by mass of vanadium, then dried and fired, and further, the impurity content of sodium, potassium, calcium, and magnesium becomes 0.01 to 0.15% by mass. To prepare a catalyst carrier,
A method for producing a hydrocarbon from a synthetic gas, which comprises supporting cobalt on the catalyst carrier. The method for producing a hydrocarbon from a synthetic gas according to claim 5, wherein the content of sodium in the catalyst carrier is 0.01 to 0.10% by mass. Hydrocarbon from the synthetic gas according to claim 5 or 6, wherein the catalyst is produced so that the impurity content of sodium, potassium, calcium, and magnesium is 0.01 to 0.15% by mass. A method for manufacturing a catalyst. In producing a catalyst carrier by incorporating vanadium into the silica,
A catalyst carrier is prepared by impregnating the silica with vanadium using an impregnation method, an infant wetness method, a precipitation method, or an ion exchange method, and then performing a drying treatment, a drying treatment, and a firing treatment. The method for producing a catalyst for producing a hydrocarbon from the synthetic gas according to any one of claims 5 to 7. Producing a hydrocarbon from syngas using the catalyst according to any one of claims 1 to 4 or the catalyst produced by the production method according to any one of claims 5 to 8. A method for producing a hydrocarbon from a synthetic gas characterized by. The method for producing a hydrocarbon from a synthetic gas according to claim 9, wherein the hydrocarbon is produced by a liquid phase reaction in a slurry bed. In the liquid phase reaction, the one-pass CO conversion rate, which is the CO conversion rate in a state where the catalyst amount, the synthetic gas supply amount, the reaction temperature, and the reaction pressure are adjusted and the synthetic gas is passed through the reactor only once, is 40 to 95%. The method for producing a hydrocarbon from the synthetic gas according to claim 10 . A catalyst carrier used in catalysts for producing hydrocarbons from syngas.
The main component is silica, the vanadium content is 0.1 to 10.0% by mass, and the total impurity content of sodium, potassium, calcium, and magnesium is 0.01 to 0.15% by mass. Characteristic catalyst carrier. The catalyst carrier according to claim 12, wherein the sodium content is 0.01 to 0.10% by mass. The catalyst carrier according to claim 12 or 13, wherein the content of vanadium is 0.2 to 2.0% by mass.