JP2007061770A - Catalyst for manufacturing hydrocarbon from synthesis gas, method for manufacturing catalyst, and method for manufacturing hydrocarbon from synthesis gas using catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a Fischer-Tropsch (FT) synthesis catalyst having a high productivity of manufacturing a liquid C<SB>5+</SB>hydrocarbon, a method for manufacturing the catalyst, and a method for manufacturing a hydrocarbon from a synthesis gas using the catalyst. <P>SOLUTION: The FT synthesis catalyst comprises iron, magnesium, calcium, copper and potassium, and a compound comprising at least one or two element(s) selected from molybdenum, vanadium, tungsten, niobium, boron, zirconium, zinc, chromium, manganese, and titanium, or comprising at least one compound prepared by incorporating at least one compound selected from silica and alumina into the compound prepared above. A method for manufacturing the catalyst and a method for manufacturing a hydrocarbon from a synthesis gas using the catalyst are also provided in the present invention. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a catalyst for producing hydrocarbons from synthesis gas by hydrogenating carbon monoxide, a method for producing the same, and a method for producing hydrocarbons from synthesis gas using the catalyst.

  In recent years, environmental problems such as global warming have become apparent, and H / C is higher than other hydrocarbon fuels, coal, etc., and carbon dioxide emissions that cause global warming can be suppressed. The importance of natural gas, which is abundant in volume, has been reviewed, and its demand is expected to increase in the future. Under such circumstances, after the conversion of natural gas to synthesis gas, development of technology to convert the synthesis gas into liquid hydrocarbon fuels such as kerosene and light oil with excellent transportability and handling properties using the FT synthesis reaction It is done vigorously in various places.

Since it was discovered that this FT synthesis reaction proceeds in the presence of iron-based compounds in the 1920s, iron-based catalysts have been improved, and in the 1950s it was industrialized in South Africa's Sasol (100Fe / 5Cu / 4 in this process). 2K / 25SiO ₂ has been used as a catalyst (see Non-Patent Document 1) and has reached the present. The iron-based catalyst used in this reaction is capable of handling a wide range of hydrogen / carbon monoxide synthesis gas as a raw material compared to cobalt-based catalysts that have been energetically studied in recent years. There is. In addition, a report from some research institutions (see Non-Patent Document 2) shows that when Fe / 6Mn is used as the catalyst, even if about 100 ppm of hydrogen sulfide is contained in the raw material, it is difficult to be poisoned by the catalyst. It has a feature of high resistance to sulfur poisoning. Furthermore, the liquid hydrocarbon product obtained by the FT synthesis reaction using an iron-based catalyst contains a larger amount of olefins than the product using a cobalt-based catalyst, which is the mainstream of the current development. It has a number of features such as being able to be developed not only for fuel applications but also for chemical raw materials.

  Against this background, since the 1980s, the development of iron-based catalysts that greatly surpass the performance of industrial catalysts has been actively promoted. So far, development products that surpass industrial catalysts with productivity of liquid hydrocarbons having 5 or more carbon atoms, which is an indicator of high activation of the catalyst, such as 100Fe / 10Zn / 2Cu / 4K (see Non-Patent Document 3) and 100Fe / 1.4K / 4.6Si (see Non-Patent Document 4) has been reported, but compared to cobalt-based catalysts, the productivity of liquid hydrocarbons is low, and iron-based catalysts with higher activity Development has become a major issue.

  In addition, this FT synthesis reaction is an exothermic reaction in which synthesis gas is converted into hydrocarbon using a catalyst, but it is extremely important to effectively remove reaction heat for stable operation of the plant. The reaction formats that have been proven so far include gas phase synthesis processes (fixed bed, spouted bed, fluidized bed) and liquid phase synthesis processes (slurry bed), which have their respective characteristics. A slurry bed liquid phase synthesis process, which has high removal efficiency and does not cause accumulation of high-boiling hydrocarbons produced on the catalyst and accompanying reaction tube clogging, has attracted attention and is being energetically developed.

  In general, the particle diameter of the FT synthesis reaction catalyst is preferably as small as possible from the viewpoint of reducing the possibility that the diffusion of heat and substances becomes rate-limiting. However, in the FT synthesis reaction using a slurry bed, high boiling point hydrocarbons of the generated hydrocarbons are accumulated in the reaction vessel, so that a solid-liquid separation operation between the catalyst and the product is necessarily required. If the particle diameter of the particles is too small, there arises a problem that the efficiency of the separation operation is greatly reduced. Therefore, there is an optimum particle size range for the catalyst for the slurry bed, but as shown below, the catalyst may be destroyed and powdered during the reaction, and the particle size may be reduced. Caution must be taken.

That is, the FT synthesis reaction in the slurry bed is often operated at a considerably high raw material gas superficial velocity (0.1 m / second or more), and the catalyst particles collide violently during the reaction. Insufficient wear (powder resistance) may reduce the catalyst particle size during the reaction, resulting in inconvenience in the separation operation. Furthermore, in the iron-based catalyst, the main active species is considered to be microcrystalline iron carbide formed on the iron oxide surface (see Non-Patent Document 5), and not only the catalyst powder itself but also iron oxide during the FT synthesis reaction. In some cases, cracking and pulverization are likely to occur at the interface with iron carbide, resulting in inconvenience in the separation operation as described above.
D. B. Bukuro et al. , Ind. Eng. Chem. Res. , 38 (9), 3270 (1999) Muneyoshi Yamada et al., Abstracts of Annual Meeting of Japan Petroleum Institute, 44, 128 (2002) S. Li et al. , J. et al. Catal. , 206, 202 (2002) A. P. Raje et al. , J. et al. Catal. , 180, 36 (1998) A. Zhang et al. , Am. Chem. Soc. Div. Pet. Chem. , 44 (1), 100 (1999)

  As described above, the current catalytic activity is not yet sufficient, and the development of a further highly active catalyst has been an urgent need.

  Accordingly, an object of the present invention is to provide an iron-based FT synthesis catalyst having excellent catalytic activity such as high liquid hydrocarbon productivity, a method for producing the catalyst, and a method for producing hydrocarbons using the catalyst. To do.

  In addition, during the reaction, microcrystalline iron carbide produced on the iron oxide surface is likely to be cracked or pulverized at the interface with the iron oxide, which is often a problem particularly in the slurry bed.

  Accordingly, an object of the present invention is to provide a catalyst for FT synthesis having higher catalyst strength and wear resistance and a method for producing the catalyst.

  The present invention relates to an iron-based FT synthesis catalyst having high activity, a method for producing the catalyst, and a method for producing hydrocarbons using the catalyst. Further details are as described below.

  (1) It consists of a compound having one or more of iron, magnesium, calcium, copper, and potassium, and molybdenum, vanadium, tungsten, niobium, boron, zirconium, zinc, chromium, manganese, and titanium. A catalyst for producing hydrocarbons from a characteristic synthesis gas.

  (2) The catalyst which manufactures a hydrocarbon from the synthesis gas of (1) description which contains at least any one of a silica and an alumina in the said catalyst.

(3) A method for producing the catalyst according to (1), comprising iron, magnesium, and calcium ions, and molybdenum, vanadium, tungsten, niobium, boron, zirconium, zinc, chromium, manganese, and titanium. After filtering and washing the compound produced by the precipitation method from a solution containing one or more ions, the compound after treatment and a solution containing copper and potassium ions are mixed, dried, and fired. After sizing or molding,
Alternatively, the compound after filtration and washing treatment is dried and baked, and the sized or molded compound is impregnated with a solution containing copper and potassium ions and further dried and baked. A method for producing a catalyst for producing hydrocarbons from synthesis gas.

  (4) A method for producing the catalyst according to (2), comprising iron, magnesium, and calcium ions, and molybdenum, vanadium, tungsten, niobium, boron, zirconium, zinc, chromium, manganese, and titanium. After filtering and washing the compound produced by the precipitation method from a solution containing one or two or more kinds of ions, a mixture of the treated compound and a solution containing copper and potassium ions was slurried. A method for producing a catalyst for producing hydrocarbons from synthesis gas, characterized in that at least one of silica sol and alumina sol is added to a liquid, and then formed into a spherical shape by a spray method.

  (5) A method for producing hydrocarbons from synthesis gas by bringing synthesis gas into contact with the catalyst according to (1) or (2).

  According to the present invention, an iron-based FT synthesis catalyst having a high activity and excellent catalytic activity such as high liquid hydrocarbon productivity can be produced, and a synthesis gas is brought into contact with the catalyst to produce a synthesis gas with high efficiency. Liquid hydrocarbons can be produced from

  The present invention is described in further detail below.

  The inventors of the present invention have intensively studied paying attention to the constituent elements and composition constituting the catalyst. As a result, the high productivity level of the liquid hydrocarbon can be greatly improved, and the activity is not impaired by using a specific production method. In addition, the inventors have found that it is possible to produce a high-strength catalyst with high wear resistance, and have reached the present invention.

That is, the iron-based FT synthesis catalyst of the present invention comprises a compound containing iron, magnesium, calcium, copper, and potassium, and further having one or more elements that can be compounded with iron. As a result of intensive studies by the present inventors, as an element other than iron, which is the main active ingredient, copper, which has been conventionally effective as a co-catalyst, and magnesium, magnesium and calcium suppress CO ₂ selectivity (production amount). It is effective against that. This is because magnesium and calcium are mainly present as metal oxides and show basicity, so CO ₂ produced during the FT synthesis reaction is easily adsorbed on the surface, causing a secondary reaction with hydrogen in the source gas. by CO ₂ is consumed, it is considered to have a function of suppressing CO ₂ generation. Furthermore, metal elements that can form a compound with iron, such as molybdenum, vanadium, tungsten, niobium, boron, zirconium, zinc, chromium, manganese, and titanium, are mainly composed of iron oxide as a matrix by forming a compound with iron as the main active metal. By finely depositing in the iron compound phase and finely dividing the matrix phase, it is considered that the active species of iron precipitated on the surface from the iron compound phase is finely dispersed on the catalyst surface and the catalytic activity is improved.

  Further, another iron-based FT synthesis catalyst of the present invention includes iron, magnesium, calcium, copper, and potassium, and a compound having one or more elements that can be compounded with iron, silica, alumina. It is a compound containing at least 1 type of oxide chosen from these.

  Here, silica and alumina oxides are often used in catalytic reaction fields as catalyst carriers. However, as a result of intensive studies by the present inventors, it was found that the FT synthesis reaction proceeds at a higher reaction rate by containing each oxide of silica and alumina. This is because the oxides of silica and alumina alone or both are contained in the above compound so that the oxides of silica and alumina are iron, magnesium, calcium, copper and potassium, and molybdenum, vanadium, tungsten and niobium. , Boron, zirconium, zinc, chromium, manganese, titanium, and the crystal phase of the compound centered on an oxide containing one or more elements is further finely divided and highly dispersed in the compound solid phase. From this, it is presumed that the active species of iron precipitated on the surface from each crystal phase can be expressed by a more highly dispersed state.

  In any of the catalysts for FT synthesis of the present invention, iron as a main active component exists mainly as iron oxide before the reaction, but it is activated by circulating synthesis gas under a constant temperature. As a result, it is considered that a part of them changes to microcrystalline iron carbide and exhibits a catalytic function.

Furthermore, the catalyst of the present invention is an oxide, a carbonic acid compound, a nitric acid compound, a sulfuric acid compound, characterized in that the iron element content in the compound (in the catalyst) is 1 to 60% by mass, or these Is a mixture of these compounds. Here, when the content of the iron element is less than 1% by mass with respect to the total amount, the catalytic activity is not sufficient, and when the content exceeds 60% by mass, the functions of other components added as a co-catalyst are present. There is a problem that the catalyst cannot be sufficiently exhibited and a highly active catalytic activity that suppresses the amount of CO ₂ generated cannot be sufficiently obtained. Further, the content of the iron element in the compound is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.

And the catalyst of this invention is characterized by the content of the magnesium element in a compound being 1-50 mass%. Here, when the content of the magnesium element is less than 1% by mass, it is not preferable because the function of suppressing the amount of generated CO ₂ exerted by showing the basicity of magnesium as an oxide is not sufficient. On the other hand, when the content of magnesium element exceeds 50% by mass, the content of catalytically active iron is reduced, so that the catalytic activity is not sufficient.

Furthermore, the catalyst of the present invention is characterized in that the content of calcium element in the compound is 1 to 50% by mass. Here, when the content of the calcium element is less than 1% by mass, it is not preferable because the function of suppressing the amount of CO ₂ generation exerted by the calcium being basic as an oxide is not sufficient as in the case of magnesium. On the other hand, when the content of calcium element exceeds 50% by mass, the content of catalytically active species of iron decreases, so that the catalytic activity is not sufficient.

  In addition, the catalyst of the present invention is characterized in that the content of copper element in the compound is 0.01 to 10% by mass. Here, when the content of the copper element is less than 0.01% by mass, it promotes the reduction of iron, which is mainly in an oxide state in the compound, to metallic iron or iron carbide in a synthesis gas atmosphere. The function as a co-catalyst cannot be sufficiently exhibited, and the catalytic activity does not increase. Further, when the content of the copper element exceeds 10% by mass, the content of the catalytically active species of iron is reduced accordingly, so that the catalytic activity is lowered.

  And the catalyst of this invention is 0.01-10 mass% of content of the potassium element in a compound, It is characterized by the above-mentioned. Here, when the content of potassium element is less than 0.01% by mass, as in the case of copper, iron existing mainly in an oxide state in the compound is reduced to metallic iron or iron carbide in a synthesis gas atmosphere. The function as a co-catalyst for promoting the formation of the catalyst cannot be sufficiently exhibited, and the catalytic activity does not increase. In addition, when the content of potassium element exceeds 10% by mass, the content of catalytically active species of iron is reduced accordingly, so that the catalytic activity is lowered.

  In addition, the catalyst of the present invention is characterized in that the total content of elements that can be compounded with one or two or more kinds of iron in the compound is 1 to 50% by mass. Here, if the total content of elements that can be compounded with iron is less than 1% by mass, high activity may not be obtained. Further, when the total content of elements that can be compounded with iron exceeds 50% by mass, the content of iron as a catalytically active species becomes too small, and the catalytic activity is lowered.

  In addition to the above elements, inevitable impurities that are mixed in the catalyst manufacturing process or the like may be included. However, from the viewpoint of improving the catalyst activity, it is preferable that the amount of impurities is small, and it is desirable that impurities are not mixed as much as possible.

  The catalyst of the present invention is a powder, a molded product, or a molded product, and is preferably sieved so that the average particle size is 10 μm to 1 mm. When the average particle size is less than 10 μm, the efficiency of the solid-liquid separation operation between the catalyst and the product may be greatly reduced. On the other hand, when the average particle diameter exceeds 1 mm, the surface area becomes small and the catalytic activity cannot be sufficiently exhibited, which is not preferable. Here, the particle diameter is a value measured by a laser diffraction method.

And the catalyst of this invention is manufactured so that the specific surface area may be 10-500 m < ² > / g. In general, the larger the specific surface area of the catalyst, the more advantageous in order to develop good catalytic activity. However, if the specific surface area is larger than 500 m ² / g, the catalyst strength is lowered, which is not preferable. On the other hand, if the specific surface area is smaller than 10 m ² / g, the efficiency of contribution of the active metal to the reaction is lowered, so that sufficient catalytic activity may not be obtained. And more preferably, it is 20-400 m < ² > / g. Here, the specific surface area is a measured value obtained by the BET method by adsorption / desorption of nitrogen gas.

  On the other hand, as a result of intensive studies by the present inventors on the production method of the catalyst for FT synthesis of the present invention, it is a production method that satisfies the above requirements, and is iron, magnesium, calcium, and one or two of the aforementioned The solution containing the ions of the element that can be compounded with iron as described above is filtered and washed with the compound produced by the precipitation method, and then the solution containing the ions of copper and potassium is mixed to adhere the copper and potassium to the surface of the compound. Is. In addition, the precipitation method said here is a compound containing the target component in the state of hydroxide or the like by controlling the pH to the solution containing the target component ion using a precipitant and adjusting the solubility product constant. It is to be formed.

  Here, the compound obtained by precipitation is filtered and washed because of the precipitant component existing in the precipitation liquid, iron, magnesium, and calcium, and the elements that can be compounded with one or more kinds of iron as described above. This is because the anion component in each raw material compound used when the ions are made into a solution is removed.

  In addition, the solution containing the copper and potassium ions is attached to the surface of the filtered and washed compound produced by the precipitation method here, taking in a very small amount of copper and potassium as described above in the precipitation process. This is to ensure that it is supported on the surface of the precipitate without being damaged.

  The term “adhesion” as used herein refers to precipitates from a solution containing iron, magnesium, calcium, and an element that can be compounded with one or more kinds of iron as described above, in a slurry or cake containing moisture. In a state, it is physically mixed with a solution containing copper and potassium ions, and the water is evaporated while stirring under heating, or the precipitate is dried and baked, and then sieved. By immersing the granulated powder or a molded body molded by a compression molding machine as necessary in a solution containing copper and potassium ions, and evaporating water under heating, iron, magnesium, calcium, and It means that copper and potassium are supported on the compound composed of an element that can be compounded with one or two or more kinds of iron as described above.

  Finally, the compound obtained here is calcined at a temperature equal to or higher than the reaction temperature of the FT synthesis reaction, and the calcining temperature is preferably in the range of 200 to 1200 ° C. A calcination temperature of less than 200 ° C. is not preferable because the temperature is too low and sintering does not proceed and high catalytic activity cannot be obtained. On the other hand, when the calcination temperature exceeds 1200 ° C., the surface area of the compound obtained by excessive sintering is reduced, and high catalytic activity cannot be obtained.

  In addition, each compound of iron, magnesium, calcium, copper, potassium, and an element that can be compounded with iron used as a starting material in this production method is not particularly limited as long as each component can be made into an aqueous solution as an ion. For example, inorganic compounds such as nitrates, hydroxides, carbonates, sulfates and halides, and organic compounds such as acetates are preferably used.

  In the precipitation step, since the pH and temperature during precipitation greatly affect the pore structure, crystal size, etc. of the formed precipitate, a uniform compound can be formed by controlling and maintaining each condition. Therefore, it is preferable to control the pH of the precipitation solution in the range of 6 to 10 and the temperature in the range of room temperature to 90 ° C, and the pH of the solution is in the range of 7 to 9 and the temperature in the range of 50 to 80 ° C. preferable. When the precipitation is carried out under a condition where the pH is greater than 9, it depends on the kind of the precipitant, but it is less preferred since it may form a complex compound to increase the solubility and hardly generate a precipitate. On the other hand, when the pH is smaller than 7, the solubility of the target component in water tends to be high and precipitation does not easily occur.

  Furthermore, when the temperature is lower than 50 ° C., it may be difficult to dissolve each starting material of elements that can be compounded with iron, magnesium, calcium, and iron at a high concentration. On the other hand, when the temperature is higher than 80 ° C., the solubility becomes high and precipitation is unlikely to occur, which may reduce the yield.

  Here, as the precipitating agent, an aqueous sodium carbonate solution, aqueous ammonia or the like is preferably used, but is not particularly limited thereto.

  Furthermore, as a result of intensive studies by the present inventors, as a method for producing a high-strength catalyst that prevents pulverization during the reaction of the catalyst, at least one of silica sol and alumina sol is added to the solution containing the compound produced by the precipitation method. After the addition, it is formed into a spherical shape by a spraying method. At least one of the silica sol and the alumina sol added here functions as a binder that binds the precipitate particles to form a spherical shape, and changes to silica and alumina after firing to promote the above-described FT synthesis reaction. Take on. In the compound after the final molded powder is fired, the added silica sol and alumina sol exist as silica and alumina, respectively, but the silica sol and alumina sol are added to the solution containing the compound produced by the precipitation method at the time of molding. The ratio is preferably such that the content of at least one of silica and alumina in the compound finally obtained after firing is 1 to 90% by mass. When the addition amount of at least one of silica sol and alumina sol is less than 1% by mass in the content of at least one of silica and alumina of the compound after firing, the addition effect is hardly seen, which is not preferable. Further, when the addition amount of at least one of silica sol and alumina sol exceeds 90 mass% in the content of at least one of silica and alumina in the compound after firing, the content of iron as a catalytically active species Therefore, the catalyst activity is not sufficiently obtained, which is not preferable.

  Next, the FT synthesis reaction using the iron-based FT synthesis catalyst of the present invention will be described. That is, as a metal component described above, a compound comprising an element that can be compounded with iron, magnesium, calcium, copper, potassium, iron, or a compound containing at least one of silica and alumina in this compound is used as a catalyst, and synthesis gas is used for this. Contact is made to produce hydrocarbons from synthesis gas.

  That is, the catalyst is filled in the reaction tank and the synthesis gas is circulated, and any of a fixed bed, a spouted bed, a fluidized bed, and a slurry bed can be suitably used as the reaction tank.

  Here, the synthesis gas refers to a gas in which the total of hydrogen and carbon monoxide, for example, produced by converting natural gas or the like is 50% by volume or more of the total, and for the iron-based FT synthesis catalyst of the present invention. The molar ratio of hydrogen and carbon monoxide (hydrogen / carbon monoxide) in the synthesis gas is preferably in the range of 0.5 to 4.0. When the molar ratio of hydrogen to carbon monoxide is less than 0.5, the amount of hydrogen present in the raw material gas is too small, so that the hydrogenation reaction of carbon monoxide (FT synthesis reaction) is difficult to proceed, and liquid carbonization This is not preferable because the productivity of hydrogen does not increase. When the molar ratio of hydrogen to carbon monoxide exceeds 4.0, the amount of carbon monoxide present in the raw material gas is too small, so that the productivity of liquid hydrocarbons does not increase regardless of the catalyst activity. Is not preferable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

Example 1
13.4 g of iron nitrate, 25.6 g of magnesium nitrate, 2.4 g of calcium nitrate and 0.6 g of vanadium pentoxide are precisely weighed and added to 300 cc of water to prepare a mixed aqueous solution under heating, and the solution is stirred with a stirrer. In this state, an aqueous ammonia solution was gradually added so as to maintain the temperature of the liquid component (precipitation liquid) at the time of precipitation at 60 ° C. and pH of 8, thereby forming a precipitate. Thereafter, the mixture was aged by continuing stirring for 1 hour while being kept at 60 ° C., and then allowed to stand at room temperature for 2 hours, and the precipitate was filtered and washed. To the precipitate (compound), 0.08 g of copper nitrate and 0.34 g of potassium nitrate were precisely weighed, and a mixed aqueous solution prepared by adding to 10 cc of water was added and mixed well. The slurry thus obtained was dried at 120 ° C. for 12 hours and then calcined in air at 400 ° C. for 4 hours to obtain a compound (mainly oxide) having a molar ratio of 100Fe / 300Mg / 30Ca / 1Cu / 10K / 10V. It was.

The compound powder was pressed at 600 kg / cm ² with a compression molding machine, and then sufficiently pulverized to adjust the particle size to 22 to 42 mesh (355 to 710 μm) to prepare a catalyst. The specific surface area of this preparation was 124 m ² / g.

Using 0.5 g of the catalyst prepared in this manner, 30 mL of FT wax (FT-100: manufactured by Nippon Seiki) as a solvent was charged into an autoclave with an internal volume of 100 mL, and then 270 ° C. and 0.1 MPa (absolute pressure). While rotating the stir bar at 800 min ⁻¹ , the synthesis gas (67% hydrogen, 33% carbon monoxide, H ₂ / CO = 2) was passed for 1 h at 100 ml / min to activate the catalyst. After processing to form iron carbide on the catalyst surface, the pressure in the autoclave is increased to 2.0 MPa-G (gauge pressure), and the synthesis gas is W (catalyst mass) / F (synthesis gas flow rate) = The FT synthesis reaction was carried out under conditions of 2.5 (g · h / mol). The performance of the catalyst was judged by CO conversion, CH ₄ selectivity, CO ₂ selectivity, and C ₅₊ liquid hydrocarbon productivity, which were calculated from the concentration of each component in the outlet gas by the following formula.

C ₅₊ liquid hydrocarbon productivity (g / kg-cat.h) = [unit mass of catalyst, number of CO moles per unit time] × [CO conversion rate] × [1- (C ₁ -C ₄ selectivity) ] × [Average molecular weight of hydrocarbon (= 14)]
Was subjected to FT synthesis reaction under such conditions, the results shown in Table 1 were obtained, it was confirmed that C ₅₊ productivity is high and CO ₂ selectivity exerts a relatively low high activity performance .

(Example 2)
Except that the molar ratio of the product finally obtained by using 5 (NH ₄ ) ₂ O · 12WO ₃ · 5H ₂ O instead of vanadium is 100Fe / 300Mg / 30Ca / 1Cu / 10K / 10W The compound was prepared as in 1. The specific surface area of this preparation was 118 m ² / g. When an FT synthesis reaction was carried out using this compound, the results shown in Table 1 were obtained, and it was confirmed that the C ₅₊ productivity was high and the CO ₂ selectivity was relatively low, exhibiting highly active performance.

(Example 3)
The compound is obtained in the same manner as in Example 1 except that boric acid (H ₃ BO ₃ ) is used instead of vanadium and the molar ratio of the final product is 100Fe / 300Mg / 30Ca / 1Cu / 10K / 10B. Prepared. The specific surface area of this preparation was 107 m ² / g. When the FT synthesis reaction was carried out using this compound, the results shown in Table 1 were obtained, and it was confirmed that the C5 ₊ productivity was high and the CO ₂ selectivity was relatively low, exhibiting a highly active performance. It was.

Example 4
The same as in Example 1 except that the molar ratio of the product finally obtained using zirconium nitrate oxide (ZrO (NO ₃ ) ₂ ) instead of vanadium is 100Fe / 300Mg / 30Ca / 1Cu / 10K / 10Zr. The compound was prepared. The specific surface area of this preparation was 95 m ² / g. When the FT synthesis reaction was carried out using this compound, the results shown in Table 1 were obtained, and it was confirmed that the C5 ₊ productivity was high and the CO ₂ selectivity was relatively low, exhibiting a highly active performance. It was.

(Example 5)
The same as in Example 1 except that zinc nitrate (Zn (NO ₃ ) ₂ ) is used instead of vanadium and the molar ratio of the product finally obtained is 100Fe / 300Mg / 30Ca / 1Cu / 10K / 10Zn. The compound was prepared. The specific surface area of this preparation was 102 m ² / g. When an FT synthesis reaction was carried out using this compound, the results shown in Table 1 were obtained, and it was confirmed that the C ₅₊ productivity was high and the CO ₂ selectivity was relatively low, exhibiting highly active performance.

(Example 6)
A compound was prepared in the same manner as in Example 1 except that NH ₄ NbF ₆ was used instead of vanadium and the final product molar ratio was 100Fe / 300Mg / 30Ca / 1Cu / 10K / 10Nb. The specific surface area of this preparation was 95 m ² / g. When the FT synthesis reaction was carried out using this compound, the results shown in Table 1 were obtained, and it was confirmed that the C5 ₊ productivity was high and the CO ₂ selectivity was relatively low, exhibiting a highly active performance. It was.

(Example 7)
Compound similar to Example 1 except that (NH ₄ ) ₆ Mo ₇ O ₂₄ is used instead of vanadium and the molar ratio of the product finally obtained is 100Fe / 300Mg / 30Ca / 1Cu / 10K / 10Mo Was prepared. The specific surface area of this preparation was 88 m ² / g. When the FT synthesis reaction was carried out using this compound, the results shown in Table 1 were obtained, and it was confirmed that the C5 ₊ productivity was high and the CO ₂ selectivity was relatively low, exhibiting a highly active performance. It was.

(Example 8)
The compound obtained in the same manner as in Example 1 except that the molar ratio of the product finally obtained using chromium (III) nitrate nonahydrate instead of vanadium is 100Fe / 300Mg / 30Ca / 1Cu / 10K / 10Cr. Was prepared. The specific surface area of this preparation was 90 m ² / g. Was subjected to FT synthesis reaction using the present compounds, the results shown in Table 2 is obtained, it is confirmed that the C ₅₊ productivity is high and CO ₂ selectivity exerts a relatively low high activity performance It was.

Example 9
A compound was prepared in the same manner as in Example 1 except that manganese nitrate was used instead of vanadium and the molar ratio of the product finally obtained was 100Fe / 300Mg / 30Ca / 1Cu / 10K / 10Mn. The specific surface area of this preparation was 112 m ² / g. Was subjected to FT synthesis reaction using the present compounds, the results shown in Table 2 is obtained, it is confirmed that the C ₅₊ productivity is high and CO ₂ selectivity exerts a relatively low high activity performance It was.

(Example 10)
A compound was prepared in the same manner as in Example 1 except that titanium sulfate was used instead of vanadium and the molar ratio of the product finally obtained was 100Fe / 300Mg / 30Ca / 1Cu / 10K / 10Ti. The specific surface area of this preparation was 105 m ² / g. Was subjected to FT synthesis reaction using the present compounds, the results shown in Table 2 is obtained, it is confirmed that the C ₅₊ productivity is high and CO ₂ selectivity exerts a relatively low high activity performance It was.

(Example 11)
To the slurry prepared to be 100Fe / 300Mg / 30Ca / 1Cu / 10K / 10V in the same manner as in Example 1, the silica sol was added so that the SiO _{2 in} the catalyst after calcination was 20% by mass, A slurry was prepared. Thereafter, spray drying was carried out under conditions such that the average particle diameter was about 50 μm, and the powder obtained was calcined at 400 ° C. in air for 4 hours. The specific surface area of this preparation was 280 m ² / g. Was subjected to FT synthesis reaction using the present compounds, the results shown in Table 2 is obtained, it is confirmed that the C ₅₊ productivity is high and CO ₂ selectivity exerts a relatively low high activity performance It was. Regarding this preparation, the catalyst after the reaction and after the reaction for 500 hours was collected and the particle size distribution was measured. The mass ratio of the particles of 20 μm or less was 0.28% before the reaction and after the reaction for 500 hours. Was almost the same as 0.32%, and the preparation was extremely small to be broken or pulverized in the reaction.

(Example 12)
Addition of alumina sol to slurry prepared to be 100Fe / 300Mg / 30Ca / 1Cu / 10K / 10V in the same manner as in Example 1 so that Al ₂ O _{3 in} the catalyst after calcination is 20% by mass And a slurry was prepared. Thereafter, spray drying was carried out under conditions such that the average particle diameter was about 50 μm, and the powder obtained was calcined at 400 ° C. in air for 4 hours. The specific surface area of this preparation was 265 m ² / g. Was subjected to FT synthesis reaction using the present compounds, the results shown in Table 2 is obtained, it is confirmed that the C ₅₊ productivity is high and CO ₂ selectivity exerts a relatively low high activity performance It was. Regarding this preparation, the catalyst before the reaction and after the reaction for 500 hours was collected and the particle size distribution was measured in the same manner as in Example 11. The mass ratio of particles of 20 μm or less was 0.33 before the reaction. %, After 500 hours of reaction, it was almost the same as 0.38%, and the preparation was extremely small to be broken or pulverized during the reaction.

(Example 13)
An aqueous solution obtained by adding the same 5 (NH ₄ ) ₂ O · 12WO ₃ · 5H ₂ O as in Example 2 to the same mixed aqueous solution as in Example 1 was prepared, and finally precipitated by the same manner as in Example 1. A compound was prepared in the same manner as in Example 1 except that the molar ratio of the obtained product was 100Fe / 300Mg / 30Ca / 1Cu / 10K / 10V / 10W. The specific surface area of this preparation was 112 m ² / g. Was subjected to FT synthesis reaction using the present compounds, the results shown in Table 2 is obtained, it is confirmed that the C ₅₊ productivity is high and CO ₂ selectivity exerts a relatively low high activity performance It was.

(Comparative Example 1)
The industrial catalysts (100Fe / 5Cu / 4.2K / 25SiO 2) equivalent was prepared as follows. That is, iron nitrate, copper nitrate, and tetraethoxysilane were precisely weighed so that the molar ratio of each metal element was 100: 5: 25, a mixed solution was prepared under heating, and the solution was stirred with a stirrer. In this state, an aqueous ammonia solution was gradually added so as to maintain the temperature of the aqueous solution at 60 ° C. and the pH at 9, thereby forming a precipitate. Thereafter, the mixture was aged by continuing stirring for 1 hour while being kept at 60 ° C., and then allowed to stand at room temperature for 2 hours, and then the precipitate was filtered. A potassium nitrate aqueous solution was mixed with the precipitate. The slurry thus obtained was dried at 120 ° C. for 12 hours and then calcined in air at 400 ° C. for 4 hours to obtain a compound having the above molar ratio. The compound powder was pressed at 600 kg / cm ² with a compression molding machine, and then sufficiently pulverized to adjust the particle size to 22 to 42 mesh (355 to 710 μm) to prepare a catalyst. When this compound was used to carry out the FT synthesis reaction in the same manner as in Example 1, the results shown in Table 2 were obtained, and the CO ₂ selectivity was high and the C ₅₊ liquid hydrocarbon productivity was low. Was confirmed.

(Comparative Example 2)
Among the highly active catalysts under development, a developed catalyst (100Fe / 1.4K / 4.6Si) equivalent product shown in Non-Patent Document 4 was prepared as follows. That is, iron nitrate and tetraethoxysilane are precisely weighed so that the molar ratio of each metal element is 100: 4.6, a mixed solution is prepared under heating, and the solution is stirred with a stirrer. Aqueous ammonia solution was gradually added so as to maintain the temperature of the aqueous solution at 60 ° C. and the pH at 9, thereby forming a precipitate. Thereafter, the mixture was aged by continuing stirring for 1 hour while being kept at 60 ° C., and then allowed to stand at room temperature for 2 hours, and then the precipitate was filtered. A potassium nitrate aqueous solution was mixed with the precipitate. The slurry thus obtained was dried at 120 ° C. for 12 hours and then calcined in air at 400 ° C. for 4 hours to obtain a compound having the above molar ratio. The compound powder was pressed at 600 kg / cm ² with a compression molding machine, and then sufficiently pulverized to adjust the particle size to 22 to 42 mesh (355 to 710 μm) to prepare a catalyst. Using this compound, the FT synthesis reaction was carried out in the same manner as in Example 1. As a result, the results shown in Table 2 were obtained, and the C ₅₊ liquid hydrocarbon productivity was higher than that of the industrial catalyst. It was confirmed that ₂ selectivity will become very large.

Claims (5)

  It is composed of a compound having one or more of iron, magnesium, calcium, copper, and potassium, and molybdenum, vanadium, tungsten, niobium, boron, zirconium, zinc, chromium, manganese, and titanium. Catalyst that produces hydrocarbons from synthesis gas.   The catalyst for producing hydrocarbons from synthesis gas according to claim 1, wherein the catalyst contains at least one of silica and alumina. A method for producing the catalyst according to claim 1, wherein iron, magnesium, and calcium ions, and one or two of molybdenum, vanadium, tungsten, niobium, boron, zirconium, zinc, chromium, manganese, and titanium. After filtering and washing the compound produced by the precipitation method from a solution containing more than one species of ions, the compound after treatment and a solution containing copper and potassium ions are mixed, dried, baked, and adjusted. Grain or mold,
Alternatively, the compound after filtration and washing treatment is dried and fired, and then the sized or molded compound is impregnated with a solution containing copper and potassium ions and further dried and fired. A method for producing a catalyst for producing hydrocarbons from synthesis gas.   3. A method for producing a catalyst according to claim 2, wherein one or two of iron, magnesium and calcium ions and molybdenum, vanadium, tungsten, niobium, boron, zirconium, zinc, chromium, manganese and titanium are used. After filtering and washing the compound produced by the precipitation method from a solution containing more than one species of ions, the mixture of the compound after treatment and a solution containing copper and potassium ions is slurried into a slurry of silica sol A method for producing a catalyst for producing hydrocarbons from synthesis gas, comprising adding at least one of alumina sol and then forming a spherical shape by a spray method.   A method for producing hydrocarbons from synthesis gas by bringing synthesis gas into contact with the catalyst according to claim 1.