KR101026536B1 - Fe-based catalyst for the reaction of Fischer-Tropsch synthesis and preparation method thereof - Google Patents

Abstract

The present invention relates to an iron-based catalyst for Fischer-Tropsch synthesis (FTS) reaction and a method for preparing the same. More specifically, the present invention relates to iron on a cerium-zirconium oxide support prepared by a sol-gel method. The present invention relates to a novel catalyst having potassium as an active ingredient supported by one or more enhancer metals selected from copper, manganese, and cobalt, and a method for producing the same, using as a main component.

The iron-based catalyst according to the present invention is able to secure stable catalytic activity for a long time when applied to Fischer-Tropsch synthesis reaction using syngas, and exhibits high conversion of carbon monoxide and low selectivity for methane, which is a major byproduct. It is excellent in improving the yield of high boiling point hydrocarbons and light olefins (C ₂ -C ₄ light hydrocarbons).

Fischer-Tropsch Synthesis (FTS) reaction, iron, cerium-zirconium oxide, high boiling hydrocarbons, light olefins, sol-gel methods

Description

Fe-based catalyst for the reaction of Fischer-Tropsch synthesis and preparation method

The present invention relates to an iron-based catalyst for Fischer-Tropsch synthesis (FTS) reaction and a method for producing the same.

The technology of converting liquid hydrocarbons using syngas starts with the reaction of producing syngas through reforming of natural gas and gasification such as coal and biomass. In general, Fischer-Tropsch synthesis (FTS) reaction is a reaction for generating hydrocarbon compounds from syngas and is performed by the following main representative reactions on iron-based and cobalt-based catalysts.

(1)

(One)

(2)

(2)

(3)

(3)

The water-gas shift (WGS) reaction of the reaction formula (2), which is in competition with the FTS reactions of the reaction schemes (1) and (3), results in carbon dioxide being reacted with carbon monoxide and water generated from the reaction scheme (1). And hydrogen is generated. Therefore, the water produced in Scheme (1) changes the ratio of hydrogen and carbon monoxide in the entire Fischer-Tropsch synthesis reaction, which is known to occur particularly well on the iron-based catalyst having excellent WGS reaction activity. As the catalyst used in the Fischer-Tropsch process, catalysts of different components are used depending on reaction conditions and desired products. As a representative example thereof, as a main active component of the catalyst, one or more components selected from Group 7A (cobalt, ruthenium, iron, or nickel) on the standard periodic table, and components used as additionally added enhancers or structural stabilizers, etc. Fischer-Tropsch catalysts have been reported to be manufactured and used using at least one or more of elements of Group 3A, Group 4A, Group 5A, Group 6A, etc., and Group 1B elements in the phases. [US Patent No. 7067562] B2].

In the Fischer-Tropsch synthesis reaction, the distribution of the product varies depending on the main active ingredient. However, in general, the Fischer-Tropsch synthesis reaction exhibits excellent reaction activity when the H ₂ / CO ratio is 2.0. This is explained by the Schulz-Flory mechanism. However, as is well known, the Fischer-Tropsch synthesis reaction using iron-based catalysts is predominantly due to its activity against high water gas shift reactions, resulting in the addition of hydrogen to the broad H ₂ / CO The Fischer-Tropsch synthesis reaction using the cobalt system has a superior H ₂ / CO molar ratio because the reaction of Scheme (1) is superior and the activity of the water gas conversion reaction is small while the activity of the molar ratio (0.7 to 2.0) is excellent. It is characterized by excellent activity at (˜2.0). In addition, the iron-based catalyst in the Fischer-Tropsch synthesis reaction can be manufactured at a lower cost than the cobalt-based catalyst, has a unique high catalytic activity by the WGS reaction, and due to the high water gas shift reaction activity, coal and Fisher, even when using synthesis gas (H ₂ / CO <1.0) of the lower H ₂ / CO molar ratio that is generated from biomass-to add in the advantage of being conducted to Tropsch reaction smoothly to adjust the H ₂ / CO ratio There is an advantage that does not require the introduction of a process for. Thus, when the Fischer-Tropsch reaction is performed using an iron-based catalyst having excellent activity for water gas conversion, it is an excellent advantage for the process development for the treatment of syngas having a low H ₂ / CO molar ratio. It has

On the other hand, the cobalt-based catalyst has a disadvantage in that it exhibits excellent catalytic activity only when the H ₂ / CO molar ratio generated from natural gas is about -2.0, but the cobalt-based catalyst is used in the Fischer-Tropsch synthesis reaction. Compared to iron-based catalysts, the reaction proceeds at low temperatures, which is advantageous in producing paraffinic hydrocarbons such as liquids and waxes, and selectively requires hydrocarbons (naphtha, diesel, and waxes) by additional hydrotreating. The manufacturing process is required. On the other hand, iron-based catalysts used at high temperatures have the advantage of being able to be used as a raw material for producing various chemical products or petrochemical products by utilizing the direct formation reaction of mainly C ₂ -C ₄ olefins.

In general, iron-based catalysts for Fischer-Tropsch synthesis reactions are manufactured and used by melting or precipitation. In the case of using the precipitation method, the iron catalyst precipitated in the aqueous solution is composed of iron hydroxide and iron oxide, and is used to prepare an iron-based catalyst after washing, drying and firing. The iron-based catalyst prepared by the precipitation method can produce a liquid product having a high boiling point in the slurry reactor, but has a disadvantage in that the activity of the catalyst due to abrasion of the catalyst decreases. However, iron-based catalysts prepared by melting iron ore are generally used with cocatalysts, and have good catalytic resistance but low catalytic activity compared to catalysts prepared by precipitation. Only half this is reported [Fuel Processing Technology 30 (1992) 83]. In addition, iron-based catalysts for Fischer-Tropsch synthesis reactions can also be prepared by the spray-drying method, in which case the wear resistance of the catalyst is improved and the catalyst activity is not significantly affected. It has been reported to improve the physical strength of the catalyst without the need [Industrial & Engineering Chemistry Research 40 (2001) 1065).

In general, iron-based catalysts are prepared by including one or more cocatalysts to assist in the adsorption capacity of CO or reducing iron. In particular, the addition of potassium (potassium) to the iron-based catalyst is known to increase the yield for high molecular weight high boiling hydrocarbons. The effects of potassium on the behavior of iron-based catalysts can be summarized as follows.

1) The α value is increased by increasing the average molecular weight of the hydrocarbon product and the selectivity of the olefin is increased by increasing the ratio to olefin / paraffin in the hydrocarbon product.

2) It helps to suppress the deactivation of the catalyst, the optimal potassium concentration increases the activity of the Fischer-Tropsch synthesis reaction and has the advantage of reducing the selectivity of methane.

In addition, in the case of copper used as a promoter, it is known to have an effect of improving the reducibility of iron. However, copper is more effective than potassium in the Fischer-Tropsch reaction rate because it promotes the reducibility of iron, but decreases the activity for the water gas shift reaction, and therefore uses a synthesis gas with a low H ₂ / CO molar ratio ( In the case of using coal and biomass), there is a disadvantage in that it is not possible to maintain a suitable H ₂ / CO ratio for the Fischer-Tropsch synthesis during the reaction. To compensate for this, a method of selectively synthesizing C ₅₊ hydrocarbons at a high conversion rate of carbon monoxide using copper and metal elements of Groups 1A or 2A as a promoter for iron-manganese without support has been reported [ United States Registered Patent # 5118715].

It is important to maintain a large specific surface area in order to increase the dispersibility of active ingredient particles and increase the activity of iron as an active ingredient during the preparation of the catalyst. do. In the case of silica, which is mainly used as a binder, it is mainly used in a fixed bed reactor by adding iron to the catalyst after precipitation of the iron component. When silica is included in the iron-based catalyst for Fischer-Tropsch synthesis, the concentration of the active ingredient generally decreases with the increase in the amount of the support, but the dispersity of the metal is maintained to increase the concentration of the active metal ingredient iron. It is known to have an effect. In addition, previous studies have been reported to improve the selectivity for light olefins by co-precipitating cobalt in iron-based catalyst components for Fischer-Tropsch synthesis reactions in slurry reactors. Catalysis A: General 296 (2005) 222]. In order to improve the reactivity of the catalyst and to ensure long-term performance of the iron-based catalyst, it is reported that it is desirable to add potassium, copper, manganese, and the like, which are finally enhancers.

On the other hand, according to the previous research results of the team, a zeolite-containing iron-based catalyst was used as a catalyst system used in the Fischer-Tropsch synthesis reaction to increase the selectivity from syngas to high boiling hydrocarbons and light olefins. Zeolites having a specific surface area of 200 to 500 m 2 / g and a molar ratio of Si / Al of 50 or less are converted to hydrogen form, or a single metal precursor or binary metal precursor of IA, IIA, Zr, P and lanthanum is used. It has been disclosed a technique that is used by pre-treatment by ion exchange or supported by using the method [Korean Patent Publication No. 2009-0038267].

The present invention ensures high catalytic activity and stability and improves the selectivity to high boiling point hydrocarbons and light hydrocarbons, as compared to iron-based catalysts, which are generally reported as catalysts for Fischer-Tropsch synthesis reactions. Providing an iron-based catalyst is a problem to be solved.

The present invention provides a method for preparing a cerium-zirconium oxide (Ce _x Zr _1-x O ₂ ) support by a sol-gel method as a support supporting an iron catalyst and an enhancement metal. Let's do the task.

The present invention is an iron-based catalyst for the new Fischer-Tropsch synthesis reaction that can increase the dispersibility and activity of the iron catalyst, and to inhibit the deactivation of the catalyst under the Fischer-Tropsch synthesis reaction conditions to increase the long-term stability It is an object of the present invention to provide a method for producing the same.

The present invention, 100 parts by weight of the cerium-zirconium oxide support, 5 to 50 parts by weight Fe, 0 to 15 parts by weight (preferably 0.001 to 15 parts by weight), and 0.25 to 10 metal elements selected from Cu, Co and Mn The above problem is solved by providing a catalyst for Fischer-Tropsch synthesis reaction of iron-based parts by weight.

In addition, the present invention comprises the steps of preparing a cerium-containing liquid by adding a cerium precursor aqueous solution to a mixed solution of citric acid and ethylene glycol; Preparing a zirconium-containing liquid by adding an aqueous solution of zirconium precursor to a mixed solution of citric acid and ethylene glycol; Preparing a sol (Sol) by thoroughly stirring the mixed solution of the cerium-containing solution and the zirconium-containing solution at 50 to 100 ° C., and then heating at 120 to 150 ° C. to completely remove water contained in the mixed solution; Calcining the sol by heating up stepwise in a range of 100 to 500 ° C. at a temperature rising rate of 3 to 7 ° C./min; By providing a method for producing a cerium-zirconium oxide support for a Fischer-Tropsch synthesis reaction catalyst of iron series by a sol-gel reaction comprising a, to solve the above problems.

In addition, the present invention comprises the steps of preparing a cerium-containing liquid by adding a cerium precursor aqueous solution to a mixed solution of citric acid and ethylene glycol; Preparing a zirconium-containing liquid by adding an aqueous solution of zirconium precursor to a mixed solution of citric acid and ethylene glycol; Preparing a sol (Sol) by thoroughly stirring the mixed solution of the cerium-containing solution and the zirconium-containing solution at 50 to 100 ° C., and then heating at 120 to 150 ° C. to completely remove water contained in the mixed solution; Step by heating the sol step by step in a range of 100 to 500 ℃ at a temperature increase rate of 3 to 7 ℃ / min to prepare a cerium-zirconium oxide support; And impregnating the cerium-zirconium oxide support with a Fe metal precursor, a precursor of an enhancement metal (M) selected from Cu, Co, and Mn, and, if necessary, a K precursor by impregnation or coprecipitation. By providing a method for producing an iron-based Fischer-Tropsch catalyst comprising a, to solve the above problems.

The iron-based catalyst using cerium-zirconium oxide prepared by the sol-gel method proposed by the present invention as a support is used in the Fischer-Tropsch synthesis reaction to improve the conversion rate of carbon monoxide and reduce the selectivity to methane, the main byproduct. The effect of improving the yield to high boiling hydrocarbons and light olefins is excellent.

The present invention is a catalyst system suitable for the selective production of high boiling point hydrocarbons and light olefins using a synthesis gas prepared from natural gas. Iron and an enhancement metal on a cerium-zirconium oxide support prepared by the sol-gel method and Accordingly, the present invention relates to an iron-based catalyst for Fischer-Tropsch synthesis reaction prepared by supporting potassium metal by impregnation or coprecipitation.

Hereinafter, the present invention will be described in detail.

The catalyst for the Fischer-Tropsch synthesis reaction of the iron series of the present invention is based on 100 parts by weight of the cerium-zirconium oxide support, Fe 5-50 parts by weight, K 0-15 parts by weight (preferably 0.001-15 parts by weight). Parts) and 0.25 to 10 parts by weight of one metal element selected from Cu, Co and Mn. In particular, in the catalyst of the present invention, M / Fe, which is a weight ratio of the enhancement metal (M) selected from Cu, Co, and Mn with respect to iron (Fe) metal as the main active component, maintains a range of 0.05 to 0.20, and iron (Fe) K / Fe, the weight ratio of K metal to metal, is maintained in the range of 0.0 to 0.3 (preferably 0.01 to 0.3). And Ce / Zr, which is a weight ratio of Ce to zirconium (Zr) in cerium-zirconium oxide (Ce _x Zr _1-x O ₂ ) used as a support of the active ingredient, maintains a range of 0.05 to 0.50. There is this.

In general, in the Fischer-Tropsch reaction for producing liquid hydrocarbons using syngas, iron-based catalysts have been reported to exhibit wide product distribution and low olefin selectivity by the Fischer-Tropsch synthesis mechanism. The selectivity of C ₂ -C ₄ hydrocarbons is about 30%, of which the olefin selectivity is reported to be as low as about 80%. In addition, the Fischer-Tropsch synthesis reaction showed that the maximum yield of C ₂ -C ₄ hydrocarbons could not exceed 56% according to the Anderson-Schulz-Flory polymerization model due to the nature of the CH ₂ chain growth mechanism. It is known.

According to the results of the previous research of the team, Korean Patent Application Publication No. 2009-0038267 and Patent Application No. 2008-0058457 are methods for producing light olefins from syngas and secondary thermal decomposition of high boiling hydrocarbons or acid catalysts of zeolite series. A method of improving the selectivity to olefins has been reported through a method of catalytic pyrolysis using a hybrid catalyst using. In the preceding studies, methane, a by-product produced during the reaction, was used to improve the yield of C ₂ -C ₄ and to increase the carbon efficiency on the catalyst prepared by impregnating or co-precipitating an iron catalyst with a zeolite or calcium oxide support. And by recycling the carbon dioxide used in the reforming (Reforming) reaction to improve the productivity of the light olefins while presenting a method to maximize the use of by-products. For example, in Korean Patent Application No. 10-2008-0058457, the iron-based catalyst is an active ingredient in the hydrogenation reaction of carbon monoxide, and Fe is 10 to 70% by weight relative to the weight of the zeolite support, Cu is 1 to 10% by weight and K has also suggested a method of using a Fe-Cu-K-based catalyst containing 1 to 10% by weight as an active ingredient.

In the present invention, the iron-based catalyst used in the Fischer-Tropsch synthesis reaction is contained in the cerium-zirconium oxide support by impregnation or coprecipitation to minimize the selectivity to high by-products of hydrocarbons and light hydrocarbons by minimizing the selectivity to methane as a by-product. A novel catalyst system for improvement is presented.

Iron (Fe) precursors used to prepare the catalyst according to the invention include iron nitrate hydrate (Fe (NO ₃ ) ₃ H ₂ O), iron acetate (Fe (CO ₂ CH ₃ ) ₂ ), iron oxalate Fe (II) and Fe (III) precursors such as hydrate (Fe (C ₂ O ₄ ) ₃ H ₂ O), iron acetylacetonate (Fe (C ₅ H ₇ O ₂ ) ₃ ), and iron chloride (FeCl ₃ ) Can be used. In addition, copper (Cu), cobalt (Co) or manganese (Mn) metal element as an additionally used to improve the reducibility and dispersibility of iron (Fe) in the acetate, nitrate or chloride-based metal precursor compound One or a mixture of two or more selected may be used. In addition, in the present invention, potassium (K) may be additionally used as a component for improving the selectivity of the olefin, and the potassium (K) precursor may be selected from K ₂ CO ₃ , KOH, and KHCO ₃ .

The Fe-Cu (or Co, Mn) -K-based catalyst prepared by using the iron precursor, the enhancer metal precursor, and the potassium precursor is supported on the cerium-zirconium oxide support by impregnation or coprecipitation. It will be prepared. The prepared catalyst needs to be calcined in the region of 300 to 700 ° C. to stabilize the structure of the catalytically active component in advance.

Hereinafter, the method for preparing the iron-based catalyst according to the present invention described above will be described in more detail.

First, a cerium-zirconium oxide support is prepared. The preparation process of the support includes the steps of preparing a cerium-containing solution by adding a cerium precursor aqueous solution to a mixed solution of citric acid and ethylene glycol; Preparing a zirconium-containing liquid by adding an aqueous solution of zirconium precursor to a mixed solution of citric acid and ethylene glycol; The mixture containing the cerium-containing liquid and zirconium-containing liquid was stirred at 50 to 100 ° C., and then heated at 120 to 150 ° C. for 5 to 10 hours to completely remove water contained in the mixed liquid to prepare a sol. Steps; The sol is maintained at 100, 150, 200, and 300 ° C. for 0.5 to 2 hours at a heating rate of 3 to 7 ° C./min, and for 2 to 10 hours at 350 to 450 ° C., and finally at 470 to 550 ° C. Calcining stepwise to maintain for 3 to 5 hours; It is made, including.

As the cerium and zirconium precursors used for preparing the support, an acetate, nitrate or chloride-based metal precursor compound may be used. In the present invention, as an embodiment, cerium-zirconium oxide by sol-gel method using cerium nitrate (Ce (NO ₃ ) ₂ 6H ₂ O) and zirconium oxynitrate (ZrO (NO ₃ ) ₂ xH ₂ O) It presents a method of preparing. In more detail, the above-described method for preparing the support is required to dissolve the metal precursor for 20 to 50 minutes while stirring the citric acid and ethylene glycol at 40 to 70 ℃. That is, the cerium and zirconium precursors are dissolved in 10 to 30 mL of water to completely dissolve, and then slowly added to the mixed solution of citric acid and ethylene glycol, thereby preparing a cerium-containing solution and a zirconium-containing solution. Then, the mixed solution of the cerium-containing solution and zirconium-containing solution prepared above was stirred at 50 to 100 ° C. for 20 to 50 minutes, and then heated at 120 to 150 ° C. for 2 to 5 hours. By completely removing the water contained in Prepare a sol solution. Preferably, the mixed solution is heated at 120 to 150 ° C., but when the heating temperature is lower than 120 ° C., the temperature is too low to remove water. When the temperature exceeds 150 ° C., cerium- A disadvantage is that the particles of zirconium hydrate are not evenly synthesized. The sol solution prepared above was maintained at 100, 150, 200, and 300 ° C. for 0.5 to 2 hours at a heating rate of 3 to 7 ° C./min, respectively, at 350 to 450 ° C. at 2 to 3 ° C. to maximize the surface area of the support. It was maintained for 10 hours, and finally a cerium-zirconium oxide support was prepared through a stepwise firing process maintained at 470 to 550 ° C. for 3 to 5 hours. When the sol (Sol) solution was rapidly increased in firing temperature, a support having a large specific surface area could not be obtained due to entanglement of the cerium-zirconium oxide precursor, but firing was performed by sequentially raising the temperature as suggested by the present invention. In this case, a cerium-zirconium oxide support having a large specific surface area can be obtained. The cerium-zirconium oxide support prepared by the above method has a specific surface area of 5 to 50 m 2 / g. The larger the specific surface area, the better the dispersibility of the active ingredient iron and the enhancer, but the specific surface area is 5 If less than m 2 / g, the dispersibility of iron is greatly reduced. In addition, when the cerium-zirconium oxide support has a specific surface area of more than 50 m 2 / g, a problem of decreasing the strength of the catalyst may occur, so the support of the present invention needs to maintain the specific surface area. In addition, the weight ratio of the metal component of Ce / Zr in the cerium-zirconium oxide (Ce _x Zr _1-x O ₂ ) is preferably maintained in the range of 0.05 to 0.50. When the weight ratio of Ce / Zr metal is less than 0.05, ZrO the amount of acid sites of the _second increase methane and may result in the increased problem that the selectivity of by-products other than CO _2, and the weight ratio of Ce / Zr metals increase the production of favorable base point to produce a by-product, even if it exceeds 0.5 Since the generation of by-products may increase, maintaining the metal weight ratio of Ce / Zr in the region may suppress generation of by-products such as methane and at the same time suppress the deactivation of the catalyst.

On the other hand, the present invention is characterized by a method for producing an iron-based catalyst for Fischer-Tropsch reaction using a cerium-zirconium oxide support prepared by the method described above.

That is, to prepare an iron-based catalyst, adding a cerium precursor solution to the mixed solution of citric acid and ethylene glycol to prepare a cerium-containing liquid; Preparing a zirconium-containing liquid by adding an aqueous solution of zirconium precursor to a mixed liquid of citric acid and ethylene glycol; The mixture containing the cerium-containing liquid and zirconium-containing liquid was stirred at 50 to 100 ° C., and then heated at 120 to 150 ° C. for 5 to 10 hours to completely remove water contained in the mixed liquid to prepare a sol. Steps; The sol is maintained at 100, 150, 200, and 300 ° C. for 0.5 to 2 hours at a heating rate of 3 to 7 ° C./min, and for 2 to 10 hours at 350 to 450 ° C., and finally at 470 to 550 ° C. Preparing a cerium-zirconium oxide support by step firing maintained for 3 to 5 hours; And supporting the cerium-zirconium oxide support with a Fe metal precursor, a precursor of a metal (M) selected from Cu, Co, and Mn, and a K metal precursor, if necessary, by impregnation or coprecipitation. To prepare a catalyst for the iron-based Fischer-Tropsch synthesis reaction comprising a.

In more detail, the method for preparing the catalyst is described in the above-described cerium-zirconium oxide support, which is an active metal Fe metal precursor, M metal (Cu, Co and / or Mn) precursor, if necessary K metal The precursor was supported to prepare an iron catalyst for Fischer-Tropsch synthesis reaction. The Fe metal precursor is used to maintain 5 to 50 parts by weight of the iron (Fe) metal based on 100 parts by weight of the support, and the M metal (Cu, Co and / or Mn) precursor is based on 100 parts by weight of the metal (M ) Is used so that the supporting amount of 0.25 to 10 parts by weight, and the K metal precursor is such that the supporting amount of potassium (K) metal is 0 to 15 parts by weight, preferably 0.001 to 15 parts by weight based on 100 parts by weight of the support. Use as a range. At this time, M / Fe, which is the weight ratio of the metal (M) selected from Cu, Co, and Mn with respect to iron (Fe), which is a main active component, is maintained in the range of 0.05 to 0.20, and potassium (K) with respect to iron (Fe). K / Fe which is the weight ratio of a component is 0.0-0.3, Preferably it maintains the range of 0.01-0.3, and a catalyst is manufactured.

In the catalyst production method of the iron-based catalyst by the impregnation method of the present invention, the iron precursor, the M metal (Cu, Co and / or Mn) precursor introduced into the promoter, and the potassium precursor are each used simultaneously or sequentially. The catalyst for Fischer-Tropsch synthesis reaction was prepared by supporting the cerium-zirconium oxide support using the immersion method. More specifically, the iron precursor includes iron nitrate hydrate (Fe (NO ₃ ) ₃ 9H ₂ O), iron acetate (Fe (CO ₂ CH ₃ ) ₂ ), iron oxalate hydrate (Fe (C ₂ O ₄ ) One or two or more selected from Fe (II) and Fe (III) precursors composed of ₃ 6H ₂ O), iron acetylacetonate (Fe (C ₅ H ₇ O ₂ ) ₃ ), iron chloride (FeCl ₃ ), and the like. Mixed precursors can be used. Copper, cobalt or manganese precursors used as enhancers may use precursor compounds such as acetates, nitrates, oxalates, chlorides. As the potassium precursor, one or two or more mixed precursors selected from K ₂ CO ₃ , KOH, and KHCO ₃ may be used.

The iron-based catalyst prepared by the above method is dried in an oven at 100 ° C. or higher for one day, and then used in a Fischer-Tropsch synthesis reaction catalyst in the range of 300 to 700 ° C., preferably in the range of 400 to 600 ° C. It is fired and used. In this case, when the firing temperature is less than 300 ℃, the uniform dispersion of the iron and the enhancer as the active ingredient may be lowered, the reactivity may be reduced, and even if the firing temperature exceeds 700 ℃ active point due to aggregation of the active ingredient is reduced There may be a need to maintain the above area since the reactivity may be reduced.

In the catalyst preparation method of the iron series by the coprecipitation method of the present invention, the M metal (Cu, Co and Co) introduced into the iron precursor, the potassium precursor and the promoter on the slurry of cerium-zirconium oxide prepared by the sol-gel method And / or Mn) precursor may be prepared by coprecipitation under an aqueous solution so that the pH is in the range of 7 to 8, then aged in the range of 40 to 90 ° C., followed by filtration and washing of the precipitate. In the coprecipitation, a basic precipitant may be used to maintain pH 7 to 8, and the basic precipitant may specifically use sodium carbonate, calcium carbonate and ammonium carbonate and ammonia water. The aging time of the catalyst is appropriately maintained in the range of 0.1 to 10 hours, preferably 0.5 to 8 hours, which helps to form a catalyst of the iron-based catalyst having excellent activity in the range of aging time given, and the aging time is 0.1 hours. If less, the dispersibility of Fe-Cu (or Co and Mn) components decreases, which is disadvantageous in terms of the Fischer-Tropsch synthesis reaction, and if it exceeds 10 hours, the Fe-Cu (or Co and Mn) particle sizes increase. It is not suitable because the active point decreases and the synthesis time is increased, which is not economical. For the Fe-Cu (or Co and Mn) catalyst prepared by the co-precipitation method, the potassium component may be used by preparing an iron-based catalyst such that K / Fe is maintained in a range of 0.0 to 0.3.

Fischer-Tropsch synthesis catalyst prepared by the above method is used in the reaction after reducing in a hydrogen atmosphere in the region of 200 ~ 700 ℃ in a fixed bed, fluidized bed and slurry reactor, the reduced catalyst is a general Fischer-Tropsch The reaction is carried out under similar reaction conditions as the synthesis reaction. Specifically, the reaction temperature is 250 to 400 ° C., the reaction pressure is preferably performed at 5 to 60 kg / cm 2 and the space velocity is 500 to 10000 h ⁻¹ , but is not limited thereto. no.

The iron-based catalyst prepared by the above method may be usefully used as a catalyst for Fischer-Tropsch synthesis reaction. Specifically, the molar ratio of carbon monoxide: hydrogen: argon (internal standard) as a reactant at a reaction temperature of 300 ° C., a reaction pressure of 10 kg / cm 2, and a space velocity of 2000 L / kg _cat hr is 31.7: 63.3: 5.0. When the Fischer-Tropsch reaction is carried out at a fixed rate, the carbon monoxide conversion is at least 90 carbon mol%, and the yield of C ₅₊ hydrocarbons, specifically naphtha, diesel, middle oil, heavy oil and wax, is at least 30 carbon mol%. The selectivity to methane (C ₁ ), a major byproduct, is in the range of 10 carbon mole% or less.

Such the present invention will be described in detail based on the following examples, but the present invention is not limited by the following examples.

Example 1 Preparation of 20Fe-2Cu-4K / Ce _0.05 Zr _0.95 O ₂ Catalyst

1) Preparation of Cerium-zirconium Oxide Support

The cerium-zirconium oxide support was prepared by the sol-gel method.

First, dissolve 12.1 g of citric acid and 14.3 g of ethylene glycol at 60 ° C. for 30 minutes while stirring, and then 2.5 g of cerium nitrate hydrate (Ce (NO ₃ ) ₂ 6H ₂ O) used as a cerium precursor. It was dissolved in a minimum amount of water of 30 mL or less to completely dissolve, and then slowly added to the prepared solution (A) of citric acid and ethylene glycol. At this time, citric acid was used 10 times the number of moles of cerium-zirconium metal, ethylene glycol was used at 40 times the number of moles of cerium-zirconium metal. In the same manner, dissolve 351.9 g of citric acid and 417.8 g of ethylene glycol at 60 ° C. for 30 minutes while stirring, and then 30 mL of 38.9 g of zirconium (IV) oxychloride precursor (ZrCl ₂ O 8H ₂ O; zirconium (IV) oxychloride octahydrate). It was dissolved in the following water to completely dissolve, and then slowly added to the prepared solution (B) of citric acid and ethylene glycol. The solution A and B were mixed and stirred at 60 ° C. for 30 minutes, and then the solution was heated at 120 to 130 ° C. for 5 hours to completely remove the water contained in the solution. The sol material prepared by the above method was maintained at 100, 150, 200, and 300 ° C. for 1 hour at a temperature increase rate of 5 ° C./min, and maintained at 400 ° C. for 2 hours to maximize the surface area of the support. The final temperature was calcined while maintaining at 500 ° C. for 4 hours. At this time, the composition of the cerium-zirconium oxide prepared by the sol-gel method was 5% by weight Ce-95% by weight Zr based on the metal and is expressed as Ce _0.05 Zr _0.95 O ₂ .

2) Preparation of 20Fe-2Cu-4K / Ce _0.05 Zr _0.95 O ₂ Catalyst

Using 3 g of the powdered cerium-zirconium oxide support, iron, copper, and potassium precursors were 4.41 g of iron nitrate hydrate (Fe (NO ₃ ) ₃ H ₂ O), and copper nitrate hydrate (Cu ( NO ₃ ) ₂ H ₂ O) 0.29 g and potassium carbonate (K ₂ CO ₃ ) were dissolved in 60 mL of tertiary distilled water at the same time, mixed and stirred at 60 ° C for at least 6 hours. Removed. Thereafter, after drying at 105 ° C. for 12 hours or more, the product was calcined in an air atmosphere at 500 ° C. for 5 hours to prepare a catalyst for Fischer-Tropsch synthesis reaction containing iron-copper-potassium / cerium-zirconium oxide. At this time, the composition of the catalyst for Fischer-Tropsch synthesis reaction is based on 100 parts by weight of cerium-zirconium oxide, 20 parts by weight of Fe, 2 parts by weight of Cu, 4 parts by weight of "20Fe-2Cu-4K / Ce _0.05 Zr _0.95 O ₂ Catalyst ".

0.3 g of catalyst was charged to a 1/2 inch stainless fixed bed reactor before starting the reaction using the prepared catalyst. Carbon monoxide as a reactant at a reaction temperature of 300 ° C., reaction pressure of 10 kg / cm 2, space velocity of 2000 L / kg _cat hr after 12 hours reduction treatment at 450 ° C. hydrogen (5 vol% H ₂ / He) atmosphere. The Fischer-Tropsch reaction was carried out by injecting the molar ratio of argon (internal standard) into the reactor at a fixed ratio of 31.7: 63.3: 5.0. The reaction results are shown in the following Table 1 using an average value of 10 hours after the reaction time 60 hours in which the activity of the catalyst is stabilized and maintained.

Example 2. Preparation of 20Fe-2Cu-4K / Ce _0.08 Zr _0.92 O ₂ Catalyst

Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 8 wt% Ce-92 wt% Zr based on metal, and was expressed as Ce _0.08 Zr _0.92 O ₂ . Fischer-Tropsch synthesis catalyst was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, and the final catalyst composition was based on 100 parts by weight of cerium-zirconium oxide. 20 parts by weight, 2 parts by weight of Cu and 4 parts by weight of "20Fe-2Cu-4K / Ce _0.08 Zr _0.92 O ₂ catalyst".

Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the reaction time 60 hours, the activity of the catalyst is stabilized and maintained It was.

Example 3. Preparation of 20Fe-2Cu-4K / Ce _0.15 Zr _0.85 O ₂ Catalyst

Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 15 wt% Ce-85 wt% Zr based on the metal, and was expressed as Ce _0.15 Zr _0.85 O ₂ . Fischer-Tropsch synthesis catalyst was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, and the final catalyst composition was based on 100 parts by weight of cerium-zirconium oxide. 20 parts by weight, 2 parts by weight of Cu, and 4 parts by weight of "20Fe-2Cu-4K / Ce _0.15 Zr _0.85 O ₂ catalyst".

Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the reaction time 60 hours, the activity of the catalyst is stabilized and maintained It was.

Example 4 Preparation of 20Fe-2Cu-4K / Ce _0.50 Zr _0.50 O ₂ Catalyst

Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 50 wt% Ce-50 wt% Zr based on the metal, and was expressed as Ce _0.50 Zr _0.50 O ₂ . Fischer-Tropsch synthesis catalyst was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, and the final catalyst composition was based on 100 parts by weight of cerium-zirconium oxide. 20 parts by weight, 2 parts by weight of Cu, and 4 parts by weight of "20Fe-2Cu-4K / Ce _0.50 Zr _0.50 O ₂ catalyst".

Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the reaction time 60 hours, the activity of the catalyst is stabilized and maintained It was.

Example 5. Preparation of 5Fe-0.5Cu-1K / Ce _0.08 Zr _0.92 O ₂ Catalyst

Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 8 wt% Ce-92 wt% Zr based on metal, and was expressed as Ce _0.08 Zr _0.92 O ₂ . Fischer-Tropsch synthesis catalyst was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, but the catalyst was changed by changing the content of Fe, Cu and K as active metal components. The composition of the final catalyst prepared was "5Fe-0.5Cu-1K / Ce _0.08 Zr _0.92 O ₂ catalyst" having 5 parts by weight of Fe, 0.5 parts by weight of Cu, and 1 part by weight of K based on 100 parts by weight of cerium-zirconium oxide. . In this case, the specific surface area of the prepared catalyst was 35.6 m 2 / g, and the average pore size was 13.2 nm.

Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the reaction time 60 hours, the activity of the catalyst is stabilized and maintained It was.

Example 6. Preparation of 30Fe-3Cu-6K / Ce _0.08 Zr _0.92 O ₂ Catalyst

Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 8 wt% Ce-92 wt% Zr based on metal, and was expressed as Ce _0.08 Zr _0.92 O ₂ . Fischer-Tropsch synthesis catalyst was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, but the catalyst was changed by changing the content of Fe, Cu and K as active metal components. It was prepared, and the composition of the prepared final catalyst was "30Fe-3Cu-6K / Ce _0.08 Zr _0.92 0 ₂ catalyst" which is 30 parts by weight of Fe, 3 parts by weight of Cu, and 6 parts by weight of K based on 100 parts by weight of cerium-zirconium oxide. At this time, the specific surface area of the prepared catalyst was 29.6 m 2 / g, and the average pore size was 12.9 nm.

Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the reaction time 60 hours, the activity of the catalyst is stabilized and maintained It was.

Example 7. Preparation of 40Fe-4Cu-8K / Ce _0.08 Zr _0.92 O ₂ Catalyst

Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 8 wt% Ce-92 wt% Zr based on metal, and was expressed as Ce _0.08 Zr _0.92 O ₂ . Fischer-Tropsch synthesis catalyst was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, but the catalyst was changed by changing the content of Fe, Cu and K as active metal components. The prepared final catalyst had a composition of “40Fe-4Cu-6K / Ce _0.08 Zr _0.92 O ₂ catalyst” which is about 40 parts by weight of Fe, 4 parts by weight of Cu, and 6 parts by weight of K based on 100 parts by weight of cerium-zirconium oxide. At this time, the specific surface area of the prepared catalyst was 19.3 m 2 / g, and the average pore size was 16.5 nm.

Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the reaction time 60 hours, the activity of the catalyst is stabilized and maintained It was.

Example 8 Preparation of 20Fe-2Cu / Ce _0.08 Zr _0.92 O ₂ Catalyst

Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 8 wt% Ce-92 wt% Zr based on metal, and was expressed as Ce _0.08 Zr _0.92 O ₂ . Fischer-Tropsch synthesis catalyst is prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, but includes only active metal components Fe and Cu and no K component. A catalyst was prepared, and the composition of the prepared final catalyst was “20Fe-2Cu / Ce _0.08 Zr _0.92 O ₂ catalyst” which is 20 parts by weight of Fe and 2 parts by weight of Cu based on 100 parts by weight of cerium-zirconium oxide. At this time, the specific surface area of the prepared catalyst was 24.6 m 2 / g, and the average pore size was 15.5 nm.

Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the reaction time 60 hours, the activity of the catalyst is stabilized and maintained It was.

Example 9 Preparation of 20Fe-2Mn-4K / Ce _0.08 Zr _0.92 O ₂ Catalyst

Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 8 wt% Ce-92 wt% Zr based on metal, and was expressed as Ce _0.08 Zr _0.92 O ₂ . A catalyst for Fischer-Tropsch synthesis reaction was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, but the active metals included Fe and K, but the metal used as an enhancer. A catalyst was prepared using manganese nitrate hydrate (Mn (NO ₃ ) ₂ 6H ₂ O) among the components, and the composition of the prepared final catalyst was 20 parts by weight of Fe and 100 parts by weight of Mn 2 based on 100 parts by weight of cerium-zirconium oxide. "20Fe-2Mn / Ce _0.08 Zr _0.92 O ₂ Catalyst".

Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the reaction time 60 hours, the activity of the catalyst is stabilized and maintained It was.

Example 10 Preparation of 20Fe-2Co-4K / Ce _0.08 Zr _0.92 O ₂ Catalyst

Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 8 wt% Ce-92 wt% Zr based on metal, and was expressed as Ce _0.08 Zr _0.92 O ₂ . A catalyst for Fischer-Tropsch synthesis reaction was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, but the active metals included Fe and K, but the metal used as an enhancer. A catalyst was prepared using cobalt nitrate hydrate (Co (NO ₃ ) ₂ H ₂ O) among the components, and the composition of the prepared final catalyst was 20 parts by weight of Fe and 100 parts by weight of Co 2 based on 100 parts by weight of cerium-zirconium oxide. , K 4 parts by weight of "20Fe-2Co-4K / Ce _0.08 Zr _0.92 O ₂ catalyst".

Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the reaction time 60 hours, the activity of the catalyst is stabilized and maintained It was.

Comparative Example 1. Preparation of 20Fe-2Cu-4K / ZrO ₂ catalyst

Unlike Example 1, zirconia (ZrO ₂ ) manufactured by Kanto was used as the metal oxide support, and the catalyst for Fischer-Tropsch synthesis reaction was prepared in the same manner as in the catalyst production method of Example 1, and the final catalyst composition Silver was "20Fe-2Cu-4K / ZrO ₂ catalyst" which was 20 parts by weight of Fe, 2 parts by weight of Cu, and 4 parts by weight of K based on 100 parts by weight of cerium-zirconium oxide.

Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the reaction time 60 hours, the activity of the catalyst is stabilized and maintained It was.

Comparative Example 2. Preparation of 20Fe / Ce _0.08 Zr _0.92 O ₂ Catalyst

Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 8 wt% Ce-92 wt% Zr based on metal, and was expressed as Ce _0.08 Zr _0.92 O ₂ . The catalyst for Fischer-Tropsch synthesis reaction was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, but the active component was prepared to include only the Fe component, thereby preparing the final catalyst. It was a "20Fe / Ce _0.08 Zr _0.92 O ₂ catalyst" loaded with 20 parts by weight of Fe based on 100 parts by weight of cerium-zirconium oxide. At this time, the specific surface area of the prepared catalyst was 37.8 m 2 / g, and the average pore size was 13.8 nm.

Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the reaction time 60 hours, the activity of the catalyst is stabilized and maintained It was.

Comparative Example 3. Preparation of 20Fe-4K / Ce _0.08 Zr _0.92 O ₂ Catalyst

Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 8 wt% Ce-92 wt% Zr based on metal, and was expressed as Ce _0.08 Zr _0.92 O ₂ . Fischer-Tropsch synthesis catalyst was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, but the active ingredient was prepared to include only the Fe component and the K component. The composition of the catalyst was “20Fe-4K / Ce _0.08 Zr _0.92 O ₂ catalyst” which is 20 parts by weight of Fe and K 4 parts by weight based on 100 parts by weight of cerium-zirconium oxide. At this time, the specific surface area of the prepared catalyst was 42.4 m 2 / g, and the average pore size was 14.8 nm.

Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the reaction time 60 hours, the activity of the catalyst is stabilized and maintained It was.

Comparative Example 4. Preparation of 20Fe-2Cu-4K / Ce _0.92 Zr _0.08 O ₂ Catalyst

Cerium-zirconium oxide was prepared in the same manner as in Example 1, but was prepared by changing the Ce / Zr ratio of the support, the composition of the prepared support to be 92% by weight Ce--8% by weight Zr based on the metal Ce _0.92 Zr _0.08 O ₂ . Fischer-Tropsch synthesis catalyst was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, and the final catalyst composition was based on 100 parts by weight of cerium-zirconium oxide. 20 parts by weight, 2 parts by weight of Cu and 4 parts by weight of "20Fe-2Cu-4K / Ce _0.92 Zr _0.08 O ₂ catalyst".

Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the reaction time 60 hours, the activity of the catalyst is stabilized and maintained It was.

division Catalyst composition
(Parts by weight) Ce / (Ce + Zr)
(Weight ratio) Conversion rate (C mole%) Selectivity (C Mole%) C ₅₊
yield CO CO to CO2 CH ₄ C _2-4 C ₅₊ Example 1 20Fe-2Cu-4K /
CeZrO2 0.05 96.0 34.9 6.2 20.6 73.1 44.7 Example 2 20Fe-2Cu-4K /
CeZrO2 0.08 91.7 36.8 7.2 24.5 68.3 37.5 Example 3 20Fe-2Cu-4K /
CeZrO ₂ 0.15 94.8 35.0 6.9 22.7 70.5 42.2 Example 4 20Fe-2Cu-4K /
CeZrO ₂ 0.50 92.3 36.4 6.8 21.3 71.9 40.2 Example 5 5Fe-0.5Cu-1K /
CeZrO ₂ 0.08 91.3 38.3 8.7 26.6 64.8 34.3 Example 6 30Fe-3Cu-6K /
CeZrO ₂ 0.08 95.4 36.6 6.9 23.1 70.1 41.2 Example 7 40Fe-4Cu-8K /
CeZrO ₂ 0.08 95.5 35.6 6.0 21.6 72.4 43.4 Example 8 20Fe-2Cu /
CeZrO ₂ 0.08 93.9 37.8 9.2 26.0 64.8 36.4 Example 9 20Fe-2Mn-4K /
CeZrO ₂ 0.08 90.4 38.5 7.3 30.3 62.5 32.4 Example 10 20Fe-2Co-4K /
CeZrO ₂ 0.08 92.2 39.2 9.6 29.6 60.9 32.3 Comparative Example 1 20Fe-2Cu-4K /
ZrO ₂ - 36.3 14.9 10.4 27.9 61.7 13.2 Comparative Example 2 20Fe /
CeZrO ₂ 0.08 86.9 36.8 28.2 44.6 27.2 13.6 Comparative Example 3 20Fe-4K /
CeZrO ₂ 0.08 87.9 39.0 15.7 35.4 48.9 23.9 Comparative Example 4 20Fe-2Cu-4K /
CeZrO ₂ 0.92 81.5 36.5 17.4 36.0 46.6 21.0

As shown in Table 1, the weight ratio of the metal component of Ce / Zr as the support is a cerium-zirconium oxide (Ce _x Zr _1-x O ₂ ) support prepared by the sol-gel method, as proposed by the present invention. It is in the range of 0.50 and the content of the metal supported on the basis of 100 parts by weight of the iron is from 5 to 50 parts by weight of Fe, from 0 to 15 parts by weight of K, 0.25 to 10 parts by weight of one kind of metal selected from the promoters Cu, Co and Mn. A series of catalysts (Examples 1-10) were used in Fischer-Tropsch synthesis reactions with a carbon monoxide conversion of at least 90.4 carbon mole%, a C ₅₊ hydrocarbon yield of at least 32.3 carbon mole%, and selectivity of methane as a byproduct. It showed excellent catalytic activity with 9.6 carbon mole% or less. On the other hand, cerium - if not using zirconium oxide support (Comparative Example 1) and when enhancers of Cu, that does not contain the first metal element selected from among Co and Mn (Comparative Examples 2 and 3), C _{5 + The} yield of hydrocarbon was low, and the activity of the catalyst was low even when the weight ratio of the metal component of Ce / Zr of cerium-zirconium oxide (Ce _x Zr _1-x O ₂ ) was 0.92 (Comparative Example 4).

In addition, Figure 1 shows the reaction temperature of 300 ℃, reaction pressure 10 kg / ㎠, space velocity 2000 L / kg _cat hr under the catalyst prepared in Examples 1, 2, Comparative Example 1, and Comparative Example 4 In the case of Fischer-Tropsch synthesis reaction with the molar ratio of carbon monoxide: hydrogen: argon (internal standard) reactant under the conditions of 31.7: 63.3: 5.0, the graph showing the conversion rate of carbon monoxide over time according to the reaction time. to be. 1, it can be seen that the catalysts of the present invention (Examples 1 and 2) using cerium-zirconium oxide as a support are significantly inhibited from deactivation of the catalyst when compared with the catalyst of Comparative Example 1 using zirconium oxide as a support. have.

Therefore, the iron-based catalyst prepared by using a cerium-zirconium oxide prepared by the sol-gel method with a metal weight ratio of Ce / Zr as a support as suggested in the present invention is a catalyst for Fischer-Tropsch synthesis reaction. It can be used to ensure that the deactivation of the catalyst according to the reaction time is very small, but the effect of suppressing the production of by-product methane can be secured, it can be helpful to secure a stable process when using the catalyst It could be confirmed through the present invention.

In response to the recent rapidly rising oil price problem, the development of catalyst technology to selectively produce light olefins, which are the basic raw materials of petrochemicals, and high-boiling hydrocarbons for the manufacture of clean fuels, has led to the development of efficient Fischer-Tropsch processes. Therefore, it can be an important factor for securing competitiveness. In particular, according to the improvement of the Fischer-Tropsch reaction catalyst can improve the thermal efficiency and carbon utilization efficiency of the entire process.

The iron-based Fischer-Tropsch catalyst proposed by the present invention using a cerium-zirconium oxide as a support improves carbon monoxide conversion and reduces selectivity to methane, a major by-product, and thus yields high yields of hydrocarbons and light olefins. The improved effect is expected to greatly contribute to the future development of the Fischer-Tropsch process.

FIG. 1 shows the conversion rate of carbon monoxide according to reaction time when Fischer-Tropsch synthesis reaction was carried out using the catalysts prepared in Examples 1, 2, and 1 and 4 One graph.

Claims (15)

Iron, characterized in that 5 to 50 parts by weight of iron (Fe) and 0.25 to 10 parts by weight of a metal element selected from copper (Cu), cobalt (Co) and manganese (Mn) are supported on 100 parts by weight of the cerium-zirconium oxide support. Fischer-Tropsch synthesis catalyst. The iron-based Fischer-Tropsch synthesis reaction catalyst according to claim 1, wherein 0.001 to 15 parts by weight of potassium (K) is further loaded on 100 parts by weight of the cerium-zirconium oxide support. The method according to claim 1 or 2, The cerium-zirconium oxide support is a catalyst for the iron-based Fischer-Tropsch synthesis reaction, characterized in that prepared by the sol-gel method. The method according to claim 1 or 2, The cerium-zirconium oxide support catalyst for iron-based Fischer-Tropsch synthesis reaction, characterized in that the specific surface area of 5 to 50 m 2 / g. The method according to claim 1 or 2, M / Fe, which is the weight ratio of the metal (M) selected from Cu, Co, and Mn to the iron (Fe) metal, maintains a range of 0.05 to 0.20, and the weight ratio of potassium (K) metal to the iron (Fe) metal. A catalyst for the Fischer-Tropsch synthesis reaction of an iron series, wherein phosphorus K / Fe maintains a range of 0.0 to 0.3. The method according to claim 1 or 2, The cerium-zirconium oxide is a catalyst for the iron-based Fischer-Tropsch synthesis reaction characterized in that Ce / Zr, the weight ratio of Ce to zirconium (Zr) is maintained in the range 0.05 ~ 0.50. Preparing a cerium-containing liquid by adding an aqueous cerium precursor solution to a mixed solution of citric acid and ethylene glycol; Preparing a zirconium-containing liquid by adding an aqueous solution of zirconium precursor to a mixed solution of citric acid and ethylene glycol; Preparing a sol (Sol) by thoroughly stirring the mixed solution of the cerium-containing solution and the zirconium-containing solution at 50 to 100 ° C., and then heating at 120 to 150 ° C. to completely remove water contained in the mixed solution; And Calcining the sol by heating up stepwise in a range of 100 to 500 ° C. at a temperature rising rate of 3 to 7 ° C./min; A method of producing a cerium-zirconium oxide support for an iron-based Fischer-Tropsch synthesis reaction catalyst by a sol-gel reaction comprising a. The method of claim 7, wherein The cerium precursor is cerium nitrate, the zirconium precursor is zirconium oxynitrate, characterized in that the manufacturing method of cerium-zirconium oxide support. The method of claim 7, wherein The cerium-zirconium oxide support has a specific surface area of 5 to 50 m 2 / g A method for producing a cerium-zirconium oxide support. The method of claim 7, wherein The cerium-zirconium oxide is a method for producing a cerium-zirconium oxide support, characterized in that the weight ratio of the metal component of Ce / Zr maintains 0.05 to 0.50 range. Preparing a cerium-containing liquid by adding an aqueous cerium precursor solution to a mixed solution of citric acid and ethylene glycol; Preparing a zirconium-containing liquid by adding an aqueous solution of zirconium precursor to a mixed solution of citric acid and ethylene glycol; Preparing a sol (Sol) by thoroughly stirring the mixed solution of the cerium-containing solution and the zirconium-containing solution at 50 to 100 ° C., and then heating at 120 to 150 ° C. to completely remove water contained in the mixed solution; And Step by heating the sol step by step in a range of 100 to 500 ℃ at a temperature increase rate of 3 to 7 ℃ / min to prepare a cerium-zirconium oxide support; And Obtaining a catalyst on the cerium-zirconium oxide support by impregnation or co-precipitation of a Fe metal precursor and a precursor of an enhancement metal (M) selected from Cu, Co, and Mn; Fischer-Tropsch catalyst of the iron-based method comprising a. 12. The method of claim 11, wherein a potassium (K) precursor is further supported on the cerium-zirconium oxide support. The method of claim 11, The Fe metal precursor is one or two or more mixed precursors selected from Fe (II) and Fe (III) precursors consisting of iron nitrate hydrate, iron acetate, iron oxalate hydrate, iron acetylacetonate and iron chloride. Method for producing a catalyst for the Fischer-Tropsch synthesis reaction of the iron series. 13. The method according to claim 11 or 12, The Fe metal precursor, the precursor of the enhancement metal (M), and the potassium (K) precursor have a weight ratio of 0.05 to M (Fe) of the enhancement metal (M) selected from Cu, Co, and Mn with respect to the iron (Fe) metal. Fischer-Tropsch synthesis reaction of iron-based, characterized in that it is used within the range to maintain 0.20, K / Fe which is the weight ratio of the potassium (K) metal to the iron (Fe) metal to maintain 0.0 ~ 0.3 Method for preparing a catalyst. 13. The method according to claim 11 or 12, The method for preparing a catalyst for Fischer-Tropsch synthesis reaction of iron-based, characterized in that it further comprises the step of calcining the prepared catalyst at 300 ~ 700 ℃.

Images