KR20110059437A - The catalyst of fe-mg based for fischer-tropsch synthesis, and preparation and application method of the same - Google Patents

Abstract

PURPOSE: Iron-magnesium-based catalyst for fischer-tropsch synthesis and methods for manufacturing and using the same are provided to improve the selectivity of C12 or more hydrocarbon and the conversion rate to carbon monoxide in the fischer-tropsch synthesizing reaction. CONSTITUTION: Iron-magnesium-based catalyst includes iron(Fe), magnesium(Mg), copper(Cu), and potassium(K). An ammonium carbonate solution is added to the mixed aqueous solution of iron precursor and magnesium precursor. The pH of the mixed aqueous solution is regulated into neutral pH. The mixed aqueous solution is filtered, cleaned, dried, and sintered to obtain iron-magnesium mixture. Potassium precursor and copper precursor are immerged in the mixed aqueous solution. Drying and sintering operations are followed.

Description

Fischer-Tropsch synthesis iron-magnesium-based catalyst, its preparation and application technology {The Catalyst of Fe-Mg Based for Fischer-Tropsch Synthesis, and Preparation and Application Method of the Same}

The present invention relates to an iron-magnesium-based catalyst used in the Fischer-Tropsch process, a method for preparing the same, and a method for preparing synthetic petroleum using the same. And a Fischer-Tropsch synthesis reaction using syngas on the catalyst.

The Fischer-Tropsch process is a process for producing hydrocarbons from syngas, hydrogen and carbon monoxide, in 1923, when German chemists Fischer and Tropsch developed a technique for producing synthetic fuel from syngas. It started for the first time.

Carbon monoxide and hydrogen mainly use water gas or natural gas from coal or coke, and the Fischer-Tropsch synthesis reaction broadly includes paraffin and olefin hydrocarbons and alcohols from water gas. Although the reaction products vary depending on the type of catalyst, reaction temperature, pressure, etc., the main reactions include the following. The raw material gas is supplied to the catalyst layer at a reaction temperature of 200 to 350 ° C. and atmospheric pressure of 300 atm to obtain hydrocarbon oils of about 100 g per 1 m ^{3 of} the raw material gas. When the catalyst is cobalt or nickel-based, reactions that mainly produce chain-like hydrocarbons and water occur, resulting in low octane values. You can get u.

In the 19th century, Sabatiee was able to produce methane by catalytic hydrogenation of carbon monoxide. BASF, Germany, took note of this and succeeded in methanol synthesis in 1921. Meanwhile, F. Fisher and H. Tropsch, who worked for the company, advanced their research and obtained liquids containing oxidizing compounds in 1923, naming them Synthol. Cintol was unsuitable as a fuel, but synthin, which pyrolyzed, became a substitute for gasoline.

This method was developed into synthetic petroleum synthesizing method by lowering the reaction pressure to produce hydrocarbon oil. In 1936, it produced 50,000 tons of artificial synthetic oil per year. Currently, South Africa has been manufacturing artificial synthetic oil from the Coal to Liquid (CTL) process since 1954 under the name of the SASOL Plan because of the low supply of coal from open pit.

Sasol and Shell developed the Gas to Liquid (GTL) process, which uses natural gas to produce synthetic oil, from the mid-1950s in Secunda, South Africa, and in 1993, in Binturu, Malaysia. Since commercial production.

The Fischer-Tropsch reaction is a reaction for producing a liquid hydrocarbon by reacting a synthesis gas containing carbon monoxide and hydrogen under a catalyst. Generally, a reaction temperature of 200 to 350 ° C. using an iron (Fe) and a cobalt (Co) catalyst is used. And at atmospheric pressure of ~ 30 atm. The main reaction mechanisms involved in the synthetic oil production process are as follows.

CO + 2H ₂ → -CH _2- + H ₂ O (1)

CO + 3H ₂ → CH ₄ + H ₂ O (2)

CO + H₂O → CO₂ + H₂ (3)

2CO ↔ C + CO₂ (4)

To date, the Fischer-Tropsch reaction has been studied for the preparation of various catalysts, wherein the activity of the catalyst is directly related to the amount of reaction product. Iron-based catalysts are characterized by low cost, low methane production at high temperatures, and high olefin selectivity. However, in addition to hydrocarbons, there are disadvantages in that a lot of by-products such as alcohol, aldehydes and ketones are generated.

Metallic compounds effective for the Fischer-Tropsch synthesis reaction include nickel (Ni), iron (Fe), cobalt (Co), ruthenium (Ru), and the like. ME Dry The Fischer Tropsch process: 1950-2000. Catalysis Today, 2002 Elsevier. Of these, ruthenium is too expensive [.E. Iglesia, S. Soled, R. A. Fiato, US Patent No. 4,738,948 (1988)], nickel has a problem that the selectivity of the methane is too large, eventually iron and cobalt-based catalysts are used commercially. Iron and cobalt-based catalysts are manufactured by adding various cocatalysts for the purpose of increasing the activity, selectivity, and thermal stability of the reaction. Various metal oxides are used as commercial catalysts.

Iron catalysts are generally used for the synthesis of C _{11 and} higher olefins [Schulz, et al., Conference on Natural Gas II, Elsevier, Amsterdam, Surf. Sci. Ser. 81 (1994) 455; DB Bukur, K. Okabe, MP Rosynek, C. Li, D. Wang, KRPM Rao, GP Huffman, J. Catal. 155 (1995) 353; DB Bukur, L. Nowicki, RK Manne, X. Lang, J. Catal. 155 (1995) 366.].

The present invention provides a novel iron-magnesium-based Fischer-Tropsch synthesis catalyst having a higher selectivity of C ₁₂ or more olefins than the conventional iron catalyst, a method for preparing the same, and a Fischer-Tropsch synthesis reaction using syngas on the catalyst. It is about.

The present invention provides a Fischer-Tropsch synthesis iron-magnesium-based catalyst capable of maximizing the production of C ₁₂ or more olefins which are distributed at a relatively high price as a Fischer-Tropsch synthesis catalyst for preparing liquid hydrocarbons, and a method for preparing the same. It is a problem to provide and to apply to Fischer-Tropsch synthesis for synthetic oil production.

The present invention relates to a catalyst in which magnesium is introduced into an iron catalyst for synthesizing petroleum for iron, copper, and potassium, wherein magnesium introduced into the iron catalyst increases the conversion rate of carbon monoxide in the iron catalyst, and copper reduces the catalyst on the iron catalyst. Lowering the temperature reduces the energy required, and potassium increases the selectivity of products in the olefin and wax ranges. The new composition of the Fischer-Tropsch iron-magnesium-based catalyst can increase the dispersibility and reduction of the active ingredient, maintain high conversion of carbon monoxide and stable production of wax products.

Fischer-Tropsch catalysts, which are attracting attention as an alternative to the rapidly changing oil price problem, play a big role in securing technological competitiveness, manufacturing high value-added compounds, and securing process efficiency.

Therefore, when the iron-magnesium-based catalyst which improves the conversion rate of carbon monoxide proposed in the present invention and has excellent selectivity of hydrocarbons having C ₁₂ or more is applied, it is possible to secure a process for stably producing a hydrocarbon product by utilizing it in a competitive process.

The present invention relates to an iron-magnesium catalyst for synthesizing petroleum including iron, magnesium, copper, and potassium, and to an iron-magnesium catalyst for synthesizing petroleum, comprising 0.04 to 0.25 mol of magnesium per mole of iron. will be.

In another aspect, the present invention is to attach the ammonium carbonate solution to the mixed aqueous solution of iron precursor and magnesium precursor to adjust the pH of the mixed aqueous solution to neutral; Filtering and washing the mixed aqueous solution of pH adjustment, followed by drying and calcining to obtain a mixture of iron-magnesium; Supporting the potassium precursor and the copper precursor in the iron-magnesium mixture; And it relates to a method for producing iron-magnesium-based catalyst for synthetic petroleum production comprising the step of drying and calcining the iron-magnesium mixture loaded with the potassium precursor and the copper precursor.

The Fischer-Tropsch reaction is of great importance because the preparation of various catalysts has been studied in which the activity of the catalyst is directly related to the yield of the reaction product. Nickel (Ni), iron (Fe), cobalt (Co), ruthenium (Ru), etc. may be used as the effective metal component for the Fischer-Tropsch synthesis reaction. However, iron and cobalt catalysts are generally used commercially. have. In particular, iron-based catalysts are generally used for the synthesis of C _{11 and} higher olefins.

The present invention relates to such an iron-based catalyst, characterized in that a certain amount of magnesium introduced into the iron-based catalyst for excellent CO conversion characteristics.

Magnesium introduced in the iron-based catalyst increases the conversion rate of carbon monoxide in the iron-based catalyst. However, when the magnesium content is less than 0.04 molar ratio with respect to 1 mole of iron, the effect of magnesium is inadequate, and when the content of magnesium is more than 0.25 molar ratio, adverse effects that may adversely affect the active site of the catalyst may occur.

The concentration of magnesium is very important when magnesium is supported on an iron catalyst. If the magnesium concentration is too low, it will adversely affect the active site of the catalyst and the reaction activity is lowered, which does not show the promoting effect of supporting magnesium. In addition, if the molar ratio of magnesium is too high, it promotes the water gas shift reaction, which increases the water gas shift reaction in which carbon monoxide reacts with water to convert to carbon dioxide, thereby reducing the Fischer-Tropsch synthesis reaction. There is also a problem that the selectivity of (higher hydrocarbon) is also lowered. In addition, since the selectivity of the low hydrocarbon (lower hydrocarbon) is too high when the molar ratio of magnesium increases, the concentration of magnesium in the proper ratio is important. When the catalyst is prepared at a too low ratio, that is, the molar ratio of magnesium is less than 0.04, the reaction activity, that is, the conversion rate is lowered. 0.2, most preferably 0.1.

Copper serves to lower the reduction temperature of the catalyst on the iron catalyst, and potassium increases the selectivity of products in the olefin and wax ranges [L. Guczi and P. Putanov, Stud. Surf. Sci. Catal. 61 (1991), p. 251; 7. M.S. Luo and B.H. Davis, Appl. Catal. A: Gen. 246 (2003), p. 171.].

The iron-magnesium-based catalyst for synthesizing petroleum may be prepared by attaching an ammonium carbonate solution to a mixed aqueous solution of an iron precursor and a magnesium precursor to adjust the pH of the mixed aqueous solution to neutrality; Filtering and washing the mixed aqueous solution of pH adjustment, followed by drying and calcining to obtain a mixture of iron-magnesium; Carrying out a potassium precursor and a copper precursor in the iron-magnesium mixture; And drying and firing the iron-magnesium mixture on which the potassium precursor and the copper precursor are supported.

Examples of the iron precursor include iron nitrate (IRON (III) NITRATE), iron chloride (IRON (III) CHLORIDE), ferric ammonium sulfate (AMMONIUM IRON (III) SULFATE), iron phosphate (IRON (III) PHOSPHATE), and fluoride. Iron (IRON (III) FLUORIDE) and iron bromide (IRON (III) BROMIDE) and the like may be used, but is not limited thereto.

Examples of the potassium precursors include potassium acetate (POTASSIUM ACETATE), potassium bicarbonate (POTASSIUM BICARBONATE), potassium boron hydride (POTASSIUM BOROHYDRIDE), potassium bromide (POTASSIUM BROMATE), potassium bromide (POTASSIUM BROMIDE), potassium carbonate (POTASSIUM) CARBONATE, Potassium Chloride, Potassium Chloride, Potassium Citrate, Potassium Cyanide, Potassium Sulphate, Potassium Sulphate, Potassium Fluoride ), Potassium formate (POTASSIUM FORMATE), potassium hydroxide (POTASSIUM HYDROXIDE), potassium iodide (POTASSIUM IODATE), potassium nitrate (POTASSIUM NITRATE), potassium nitrite (POTASSIUM NITRITE), potassium sulfate (POTASSIUM SULFATE), etc. However, it is not limited thereto.

Examples of the copper precursor include copper acetyl acetate (COPPER (II) ACETYLACETONATE), copper sulfate (COPPER (II) SULFATE), copper chloride (COPPER (II) CHLORIDE), copper nitrate (COPPER (II) NITRATE), copper carbonate (COPPER (II) CARBONATE), copper bromide (COPPER (II) BROMIDE), copper fluoride (COPPER (II) FLUORIDE) and the like may be used one or more, but is not limited thereto.

The mixed aqueous solution of the iron precursor and the magnesium precursor can be prepared by adding a certain amount of ammonium carbonate solution, wherein the aqueous solution temperature is preferably in the range of 70 ~ 90 ℃. A neutral solution is prepared by attaching to the mixed aqueous solution while controlling the amount of the ammonium carbonate solution. After filtration and washing with water, drying and baking are performed. At this time, the drying is preferably performed at 110 to 130 ° C. for 10 to 14 hours, and the firing is performed at about 300 to 400 ° C. for about 1 hour. A catalyst is prepared by supporting a potassium precursor and a copper precursor in a mixture of calcined iron-magnesium, and drying and calcining a mixture of iron-magnesium on which the potassium precursor and a copper precursor are supported, wherein the drying is about 100 to 120 ° C. For 2 hours, firing is preferably performed at 350 to 450 ° C. for 3 to 5 hours.

As such, synthetic petroleum may be prepared by performing the Fischer-Tropsch reaction using the iron-magnesium-based catalyst according to the present invention. At this time, the synthetic oil production conditions are not particularly limited, but preferably may be carried out under the reaction conditions of the reaction temperature 100 ~ 300 ^° C, reaction pressure 10 ~ 50 bar and H ₂ / CO = 1 ~ 2.

In order to facilitate a more clear understanding of the present invention, the contents of the present invention will be described in detail through preferred catalyst preparation examples, catalyst characterization examples, and catalytic reaction examples. However, these examples are only presented to understand the content of the present invention, the scope of the present invention is not limited to these examples.

[ Catalyst Production Example ]

catalyst Manufacturing example  One. Mg  0.0435 Molar  Catalyst preparation

61.88 ml and 1.26 ml of 1.4 M iron nitrate (Fe (NO ₃ ) ₂ 9H ₂ O) and 3.0 M magnesium nitrate (Mg (NO ₃ ) ₂ 6H ₂ O) solutions were added dropwise to 50 ml of water at 80 ° C, and then 1.0M PH 7 was adjusted by adding ammonium carbonate solution (NH ₄ ) ₂ CO ₃ ). Thereafter, the precipitate was separated through filtration and washed repeatedly with distilled water, dried at 120 ° C. for 12 hours, and calcined at 350 ° C. for 1 hour.

The calcined iron-magnesium compound was impregnated with 7.59 ml and 7.60 ml of 2 wt% aqueous potassium carbonate (K ₂ CO ₃ ) and 1 wt% copper nitrate (Cu (NO ₃ ) ₂ 3H ₂ O) solutions, respectively. It was supported. The supported material was dried again at 110 ° C. for 2 hours, and then calcined at 400 ° C. for 4 hours to prepare a catalyst.

catalyst Manufacturing example  2. Mg  0.1 Molar  Catalyst preparation

Prepared in the same manner as in Example 1, except that 71.42 ml and 3.33 ml of 1.4M iron nitrate (Fe (NO ₃ ) ₂ 9H ₂ O) and 3.0M magnesium nitrate (Mg (NO ₃ ) ₂ 6H ₂ O) aqueous solution, respectively The catalyst was prepared by dropwise addition to 50 ml of water at 80 ° C.

catalyst Manufacturing example  3. Mg  0.2 Molar  Catalyst preparation

In the same manner as in Example 1, 72.15ml, 6.67ml of 1.4M iron nitrate (Fe (NO ₃ ) ₂ 9H ₂ O) and 3.0M magnesium nitrate (Mg (NO ₃ ) ₂ 6H ₂ O) aqueous solution were 80 ° C. The catalyst was prepared by dropwise addition to 50 ml of water.

Catalyst Comparison Manufacturing example  One. Mg Preparation of a catalyst not containing

72.15 ml of a 1.4 M aqueous solution of iron nitrate (Fe (NO ₃ ) ₂ 9H ₂ O) was added to 50 ml of water at 80 ° C., and a pH of 7 was added by adding 1.0 M aqueous ammonium carbonate (NH ₄ ) ₂ CO ₃ ) solution. Thereafter, the precipitate was separated through filtration and washed repeatedly with distilled water, dried at 120 ° C. for 12 hours, and calcined at 350 ° C. for 1 hour.

9.97 ml and 9.97 ml of 2 wt% potassium carbonate (K ₂ CO ₃ ) and 1 wt% copper nitrate (Cu (NO ₃ ) ₂ 3H ₂ O) aqueous solutions were added to the calcined compound, and supported by impregnation. . The supported material was dried again at 110 ° C. for 2 hours, and then calcined at 400 ° C. for 4 hours to prepare a catalyst.

[Catalyst Characteristics Analysis example ]

Catalyst Characteristics Analysis example  1. Catalyst Fe  Crystal Size, BET  Surface area and pore size measurement

The structural properties and the textural properties of the catalysts of Catalyst Preparation Example 1-3 and Comparative Catalyst Preparation Example 1 were measured and shown in Table 1 below.

The particle size of the active metal was measured by X-ray diffraction analysis, and the BET surface area and the pore size of the particles were measured by physical adsorption of nitrogen.

Structure and Structure Characteristics of Catalysts catalyst Mg / Fe
(Atomic costs) Crystal size ^a , (nm) BET SA ^b (m ² / g) Total porosity (vol ^b ., Cc / g) Micropores
(vol ^c ., cc / g) Average pore size ^d
(A) Catalyst Preparation Example 1 0.0435 14.3 27.61 0.0519 2.213 x 10 ^-3 74.6 Catalyst Preparation Example 2 0.1 14.1 28.89 0.3196 3.241 x 10 ^-3 442.6 Catalyst Preparation Example 3 0.2 13.9 36.05 0.0524 3.421 x 10 ^-3 64.8 Catalyst Comparison Preparation Example 1 0 15.2 31.78 0.2163 3.024 x 10 ^-3 272.3

^a Calculated by the Scherrer equation using XRD measurements.

^b N ₂ - adsorption isotherm derived from a (N ₂ -Adsorption Isotherm).

N ^c ₂ - calculated as 't' from the plot of the adsorption isotherm (N ₂ -Adsorption Isotherm).

^d Derived from the Pore Size Distribution.

As can be seen in Table 1, the more the magnesium is added, the smaller the particle size of iron, which is the active metal, while there is no decrease in the BET surface area, and the pore size did not show an unusual change.

Catalyst Characteristics Analysis example  2. XRD  analysis

Crystal size and structural characteristics of the catalysts of Preparation Example 1-3 and Comparative Catalyst Preparation Example 1 were measured using XRD and are shown in FIG. 1.

In Comparative Example 1 catalyst containing no magnesium, a peak coinciding with the α-Fe ₂ O ₃ hematite phase (indexed as JCPDS file No. 84-0311) was found. The peak 2θ value was 24.2˚, 33.2 °, 35.6 °, 40.8 °, 49.5 °, 54.1 °, 57.6 °, 62.3 ° and 64.0 °. In addition, the peak of α-Fe ₂ O ₃ catalyst in other embodiments 1 to 3 the catalyst was observed. As magnesium was supported, no other peak was observed, indicating that magnesium was well dispersed in the catalyst at a low concentration. As the concentration of magnesium increased, the peaks of (012), (104), (110), and (024) were observed. Decreased little by little. This was confirmed that the peak size was reduced by decreasing the crystallite size of the catalyst.

Catalyst Characteristics Analysis example  3. TEM  analysis

Particle sizes of the catalysts of Catalyst Preparation Example 1-3 and Catalyst Comparative Preparation Example 1 were measured, and the results are shown in FIG. 2.

Most of the crystals of Comparative Preparation Example 1 appeared to have an oval shape, and it was confirmed that the crystals of Catalyst Preparation Example 1 had a circular shape. In Catalyst Preparation Example 2, crystals of elliptical shape and circular shape were formed in an irregular shape. In Catalyst Preparation Example 3, circular crystals were formed in different sizes.

In addition, the size of the crystals decreased as magnesium was added, which is consistent with the size reduction of the crystals in the XRD data. In addition, Comparative Example 1 of the catalyst containing no magnesium was found to be different from that of the other catalyst containing magnesium as a whole.

Catalyst Characteristics Analysis example  4. TPR  analysis

Catalyst Preparation Example 1-3 and Comparative Example 1 The catalyst of Preparation Example 1 was shown in FIG. 3 by measuring the reducibility according to temperature using a Temperature Programmed Reduction (TPR).

The temperature reduction method is an experimental method to investigate the ease of reduction of a solid material such as a catalyst. It is to investigate the ease of reduction and the reduction mechanism of the sample by raising the sample at a constant rate in a reducing gas (mainly hydrogen) and measuring the reduction of the reducing gas. The temperature reduction method was measured using hydrogen on the catalysts of Comparative Preparation Example 1 and Catalyst Preparation Examples 1-3.

The first peak was observed at temperatures ranging from 300 to 400 ° C. on all catalysts of Catalyst Preparation Examples 1-3 and Comparative Catalyst Preparation Example 1. The first peak is a peak in which Fe ₃ O ₄ is reduced to FeO, it was confirmed that the peak moves to a lower temperature as the magnesium component increases. This means that the addition of magnesium results in the reduction of Fe ₃ O ₄ at low temperatures through interaction with the support or magnesium, which means that the catalyst can be activated with less energy.

However, in the catalyst of Preparation Example 1, the peak moved to a high temperature while Fe ₃ O ₄ was directly reduced to FeO. In addition, the second broad peak is a peak appearing as FeO is reduced to Fe. This reaction is a very slow reaction, and thus the peak was found to be wide.

[ Example ]

Example  1. Catalyst Manufacturing example  Fischer- on catalyst of 1 Tropsey  Reaction

0.5 g of the catalyst of Preparation Example 1 was charged onto a Fischer-Tropsch fixed bed reactor, and then the reaction was allowed to proceed for 40 hours. Reaction conditions were carried out at 250 ℃, 20 bar, H ₂ / CO = 2 (volume ratio) while the reaction gas product on-line GC (TCD, FID) and the resulting liquid product off-line GC (FID) Analyzed using. The conversion of CO and H ₂ , the selectivity of hydrocarbons and the selectivity of olefins as a result of the reaction experiment are shown in Table 2 below.

Example  2. Catalyst Manufacturing example  Fischer on 2 catalysts Tropsey  Reaction

The Fischer-Tropsch reaction experiment was carried out under the same reaction conditions using the catalyst of Catalyst Preparation Example 2 instead of Catalyst Preparation Example 1 in Example 1. Conversion rates of CO and H ₂ , selectivity of hydrocarbons and selectivity of olefins are summarized in Table 2.

Example  3. Catalyst Manufacturing example  Fischer- on 3 catalysts Tropsey  Reaction

The Fischer-Tropsch reaction experiment was carried out under the same reaction conditions using the catalyst of Catalyst Preparation Example 3 instead of Catalyst Preparation Example 1 in Example 1. Conversion rates of CO and H ₂ , selectivity of hydrocarbons and selectivity of olefins are summarized in Table 2.

Comparative example  1. Catalyst Comparison Manufacturing example  Fischer- on catalyst of 1 Tropsey  Reaction

Fischer-Tropsch reaction experiments were carried out under the same reaction conditions using the catalyst of Comparative Preparation Example 1 instead of Catalyst Preparation Example 1 in Example 1. Conversion rates of CO and H ₂ , selectivity of hydrocarbons and selectivity of olefins are summarized in Table 2.

Comparative Example 1 Example 1 Example 2 Example 3 catalyst Catalyst Comparative Preparation Example 1 Catalyst Preparation Example 1 Catalyst Preparation Example 2 Catalyst Preparation Example 3 CO conversion (%) 45.4 54.3 60.6 60.1 H ₂ conversion (%) 42.7 42.2 43.3 43.6 HC selectivity (wt%) CH ₄ 6.01 3.94 4.74 7.26 C ₂ -C ₄ 6.12 5.87 6.91 9.12 C ₂ ⁼ -C ₄ ⁼ 4.04 2.48 3.01 4.19 C ₅ -C ₁₁ 1.63 1.58 1.66 2.84 C ₅ ⁼ -C ₁₁ ⁼ 0.86 0.76 0.83 1.58 C ₁₂ -C ₁₈ 26.04 21.39 22.09 25.47 C ₁₂ ⁼ -C ₁₈ ⁼ 32.63 27.28 31.61 36.89 C ₁₉ -C ₂₅ 60.18 67.22 64.59 55.39 Olefin selectivity (wt%) C ₂ ⁼ -C ₄ ⁼ / C ₂ -C ₄ 0.66 0.42 0.44 0.46 C ₅ ⁼ -C ₁₁ ⁼ / C ₅ -C ₁₁ 0.52 0.48 0.50 0.55

As can be seen in Table 2, after 40 hours of reaction, the conversion rate of CO on the catalyst of Comparative Preparation Example 1 containing no magnesium was about 43%, whereas the magnesium Preparation Catalysts of Examples 1, 2, and 3 were added. On the catalyst it was confirmed that the conversion of CO is very high, such as 54-60%. Comparing the results of Examples 1-3 on the catalyst with magnesium added, the average conversion of CO on the catalyst with magnesium increased by 10-15%, but the conversion of H ₂ did not increase significantly.

In addition, it can be seen that the selectivity of C ₁ -C ₁₁ is relatively lower than C ₁₂ ⁺ on the catalyst of Comparative Example 1 without magnesium and Catalyst Preparation Example 1-3 with magnesium added, and C ₁₂ It can be seen that the selectivity of -C ₂₅ is significantly high. Therefore, it can be confirmed that the selectivity for C ₁₂ or more hydrocarbons is excellently maintained in the conventional iron catalyst and the iron-magnesium catalyst according to the present invention.

In the present invention, it was confirmed that the iron catalyst can increase the activity and wax selectivity of the Fischer-Tropsch reaction by adding a certain amount of magnesium component, and as a whole magnesium is supported, it affects the CO conversion rate and observes the selectivity and the like. As a result, it was confirmed that they are equivalent to or more than conventional iron catalysts.

1 is an XRD analysis result of the catalyst prepared in Preparation Example and Comparative Preparation Example of the present invention.

2 is a TEM analysis result of the catalyst prepared in Preparation Example and Comparative Preparation Example of the present invention.

3 is a result of TPR analysis of the catalyst prepared in Preparation Examples and Comparative Preparation Examples of the present invention.

Claims (7)

Iron, magnesium, copper and potassium, wherein the magnesium is iron-magnesium-based catalyst for synthetic petroleum production, characterized in that contained in a ratio of 0.04 to 0.25 mol per 1 mol of iron. Attaching an ammonium carbonate solution to the mixed aqueous solution of the iron precursor and the magnesium precursor to adjust the pH of the mixed aqueous solution to neutral; Filtering and washing the mixed aqueous solution of pH adjustment, followed by drying and calcining to obtain a mixture of iron-magnesium; Supporting the potassium precursor and the copper precursor in the iron-magnesium mixture; And Four steps of drying and firing the iron-magnesium mixture loaded with the potassium precursor and the copper precursor Iron-magnesium-based catalyst production method for producing synthetic oil comprising a. The method of claim 2, wherein the iron precursor is at least one compound selected from iron nitrate, iron chloride, ferric ammonium sulfate, iron phosphate, iron fluoride, and iron bromide. 3. The magnesium precursor is at least one compound selected from the group consisting of magnesium sulfate, magnesium chloride, magnesium nitrate, magnesium iodide, magnesium phosphate, magnesium hydride, magnesium fluoride, magnesium bromide and magnesium ammonium phosphate. A method for producing an iron-magnesium catalyst for producing synthetic oil. The method of claim 2, wherein the potassium precursor is potassium acetate, potassium bicarbonate, potassium boron hydride, potassium bromide, potassium bromide, potassium carbonate, potassium chlorate, potassium chloride, potassium citrate, potassium cyanide, potassium sulfate, potassium ethoxide, fluoride Potassium, potassium formate, potassium hydroxide, potassium iodide, potassium nitrate, potassium nitrite, potassium sulfate is a method for producing an iron-magnesium catalyst for the production of synthetic petroleum, characterized in that at least one compound selected from the group consisting of. The method of claim 2, wherein the copper precursor is at least one compound selected from the group consisting of copper acetyl acetate, copper sulfate, copper chloride, copper nitrate, copper carbonate, copper bromide and copper fluoride Method for producing a catalyst. Synthetic petroleum oil by Fischer-Tropsch reaction on the iron-magnesium catalyst prepared according to claim 1 under the reaction conditions of 100 ~ 300 ^o C, reaction pressure 10 ~ 50 bar and H ₂ / CO = 1 ~ 2 How to prepare.

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