KR101059413B1 - Metal Structure, Method for Manufacturing Metal Structure, and Metal Structure Catalyst for Autothermal Reforming Catalyst Layer for Synthesis of Fischer-Tropsch Liquefaction Process - Google Patents

Abstract

The present invention relates to a metal structure for the autothermal reforming catalyst layer, a method for producing a metal structure, and a metal structure catalyst for syngas production for the Fischer-Tropsch liquefaction process, the object of which is to convert methane into hydrogen and carbon monoxide in the main reaction, The present invention provides a metal structure, a method for producing a metal structure, and a metal structure catalyst for use in an autothermal reformer catalyst layer obtaining a hydrogen and carbon monoxide ratio (H ₂ / CO ≒ 2) suitable for the Fischer-Tropsch process.

According to an aspect of the present invention, there is provided a metal structure for an autothermal reforming catalyst layer for preparing a synthesis gas for a Fischer-Tropsch liquefaction process, the metal support being a metal monolith; 30 to 60 parts by weight of magnesium oxide (MgO) based on 100 parts by weight of gamma alumina coated on the surface of the metal monolith to carry the active species catalyst metal, and cerium in the form of oxide as a promoter 34.7 to 38.6 Part by weight, 8.8 to 14 parts by weight of barium (Ba), 1.1 to 2 parts by weight of strontium (Sr); Metal structure for the autothermal reforming catalyst layer for the synthesis of the fischer-Tropsch liquefaction process composed of metal oxide and its preparation And a metal structure catalyst having palladium supported on the metal structure.

Metal Oxide, Magnesium Oxide, Palladium, Autothermal Modification, Metal Structure

Description

Metal-structure for catalyst layer for autothermal methane reforming to synthetic gas for Fischer-Tropsch process, manufacturing method for autothermal reforming catalyst layer for syngas production for Fischer-Tropsch liquefaction process eg and metal-structured catalyst

The present invention relates to a metal structure for an autothermal reforming catalyst layer, a method for producing a metal structure, and a metal structure catalyst for preparing a synthesis gas for a Fischer-Tropsch liquefaction process. Specifically, the active metal catalyst has thermal stability. The present invention relates to a metal structure including an enhancer, and a method of treating the surface of the metal structure to physically prevent the metal catalyst and the metal catalyst supported by the wash coating on the metal structure from physically agglomerating during the reaction.

In addition to fuel cells and small hydrogen generators, fuel reformers are in demand as reformers for natural gas and methane for syngas production. In particular, the development of gas fields, which are difficult to develop due to economic reasons such as small and remote gas wells (stranded or remote gas wells), is being used, and the possibility of their use is increasing due to the tightening of high oil prices and GHG emission regulations.

As of 2004, the amount of gas burned was 10 billion ft ³ per day, which is 25% of the EU's daily use or 17% of the US's use of gas per day. When classifying under the current criteria reserves 1 trillion ^{ft 3 (1 Trillion cubic feet,} Tcf) with a small gas fields, gas fields, depending on the size of about 1,400 that were investigated are scattered around the world.

Since methane, which is the main component of natural gas, has a very large binding energy of carbon atoms and hydrogen atoms of methane by forming an SP ₃ hybrid orbit, very large energy is required to activate methane.

There are various methods of reforming fuel using methane. Generally, 1) steam reforming, 2) partial reforming, and 3) autothermal reforming are used.

In the case of the steam reforming method, the reaction occurs even without a catalyst at 1300 ° C. or higher, but when a catalyst such as Pt or Rh occurs, the reaction occurs at 800 ° C. The hydrogen and carbon monoxide ratio of the produced synthesis gas is known to be about 3. . However, this method requires about three times as much steam as methane, a strong endothermic reaction, which consumes a lot of energy, and the hydrogen-carbon monoxide ratio is not suitable for Fischer-Trosch syngas.

In addition, in the case of the partial oxidation reforming method, the catalyst volume is advantageously compacted to about 1/100 of the steam reforming on the basis of the same treatment amount, but the hydrogen to carbon monoxide ratio of 1.5 is also not suitable.

In addition, in the autothermal reforming method, in order to complement the partial oxidation reforming method, an endothermic steam reforming reaction and an exothermic partial oxidation reforming reaction occur simultaneously, thereby reducing operating energy. It is effective, and the ratio of hydrogen and carbon monoxide, which is a product, can be controlled by controlling the supply ratio of water and oxygen, which is a reactant, and has emerged as an important utilization method that can generate hydrogen and carbon monoxide ratio of approximately 2. The ability to meet these characteristics is why the current trend is autothermal reforming (Oryx Plant, Sasol).

Patent trends investigated for syngas production for the Fischer-Tropsch process show that gas liquefaction technology in generators has been on the rise since the 1990s, with the most active patent activity in the US, and syngas in Japan. The manufacturing sector dominated, while other regional patents prevailed in the Fischer-Tropsch process.

Within each sector, there was a trend toward higher proportions in the process than in the production of catalysts. This is important for good catalysts, but technology such as reactor structure, reaction period connection, and operating conditions for high efficiency of reforming equipment is also important.

In the case of syngas production, representative patents cited widely include catalyst parts (Ni-based US 5,368,835, precious metals-based US 6,293,979, catalyst structure US 4,793,904), and thermal reforming in the process field is US 5,023,276 (June 11, 1991, ENGELHARD CORP. , Partial hydrogen oxidation, US 6,016,868 (2000, 1.25, World Energy Systems), and steam reforming were US 4,579,985 (April 1, 1986, ENGELHARD CORP.).

In particular, the patent on noble metal catalysts used in syngas production (US 6,293,979) describes a technique using a catalyst in which cobalt oxide is deposited on a support in which Be, Mg, Ca or a mixture thereof is pre-coated upon conversion of methane or natural gas into syngas. The autothermal reforming (US 5,023,276) patent is a technique for producing hydrogen enriched gas from hydrocarbon-based raw materials using a catalytic partial oxidation method and a selective steam reforming method. In addition, although a catalyst (USP 6,293,979) supporting an alkali metal on the outer surface of an inert support and then co-precipitating nickel and cobalt has been disclosed, a large number of studies have reported on an effective autothermal reforming device. The results of studies on the catalyst composition and the suitable composition ratio which are highly active in the reaction have not been reported.

When used in reformers, the shape of the catalyst is usually divided into powder, pellet and monolithic. In addition, the monolith type catalyst, which has a honeycomb-shaped rod-shaped void space, is easily transferred through the wall, so that the temperature of the catalyst is uniform and the pressure loss is low. (Ceramic monolith, US 5,648,582; zirconia (ZrO ₂ ) based monolith, US 5,639,401; metal monolith, US 5,786,296, 5,648,582 and 6,221,280 B1, EP 303438, Feb. 1989, Freni et al., J. of Power Sources 87 ( 2000), 28-38). Taking advantage of these advantages, the more complementary method is a method in which cells of metal meshes are arranged in an irregular arrangement to improve the reactivity by causing a channel of the reaction gases spatially rather than linearly.

However, metal oxides washcoat on conventional metal monoliths can be easily desorbed by the effects of reactants and product gases and water vapor having a high space velocity, which gradually degrades the reactivity or adversely affects the pressure to the material in the subsequent process. Can be crazy This is another reason for the lowering of reactivity as it is differentiated from the lowering of the intrinsic activity of the catalyst.

An object of the present invention for solving the above problems is to convert the methane into hydrogen and carbon monoxide as the main reaction, the autothermal reformer catalyst layer to obtain a hydrogen and carbon monoxide ratio (H ₂ / CO ≒ 2) suitable for Fischer-Tropsch process It is to provide a metal structure used for.

Another object of the present invention is to provide a method for producing a metal structure used in the autothermal reformer catalyst layer for the synthesis gas production reaction for Fischer-Tropsch liquefaction process.

Another object of the present invention is to convert the methane into hydrogen and carbon monoxide in the main reaction, while the metal structure catalyst used in the autothermal reformer catalyst layer to obtain a hydrogen and carbon monoxide ratio (H ₂ / CO ≒ 2) suitable for Fischer-Tropsch process To provide.

The present invention to achieve the object as described above and to remove the drawbacks of the prior art in the fissure-Tropsch liquefaction process for the self-reforming catalyst layer metal structure for syngas production,

A metal monolith which is a metal support;

30 to 60 parts by weight of magnesium oxide (MgO) based on 100 parts by weight of gamma alumina coated on the surface of the metal monolith to carry the active species catalyst metal, and cerium in the form of oxide as a promoter 34.7 to 38.6 Part by weight, 8.8 to 14 parts by weight of the barium (Ba), 1.1 to 2 parts by weight of strontium (Sr); metal for autothermal reforming catalyst layer for the synthesis of the Fischer-Tropsch liquefaction process, characterized in that composed of By providing a structure.

The gamma alumina has a specific surface area of greater than 100 m ² / g.

The component of the metal monolith constituting the metal structure is characterized in that any one selected from sus (SUS), titanium (Ti) or FeCrAlloy (FeCrAlloy).

Metal monolith constituting the metal structure is characterized in that using a wire of 100 ~ 150 micrometers thick.

In addition, the present invention is a metal structure catalyst for the autothermal reforming catalyst layer for the synthesis of synthesis gas for Fischer-Tropsch liquefaction process,

It is achieved by providing a metal structure catalyst for an autothermal reforming catalyst layer for preparing a synthesis gas for the Fischer-Tropsch liquefaction process, characterized in that 3 to 7 parts by weight of palladium metal is supported with respect to 100 parts by weight of the metal oxide of the metal structure. .

In addition, the present invention provides a method for producing a metal structure for the autothermal reforming catalyst layer for the synthesis gas for Fischer-Tropsch liquefaction process,

30 to 60 parts by weight of magnesium oxide (MgO) based on 100 parts by weight of gamma alumina by adjusting the applied voltage and the concentration of the electrolyte in the surface of the metal monolith, and oxide-formed cerium (Ce) 34.7 An electrochemical step of forming a metal oxide composed of 38.6 parts by weight, 8.8-14 parts by weight of barium (Ba), and 1.1-2 parts by weight of strontium (Sr);

Heat treatment in a furnace under an oxidizing atmosphere to produce a desired shape by controlling the roughness of the metal oxide formed in the metal monolith; autothermal reforming catalyst layer for manufacturing a synthesis gas for the Fischer-Tropsch liquefaction process It is achieved by providing a method for producing a metal structure for use.

Electrochemical surface treatment of the metal monolith to form a metal oxide,

Washing the metal monolith with a detergent;

Then, in a 0.5 to 1 wt% hydrofluoric acid (HF) or ammonium fluoride (NH ₄ F) electrolyte, a copper, iron, or platinum coil is used as a negative electrode as a negative electrode, and the metal monolith is cleaned and applied with a voltage. It characterized by consisting of; electrochemical treatment step of forming a metal oxide on the surface of the monolith.

It is characterized in that the voltage applied to the two electrodes of the positive electrode and the negative electrode is oxidized for 0.5 to 1 hour in the range of 5 ~ 10V.

The heat treatment step is characterized in that carried out in the oxidation atmosphere of 700 ~ 1100 ℃ air or oxygen.

The component of the metal monolith constituting the metal structure is characterized in that any one selected from sus (SUS), titanium (Ti) or FeCrAlloy (FeCrAlloy).

Metal monolith constituting the metal structure is characterized in that using a wire of 100 ~ 150 micrometers thick.

According to the present invention, the metal catalyst coated on the metal monolith may be included to enhance the thermal stability of the active metal catalyst constituting the metal structure catalyst, so that the metal catalyst may physically maintain high dispersion. When manufacturing metal structures, by maintaining the dispersion of metals supported in two directions by electrochemical pretreatment and heat treatment of the surface roughness, etc., the synthesis gas for Fischer-Tropsch liquefaction process is stable and efficient in small amount. The catalyst layer of the autothermal reforming reactor for manufacturing, and pretreated metal monoliths such as shape changes such as roughness can prevent the metal oxide metal carrier coated in a general chemical process from being detached and adversely affect the reactivity and rise in post process pressure. Can be useful with such advantages In one invention, the invention is expected to be greatly utilized.

Hereinafter, the configuration and the operation of the embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

The present invention relates to a metal structure and a metal structure consisting of a metal monolith and an oxide metal constituting a metal structure catalyst constituting the catalyst layer used in the methane autothermal reforming device for the synthesis of Fischer-Tropsch liquefaction process (H ₂ / CO ≒ 2) The present invention relates to a metal structure catalyst formed by supporting a catalytic metal, which is an active species metal, on a metal oxide metal of a manufactured metal structure. Here, the catalytic metal constituting the metal structure catalyst is completed by being wash-coated after being supported on the metal oxide.

The composition of the metal structure catalyst proposed in the present invention is composed of 3 to 7 parts by weight of palladium metal supported on 100 parts by weight of the metal oxide constituting the metal structure.

The reason for limiting the palladium composition ratio is that when the content is less than 3 parts by weight, the progress of the reaction is not sufficient, so that the minimum supported amount is limited to 3 parts by weight. In this case, the catalyst active point may be reduced due to sintering, so the content is limited to 7 parts by weight.

Metal oxide according to the present invention is 30 to 60 parts by weight of magnesium oxide (MgO) with respect to 100 parts by weight of gamma alumina (γ-alumina) having a specific surface area of more than 100 m ² / g, Cerium (Ce), a promoter (Ce), Barium (Ba) and strontium (Sr) are composed of 34.7 to 38.6 parts by weight, 8.8 to 14 parts by weight and 1.1 to 2 parts by weight in the form of each oxide.

In the case of the above-mentioned enhancers, cerium improves the dispersion of PdO as a catalyst and reaction with oxygen, strontium increases thermal stability of PdO to prevent sintering, and barium prevents phase transition of alumina. It prevents the decrease of specific surface area and maintains stability. However, in the case of the enhancer, the effect is not exhibited below the lower limit of the numerical value, and in the case of the upper limit, the catalyst may be hindered by lowering the surface exposure of the active substance PdO.

According to an aspect of the present invention, there is provided a method of manufacturing a metal structure carrying a metal catalyst, the method comprising: an electrochemical step of forming a metal oxide by controlling an applied voltage and a concentration of an electrolyte in a metal monolith surface; And heat treatment in a furnace under an oxidizing atmosphere to produce a desired shape by adjusting the roughness of the metal oxide formed on the metal monolith.

Electrochemical surface treatment of the metal monolith to form a metal oxide may include washing the metal monolith with a detergent; Then, in the 0.5 ~ 1 wt% hydrofluoric acid (HF) or ammonium fluoride (NH ₄ F) electrolyte, the copper, iron, or platinum coil is used as a negative electrode as a negative electrode, and the metal monolith is cleaned and the voltage is applied to the metal monolith. Electrochemical treatment step of forming a metal oxide on the surface; consists of.

Here, the voltage applied to both the positive electrode and the negative electrode is oxidized in the range of 5 to 10V for about 0.5 to 1 hour. The reason for the numerical limitation is that when the voltage is less than 5V, the generation of oxide becomes irregular, and when the voltage exceeds 10V, the oxide layer is detached or the structure is dissolved. This is because the metal oxide is well formed by the best anodization when oxidized for 0.5 to 1 hour.

In addition, the reason why 0.5 wt% of hydrofluoric acid (HF) or ammonium fluoride (NH ₄ F) is used as an electrolyte is that if it is less than 0.5 wt%, the applied voltage for surface treatment is high and takes a long time. In addition, when it exceeds 1% by weight, oxidation proceeds rapidly even at low applied voltage, making it difficult to manufacture a stable electrode.

In addition, the heat treatment step is performed in an oxidation atmosphere such as air or oxygen at 700 to 1100 ° C. The reason for the numerical limitation is that the lower the lower limit value, the less the change in roughness, and the higher the upper limit value, the higher the upper limit value leads to a change in crystal phase or roughness. Because.

As the component of the metal monolith constituting the metal structure, any one selected from sus (SUS), titanium (Ti), or FeCrAlloy is used.

The heat treatment temperature can be variously adjusted from 700 ℃ to 1100 ℃ according to the formation of a metal material and the desired oxide layer. The reason for limiting the temperature value is that crystals do not form when lower than 700 ° C., whereas when higher than 1100 ° C., surface agglomeration occurs and the surface area decreases.

The metal monolith constituting the metal structure uses a wire having a thickness of 100 to 150 micrometers because lower workability lowers the workability and easily deforms, and if the upper limit is higher than the upper limit, the monolithic metal is filled with unnecessary volume. .

The present invention is a metal structure including a promoter (promoter) to enhance the thermal and mechanical properties so that the metal catalyst such as palladium to withstand the reaction conditions by going through the process according to the manufacturing method of the metal structure as described above (support) ) And the dispersity of the active metal catalyst.

1 is a methane conversion result using the autothermal reforming reaction of the catalyst layer for each support used for the present invention, Figure 2 is a conceptual diagram of the autothermal reforming reactor used for the present invention.

First, referring to FIG. 2, the reforming apparatus and the entire reaction process used to evaluate the performance of the metal structure catalyst and the other catalyst of the present invention are described. An autonomous reforming reactor includes a starter connected to a power supply at an upper end thereof. A catalyst layer wash-coated with a catalyst is provided on the metal oxide formed in the metal monolith spaced apart from the lower portion.

The starting device is configured such that a pressurized SUS electrode is welded to prevent short circuits and short circuits at both ends of a metal monolith type object for keeping the reactant flow path constant, so that power of a power supply is applied.

The inlet (not shown) and the outlet (not shown) of the gas are formed at the upper and lower portions of the reformer reactor forming the outside.

The catalyst layer is installed on the inner diameter of the high temperature insulation material (not shown) installed in the inner circumferential direction of the autothermal reforming reactor case, the high temperature insulation material to fill the space between the catalyst layer and the case wall of the reformer reactor to prevent heat loss of the catalyst layer. .

Referring to the entire system including the autothermal reforming reactor configured as described above, the upper part of the autothermal reforming reactor to which the power supply is connected, the steam and the steam just before entering the autothermal reforming reactor after the reaction of methane or city gas and oxygen as the reaction medium is mixed in the mixing buffer Joined and supplied, oxygen is preheated through a heat exchanger and mixed with methane or city gas. The mixing buffer (buffer) is a device that serves as a space or time to mix the methane and oxygen well. The reactor consisting of methane and oxygen was injected with a volume ratio of oxygen (O ₂ ) to 0.59, the steam / carbon ratio was 0.3, and the catalyst layer had a space velocity of 100,000 hr ⁻¹ .

Since the synthesis gas discharged after the reaction in the autothermal reforming reactor is configured to be cooled by heat exchange by the temperature difference with oxygen while passing through the heat exchanger.

The material of the autothermal reforming reactor and the heat exchanger can be made of a low cost material such as stainless steel.

In addition, although not shown, it was installed inside the case of the autothermal reforming reactor, and the thermocouple was used to measure the temperature of the front end of the coil type starter, the coil and the catalyst layer, and the rear end of the catalyst layer.

Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to preferred embodiments. However, these embodiments do not limit the scope of the present invention.

(Example 1)-Autothermal reforming performance of each support (methane conversion and stability)

Palladium (Pd) was commonly used as the active component of the catalyst used in the present invention, and the metal oxide supporting the catalyst was alumina, Ce-Ba-Sr-alumina, MgO (30%)-alumina, MgO (60%). ) -Alumina, Ce-Ba-Sr-MgO (30%)-alumina and Ce-Ba-Sr-MgO (60%)-alumina were used (see FIG. 1).

As shown in FIG. 1, for methane conversion, alumina, Ce-Ba-Sr-alumina, MgO (30%)-alumina (or MgAl ₂ O ₄ (30)), MgO (60%)-alumina (or MgAl ₂ O ₄ (60)) The support showed a marked decrease in activity, but less than that, Ce-Ba-Sr-MgO (60%)-alumina also slowly decreased. However, Ce-Ba-Sr-MgO (30%)-alumina showed a tendency that activity is hardly decreased and activity is maintained in 100 hours of continuous experiments.

The addition of alkali metal salts, such as MgO, to the catalyst can enhance the catalyst's durability by converting deposited carbon into water and reacting with carbon monoxide to hydrogen, which is a common carbon precipitation problem in hydrocarbon conversion reactions. In addition, alkali metals slow the carbon deposition rate by reducing the number of acidic acid sites, but if the amount is too high, the number of acidic sites, which are active sites, may decrease rapidly, resulting in poor reactivity.

Methane Conversion Rate (%) = {Outlet Gas (CO + CO ₂ ) Flow Rate} ㅧ 100 / {Outlet Gas (CH ₄ + CO + CO ₂ ) Flow Rate}

Example 2-Catalyst Analysis by Support

Temperature Programmed Reduction (TPR) analysis was performed to investigate the reduction properties of the catalysts for each support used in the present invention. FIG. 3A shows MgO (30%)-alumina (or MgAl ₂ O ₄ (30)), FIG. 3B shows MgO (60%)-alumina (or MgAl ₂ O ₄ (60)) and FIG. 3C received In the case of a spinel. 3B and 3C show instability in which many changes occur due to a large number of peaks of reducing properties with respect to temperature, but FIG. 3A shows a stable tendency in addition to the peak at which Pd is reduced.

Table 1 shows the specific surface area and metal dispersion of the catalysts used for each support.

Table 1 Catalyst Analysis by Support

Even for the specific surface area, the value of MgO (30%)-alumina (or MgAl ₂ O ₄ (30)) is much higher than that of MgO (60%)-alumina (or MgAl ₂ O ₄ (60)) and the spinel provided. High, and metal dispersion showed the same trend. Among them, Ce-Ba-Sr-MgO (30%)-alumina was measured as 74.707 m ² / g for metal dispersion, and the highest measured value was found. These results agree very well with the reactivity results mentioned in Example 1.

Metal dispersion (%) = {number of chemisorption sites ㅧ 100} / number of supported metal atoms

(Example 3)-Shape comparison by metal structure pretreatment

SEM images were analyzed for changes in the shape of the same catalyst washcoat through the pretreatment of the metal structure. Figure 4a is a photograph washcoat without conventional pretreatment, Figure 4b is a photograph washwashing the catalyst after the electrochemical surface treatment. It can be seen that the dispersion degree of the metal palladium catalyst is much improved. FIG. 5 further enlarges 1.5 times of FIG. 4b to perform energy dispersive X-ray spectroscopy (EDS) analysis to confirm the composition of points A and B. FIG. As shown in Table 2 and Table 3 below, the brightly glowing circular portion in FIGS. 4B and 5 is about 10.83 wt% portion (P region) and the dark portion is stably dispersed to 3.23 wt% (region A). Confirmed the results. FIG. 5 is an enlarged photograph of one point of FIG. 4B, in which A and B circular regions of FIG. 5 refer to regions of palladium with respect to three-dimensional space regions as well as surface regions on the photograph.

Table 2. Point A

Element weight% Atomic% O 45.05 59.12 Al 51.71 40.24 Pd 3.23 0.64 Total 100.00

Table 3. Point B

Element weight% Atomic% O 46.70 63.84 Al 41.30 33.48 Pd 10.83 2.23 Other (Fe) 1.17 0.46 Total 100.00

The present invention is not limited to the above-described specific preferred embodiments, and various modifications can be made by any person having ordinary skill in the art without departing from the gist of the present invention claimed in the claims. Of course, such changes will fall within the scope of the claims.

1 is a result of methane conversion using the autothermal reforming reaction of the catalyst layer for each support used for the present invention,

2 is a conceptual diagram of an autothermal reforming reactor used for the present invention,

Figure 3a is a temperature-dependent reduction trend (TPR analysis) of the MgO (30%)-alumina (or MgAl ₂ O ₄ (30)) support used for the present invention,

Figure 3b is the temperature-dependent reduction trend (TPR analysis) of the MgO (60%)-alumina (or MgAl ₂ O ₄ (60)) support used for the present invention,

Figure 3c is the temperature-dependent reduction trend (TPR analysis) of the provided spinel support used for the present invention,

Figure 4a is an electron micrograph (SEM) of the sample fired after the washcoat mixed with alumina powder, alumina sol and Pd precursor without pretreatment of the metal structure,

Figure 4b is an electron micrograph (SEM) of the sample fired after mixing the alumina sol and Pd precursor after the pretreatment of the metal structure for the present invention,

FIG. 5 is an electron microscope (SEM) photograph showing a bright round part and a dark part after point 1.5 times of magnification of FIG. 4B.

Claims (11)

In the metal structure for the autothermal reforming catalyst layer for the synthesis gas for Fischer-Tropsch liquefaction process, A metal monolith which is a metal support; 30 to 60 parts by weight of magnesium oxide (MgO) based on 100 parts by weight of gamma alumina coated on the surface of the metal monolith to carry the active species catalyst metal, and cerium in the form of oxide as a promoter 34.7 to 38.6 Part by weight, 8.8 to 14 parts by weight of the barium (Ba), 1.1 to 2 parts by weight of strontium (Sr); metal for autothermal reforming catalyst layer for the synthesis of the Fischer-Tropsch liquefaction process, characterized in that composed of Structure. The method according to claim 1, The gamma alumina (γ-alumina) has a specific surface area of more than 100m ² / g metal structure for the autothermal reforming catalyst layer for the synthesis gas for Fischer-Tropsch liquefaction process. The method according to claim 1, The component of the metal monolith constituting the metal structure is any one selected from sus (SUS), titanium (Ti) or FeCrAlloy (FiCr-Tropsch liquefaction process) autothermal reforming catalyst layer for syngas production Metal structure. The method according to claim 1, Metal monolith constituting the metal structure is a metal structure for the autothermal reforming catalyst layer for the synthesis gas for Fischer-Tropsch liquefaction process, characterized in that using a wire of 100 ~ 150 micrometers thick. In the manufacturing method of the metal structure for the autothermal reforming catalyst layer for producing a synthesis gas for Fischer-Tropsch liquefaction process, 30 to 60 parts by weight of magnesium oxide (MgO) based on 100 parts by weight of gamma alumina by adjusting the applied voltage and the concentration of the electrolyte in the surface of the metal monolith, and oxide-formed cerium (Ce) 34.7 An electrochemical step of forming a metal oxide composed of 38.6 parts by weight, 8.8-14 parts by weight of barium (Ba), and 1.1-2 parts by weight of strontium (Sr); Heat treatment in a Fischer-Tropsch liquefaction process for syngas production, comprising the step of: heat-treating in a furnace under an oxidizing atmosphere to control the roughness of the metal oxide formed in the metal monolith to produce a desired shape. Method for producing a metal structure for the catalyst layer. The method according to claim 5, Electrochemical surface treatment of the metal monolith to form a metal oxide, Washing the metal monolith with a detergent; The metal monolith is then connected to a metal monolith, which is cleaned at a positive electrode using a copper, iron or platinum coil as a negative electrode, in a 0.5 to 1 wt% hydrofluoric acid (HF) or ammonium fluoride (NH ₄ F) electrolyte. Electrochemical treatment step of forming a metal oxide on the surface; Fischer-Tropsch liquefaction process for producing a metal structure for the autothermal reforming catalyst layer for the synthesis gas for liquefaction process. The method according to claim 6, The method of manufacturing a metal structure for the autothermal reforming catalyst layer for producing a synthesis gas for the Fischer-Tropsch liquefaction process, characterized in that the voltage applied to the two electrodes of the positive electrode and the negative electrode in the range of 5 ~ 10V for about 0.5 to 1 hour. The method according to claim 5, The heat treatment step is a method for producing a metal structure for the autothermal reforming catalyst layer for manufacturing a synthesis gas for Fischer-Tropsch liquefaction process, characterized in that carried out in the oxidation atmosphere of 700 ~ 1100 ℃ air or oxygen. The method according to claim 5, The component of the metal monolith constituting the metal structure is any one selected from sus (SUS), titanium (Ti) or FeCrAlloy (FiCr-Tropsch liquefaction process) autothermal reforming catalyst layer for syngas production Method for producing a metal structure for use. The method according to claim 5, The metal monolith constituting the metal structure is a method for producing a metal structure for the autothermal reforming catalyst layer for the synthesis gas for Fischer-Tropsch liquefaction process, characterized in that using a wire of 100 ~ 150 micrometers thick. In the metal structure catalyst for autothermal reforming catalyst layer for the synthesis of synthesis gas for Fischer-Tropsch liquefaction process, Autothermal reforming catalyst layer for manufacturing a synthesis gas for Fischer-Tropsch liquefaction process, characterized in that 3 to 7 parts by weight of palladium metal is supported with respect to 100 parts by weight of the metal oxide of the metal structure according to any one of claims 1 to 4. Metal structure catalyst.

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