KR100903271B1 - New catalysts and method to produce synthetic gas H2/CO?2 for Fischer-Tropsch process through autothermal reforming of natural gas - Google Patents

Abstract

The present invention relates to a reforming catalyst used for the production of Fischer-Tropsch liquefaction process synthesis gas (H ₂ / CO ≒ 2) from natural gas by autothermal reforming, and to a method for producing the same and the synthesis gas for Fischer-Tropsch liquefaction process using the same Regarding the manufacturing method,

Its main purpose is the partial reaction of methane or natural gas as the main reaction and the addition of hydrogen and carbon monoxide by the steam reforming reaction and the reverse water gas shift reaction. In the process, the catalyst composition and reaction conditions necessary to obtain a hydrogen to carbon monoxide ratio (H ₂ / CO 2) suitable for the Fischer-Tropsch process are presented.

The composition of the present invention is a catalyst for the Fischer-Tropsch liquefaction process composed of a high surface area alumina carrier, 1-20 wt% nickel metal and 1-15 wt% cerium metal, compared to 100 wt% of the alumina carrier, and a method for preparing the same and a synthesis gas using the same. The method is characterized by the technical idea.

Fischer-Tropsch liquefaction process, autothermal reforming, catalyst, syngas, high surface area alumina carrier, nickel, cerium

Description

Reforming catalyst used in the production of Fischer-Tropsch liquefaction process synthesis gas (H2 / CO2) from natural gas by autothermal reforming and method for producing synthesis gas for Fischer-Tropsch liquefaction process using the same catalysts and method to produce synthetic gas (H2 / CO ≒ 2) for Fischer-Tropsch process through autothermal reforming of natural gas}

The present invention relates to a reforming catalyst used for the production of Fischer-Tropsch liquefaction process synthesis gas (H ₂ / CO ≒ 2) from natural gas by autothermal reforming, and to a method for producing the same and the synthesis gas for Fischer-Tropsch liquefaction process using the same It relates to a manufacturing method, and in detail, a catalyst which has high activity of a catalyst required in the synthesis gas manufacturing process for the Fischer-Tropsch liquefaction process, target hydrogen and carbon monoxide generation ratio of 2 or less, and enhances the selectivity of hydrogen and carbon monoxide. The present invention relates to a method for producing hydrogen and carbon monoxide suitable for the Fischer-Tropsch reaction by varying the composition, the preparation method, and the conditions of water and oxygen, which are reactants using the same.

In line with the global trend of developing environmentally friendly energy, many countries not only have long-term plans for new fuel energy technology development, but also short-term pursuit of system technology improvement, emission control technology improvement, and cleanliness. It is trying to create an environment friendly environment such as energy conversion.

Hydrogen reforming is an essential process not only for obtaining pure hydrogen, but also for the DME synthesis process and gas-to-liquid (GTL) technology, and this series of processes is spotlighted as the next generation technology using natural gas. In particular, in the petrochemical sector, introduction of the GTL process is essential for the production of alternative gasoline due to oil depletion.

There are several ways to reform fuel using methane, the main component of natural gas, generally 1) Steam reforming, 2) Partial reforming, 3) Autothermal reforming Use the method.

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.

Although methane gas and water vapor usually react without catalysts at temperatures above 1300 ° C, the reactions occur at 800 ° C with catalysts such as Pt and Rh, with hydrogen and carbon monoxide ratios of about 3 Known.

However, these high temperature reaction conditions increase the volume of the device, show low efficiency due to the demanding reaction conditions, and the inappropriate ratio of hydrogen and carbon monoxide. Research on the development of catalysts and the optimum reforming conditions for producing H ₂ / CO suitable for the study.

In the steam reforming, partial oxidation reforming, and autothermal reforming reaction, almost all nickel-based catalysts are used as industrial catalysts. However, in the reforming process, the biggest problem occurs in preventing catalyst deactivation due to carbon deposition of the reforming catalyst, and research results suggest that carbon deposition can be suppressed by using a small amount of precious metal in the nickel catalyst. Based on this reforming process, using Fischer-Tropsch technology, Mossgas uses Mossel's own gas resources for the Fischer-Tropsch liquefaction process (launched in 1991) and started operation in 1993 in Bintulu, Malaysia. The diesel oil produced here has been used as a California diesel base.

Sasol, a leading manufacturer of synthetic fuels, has been pursuing two projects, coal liquefaction and natural gas liquefaction, in accordance with the government's energy self-sufficiency policy. However, steam reforming is the most efficient reforming technique, but it has a high endothermic reaction and a slow reaction rate due to the equilibrium reaction. Therefore, the scale of the process must be large, and the ratio of hydrogen and carbon monoxide produced Most of them are on the order of three, so they are not suitable for Fischer-Tropsch liquefaction processes.

To compensate for this, the steam reforming reaction, which is an endothermic reaction, and the partial oxidation reforming reaction, which is an exothermic reaction, occur simultaneously, thereby reducing operating energy and controlling the supply ratio of reactants, water and oxygen. As a result, autothermal reforming, which can control the ratio of hydrogen and carbon monoxide as a product and generate hydrogen and carbon monoxide ratio of about 2, has emerged as an important application method. This is why the trend is autothermal reforming.

In Korea, although a small reformer using natural gas or methanol as a raw material was manufactured for small use, the purpose of most reforming reactions was hydrogen production.

Hydrogen production technologies using fossil fuels, there is leverage in domestic refineries and petrochemical plants, and dozens reformer to produce hydrogen for ^{3,000 Nm 3 / h~100,000 Nm 3 /} h Operation GB are imported from abroad, and a glass factory, janja, Even in small chemical plants, many reformers producing less than 1,000 Nm ³ / h of hydrogen are being imported and operated.

However, studies on autothermal reforming for the purpose of the Fischer-Tropsch liquefaction process have not been carried out yet.

According to the researched patent trend, a zirconia-supported nickel catalyst (USP 4,026,823) having cobalt added to nickel as a steam reforming catalyst for hydrocarbons has been disclosed, and another method is to reform methane with water vapor. Catalysts (USP 4,060,498) supported by adding a proper ratio of metal and silver as cocatalysts supported on alumina, silica, magnesia, zirconia, etc., which are common carriers, have been disclosed, respectively.

The results of the study on autothermal reforming revealed a catalyst (USP 6,293,979) in which an alkali metal was supported on the outer surface of an inert support and then co-precipitated with nickel and cobalt (USP 6,293,979). Most reports have been made, and the results of studies on the catalyst composition and the suitable composition ratio which are highly active in this reforming reaction have not been reported.

An object of the present invention for solving the above problems is a partial oxidation reaction of methane or natural gas as the main reaction and the addition of steam reforming reaction and (reverse) water gas shift reaction, ( R) WGS} to convert hydrogen and carbon monoxide, the catalyst composition necessary for obtaining the hydrogen and carbon monoxide ratio (H ₂ / CO ≒ 2) suitable for the Fischer-Tropsch Process, and the preparation method and using the same It is to provide a method for producing syngas.

That is, a catalyst capable of generating a synthesis gas having H ₂ / CO of about 2, which is an active factor for methane reforming at a lower temperature than the existing process temperature through autothermal reforming, and is an important factor. as control the composition and reactant feed ratio, the optimal reaction conditions, hydrogen and carbon monoxide ratio (H ₂ / CO ≒ ₂₎ a Fischer-can be produced at a rate suitable to Tropsch liquefaction process and the high efficiency of the new catalyst and The present invention provides a method for producing the same and reaction conditions for syngas production.

The present invention, which achieves the above object and accomplishes a problem for eliminating the conventional drawback, in the catalyst for Fischer-Tropsch liquefaction process, a high surface area alumina (γ-alumina) carrier, 5.54wt% nickel relative to the carrier It is achieved by providing a reforming catalyst used in the production of Fischer-Tropsch liquefaction syngas (H ₂ / CO ≒ 2) from natural gas by autothermal reforming, characterized in that the composition is composed of 1 to 30wt% cerium.

The present invention also provides a method for preparing a catalyst for Fischer-Tropsch liquefaction process,

Dissolving the nickel precursor in water, adding high surface area alumina, stirring and evaporating the water;

Thereafter, the one-component catalyst obtained by the above step is added to a solution in which the cerium precursor is dissolved in water, followed by stirring, followed by evaporation of the water to obtain a two-component catalyst composed of nickel and cerium;

Then drying the binary catalyst composed of nickel and cerium at a temperature of 90 to 120 degrees;

Then firing at 650 to 900 degrees in an air atmosphere;

After the sintering process, the binary catalyst is manufactured from Fischer-Tropsch liquefaction process synthesis gas (H ₂ / CO ≒ 2) from natural gas by autothermal reforming, characterized in that the reduction process at a temperature of 400 ~ 900 degrees. It is achieved by providing a method for producing a reforming catalyst for use in.

In another aspect, the present invention provides a method for producing a synthesis gas (H ₂ / CO ≒ 2) for Fischer-Tropsch liquefaction process, a high surface area alumina (γ-alumina) carrier prepared according to the reforming catalyst production method, 5.54wt of nickel relative to the carrier %, By passing the reactant to a reformer having a packed bed filled with a reforming catalyst composed of 1 ~ 30wt% cerium from the natural gas by autothermal reforming, characterized in that to produce a synthesis gas (H ₂ / CO ≒ 2) It is achieved by providing a method for producing a synthesis gas for Fischer-Tropsch liquefaction process using a reforming catalyst used for the production of Fischer-Tropsch liquefaction process syngas (H ₂ / CO ≒ 2).

The present invention has been previously disclosed when an methane autothermal reforming reaction is carried out using various catalysts synthesized through a calcination and reduction process by impregnating alumina with nickel and cerium metals having various compositional values. It has the advantage of providing a highly active catalyst composition that produces a Fischer-Tropsch synthesis syngas at 750 degrees below the process temperature.

In other words, when methane is reformed by autothermal reforming in general, the activity was low.In order to bring the hydrogen and carbon monoxide ratio closer to 2, the ratio of water and oxygen must be controlled. Although thermodynamic factors in carbon monoxide-producing side reactions, such as -gas-shift reverse reactions, are known to occur under high temperature conditions above 850 degrees (Mariana MVM Souza, Martin Schmal, "Autothermal reforming of methane over Pt / ZrO ₂ / Al ₂ O ₃ catalysts ", Applied Catalysis, 2005, 19-24), the catalyst according to the present invention has a high activity and is a useful invention with the advantage that the ratio of hydrogen and carbon monoxide generation is close to 2 It is an expected invention.

Hereinafter, the configuration and the operation of the embodiments of the present invention will be described in detail with reference to the accompanying drawings.

According to the present invention, the bicomponent catalyst in which nickel and other amounts of cerium metal are supported on the surface of the highly active alumina carrier is produced by the impregnation method.

Impregnation is performed by a general method, first dissolving the nickel precursor in water, adding high surface area alumina, stirring it, and then evaporating the water, and then injecting it into a solution in which the cerium precursor is dissolved in water. Evaporating water in the same way yields a bicomponent catalyst composed of nickel and cerium. At this time, the catalyst synthesized in the manufacturing process is wet, it needs to be dried for 9 to 13 hours at a temperature of 90 ~ 120 degrees.

Since the drying temperature and time do not significantly affect the catalyst activity, the drying temperature and time need only be adjusted by adjusting the temperature and time as necessary.

The composition of the catalyst proposed in the present invention was 1-20 wt% nickel metal and 1-15 wt% cerium metal on the basis of a high surface area alumina (γ-alumina) carrier and alumina carrier ratio (100 wt%).

That is, high surface area alumina carrier 100 parts by weight, based on 100 parts by weight of the alumina carrier, is composed of 1 to 20 parts by weight of nickel metal and 1 to 15 parts by weight of cerium metal .

The reason for limiting the nickel composition ratio is that the reaction progress rate is not sufficient at 1wt% or less, thereby preventing the function as a main catalyst, thereby limiting the minimum supported amount of nickel to 1wt%, and sintering when the metal is supported in excess of the specific surface area of the carrier. Due to the phenomenon, the catalytically active point may be reduced, thereby limiting the nickel content to 20wt%.

In addition, in the case of the cerium metal acting as a promoter of the nickel metal catalyst, the reaction progress rate is insufficient as the promoter when 1 wt% or less, and the minimum amount is limited to 1 wt%, and in the case of cerium metal, the atomic weight is higher and the atomic size is larger than that of the nickel metal catalyst. Subsequently, it is possible to cover the nickel metal while supporting the cerium atom to limit the maximum content of cerium metal to 15wt% in order to preserve the activity of the nickel metal and facilitate the action of the catalyst of nickel and cerium metal.

In addition, the high surface area alumina refers to gamma alumina.

As the alumina is synthesized and fired, it is divided into alpha phase alumina, beta phase alumina, and gamma phase alumina by firing temperature. The largest surface area is gamma alumina. The specific surface area of these three aluminas is as follows.

Alpha alumina: <10 m ² / g

Beta alumina: 10 to 100 m ² / g

gamma alumina:> 100m ² / g

The dried catalyst is subjected to a calcination process, and the reason for the calcination process is to remove and remove unnecessary components or lubricants left in the catalyst at a high temperature while supporting the active material or forming the catalyst.

Firing conditions are performed at 650 ~ 900 degrees in an air atmosphere. In this case, the lower limit of the 650 ° C is limited to firing at a temperature of at least 650 ° C in order to remove unnecessary components and lubricants. As a result, the surface area of the carrier is reduced, thereby reducing the number of active site distributions. The preferred temperature is therefore 750 degrees.

In addition, the firing time is fired for 1 to 6 hours. The reason for the limitation of time is to bake at least 1 hour and to remove unnecessary components and lubricants, and after 6 hours of firing, sintering of the supported metal occurs and phase change of the carrier occurs. This is to prevent deactivation from occurring.

The calcined catalyst is hydrogen reduced at a temperature of 400 to 900 degrees. In the hydrogen atmosphere, the reduction treatment is performed at a temperature of 1 to 3 hours. The nickel and cerium metals of the catalyst are present in the form of an oxide when the catalyst is calcined. It must be reduced to the metal component. The reason for limiting the temperature in the hydrogen reduction treatment as described above is that the activity of the alumina carrier is lowered when the temperature is lower than 400 degrees, and the activity of the alumina carrier is lowered. Is lowered. Preferably, the reduction process should be performed at 500 to 800 degrees, and more preferably, the reduction process should be performed at 650 to 700 degrees to form a bicomponent metal catalyst having excellent activity.

The reason for limiting the reduction time is that at least one hour or more is required to completely reduce the nickel and cerium metal oxides, and the hydrogen reduction process is carried out for 1 to 6 hours at a high temperature condition, so that hydrogen is used for at least 3 hours. When the reduction treatment affects the catalyst structure and affects the catalyst activity decrease, the maximum value is set to 3 hours.

Reaction conditions performed in the reforming reaction using the catalyst prepared as described above is the catalyst bed temperature is 650 ~ 750 degrees filled with the catalyst of the reformer, the gas space velocity (GHSV) of the reactants ('methane / oxygen', 'methane / water') Is 31,000 ~ 48,000h ^-1 .

The reformer of the present invention used for the reaction as described above is briefly described. It is configured to generate hydrogen, carbon monoxide, carbon dioxide, water, methane and oxygen toward the bottom.

The present invention is a two body reaction in which a reaction of oxygen and methane and a reaction of water and methane occur simultaneously. Therefore, the molar ratio constituting each reactant is important, which will be described below.

One of the reactants of the present invention consists of 0.01 to 2 times the oxygen relative to the molar ratio of the constituent carbon in the hydrocarbon. The reason for this limitation is the autothermal reforming reaction in which the reaction between methane and oxygen and the reaction between methane and water occur simultaneously. , 0.01 times indicates the minimum value for the reaction of methane by oxygen, and the reaction between methane and oxygen is exothermic reaction with high heat of reaction, thereby reducing the decrease in catalyst activity caused by exotherm and facilitating heat control in the reactor. It was set to 2 times. That is, when it is less than 2 times, methane reforming is a condition that can be evened by oxygen and water.

In addition, the other one of the reactants of the present invention consists of 0.01 to 3.5 times the steam relative to the molar ratio of the constituent carbon in the hydrocarbon, this limited reason is not only partial oxidation of methane by oxygen but also reforming reaction of methane by water at the same time It was set up to allow the synthesis gas ratio (hydrogen / carbon monoxide) to be generated in the range of 1.5 to 2 with the focus on making the synthesis gas suitable for the Fischer Drop synthesis. When the water content is 0.01 times or less, the methane reforming reaction by water does not proceed, and when the water content is 3.5 times or more, the synthesis gas for Fischer Tropsch synthesis gas (hydrogen production rate) is reduced because the carbon monoxide generation rate of the synthesis gas decreases and the hydrogen production rate increases. The maximum content of water was 3.5 times as the carbon monoxide ratio could not produce 1.5 ~ 2).

The reason for limiting the temperature of the catalyst layer in the above 650 ~ 750 degrees is because the reaction should be obtained at least 650 degrees based on the input concentration can be obtained a high reaction conversion rate, the reason set to 750 degrees is hydrogen and carbon monoxide based on the ratio of the reactants added The maximum temperature was limited to 750 degrees because the maximum 750 degrees is suitable to generate a synthesis gas having a ratio of 1.5 to 2, and the energy saving effect is lowered when the ratio exceeds 750 degrees. In addition, when the experiment was carried out at 750 ° C. or higher, the phase of the high surface area alumina, which is a carrier, was changed little by time, and the specific surface area of the carrier was reduced during the reaction, thereby limiting the activity.

The reason why the gas space velocity passing through the catalyst layer is limited to 31,000 to 48,000 h ⁻¹ is that when the contact time between the catalyst and the reactant becomes longer, the amount of syngas generated by converting hydrogen and carbon monoxide into water and carbon dioxide is synthesized. Relatively decreasing, the minimum gas space velocity was set to 31,000. In addition, the reason why the 48000 was set as the maximum value was that the reaction progress due to the catalyst was insufficient when the contact time was reduced, so that the maximum gas space velocity was set to 48000.

Hereinafter, the present invention will be described in detail through examples of the present invention.

(Example 1)

Nickel-cerium binary catalyst composed of high surface area alumina carrier ratio, nickel 5.54wt%, cerium 6.65, 9.31, 10.6, 12wt%, temperature condition 650 degrees, reactant composition methane / oxygen = 2, oxygen / water = 1, gas space velocity (GHSV) 31,830h ^- experiment was performed under the conditions of ^Fig.

(Example 2)

Nickel-cerium binary catalyst composed of high surface area alumina carrier ratio, 5.54wt% nickel, cerium 2.66, 10.60, 12.00, 13.30wt% temperature condition 700 degree, reactant composition methane / oxygen = 5, water / oxygen = 1, gas the space velocity (GHSV) 31,830h ^- under the conditions of the ^first experiment was carried out to evaluate the catalyst characteristics.

(Example 3)

Nickel-cerium binary catalyst composed of high surface area alumina carrier ratio, nickel 5.54wt%, cerium 2.66, 3.99, 5.32, 7.98, 9.31, 10.60, 12.0, 13.3wt%, temperature condition 700degree, reactant composition methane / oxygen = 5 The catalytic properties evaluation experiments were carried out under the condition of water, oxygen = 15 and gas space velocity 47,770 h ^{- 1} .

(Example 4)

Nickel-cerium binary catalyst composed of high surface area alumina carrier ratio, nickel 5.54wt%, cerium 2.66, 3.99, 5.32, 7.98, 9.31, 10.60, 12.0, 13.3wt%, temperature condition 750 degree, reactant composition methane / oxygen = 5 The catalytic properties evaluation experiments were carried out under the condition of water, oxygen = 15 and gas space velocity 47,770 h ^{- 1} .

The following is a comparative example compared with the Example of this invention.

(Comparative Example 1)

Nickel catalyst composed of a high surface area alumina carrier ratio, 10wt% nickel is known as a high methane activation catalyst, and compared with the nickel-cerium bicomponent catalyst activity carried out, the same catalyst as in Example 1 as the activity comparison catalyst during the experiment The experiment was carried out under experimental conditions.

(Comparative Example 2)

Nickel catalyst composed of a high surface area alumina carrier ratio, nickel 10wt% is known as a high methane activation catalyst, and compared with the nickel-cerium bicomponent catalyst activity carried out, the same as Example 2 as the activity comparison catalyst during the experiment The experiment was carried out under experimental conditions.

(Comparative Example 3)

Nickel catalyst composed of a high surface area alumina carrier ratio, nickel 10wt% is known as a high methane activation catalyst, and compared with the nickel-cerium bicomponent catalyst activity carried out, the same as in Example 3 as the activity comparison catalyst during the experiment The experiment was carried out under experimental conditions.

The following is the result according to each said Example and the comparative example.

TABLE 1

Methane conversion and H ₂ / CO according to the cerium content of Example 1, Comparative Example 1

Reaction temperature (℃) Ni content (wt%) Ce content (wt%) Methane conversion rate (%) H ₂ / CO 650 5.54 6.65 56.6 4.0 650 5.54 9.31 51.8 3.6 650 5.54 10.6 64.5 5.4 650 5.54 12 63.8 5.5 650 10.00 0 55.0 5.2

As shown in Table 1, the higher the content of cerium metal in the catalyst at 650 ° C, the higher the activity. In particular, the catalyst with the alumina support ratio of 5.54 wt% nickel and 10.6 wt% cerium showed the highest methane conversion rate. The reaction was performed at high and low temperature conditions, and the ratio of hydrogen to carbon monoxide was in the range of 3.6 to 5.5, indicating a high hydrogen production rate.

Of course, overall low catalyst activity results were obtained, but since the activity was higher than that of the reference catalyst loaded with 10 wt% Ni in the highly active alumina, the excellent catalytic activity was demonstrated.

TABLE 2

Methane conversion and H ₂ / CO according to the cerium content of Example 2, Comparative Example 2

Reaction temperature (℃) Ni content (wt%) Ce content (wt%) Methane conversion rate (%) H ₂ / CO 700 5.54 2.66 34.2 4.0 700 5.54 10.60 59.1 3.6 700 5.54 12.00 58.9 3.6 700 5.54 13.30 68.3 3.7 700 10.00 0 60.4 3.8

In Table 2, the methane conversion rate at 700 degrees was the highest when the nickel content is 5.54wt%, the cerium content is 13.3wt%, and the catalytic activity increases as the content of cerium increases. The ratio of hydrogen to carbon monoxide ranged from 3.6 to 4.0, indicating a high hydrogen production rate.

TABLE 3

Methane conversion and H ₂ / CO according to the cerium content of Example 3, Comparative Example 3

Reaction temperature (℃) Ni content (wt%) Ce content (wt%) Methane conversion rate (%) H ₂ / CO 700 5.54 2.66 79.2 6.1 700 5.54 3.99 82.0 6.0 700 5.54 5.32 84.5 5.7 700 5.54 7.98 85.8 4.8 700 5.54 9.31 85.7 5.9 700 5.54 10.60 86.2 5.6 700 5.54 12.0 87.2 5.4 700 5.54 13.3 86.1 6.0 700 10.00 0 62.1 4.5

The amount of oxygen was maintained in the same manner as in Example 2, and the amount of water supplied was increased, and the experiment was performed under the condition of 700 degrees by changing the reactant composition. Methane conversion was 77 ~ 87.2% for the nickel-cerium catalyst. Similarly, as the cerium content was increased, the methane conversion was higher, indicating that the catalytic activity was higher. It can be seen by comparing Table 2 that the activity of the methane reforming reaction increased rapidly as the water content increased. However, the hydrogen and carbon monoxide ratio is composed of 4.5 ~ 6.7, which is due to the steam reforming effect due to water is increased than the experiment in Example 3, the hydrogen production rate is higher than the results in Table 2.

TABLE 4

Reactant conversion and H ₂ / CO according to the cerium content of Example 4

Reaction temperature (℃) Ni content (wt%) Ce content (wt%) Methane conversion rate (%) H ₂ / CO 750 5.54 2.66 62.6 1.8 750 5.54 3.99 63.6 2.4 750 5.54 5.32 73.5 2.3 750 5.54 7.98 76.3 2.4 750 5.54 9.31 80.0 2.3 750 5.54 10.60 82.3 2.3 750 5.54 12.0 83.4 2.3 750 5.54 13.3 70.2 2.3

As shown in Table 4, the reaction conditions were the same as in Example 3, and the result of methane conversion of 62.6 to 83.4% at 750 ° C. was obtained. Was produced in the entire catalyst constituted.

1 is a methane conversion graph (X: content of alumina weight ratio cerium in a nickel-cerium catalyst) from the results obtained from Examples 3 and 4, and in both conditions, as the cerium content of the nickel-cerium catalyst increases, The conversion increased, but the activity increased. On the other hand, unlike the results of Examples 1 and 2, the higher the temperature, the lower the total activity.

2 is a graph comparing H ₂ / CO from the results obtained from Example 3 and Example 4 (X: content of cerium alumina weight ratio of nickel-cerium catalyst), and the ratio of hydrogen and carbon monoxide regardless of the content of cerium at 750 degrees The result consisted of about 2 values.

Summarizing all the above results, the catalyst activity increases as the content of the catalyst and cerium increases in the autothermal reforming reaction, whereas the ratio of hydrogen and carbon monoxide is not dependent on the catalyst composition and the content of cerium. It can be seen that it is greatly influenced by the reactant composition and the reaction conditions, which is due to the thermodynamic equilibrium relationship of all side reactions that may exist in the reforming reaction.

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 methane conversion rate graph from the results obtained in Examples 3 and 4 according to the present invention (X: content of alumina weight ratio cerium in a nickel-cerium catalyst),

2 is a H ₂ / CO comparison graph (X: content of cerium in the alumina weight ratio of the nickel-cerium catalyst) from the results obtained from Examples 3 and 4 according to the present invention.

Claims (13)

delete In the Fischer-Tropsch liquefaction catalyst, A high surface area alumina carrier and 1 to 20 wt% nickel metal and 1 to 15 wt% cerium metal, compared to 100 wt% of the alumina carrier, wherein the high surface area alumina carrier is gamma alumina having a specific surface area of greater than 100 m ² / g. Reforming catalyst for the synthesis of Fischer-Tropsch liquefaction syngas (H ₂ / CO ≒ 2) from natural gas by autothermal reforming. In the method for producing a catalyst for Fischer-Tropsch liquefaction process, Dissolving the nickel precursor in water, adding high surface area alumina, stirring and evaporating water; Thereafter, the one-component catalyst obtained by the above step is added to a solution in which the cerium precursor is dissolved in water, followed by stirring, followed by evaporation of the water to obtain a two-component catalyst composed of nickel and cerium; Then drying the binary catalyst composed of nickel and cerium at a temperature of 90 to 120 degrees; Then firing at 650 to 900 degrees in an air atmosphere; After the sintering process, the binary catalyst is manufactured from Fischer-Tropsch liquefaction process synthesis gas (H ₂ / CO ≒ 2) from natural gas by autothermal reforming, characterized in that the reduction process at a temperature of 400 ~ 900 degrees. Method for producing a reforming catalyst used in the. The method of claim 3, wherein The drying step is a method for producing a reforming catalyst used in the synthesis of Fischer-Tropsch liquefaction process synthesis gas (H ₂ / CO ≒ 2) from natural gas by autothermal reforming, characterized in that lasting for 9 to 13 hours. The method of claim 3, wherein The firing step is a method for producing a reforming catalyst used in the synthesis of Fischer-Tropsch liquefaction process synthesis gas (H ₂ / CO ≒ 2) from natural gas by autothermal reforming, characterized in that it lasts for 1 to 6 hours. The method of claim 3, wherein Reducing step in the preparation of the reforming catalyst used in the synthesis of the synthesis gas for Fischer-Tropsch liquefaction process (H ₂ / CO ≒ 2) from natural gas by autothermal reforming, characterized in that lasting for 1 to 3 hours Way.. The method of claim 3, wherein The composition ratio between the nickel precursor, the cerium precursor, and the high surface area alumina carrier is 5.54 wt% of nickel metal and 1 to 14 wt% of cerium metal on the basis of the high surface area alumina carrier and the alumina carrier ratio. Method for producing a reforming catalyst used for the production of synthesis gas (H ₂ / CO ≒ 2) for Fischer-Tropsch liquefaction process from natural gas by autothermal reforming. The method of claim 3, wherein The high surface area alumina carrier is gamma alumina having a specific surface area of more than 100 m ² / g, and is used for the production of Fischer-Tropsch liquefaction synthesis gas (H ₂ / CO ≒ 2) from natural gas by autothermal reforming. Process for producing reformed catalyst Fischer-Tropsch liquefaction process for syngas (H ₂ / CO ≒ 2) manufacturing method, A reformer having a high surface area alumina carrier prepared according to any one of claims 3 to 8, and a catalyst layer filled with a reforming catalyst composed of 1 to 20 wt% nickel metal and 1 to 15 wt% cerium metal relative to 100 wt% of the alumina carrier. a reaction product (water methane, oxygen) to pass through by the synthesis gas (H ₂ / CO ≒ ₂₎ to from natural gas by autothermal reforming, characterized in that for producing Fischer-Tropsch liquefaction process a synthesis gas (H ₂ / CO ≒ for 2) A method for producing a synthesis gas for Fischer-Tropsch liquefaction process using a reforming catalyst used in the production. The method of claim 9, The reactants are used for the production of Fischer-Tropsch liquefaction process synthesis gas (H ₂ / CO / 2) from natural gas by autothermal reforming, characterized in that consisting of 0.01 to 2 times the oxygen relative to the molar ratio of the carbon in the hydrocarbon. Fischer-Tropsch liquefaction process for producing a synthesis gas using a reforming catalyst. The method of claim 9, The reactants are used for the production of Fischer-Tropsch liquefaction process synthesis gas (H ₂ / CO) 2) from natural gas by autothermal reforming, characterized in that the steam consisting of 0.01 to 3.5 times the molar ratio of the constituent carbon in the hydrocarbon. Fischer-Tropsch liquefaction process for producing a synthesis gas using a reforming catalyst. The method of claim 9, Fischer-Tropsch using the reforming catalyst used in the synthesis of Fischer-Tropsch liquefaction process synthesis gas (H ₂ / CO ≒ 2) from natural gas by autothermal reforming, characterized in that the reaction temperature of the catalyst layer is 700 ~ 750 degrees Method for producing syngas for liquefaction process. The method of claim 9, Reforming catalyst used for the production of Fischer-Tropsch liquefaction process synthesis gas (H ₂ / CO ≒ 2) from natural gas by autothermal reforming, characterized in that the gas space velocity (GHSV) of the reactants is 31,000 ~ 48,000 h ^{- 1} Fischer-Tropsch liquefaction process for the production of syngas using.

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