KR20160061766A - Catalyst for preparing synthesis gas by co2 reforming of ch4 and preparation method of synthesis gas using the samw - Google Patents

Catalyst for preparing synthesis gas by co2 reforming of ch4 and preparation method of synthesis gas using the samw Download PDF

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KR20160061766A
KR20160061766A KR1020140164583A KR20140164583A KR20160061766A KR 20160061766 A KR20160061766 A KR 20160061766A KR 1020140164583 A KR1020140164583 A KR 1020140164583A KR 20140164583 A KR20140164583 A KR 20140164583A KR 20160061766 A KR20160061766 A KR 20160061766A
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iron
solid acid
methane
carbon dioxide
reactor
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KR101730799B1 (en
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이강봉
조영상
오인환
나인욱
김재익
남윤식
유호영
최정길
홍용철
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한국과학기술연구원
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

Provided are a catalyst composition for preparing a syngas by a carbon dioxide reforming reaction of methane, and a preparation method of syngas using the carbon dioxide reforming reaction of methane. The catalyst composition comprises a mixture of solid acid and iron. The preparation method comprises the steps of: (a) injecting the catalyst composition to a reactor; and (b) injecting carbon dioxide and methane into the reactor, and producing a syngas by decomposition of carbon dioxide and methane by the catalyst composition. In the present invention, carbon dioxide and methane gas which are greenhouse gases are simultaneously decomposed to produce a syngas, thereby being recovered as resources. The catalyst composition has excellent cost-efficiency and durability.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst composition for synthesizing a synthetic gas by carbon dioxide reforming reaction of methane, and a method for producing a synthesis gas using the catalyst composition,

The present invention relates to a catalyst composition for the synthesis of synthetic gas by carbon dioxide reforming reaction of methane and a process for producing synthesis gas using the same.

Humans, who have continuously used fossil fuels such as petroleum and coal, have caused global warming by generating a large amount of greenhouse gases such as carbon dioxide, which is the post-combustion substance of fossil fuels. As a result, , And ultimately to the point of fear of human catastrophe. In order to prevent such disasters from the earth and mankind, efforts to suppress the generation of global warming gases such as carbon dioxide are necessary. Recently, researches on the utilization of hydrogen energy using nuclear energy, solar energy, and water have been increasing. However, since the raw material of nuclear energy is decaying, there is a concern that the raw material will be exhausted sometime. In addition, solar energy or hydrogen energy has a disadvantage in that the production cost is much higher than fossil energy. As a next step, we use cheap fossil energy as an energy source, capture carbon dioxide from the process, decompose it into methane, convert it to syngas composed of a mixture of carbon monoxide and hydrogen, reuse the syngas as an energy source, or It was necessary to develop a technology for manufacturing and recycling chemical products such as methanol and DME (Dimethyl ether) using the synthesis gas as a raw material.

Nickel catalysts have been used for the synthesis of conventional syngas. Nickel catalysts generate large quantities of filamentous carbon (coking), resulting in catalyst degradation and catalyst layer clogging, resulting in poor operational stability and catalyst durability There was a problem that it was low.

Energy & Fuel, Liu et al., 23, 607-612, 2009

In order to solve the above problems, the present invention is a technology for simultaneously decomposing carbon dioxide and methane gas to produce syngas to recycle carbon dioxide and methane gas as greenhouse gases. Iron (Fe) having a price of less than 10% Which is excellent in price competitiveness and high durability, by using carbon dioxide reforming reaction of methane, and to provide a synthesis gas production method using the catalyst composition.

In order to solve the above-mentioned problems, the present invention provides a catalyst composition for producing synthesis gas by carbon dioxide reforming reaction of methane, which comprises a mixture of solid acid and iron.

In one embodiment of the present invention, the catalyst composition may further comprise at least one of a metal other than iron and an electrolyte.

In one embodiment of the present invention, the solid acid is selected from the group consisting of basalt, granite, limestone, sandstone, shale, metamorphic rock, kaolinite, attapulgite, bentonite, montmorillonite, ), aluminum oxide (Al 2 O 3), titanium (TiO 2), cesium oxide (CeO 2), vanadium oxide (V 2 O 5), silicon oxide (SiO 2), chromium oxide (Cr 2 O 3), calcium sulfate (CaSO 4), manganese sulfate (MnSO 4), nickel sulfate (NiSO 4), copper sulfate (CuSO 4), cobalt sulfate (CoSO 4), sulfuric acid, cadmium (CdSO 4), magnesium sulfate (MgSO 4), iron sulfate ⅱ (FeSO 4), aluminum sulfate (Al 2 (SO 4) 3 ), calcium nitrate (Ca (NO 3) 2) , zinc nitrate (Zn (NO 3) 2) , iron nitrate ⅲ (Fe (NO 3) 3 ), aluminum phosphate (AlPO 4), iron phosphate ⅲ (FePO 4), chromate phosphate (CrPO 4) phosphate, copper (Cu 3 (PO 4) 2 ), zinc phosphate (Zn 3 (PO 4) 4 ), magnesium phosphate (Mg 3 (PO 4) 2 ), aluminum chloride (AlCl 3), titanium chloride (TiCl 4), calcium chloride (CaCl 2), fluoride Syum (CaF 2), barium fluoride (BaF 2) and may be at least one selected from the group consisting of calcium carbonate (CaCO 3).

In one embodiment of the present invention, the weight ratio of solid acid and iron in the mixture of solid acid and iron may be from 5:95 to 95: 5.

In one embodiment of the present invention, the metal except for the iron may be at least one selected from the group consisting of tungsten, molybdenum, cobalt, manganese, chromium, nickel, tungsten carbide, molybdenum carbide, tungsten molybdenum carbide, have.

In one embodiment of the present invention, the electrolyte is sodium chloride (NaCl), potassium chloride (KCl), sodium nitrate (NaNO 3), potassium nitrate (KNO 3), sodium sulfate (Na 2 SO 4), potassium sulfate (K 2 SO 4), lithium carbonate (Li 2 CO 3), sodium carbonate (Na 2 CO 3), potassium carbonate (K 2 CO 3), dihydrogen phosphate, sodium (NaH 2 PO 4) and phosphoric acid 1 sodium (Na 2 HPO 4) (NaOH), potassium hydroxide (KOH), magnesium chloride (MgCl 2 ), magnesium nitrate (Mg (NO 3 ) 2 ), calcium sulfate (CaSO 4 ), calcium hydroxide (Ca (OH) 2 ) and magnesium hydroxide Mg (OH) 2 ).

In one embodiment of the present invention, the catalyst composition comprises a mixture of solid acid and iron and a metal other than iron, wherein the mixture of solid acid and iron is at least 70% by weight based on the total weight of the catalyst, May be up to 30 wt% based on the total weight of the catalyst.

In one embodiment of the present invention, the catalyst composition comprises a mixture of solid acid and iron and an electrolyte, wherein the mixture of solid acid and iron is at least 85 wt% based on the total weight of the catalyst, May be up to 15 wt% based on weight.

In one embodiment of the present invention, the metal except for the solid acids, iron and iron may be in the form of a powder having a particle size of 20 to 500 mesh.

In one embodiment of the present invention, at least one of the metal and the electrolyte other than the iron is deposited on the pores of the solid acid, and the diameter of at least one of the metal and the electrolyte other than the iron may be 10 탆 or less.

In one embodiment of the present invention, the catalyst composition comprises a mixture of a solid acid and iron and a metal other than iron, and the metal surface coated with a metal other than iron on the solid acid surface or a metal surface A solid acid film coated with a solid acid is formed, and the thickness of the metal film or the solid acid film may be 10 nm or more and 10 m or less.

In one embodiment of the present invention, the catalyst composition comprises an electrolyte membrane coated with an electrolyte on the surface of the solid acid or a solid acid membrane coated with a solid acid on the surface of the electrolyte, including a mixture of solid acid and iron and an electrolyte , The thickness of the electrolyte membrane or the solid acid membrane may be 10 nm or more and 10 m or less.

The present invention also provides a process for preparing a catalyst composition, comprising: (a) introducing the catalyst composition into a reactor; And

(b) introducing carbon dioxide and methane into the reactor to decompose carbon dioxide and methane to produce a synthesis gas, wherein the synthesis gas is produced by the carbon dioxide reforming reaction of methane.

In one embodiment of the present invention, the inside of the reactor in the step (b) may be maintained at a temperature of 700 to 1500 K and a pressure of 0.5 to 100 atm.

In one embodiment of the present invention, when carbon dioxide and methane are injected into the reactor in the step (b), a carrier gas is injected together, and hydrogen and carbon monoxide generated in the reactor are discharged in a mixed state with the carrier gas .

In one embodiment of the present invention, the carrier gas may be at least one selected from the group consisting of hydrogen, nitrogen, and argon.

In one embodiment of the present invention, the syngas may include hydrogen and carbon monoxide.

In one embodiment of the present invention, the production method may further include (c) measuring the content of carbon dioxide, carbon monoxide, methane and hydrogen by discharging the synthesis gas produced in the reactor .

The catalyst composition for the synthesis of synthetic gas by the carbon dioxide reforming reaction of methane according to the present invention is remarkably reduced in the coking phenomenon and has excellent durability, stable operation and excellent price competitiveness. Further, according to the synthesis gas production method of the present invention, a mechanism for producing carbon and hydrogen by decomposing methane by using a catalyst including solid acid and iron, and a mechanism for producing carbon monoxide by reacting carbon and carbon dioxide And as a result, it is possible to provide a very simple synthesis gas production method of simultaneously producing a synthesis gas by decomposing a mixture of carbon dioxide and methane. Therefore, according to the synthesis gas production method of the present invention, the economical efficiency of the synthesis gas production is improved, and the synthesis gas production process can be developed.

FIG. 1 is a schematic view showing an experimental apparatus for producing synthesis gas by carbon dioxide reforming reaction of methane according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail in order to facilitate the present invention by those skilled in the art.

The present invention provides a catalyst composition for the synthesis of syngas by a carbon dioxide reforming reaction of methane, comprising a mixture of a solid acid and iron. In the present invention, the 'mixture of solid acid and iron' is also referred to as a 'solid acid mixture'.

The catalyst composition for producing synthesis gas by the carbon dioxide reforming reaction of methane according to the present invention may further comprise at least one of a metal excluding iron and an electrolyte including a mixture of solid acid and iron, Electrolyte may be included.

In the present invention, the solid acid is not particularly limited as long as it is capable of adsorbing and decomposing Lewis base by contacting with Lewis base. In an exemplary embodiment, the solid acid is selected from the group consisting of basalt, granite, limestone, sandstone, shale, metamorphic rock, kaolinite, attapulgite, bentonite, montmorillonite, zinc oxide (Al 2 O 3 ), titanium oxide (TiO 2 ), cerium oxide (CeO 2 ), vanadium oxide (V 2 O 5 ), silicon oxide (SiO 2 ), chromium oxide (Cr 2 O 3 ) CaSO 4 , MnSO 4 , NiSO 4 , CuSO 4 , CoSO 4 , CdSO 4 , MgSO 4 , FeSO 4 , FeSO 4 , 4 ), aluminum sulfate (Al 2 (SO 4 ) 3 ), calcium nitrate (Ca (NO 3 ) 2 ), zinc nitrate (Zn (NO 3 ) 2 ), iron nitrate Fe (NO 3 ) 3 , aluminum (AlPO 4), iron phosphate ⅲ (FePO 4), chromate phosphate (CrPO 4), phosphoric acid copper (Cu 3 (PO 4) 2 ), zinc phosphate (Zn 3 (PO 4) 4 ), magnesium phosphate (Mg 3 (PO 4 ) 2 ), aluminum chloride (AlCl 3 ), titanium chloride (TiCl 4 ), calcium chloride (CaCl 2 ), calcium fluoride (CaF 2 ), Barium fluoride (BaF 2 ), and calcium carbonate (CaCO 3 ).

The solid acid serves to decompose methane into carbon and hydrogen and to support the reaction of carbon dioxide and carbon to generate carbon monoxide.

In the present invention, iron acts to decompose methane into carbon and hydrogen, leading to a reaction between carbon dioxide and carbon, thereby generating carbon monoxide.

In the present invention, the weight ratio of the solid acid and iron in the mixture of the solid acid and iron may be from 5:95 to 95: 5, and preferably from 6: 9 to 9: 6. When the weight ratio of the solid acid is less than the above range, fusion between the iron particles occurs, and the surface area of the iron is rapidly decreased and the reaction ability of the iron catalyst is seriously deteriorated. When the weight ratio is larger than the above range, And the overall catalyst efficiency is lowered.

In the present invention, the metal other than iron means that not all of the metals and metal carbides are iron. The metal other than the iron is not particularly limited as long as it can activate the electron transfer in the course of the solid acid or the electron of the iron surface moving to the hydrogen ion when the solid acid or iron adsorbs and decomposes methane. The metals other than iron can contribute to the improvement of the methane decomposition efficiency upon decomposition of methane using solid acid and iron. In an exemplary embodiment, the metal except for the iron may be at least one selected from the group consisting of tungsten, molybdenum, cobalt, manganese, chromium, nickel, tungsten carbide, molybdenum carbide and tungsten molybdenum carbide or an alloy thereof.

In the present invention, the electrolyte is not particularly limited as long as the solid acid or iron adsorbs and decomposes methane and can activate the electron transfer in the process of transferring electrons of the solid acid or iron surface to the hydrogen ion of water. The electrolyte in the exemplary embodiment, the sodium chloride (NaCl), potassium chloride (KCl), sodium nitrate (NaNO 3), potassium nitrate (KNO 3), sodium sulfate (Na 2 SO 4), potassium sulfate (K 2 SO 4), acid lithium (Li 2 CO 3), sodium carbonate (Na 2 CO 3), potassium carbonate (K 2 CO 3), dihydrogen phosphate, sodium (NaH 2 PO 4), phosphoric acid 1 sodium (Na 2 HPO 4), sodium hydroxide ( NaOH), potassium hydroxide (KOH), magnesium chloride (MgCl 2), magnesium nitrate (Mg (NO 3) 2) , calcium sulfate (CaSO 4), calcium hydroxide (Ca (OH) 2) and magnesium hydroxide (Mg (OH) 2 ). ≪ / RTI >

When the catalyst composition according to the present invention comprises a mixture of solid acid and iron and a metal other than iron, the mixture of solid acid and iron is at least 70% by weight based on the total weight of the catalyst, And may be 30% by weight or less based on the total weight. When the amount of the metal other than the iron is more than 30 wt%, the amount of methane adsorbed on the solid acid and iron is reduced, and the methane decomposition efficiency is remarkably reduced. Therefore, it is more preferable to keep the content of the metal excluding iron at 20 wt% or less.

In addition, when the catalyst composition according to the present invention comprises a mixture of solid acid and iron and an electrolyte, the mixture of solid acid and iron is at least 85 wt% based on the total weight of the catalyst, By weight to 15% by weight or less. When the electrolyte is contained in an amount exceeding 15% by weight, the electrolyte inhibits the movement of electrons, and the efficiency of methane decomposition by the solid acid mixture is remarkably reduced. Therefore, it is more preferable to keep the content of the electrolyte powder at 10 wt% or less.

In the present invention, the metal except for the solid acid, iron and iron may be in the form of a powder having a particle size of 20 to 500 mesh.

Since the surface area of the powder of the metal other than the solid acid, iron and iron is smaller as the particle size is smaller, the smaller the particle size, the higher the reaction efficiency. However, when the particle size is more than 500 mesh, it may be lost to the outside of the reactor due to the flow rate of the raw material gas. When the particle size is less than 20 mesh, the reaction efficiency may be greatly lowered. Therefore, Lt; RTI ID = 0.0 > of < / RTI >

When the catalyst composition according to the present invention comprises a mixture of solid acid and iron and a metal other than iron, one or more of the metals other than iron and iron can be deposited in the pores of the solid acid powder, At least one of the metals other than iron may have a diameter of 10 mu m or less. The smaller the size of the iron and metal particles, the higher the reaction efficiency. Therefore, it is preferable that the diameter of the iron or metal particles is 10 μm or less, specifically 0.1 μm to 10 μm. If the diameter of the iron or metal particles is less than 0.1 탆, the catalytic performance may be deteriorated. If the diameter is more than 10 탆, it may result in desorption from the solid acid.

In addition, when the catalyst composition according to the present invention comprises a mixture of solid acid and iron and an electrolyte, the electrolyte particles can be deposited in the pores of the solid acid powder, and the diameter of the deposited electrolyte particles is 10 m or less. . The smaller the size of the electrolyte particle, the higher the reaction efficiency. Therefore, it is preferable that the diameter of the electrolyte particle is 10 탆 or less, specifically 0.1 탆 to 10 탆. If the diameter of the iron or metal particles is less than 0.1 탆, the catalytic performance may be deteriorated. If the diameter is more than 10 탆, it may result in desorption from the solid acid.

In the present invention, when the catalyst composition includes a mixture of solid acid and iron and a metal other than iron, a metal film coated with a metal other than iron or a solid acid-coated solid surface An acid film may be formed, and the thickness of the metal film or the solid acid film is preferably 10 nm or more and 10 m or less. When the thickness of the metal film or the solid acid film is more than 10 mu m, the amount of hydrogen and carbon monoxide generated is rather reduced.

In the present invention, when the catalyst composition includes a mixture of a solid acid and iron and an electrolyte, an electrolyte membrane coated with an electrolyte on the surface of the solid acid or a solid acid membrane coated with a solid acid on the surface of the electrolyte may be formed, The thickness of the film or the solid acid film is preferably 10 nm or more and 10 m or less. If the thickness of the electrolyte membrane or the solid acid membrane is more than 10 mu m, the amount of hydrogen and carbon monoxide generated may be reduced.

The present invention also provides a process for producing a syngas, comprising: (a) introducing a catalyst composition for synthesizing a syngas by the carbon dioxide reforming reaction of methane according to the present invention into a reactor; And

(b) introducing carbon dioxide and methane into the reactor to decompose carbon dioxide and methane to produce a synthesis gas, wherein the synthesis gas is produced by the carbon dioxide reforming reaction of methane.

Hereinafter, a synthesis gas production method according to the present invention will be described in more detail.

After the catalyst composition is introduced into the reactor through step (a), methane and carbon dioxide are injected into the reactor, and the catalyst added in step (a) simultaneously decomposes methane and carbon dioxide to produce a synthesis gas (b).

In the present invention, the synthesis gas may include hydrogen and carbon monoxide. That is, it decomposes carbon dioxide and methane by carbon dioxide reforming reaction of methane to produce hydrogen and carbon monoxide.

In the exemplary embodiment, when the mixed gas of methane and carbon dioxide is injected into the reactor in the step (b), carrier gas is injected together to discharge hydrogen and carbon monoxide generated in the reactor in a mixed state with the carrier gas . For example, the carrier gas may be at least one selected from the group consisting of hydrogen, nitrogen, and argon.

In the step (b), the two mechanisms are simultaneously operated to produce the synthesis gas.

First, the first mechanism is as follows. The negative charge formed on the carbon of methane at the positive charge of the Lewis acid site of the solid acid is adsorbed by the weak ionic bond to form the Bronsted acid site and the hydrogen of the methane Bststed acid By making a hydrogen bond with oxygen in a solid acid, methane is adsorbed in the form of a solid acid, a weak ionic bond and a hydrogen bonding double bond. When the solid acid adsorbed by methane is heated by the double bonds, the electrons are exchanged through the two bonds, and the methane adsorbed on the solid acid is decomposed into hydrogen and activated carbon (see Reaction Scheme 1 below).

Figure pat00001
(Scheme 1)

Like the methane decomposition reaction shown in Scheme 1, the hydrogen radicals are easily converted into hydrogen gas by mutual reaction, and are separated and removed from the reaction site like activated carbon. It is judged that methane is adsorbed and decomposed on the iron surface in a similar manner to the reaction formula 1 above.

Apart from the first mechanism, the second mechanism occurring in step (b) is as follows. Carbon dioxide reacts directly with activated carbon to generate hydrogen (see Scheme 2 below), and solid acid and iron serve as catalysts to catalyze this reaction.

CO 2 + C? 2CO (Reaction Scheme 2)

In the step (b), the temperature inside the reactor is maintained at 700 K to 1500 K or less, and the reactor pressure is preferably maintained within the range of 0.5 to 100 atmospheres in terms of reaction efficiency and economy.

More specifically, in the case of the methane decomposition reaction, a reaction temperature of 673 K or more can be used, and a carbon dioxide decomposition reaction can be performed at a reaction temperature of 673 K or more. However, when the temperature inside the reactor is less than 700 K, the efficiency of the methane decomposition reaction and the carbon dioxide decomposition reaction In addition, even when the reaction temperature exceeds 1500 K, the increase in the reaction efficiency can be greatly reduced, so that it is preferable to maintain the above temperature range.

On the other hand, the higher the reaction pressure inside the reactor, the greater the amount of methane adsorbed on the solid acid and iron. As a result, the higher the reaction pressure, the greater the production of hydrogen. However, as the reaction pressure increases, the carbon dioxide decomposition reaction rate gradually decreases. When the reaction pressure exceeds 100 atm, the carbon dioxide decomposition efficiency per unit time may be greatly reduced.

The lower the reaction pressure, the more advantageous the rate of carbon dioxide decomposition reaction. However, if the production of hydrogen decreases and especially the pressure inside the reactor is kept below 0.5 atmospheric pressure, the additional cost increases and methane and carbon dioxide- It is preferable that the pressure inside the reactor during the decomposition reaction of methane and carbon dioxide be maintained in the range of 0.5 to 100 atmospheres (step (b)).

In the present invention, the reactor is not particularly limited as long as it has heat-resistant and pressure-resistant materials. In an exemplary embodiment, the reactor should be capable of stably progressing the reaction to an internal temperature of 700 K to 1500 K and a pressure of 0.5 to 100 atm, and preferably contains at least 70% of iron. For example, the reactor may be made of stainless steel (SUS), carbon steel or a mixture thereof.

The method may further include (c) discharging the synthesis gas produced in the reactor and measuring the content of carbon dioxide, carbon monoxide, methane and hydrogen by gas chromatography.

The synthesis gas production process according to the present invention is schematically shown in Fig. The synthesis gas production method according to the present invention can be carried out through the continuous reaction system of FIG. 1, a continuous reaction system which can be used in the hydrogen production of the present invention will be described.

(Step (a)), a high-pressure methane stored in the methane storage vessel 20 is supplied to the gas flow rate regulator 70 (step (a)), and the solid acid mixture containing the solid acid, iron, To the mixer (60) via a gas flow meter (40) controlled by the gas flow meter (40). At this time, the carbon dioxide stored in the carbon dioxide storage vessel 25 is also supplied to the mixer 60 through the gas flow rate controller 50, which is controlled by the gas flow controller 80. The temperature of the mixer 60 is heated to 200 ° C. by the heating of the temperature controller 90, and the supplied methane and carbon dioxide are mixed in the mixer. The methane and carbon dioxide mixed in the mixer 60 are heated by the heat line 95 by adjusting the temperature controller 90 and passed through a gas inlet tube maintained at about 200 ° C. and introduced into the reactor 100. At this time, the temperature of the reactor is maintained at a desired reaction temperature by the temperature controller 160. The internal pressure of the reactor is adjusted and maintained by the pressure regulator 130, the internal temperature of the reactor is measured by the thermocouple temperature gauge 110, and the internal pressure is measured by the pressure gauge 120. The gas mixture which has been reacted in the reactor is injected into the gas chromatography 170 through the sampling vessel 150, where the components and the contents of the gas mixture discharged from the reactor are measured.

The present invention can produce syngas by decomposing a mixed gas of carbon dioxide and methane by simultaneously using a mechanism for producing hydrogen and carbon by decomposing solid acid and iron and methane, and a mechanism for producing carbon monoxide by reacting carbon dioxide with carbon, At this time, it has been studied that all various reaction conditions such as the composition and ratio of the injected catalyst composition, the type of solid acid, the kind of promoter, the addition of promoter, the temperature and the pressure condition of the reactor are optimized for synthesis gas production, will be. According to the present invention, carbon dioxide reforming of methane, which can be recycled by recycling carbon dioxide, can be accomplished in an economical and very simple manner while solving the problem of carbon dioxide atmosphere release, thereby enabling commercial mass production of syngas.

Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples and Experimental Examples of the present invention. It should be understood, however, that the invention is not limited to the following examples, comparative examples and experimental examples, and that various embodiments of the invention may be practiced within the scope of the appended claims, The disclosure is intended to be complete and to facilitate the practice of the invention to those skilled in the art.

[Experimental Example 1] Investigation of reaction characteristics using alumina and iron mixture

The characteristics of the reaction of producing hydrogen and carbon monoxide by simultaneously decomposing carbon dioxide and methane using alumina (aluminum oxide) and an iron mixture were investigated using the experimental apparatus of FIG.

9 g of alumina particles having an average size of 100 meshes and 6 g of iron particles having an average size of 200 mesh were uniformly mixed and charged into a reactor 100 (internal volume 120 ml) of FIG. 1, and then the reactor 100 was placed in a continuous reaction system Lt; / RTI >

Carbon dioxide stored in the carbon dioxide storage vessel 25 is injected into the reactor 100 at a flow rate of 50 ml / min for about 3 hours to evacuate the air remaining in the reactor to the outside of the reactor. Thereafter, the temperature of the heater inside the mixer 60 was adjusted to 200 ° C., the temperature of the hot wire surrounding the reactor 100 was adjusted to 800 ° C., the temperature inside the reactor was maintained at about 800 ° C., And the methane decomposition reaction was initiated by injecting 40 ml / min of methane and 40 ml / min of methane into the reactor, and the composition of the gas mixture produced after the reaction at intervals of 6 hours was measured by gas chromatography (170) Respectively. In Table 1, time means elapsed time after injecting both methane and carbon dioxide.

Reaction time
(time) Gaseous product concentration (%) Hydrogen carbon monoxide methane carbon dioxide 6 15.3 21.2 35.6 27.9 12 21.1 28.2 28.8 21.9 18 29.5 35.3 20.4 14.8 24 35.4 40.8 14.1 9.7 30 40.1 44.5 9.5 5.9 36 44.2 47.1 5.5 3.2 42 47.3 48.4 2.3 2.0 48 47.5 48.3 2.3 1.9

As can be seen from Table 1, the simultaneous decomposition reaction of carbon dioxide and methane maintains the product concentration uniformly after about 42 hours from the initiation of the reaction.

[Experimental Example 2] Investigation of reaction characteristics according to kinds of solid acids

The composition of the reaction products by the production of carbon dioxide and methane decomposition syngas was compared using various kinds of solid acids and iron.

9 g of the solid acid particles having an average size of 100 mesh and 6 g of the iron particles having an average size of 200 mesh were uniformly mixed and charged into the reactor 100. Carbon dioxide and methane decomposition were carried out in the same manner as in Example 1, Respectively. The volumetric content of gaseous products in the gas discharged from the reactor 100 was measured by gas chromatography (170) after 48 hours from the start of the reaction, and the results are shown in Table 2.

Example Solid acid name Gaseous product concentration (%) Hydrogen carbon monoxide methane carbon dioxide One Alumina 47.5 48.3 2.3 1.9 2 Bentonite 42.5 44.7 7.2 5.6 3 Silica 45.3 46.5 4.3 3.9 4 Titanium oxide 46.7 48.2 3.3 1.8 5 Calcium carbonate 47.5 48.1 2.5 1.9

As can be seen from Table 2, although the composition of the syngas varies depending on the type of the solid acid used in the present experiment, all the solid acid and iron mixtures simultaneously decompose carbon dioxide and methane to generate a considerable amount of hydrogen and carbon monoxide.

[Experimental Example 3] Hydrogen production according to the change of solid acid and iron mixture ratio

Hydrogen production and methane decomposition according to the variation of solid acid and iron mixing ratio were compared using titanium oxide solid acid.

The mixing ratio of the titanium oxide solid acid particles having an average size of 100 mesh and the iron particles having an average size of 200 mesh was changed as shown in Table 3 and uniformly mixed and charged into the reactor 100. In the same manner as in Experiment 1, Methane was decomposed at the same time, and the reaction characteristics were compared according to the change of mixing ratio of solid acid and iron. The volumetric content of the gaseous product in the gas discharged from the reactor 100 was measured by gas chromatography (170) after 48 hours from the start of the reaction, and the results are shown in Table 3.

Example Titanium oxide (g) / iron (g) Gaseous product concentration (%) Hydrogen carbon monoxide methane carbon dioxide 6 6/9 47.2 48.5 2.6 1.7 7 7/8 47.0 48.3 2.9 1.8 8 8/7 46.8 48.3 3.1 1.8 4 9/6 46.7 48.2 3.3 1.8

As can be seen in Table 3, although there is a difference in gas product composition depending on the mixing ratio of solid acid and iron, it can be seen that all solid acid and iron mixtures have the ability to decompose carbon dioxide and methane simultaneously.

[Experimental Example 4] Carbon dioxide and methane decomposition characteristics according to reaction temperature

Alumina solid acid was used to investigate the reaction characteristics of reaction temperature. 9 g of alumina solid acid particles having an average size of 100 mesh and 6 g of iron particles having an average size of 200 mesh were uniformly mixed and charged into a reactor 100 (internal volume 120 ml) of FIG. 1, and the temperature of the hot wire wrapped around the reactor 100 The temperature was adjusted by a temperature controller 160 to maintain the internal temperature of the reactor at the temperature shown in Table 4, and carbon dioxide and methane decomposition were carried out in the same manner as in Experimental Example 1, and the reaction characteristics were compared. The volumetric content of the gaseous products discharged from the reactor 100 was measured by gas chromatography (170) after 48 hours from the start of the reaction, and the results are shown in Table 4.

Example Reactor temperature (캜) Gaseous product concentration (%) Hydrogen carbon monoxide methane carbon dioxide 9 650 24.6 29.0 25.2 21.2 10 700 31.2 35.4 18.4 15.0 11 750 38.4 42.7 11.3 7.6 One 800 47.5 48.3 2.3 1.9 12 850 48.5 49.8 1.2 0.5

As can be seen from Table 4, the higher the reaction temperature, the higher the carbon dioxide and methane decomposition rates in the temperature range within the reactor 100 set in this experiment.

[Experimental Example 5] Carbon dioxide and methane decomposition characteristics according to reaction pressure

Silica solid acid was used to investigate the evolution of the syngas production with varying reaction pressure.

9 g of silica solid acid particles having an average size of 100 mesh and 6 g of iron particles having an average size of 200 mesh were uniformly mixed and charged into a reactor 100 (internal volume 120 ml) shown in Fig. 1 and the temperature of the heat wire wrapped around the reactor 100 The temperature inside the reactor was adjusted to 800 ° C. by adjusting the temperature of the reactor with the temperature controller 160 and the pressure of the reactor was maintained at the pressure shown in Table 5 by adjusting the pressure controller 130. And the reaction characteristics were compared. The volumetric content of the gaseous products discharged from the reactor 100 was measured by gas chromatography (170) after 48 hours from the start of the reaction, and the results are shown in Table 5.

Example Reactor pressure (atmospheric pressure) Gaseous product concentration (%) Hydrogen carbon monoxide methane carbon dioxide 3 One 45.3 46.5 4.3 3.9 14 5 43.2 45.1 6.6 5.1 15 10 40.8 42.3 9.9 7.9 16 15 38.6 40.1 11.1 10.2 17 20 35.4 37.2 14.4 13.0

As can be seen from Table 5, it can be seen that both the decomposition rate of carbon dioxide and the decomposition rate of methane are decreased when the internal pressure of the reactor 100 set in this experiment is increased.

[Experimental Example 6] Reaction characteristics due to addition of metal

The variation of syngas emission was investigated when various metal powders were mixed with bentonite solid acid and iron.

9 g of bentonite solid acid particles having an average size of 100 mesh and 5 g of iron particles having an average size of 200 mesh were homogeneously mixed and uniformly mixed with 1 g of the metal shown in Table 6 in a solid acid mixture, And the temperature of the hot wire wrapped around the reactor 100 was adjusted by a temperature controller 160 to perform a decomposition reaction of carbon dioxide and methane in the same manner as in Experimental Example 1 while maintaining the internal temperature of the reactor at 700 占 폚 And the reaction characteristics were compared. The volumetric content of the gaseous product discharged from the reactor 100 was measured by gas chromatography (170) after 48 hours from the start of the reaction, and the results are shown in Table 6.

Example Added metal Gaseous product concentration (%) Hydrogen carbon monoxide methane carbon dioxide 18 tungsten 36.2 39.4 13.4 11.0 19 molybdenum 35.6 38.2 14.0 12.2 20 manganese 34.3 37.1 12.7 13.3 21 chrome 34.8 37.9 12.2 12.5 22 cobalt 38.4 40.2 11.2 10.2 23 nickel 37.9 39.8 11.7 10.6 24 Tungsten carbide 38.1 39.5 11.5 10.9 25 Molybdenum carbide 36.5 38.9 13.1 11.5 26 Tungsten molybdenum carbide 37.6 39.9 12.0 10.5

As shown in Table 6, when the mixture of bentonite solid acid, iron and metal powder is charged into the reactor 100 and the carbon dioxide and methane decomposition reaction proceeds, there is a slight difference depending on the kind of the metal powder added, It can be seen that the amount of hydrogen and carbon monoxide generated is increased compared with the case of using only the mixture of acid and iron.

[Experimental Example 7] Water decomposition characteristics according to addition amount of metal

Changes in the amount of syngas produced when various amounts of calcium and calcium carbonate were mixed with varying amounts of solid acid and iron were investigated.

Cobalt was uniformly mixed in an amount as shown in Table 7 in a solid acid mixture in which 9 g of an average 100 mesh size solid carbonate particle and 5 g of an average 200 mesh size iron particle were uniformly mixed, 120 ml), and the temperature of the hot wire wrapped around the reactor 100 was adjusted by a temperature controller 160 to maintain the internal temperature of the reactor at 700 ° C. In the same manner as in Experimental Example 1, And the reaction characteristics were compared. The volumetric content of the gaseous product discharged from the reactor 100 was measured by gas chromatography (170) after 48 hours from the start of the reaction, and the results are shown in Table 7.

Example The added cobalt (g) Gaseous product concentration (%) Hydrogen carbon monoxide methane carbon dioxide 27 0.5 36.8 38.7 12.8 11.7 22 1.0 38.4 40.2 11.2 10.2 28 1.5 38.9 40.8 10.7 9.6 29 2.0 40.1 41.1 10.5 9.3 30 2.5 40.2 41.2 10.4 9.2

As shown in Table 7, when the cobalt powder is added, the amount of hydrogen and carbon monoxide generation is slightly increased rather than the experiment in which the alumina solid acid and iron mixture is charged, but the effect on hydrogen and carbon monoxide generation is negligible as the amount of metal powder is increased I could confirm.

[Experimental Example 8] Reaction characteristics when a solid acid was coated with a metal

The decomposition reaction characteristics of carbon dioxide and methane in the case of using a mixture of solid acid and metal were investigated.

5 g of an alumina solid acid coated with an average of 100 mesh nickel and 6 g of an iron particle having an average size of 200 mesh were uniformly mixed and charged into a reactor 100 (internal volume 120 ml) of FIG. 1, The results are shown in Table 8.

Example Nickel film thickness (nm) Gaseous product concentration (%) Hydrogen carbon monoxide methane carbon dioxide 31 250 37.8 38.7 11.8 11.7 32 500 38.9 40.2 10.7 10.2 33 750 39.1 40.8 10.5 9.6 34 1000 39.0 40.5 10.6 9.9

As shown in Table 8, when the nickel-coated alumina solid acid and iron mixture were charged, it was confirmed that the amount of hydrogen and carbon monoxide generation was reduced when the thickness of the nickel film was too thick.

[Experimental Example 9] Reaction characteristics when electrolyte was added

The reaction characteristics of solid acid and iron mixtures were investigated by mixing various electrolyte powders.

9 g of the titanium oxide solid acid particles having an average size of 100 mesh and 6 g of the iron particles having an average size of 200 mesh were uniformly mixed, 1 g of the electrolyte shown in Table 9 was further uniformly mixed, and the reactor (100; And the temperature of the hot wire wrapped around the reactor 100 was adjusted by the temperature controller 160 to maintain the internal temperature of the reactor at 750 ° C. In the same manner as in Experimental Example 1, And the reaction characteristics were compared. The volumetric content of the gaseous product discharged from the reactor 100 was measured by gas chromatography (170) after 48 hours from the start of the reaction, and the results are shown in Table 9.

Example Electrolyte name Gaseous product concentration (%) Hydrogen carbon monoxide methane carbon dioxide 35 - 38.2 42.2 11.8 7.8 36 K 2 SO 4 41.4 43.8 8.6 6.2 37 Li 2 CO 3 40.7 43.2 9.3 6.8 38 MgCl 2 40.9 43.4 9.1 6.6 39 Ca (OH) 2 41.2 43.5 8.8 6.5

As shown in Table 9, when the electrolytic is added to the solid acid and iron mixture to proceed the carbon dioxide and methane decomposition reaction, the amount of hydrogen and carbon monoxide generation increases as compared with the case where only the solid acid and iron are used to carry out the decomposition reaction with carbon dioxide and methane .

[Experimental Example 10] Water decomposition characteristics according to the amount of electrolyte added

The amount of potassium sulfate (K 2 SO 4 ) powder in solid acid and iron was varied and the reaction characteristics were investigated.

0.5 g to 3.0 g of 100 mesh of potassium sulfate (K 2 SO 4 ) powder was mixed into a solid acid mixture in which 9 g of titanium oxide solid acid particles having an average size of 100 mesh and 6 g of iron particles having an average size of 200 mesh were uniformly mixed Was charged into a reactor (100, internal volume: 120 ml) of FIG. 1, and the same reaction conditions and methods as in Experimental Example 9 were carried out. The volumetric content of the hydrogen product in the gas discharged from the reactor 100 was measured using a gas chromatography (170), and the results are shown in Table 10.

Example K 2 SO 4 (g) Gaseous product concentration (%) Hydrogen carbon monoxide methane carbon dioxide 40 0.5 39.2 42.2 10.8 7.8 36 1.0 41.4 43.8 8.6 6.2 41 1.5 41.7 44.2 8.3 5.8 42 2.0 41.5 43.9 8.5 6.1 43 2,5 41.2 43.5 8.8 6.5 44 3.0 40.5 42.8 9.5 7.2

As shown in Table 10, when the potassium sulfate powder is added, the amount of syngas generated is larger than that of charging only the solid acid and iron mixture, but when the amount of the potassium sulfate powder is increased too much, the amount of syngas generated is rather reduced .

[Experimental Example 11] Reaction characteristics in the case of depositing all the additional metals and electrolytes in a mixture of solid acid and iron

The amount of potassium sulfate (K 2 SO 4 ) powder in solid acid and iron was varied and the reaction characteristics were investigated.

9 g of an alumina solid acid powder having an average size of 100 mesh and 1 g of a nickel metal powder having an average size of 200 mesh were taken and 0.5 g to 1.5 g of K 2 SO 4 was deposited on the mixture. 5 g of iron particles having an average size of 200 mesh were homogeneously The mixed water and methane decomposition catalyst was charged into a reactor (100, internal volume: 120 ml) of FIG. 1 and tested under the same reaction conditions and methods as in Experimental Example 9. The volumetric content of the hydrogen product in the gas discharged from the reactor 100 was measured using gas chromatography 170, and the results are shown in Table 11.

Example K 2 SO 4 (g) Gaseous product concentration (%) Hydrogen carbon monoxide methane carbon dioxide 45 0.5 39.7 42.7 10.3 7.3 46 1.0 42.4 44.8 7.6 5.2 47 1.5 41.5 44.1 8.5 5.9

20 Methane storage container 25 Carbon dioxide storage container
30 Flow meter 40 Gas flow meter
50 gas flowmeter 60 mixer
70 Gas flow regulator 80 Gas flow regulator
90 Temperature controller 95 Heat line
100 Reactor 110 Temperature Meter
120 Manometers 130 Pressure regulators
140 Three-way valve 150 Sampling vessel (Sampling vessel)
160 Temperature Controller 170 Gas Chromatography

Claims (18)

A catalyst composition for the production of syngas by a carbon dioxide reforming reaction of methane, comprising a mixture of a solid acid and iron. The method according to claim 1,
Wherein the catalyst composition further comprises at least one of a metal other than iron and an electrolyte. The method according to claim 1,
The solid acid basalt, granite, limestone, sandstone, shale, metamorphic rocks, kaolinite (kaolinite), attapulgite (attapulgite), bentonite (bentonite), montmorillonite (montmorillonite), zinc oxide (ZnO), aluminum oxide (Al 2 O 3 ), titanium oxide (TiO 2), cesium oxide (CeO 2), vanadium oxide (V 2 O 5), silicon oxide (SiO 2), chromium oxide (Cr 2 O 3), calcium sulfate (CaSO 4), manganese sulfate (MnSO 4 ), nickel sulfate (NiSO 4 ), copper sulfate (CuSO 4 ), cobalt sulfate (CoSO 4 ), cadmium sulfate (CdSO 4 ), magnesium sulfate (MgSO 4 ), iron sulfate II (FeSO 4 ) Al 2 (SO 4) 3) , calcium nitrate (Ca (NO 3) 2) , zinc nitrate (Zn (NO 3) 2) , iron nitrate ⅲ (Fe (NO 3) 3 ), aluminum phosphate (AlPO 4), phosphate ⅲ (FePO 4), chromate phosphate (CrPO 4), phosphoric acid copper (Cu 3 (PO 4) 2 ), zinc phosphate (Zn 3 (PO 4) 4 ), magnesium phosphate (Mg 3 (PO 4) 2 ) , aluminum chloride (AlCl 3), titanium chloride (TiCl 4), calcium chloride (CaCl 2), calcium fluoride (CaF 2), barium fluoride (BaF 2) and One or more catalysts selected from the group consisting of calcium (CaCO 3) composition. The method according to claim 1,
Wherein the weight ratio of solid acid and iron in the mixture of solid acid and iron is from 5:95 to 95: 5. 3. The method of claim 2,
Wherein the metal other than iron is at least one selected from the group consisting of tungsten, molybdenum, cobalt, manganese, chromium, nickel, tungsten carbide, molybdenum carbide and tungsten molybdenum carbide or an alloy thereof. 3. The method of claim 2,
The electrolyte is sodium chloride (NaCl), potassium chloride (KCl), sodium nitrate (NaNO 3), potassium nitrate (KNO 3), sodium sulfate (Na 2 SO 4), potassium sulfate (K 2 SO 4), lithium carbonate (Li 2 CO 3), sodium carbonate (Na 2 CO 3), potassium carbonate (K 2 CO 3), and dihydrogen phosphate, sodium (NaH 2 PO 4), phosphoric acid 1 sodium (Na 2 HPO 4), sodium hydroxide (NaOH), potassium hydroxide the group consisting of (KOH), magnesium chloride (MgCl 2), magnesium nitrate (Mg (NO 3) 2) , calcium sulfate (CaSO 4), calcium hydroxide (Ca (OH) 2) and magnesium hydroxide (Mg (OH) 2) ≪ / RTI > 3. The method of claim 2,
Wherein the catalyst composition comprises a mixture of solid acid and iron and a metal other than iron,
Wherein the mixture of solid acid and iron is at least 70 wt% based on the total weight of the catalyst, and wherein the metal other than iron is at most 30 wt% based on the total weight of the catalyst. 3. The method of claim 2,
Wherein the catalyst composition comprises a mixture of a solid acid and iron and an electrolyte,
Wherein the mixture of solid acid and iron is at least 85 wt% based on the total weight of the catalyst, and wherein the electrolyte is 15 wt% or less based on the total weight of the catalyst. 3. The method of claim 2,
Wherein the metal except the solid acid, iron and iron is in powder form having a particle size of 20 to 500 mesh. 3. The method of claim 2,
Wherein at least one of the metal and the electrolyte other than the iron is deposited on the pores of the solid acid, and the diameter of at least one of the metal and the electrolyte other than iron is 10 占 퐉 or less. 3. The method of claim 2,
Wherein the catalyst composition comprises a mixture of solid acid and iron and a metal other than iron,
A metal film coated with a metal other than iron or a solid acid film coated with a solid acid on the metal surface except for the iron is formed on the surface of the solid acid,
Wherein the metal film or the solid acid film has a thickness of 10 nm or more and 10 占 퐉 or less. 3. The method of claim 2,
Wherein the catalyst composition comprises a mixture of a solid acid and iron and an electrolyte,
An electrolyte membrane coated with an electrolyte on the surface of the solid acid or a solid acid membrane coated with a solid acid on the surface of the electrolyte,
Wherein the thickness of the electrolyte membrane or the solid acid membrane is 10 nm or more and 10 m or less. (a) introducing the catalyst composition according to any one of claims 1 to 12 into a reactor; And
(b) introducing carbon dioxide and methane into the reactor to decompose the carbon dioxide and methane to produce a synthesis gas, wherein the synthesis gas is produced by the carbon dioxide reforming reaction of methane. 14. The method of claim 13,
Wherein the inside of the reactor in the step (b) is maintained at a temperature of 700 to 1500 K and a pressure of 0.5 to 100 atm. 14. The method of claim 13,
Wherein carbon dioxide and methane are injected into the reactor together with the carrier gas, and hydrogen and carbon monoxide generated in the reactor are discharged in a mixed state with the carrier gas in the step (b). 16. The method of claim 15,
Wherein the carrier gas is at least one selected from the group consisting of hydrogen, nitrogen, and argon. 14. The method of claim 13,
Wherein the synthesis gas comprises hydrogen and carbon monoxide. 14. The method of claim 13,
(C) measuring the content of carbon dioxide, carbon monoxide, methane and hydrogen by gas chromatography after discharging the synthesis gas produced in the reactor.
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