KR101958429B1 - Perovskite catalysts for reforming bio-gas and methods of manufacturing the same - Google Patents

Abstract

There is provided a biogas reforming catalyst in which a Cr site of LaCrO ₃ is substituted with a transition metal by doping, and a method for producing the same. The biogas reforming catalyst has excellent resistance to carbon deposition and has high activity, so that even when the fuel cell in which the catalyst is used is operated for a long time, the biogas reforming catalyst maintains high activity, and in particular, the dry reforming of biogas including methane and carbon dioxide A synthesis gas containing hydrogen, carbon monoxide and the like can be easily produced.

Description

TECHNICAL FIELD [0001] The present invention relates to a perovskite catalyst for biogas reforming, and a method for producing the same. [0002]

The present invention relates to a biogas reforming catalyst and a process for producing the same. More particularly, the present invention relates to a catalyst for dry reforming of bio-gas and a process for its preparation.

Fuel cells, one of the alternative energy sources for fossil fuels, have limited use because they rely heavily on hydrogen production and storage technologies. Therefore, the hydrogen production method has been actively studied, and the most economical and environmentally friendly method of the hydrogen production method developed so far utilizes the methane reforming reaction using the biogas generated from the biomass.

Particularly, in order to prevent energy loss due to the use of steam, a dry reforming reaction in which methane and carbon dioxide contained in the biogas are directly used can be used instead of the steam reforming reaction. In the case of the dry reforming reaction, there is no need to separate the carbon dioxide by the reforming reaction using the carbon dioxide directly, thereby maximizing the efficiency.

In this dry reforming reaction, a catalyst based on nickel (Ni) is generally used. In order to improve the dry reforming efficiency, a noble metal catalyst (Ru, Rh, Pd, etc.) Development is urgent. In addition, there is a problem that carbon deposition occurs on the surface of the catalyst to cause degradation of the activity, resulting in low durability. Therefore, it is required to develop a catalyst which is resistant to carbon deposition and efficiently decomposes methane and carbon dioxide.

In order to solve this problem, a catalyst having a perovskite structure instead of a noble metal catalyst is being used for the reforming of biogas, and a catalyst having resistance to carbon deposition is being studied.

Korean Patent Application No. 10-2013-0133251 Korean Patent Application No. 10-2012-0108535

It is an object of the present invention to provide a fuel cell that has excellent resistance to carbon deposition and high activity and maintains high activity even when the fuel cell in which the catalyst is used is operated for a long time, The present invention provides a biogas reforming catalyst capable of easily producing a synthesis gas containing hydrogen, carbon monoxide and the like during dry reforming of a biogas reforming catalyst, and a process for producing the same.

Exemplary embodiments of the present invention provide a biogas reforming catalyst comprising a compound represented by Formula 1 below.

[Chemical Formula 1]

LaCr _{1 - x} M _x O _{3 - y}

In Formula (1), M is a transition metal, x is greater than 0 and less than 1, and y is greater than or equal to 0 and less than or equal to 1.

In an exemplary embodiment of the present invention, in the method for producing a catalyst for biogas reforming according to the above-mentioned first aspect, a part of chromium (Cr) among the perovskite substances represented by LaCrO _{3 is} converted into a transition metal To prepare a compound represented by the formula (1). The method for preparing a biogas reforming catalyst according to the present invention comprises the steps of:

The catalyst for biogas reforming according to the embodiments of the present invention has high catalytic activity and excellent resistance to carbon deposition even though it contains a small amount of noble metal catalyst as compared with conventional noble metal catalysts, It is possible to carry out a dry reforming reaction using biogas (including carbon dioxide) at a large capacity while maintaining the activity. As a result, a synthesis gas having a high hydrogen ratio with high activity for a long time can be easily produced.

In addition, the biogas reforming catalyst has a perovskite structure and is structurally excellent in thermal stability. Therefore, the biogas reforming catalyst does not deteriorate its performance even in a high temperature biogas reforming reaction, and can efficiently reform the biogas at a high temperature.

Further, the catalyst for reforming biogas according to the present invention may be prepared by using deionized water or deionized water (DI water) instead of the organic solvent used in the sol-gel method , It is substantially free from impurities and can be produced as a single phase homogeneous catalyst.

In addition, since the catalyst for biogas reforming according to the present invention can be used alone without a catalyst carrier, the catalyst can be produced economically and efficiently. Further, there is an advantage that the biocatalyst for reforming of the present invention can be produced without increasing the pressure.

1 is a flowchart showing a flow of a method for producing a biogas reforming catalyst according to an embodiment of the present invention.
2 is a graph of X-ray diffractometry (XRD) of the catalyst for biogas reforming according to Examples 1 to 3 and Comparative Example 1 of the present invention.
3A is an image obtained by observing the surfaces of the catalyst for biogas reforming according to Examples 1 and 2 and the catalyst according to Comparative Example 1 with a scanning electron microscope (SEM), and FIG. (SEM) images and Energy Dispersive Spectroscopy (EDS) results before and after dry reforming of a catalyst.
4A to 4D are graphs showing the O1s section in the X-ray photoelectron spectroscopy (XPS) of the catalyst for the biogas reforming according to Examples 1 to 3 and the catalyst according to Comparative Example 1, And 4f are graphs showing the section of Ir 4f before and after the dry reforming reaction of the biogas reforming catalyst according to Example 3. Fig.
FIG. 5 is a graph showing the results of dry reforming according to the catalyst for biogas reforming according to Examples 1 to 3 and Comparative Example 1, by CH ₄ conversion. FIG.
6A and 6B are graphs showing methane conversion rates of the catalyst prepared according to Example 3 according to the temperature change.
FIG. 7 is a graph showing the results of experiments on the methane conversion rate according to the operation time in the biogas reforming catalyst according to Example 2 and Example 3 of the present invention.

Term Definition

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

The embodiments of the present invention disclosed in the present specification are for illustrative purposes only and the embodiments of the present invention can be embodied in various forms and should not be construed as limited to the embodiments described in the text .

It is to be understood that the invention is not to be limited to the specific forms disclosed, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention, As will be understood by those skilled in the art.

In the embodiment of the present invention, bio-gas refers to biomass such as sewage sludge and food waste that can be produced through anaerobic digester, gasification, and pyrolysis It is a gas-phase fuel. These biogas include methane (55-70%) and carbon dioxide (30-45%) as main components and contain impurities such as sulfur (S).

In the embodiment of the present invention, the term "dry reforming reaction" means a reaction in which carbon monoxide and methane are reacted to produce carbon monoxide and hydrogen. The dry reforming reaction is useful in terms of reuse of carbon dioxide and is an endothermic reaction, so the reaction is low. For reference, the following Reaction Scheme 1 is a reaction formula for the dry reforming reaction of carbon dioxide.

[Reaction Scheme 1]

CH ₄ + CO ₂ ↔ 2CO + 2H ₂ (ΔH ₂ = +247 kJ / mol)

In the embodiments of the present invention, a homogenous catalyst means a catalyst capable of maintaining a single phase by containing an active material substituted in a material lattice.

In the embodiment of the present invention, the long-term stability of the catalyst means that the conversion rate of the catalyst or the hydrogen selectivity (molar ratio of generated hydrogen to the consumed fuel), that is, . Thus, the improvement in the long-term stability of the catalyst means that the lifetime of the catalyst is improved.

In the embodiment of the present invention, the Sol-Gel method widely refers to a method in which a chelating action between an acid contained in a polymer resin (citric acid) and a cation dissolved in a solvent, a polymerization reaction between water as a solvent and citric acid And the effect of two polymerization reactions (esterification reaction) such as the polymerization of nitric oxide, which is the hydrate of each metal reagent, and the reaction of water and citric acid, leads to the dispersion of cations to obtain chemically uniform and stable precursor do.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is to be understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the present invention.

Illustrative Implementations  Explanation

Hereinafter, exemplary embodiments of the present invention will be described in detail.

Biogas dry For reforming  catalyst

Exemplary embodiments of the present invention are directed to a dry reforming of bio-gas catalyst for biogas reforming, more specifically, biogas comprising methane and carbon dioxide, And a catalyst for reforming the biogas.

[Chemical Formula 1]

LaCr _{1 - x} M _x O _{3 - y}

In Formula (1), M is a transition metal, x is greater than 0 and less than 1, and y is greater than or equal to 0 and less than or equal to 1.

For reference, when the transition metal is doped in the perovskite lattice structure of LaCrO ₃ , a minute change in the content of O may be caused by the doping metal. That is, the O ₃ of the perovskite in the formula (1) may be finely changed to O _3-y (y is 0 or more and 1 or less).

Conventionally, LaCrO ₃ has excellent thermal stability, is inexpensive, has excellent durability against carbon, but has a disadvantage in that the catalytic activity for biogas is somewhat low. Accordingly, the present inventors have developed a catalyst capable of enhancing the catalytic activity and securing the activity at the level of the noble metal by adding a transition metal.

The above compound may be doped with a transition metal having a part of chromium (Cr) among the perovskite materials represented by LaCrO ₃ as a transition metal, preferably a group 9 transition metal. That is, in the perovskite material having a structure of ABO ₃ , the above-mentioned compound can maintain the perovskite structure by doping and substituting a part of the B-site (Cr) with another material (transition metal).

Thus, unlike conventional catalysts, which are generally so-called heterogeneous catalysts prepared by heat treatment of the active material on a support and composed of two or more phases, the compound, when used as a catalyst, can act as a homogeneous catalyst. Therefore, the catalyst containing the compound can be produced through a minimized synthesis process, which is more advantageous in terms of process efficiency and economy than conventional catalysts.

Of the above compounds, transition metals, preferably transition metals of Group 9, substituted in the chromium sites (B-sites of the perovskite structure) have a high catalytic activity. Furthermore, since the perovskite catalyst having the ABO ₃ structure inherently has excellent resistance to sulfur (S) and carbon (C), the biogas reforming catalyst containing the above compound is highly resistant to biogas reforming Can have catalytic activity, and can also have high resistance to carbon deposition and / or catalyst poisoning.

In an exemplary embodiment, the transition metal may preferably be a transition metal corresponding to Group 9, more preferably Co, ruthenium (Rh), iridium (Ir), mite niobium (Mt), samarium (Sm) or plutonium (Pt).

In an exemplary embodiment, the transition to the chromium site (the B-site of the perovskite structure), taking into account both the single phase retention of the catalyst, the carbon deposition and / or the catalyst poisoning prevention, the active maintenance of the catalyst and the improved electrical conductivity, The amount of the metal, that is, x in the above formula (1), is preferably greater than 0 and less than or equal to 0.05 (0 < x? 0.5). Particularly, x may be preferably 0.03.

In the exemplary embodiments, the biogas reforming catalyst may be activated using an inert gas containing nitrogen (N), helium (He), argon (Ar), or the like, Lt; RTI ID = 0.0 &gt; atmosphere. &Lt; / RTI &gt; Particularly, the catalyst may be activated in a reducing atmosphere, and in a reducing atmosphere, oxygen attached to the surface of the catalyst may be removed to chemically adsorb the reactant to the active site.

In an exemplary embodiment, the biogas reforming catalyst may be a single phase homogeneous catalyst.

In an exemplary embodiment, it may be one that is usable alone without the support.

In an exemplary embodiment, the biogas reforming catalyst may be for biogas dry reforming. More specifically, when the carbon dioxide contained in the biogas is used for dry reforming, in which carbon dioxide is directly used for the reforming reaction and the carbon dioxide separation process is not further required, rather than steam reforming in which the reforming reaction proceeds, The effect can be maximized.

In an exemplary embodiment, the biogas reforming catalyst may exhibit a methane conversion of greater than 75% during a 50 to 100 hour operation at 700 ° C to 800 ° C. More specifically, the biogas reforming catalyst may exhibit a methane conversion rate of 75% or more during a 50-hour operation at 750 ° C.

In an exemplary embodiment, the biogas reforming catalyst is resistant to carbon deposition. The most problematic part of the dry reforming of biogas, including carbon dioxide, is the carbon deposition of the catalyst. Carbon deposition is a major factor in performance degradation due to the carbon generated during the reaction in the dry reforming, blocking the active sites of the catalyst. Commercial catalysts commonly used are nickel-based catalysts, which exhibit high activity at the beginning of operation and are inexpensive. However, they suffer from sintering phenomenon in high temperature dry reforming and are poor in carbon deposition and long-term performance. The biogas reforming catalyst according to the present invention has high resistance to carbon deposition as shown in the experimental results described below, and shows little difference in performance before and after the reaction.

Biogas dry For reforming  Method for producing catalyst

In the exemplary embodiments of the present invention, in the above-described method for producing a catalyst for biogas reforming, a part of chromium (Cr) in a perovskite material represented by LaCrO ₃ is doped and substituted with a transition metal, To prepare a compound represented by the above formula (1).

In an exemplary embodiment, the above-described doping substitution is accomplished by a sol-gel method (e. G., Using deionized water, DI water) as a solvent for dissolving the perovskite material represented by LaCrO ₃ Sol-Gel method).

More specifically, after dissolving the citric acid in distilled water or deionized water (DI water), nitric acid Lanthanum hexahydrate _{[La (NO 3) 3 6H} 2 O] and nitric acid chromium nona-hydrate _{[Cr (NO 3) 3 9H} 2 O] is dissolved to prepare a solution. Thereafter, a salt containing a transition metal is added, and then sufficiently agitated at 80 to 90 캜 so as to become a gel state.

The gel-state solution is subjected to heat treatment at 150 ° C to 250 ° C to primarily remove organic substances and calcine at 800 to 1000 ° C to effectively remove organic substances that may be generated during catalyst production.

Then, the produced biogas reforming catalyst may be activated to improve the activity of the catalyst.

In an exemplary embodiment, after the perovskite material is partially doped with a transition metal, the catalyst represented by Formula 1 may be activated by at least one selected from the group consisting of hydrogen, nitrogen, helium, and argon The method comprising the steps of:

In particular, the activation treatment may be performed in a reducing atmosphere. In the reducing atmosphere, the oxygen attached to the catalyst surface is removed, and the reactant can be chemisorbed to the active site.

In an exemplary embodiment, the activation treatment may be performed at a temperature between 750 [deg.] C and 900 [deg.] C using a gas comprising hydrogen as an inert gas. If the activation treatment process is carried out below the above range, the effect of improving the catalytic activity may be insufficient, and if the activation treatment process is performed in excess of the above range, the performance of the catalyst may be deteriorated.

As described above, the biogas reforming catalyst prepared according to the exemplary embodiments of the present invention may include a material having a perovskite structure. Since there is no process of supporting the catalyst on the catalyst support during the above process, the catalyst can be manufactured in a simple manner as compared with the conventional process, and the manufacturing time can be shortened.

Hereinafter, specific embodiments according to exemplary embodiments of the present invention will be described in more detail. It should be understood, however, that the invention is not limited to the embodiments described below, but that various embodiments of the invention may be practiced within the scope of the appended claims, It will be understood that the invention is intended to facilitate the practice of the invention to those skilled in the art.

Example

Example  One: LaCrO ₃ of Cr place  Co Doped  Biogas For reforming  catalyst

After dissolving 40 g of citric acid [HOC (COOH) (CH ₂ COOH) ₂ (Aldrich)] in 200 ml of primary distilled water, 21.65 g of lanthanum hexahydrate nitrate lanthanum hexahydrate [La (NO ₃ ) ₃ 6H ₂ O (Aldrich) Was dissolved together with 19 g of chromium nonahydrate [Cr (NO ₃ ) ₃ 9H ₂ O (Aldrich)]. Next, cobalt nitrate hexahydrate [Co (NO ₃ ) ₃ 6H ₂ O (Aldrich)] was added thereto, and the temperature of the hot plate was adjusted to 85 ° C, and stirring was continued until the temperature was changed to gel state. The gel-like solution was heat-treated at 200 ° C to remove organic matter, and calcined at 900 ° C in air. Accordingly, a LaCr _{0 . 95} Co _{0 . 05} O ₃ catalyst was prepared.

Example  2: LaCrO ₃ of Cr place  Rh Doped  Biogas For reforming  catalyst

40 g of citric acid [HOC (COOH) (CH ₂ COOH) ₂ (Aldrich)], 21.65 g of lanthanum hexahydrate [La (NO ₃ ) ₃ 6H ₂ O (Aldrich)], 200 ml of chromium nonahydrate Except that 19 g of [Cr (NO ₃ ) ₃ 9 H ₂ O (Aldrich)] and 0.523 g of rhodium chloride hydrate [RhCl ₃ x H ₂ O (Alpha Eisai)] were used, % Doped LaCr _0.95 Rh _0.05 O ₃ catalyst was prepared.

Example  3: LaCrO ₃ of Cr place Ir Doped  Biogas For reforming  catalyst

40 g of citric acid [HOC (COOH) (CH ₂ COOH) ₂ (Aldrich)], 21.65 g of lanthanum hexahydrate [La (NO ₃ ) ₃ 6H ₂ O (Aldrich)], 200 ml of chromium nonahydrate _{[Cr (NO 3) 3 9H} 2 O ( Aldrich) 19g, an iridium chloride hydrate [IrCl ₃ xH ₂ O (Aldrich) in example 1, and the Ir 5mol% doped by the same method except for using 0.746g the LaCr _{0. 95} Ir _{0 . 05} O ₃ catalyst was prepared.

Comparative Example  1: transition metal Do not do it.  Not LaCrO ₃  catalyst

After dissolving 40 g of citric acid [HOC (COOH) (CH ₂ COOH) ₂ (Aldrich)] in 200 ml of primary distilled water, 21.65 g of lanthanum hexahydrate nitrate lanthanum hexahydrate [La (NO ₃ ) ₃ 6H ₂ O (Aldrich) Was dissolved together with 20 g of chromium nonahydrate [Cr (NO ₃ ) ₃ 9H ₂ O (Aldrich)]. Next, the hot plate temperature was adjusted to 85 캜 and stirring was continued until the gel state was changed. The gel-like solution was heat-treated at 200 ° C to remove organic matter, and calcined at 900 ° C in air. Thus, a catalyst for Comparative Example 1 was prepared.

Experimental Example

Experimental Example  1: Evaluation of composition and structure of catalyst

X-ray diffraction (XRD) was performed on the catalysts of Examples 1 to 3 and Comparative Example 1 to evaluate the composition of the catalyst. The results are shown in Fig.

Referring to FIG. 2, catalysts according to Examples 1 to 3 and Comparative Example 1 have a perovskite structure of LaCrO ₃ as a basic structure, and a part of Cr is substituted with respective transition metals, . Accordingly, it can be seen that the catalyst of the present invention is a single phase homogeneous catalyst represented by the above formula (1), which is easily synthesized by sol-gel method using distilled water or deionized water instead of an organic solvent as a solvent.

Experimental Example  2: Evaluation of shape and carbon deposition resistance of catalyst

In order to observe the shape of the catalyst, the catalysts prepared according to Examples 1 to 3 and Comparative Example 1 were observed with a scanning electron microscope (SEM), and the results are shown in Fig.

Further, the catalyst prepared in Example 3 was sampled after a biogas dry reforming reaction at 750 ° C, and an energy dispersive spectrometer (EDS) measurement was performed while observing the shape using a scanning electron microscope. 3B. Since no trace of carbon is detected after the reforming reaction, it can be confirmed that this catalyst has a strong resistance to carbon deposition.

Experimental Example  3: Evaluation of oxygen and metal states on the catalyst surface

X-ray photoelectron spectroscopy (XPS) was performed on a small amount of the catalysts prepared according to Examples 1 to 3 and Comparative Example 1 to confirm the state of oxygen on the surface of the catalyst, 4d show the O 1s sections of Examples 1 to 3 and Comparative Example 1.

Referring to FIGS. 4A to 4D, it can be seen that the strongest peak is observed in the region of 529 eV in O1s, which is the binding energy generated by the combination of metal and oxygen, so that the surface of the catalyst is highly bound to metal and oxygen. The next bond-energy interval at 530 eV is due to the combination of oxygen and -OH functional groups. It can be deduced that the oxygen on the surface of the catalyst is not bound to the metal, have. The strongest bond energy interval of 532eV is the result of the effect of chemisorbed water during catalyst preparation.

Further, in the case of the catalyst prepared according to Example 3, the Ir 4f section was analyzed in XPS to examine the behavior before and after the reaction of Ir, and is shown in FIGS. 4e and 4f. As a result, the binding energy of Ir increases after the dry reforming reaction, and it can be seen that the Ir metal contributes to the active site of the catalyst.

Experimental Example  4: Evaluation of methane conversion of catalyst

In order to compare the difference in conversion of methane in the dry reforming reaction at 750 ° C, the differences in the conversion of methane in the dry reforming reaction at 750 ° C were compared using the catalysts prepared according to Examples 1 to 3 and Comparative Example 1, Respectively.

Specifically, after 0.2 g of the catalyst powder prepared according to Examples 1 to 3 and Comparative Example 1 was fixed in a quartz reactor, a gas having a composition of about 15% H ₂ /85% N ₂ was flown and the temperature was reduced to 800 ° C. The temperature was raised and the pretreatment was carried out for about 12 hours. After that, CH ₄ , CO ₂ and N ₂ were injected at a ratio of 1: 1: 2 at a rate of 20 ml / min while lowering the temperature to 750 ° C. After that, the gas at the outlet of the reactor was analyzed by gas chromatography to determine the conversion of methane, which can measure the catalytic performance.

Referring to FIG. 5, in Comparative Example 1, the methane conversion rate of Examples 2 and 3 was significantly higher than that of Comparative Example 1, in which no conversion reaction of methane occurred at all, and the transition metal was doped into the Cr site, It was found that the performance was increased.

Experimental Example  5: Evaluation of thermal stability of catalyst

For the evaluation of the thermal stability of the catalyst, the performance according to the temperature change of the dry reforming reaction was evaluated on the basis of the catalyst prepared according to Example 3.

Referring to FIGS. 6A and 6B, it can be seen that the methane conversion rate of the catalyst prepared according to Example 3 changes with the change of the dry reforming reaction temperature. As the temperature of the dry reforming reaction was higher, the performance of the catalyst was also increased. As a result, it was confirmed that the catalyst of the present invention had no performance deterioration due to thermal agglomeration of particles even under a high temperature dry reforming reaction.

In addition, when the supply of external heat source is temporarily stopped and the temperature is further reduced to 600 ° C., the original catalytic activity can be recovered as long as the heat is supplied again. In general, when the supply of heat is temporarily stopped during the reaction in the catalytic reaction, active sites may be lost or unexpected activity may be lowered. The catalyst of the present invention has excellent thermal stability without any decrease in activity even when the supply of heat is temporarily stopped 6a and 6b.

Experimental Example  6: Evaluation of long-term stability of catalyst

In order to evaluate the performance of the catalysts over long periods of operation, the catalysts prepared according to Examples 2 and 3 were used for the dry reforming reaction of carbon dioxide-containing biogas. The results are shown in Fig.

Specifically, after 0.2 g of the catalyst powder prepared according to Examples 2 and 3 was fixed in a quartz reactor, a gas having a composition of about 15% H ₂ /85% N ₂ was flowed to raise the temperature to 800 ° C. in a reducing atmosphere, For about 12 hours. After that, the temperature was reduced to 750 ° C, and CH ₄ , CO ₂ and N ₂ were injected at a ratio of 1: 1: 2. Thereafter, the gas at the outlet of the reactor was analyzed by gas chromatography to determine the conversion rate of methane, which can measure the catalytic performance, for 50 hours (about 75 hours in Example 3).

7, when the catalysts prepared according to Examples 2 and 3 were used, even after the reaction was performed for 50 hours or more, the resistance to carbon deposition was high, It can be confirmed. Accordingly, even when the fuel cell in which the catalyst is used is operated for a long period of time, the activity is kept high, so that the synthesis gas containing hydrogen, carbon monoxide and the like can be easily used for the biogas reforming, especially the dry reforming of biogas including methane and carbon dioxide It can be confirmed that it can be manufactured.

Claims (12)

A biogas reforming catalyst comprising a compound represented by the following formula (1):
[Chemical Formula 1]
LaCr _1-x M _x O _3-y
In formula (1)
M is a transition metal, x is greater than 0 and less than 1, y is greater than or equal to 0 and less than or equal to 1,
The transition metal is ruthenium (Rh) or iridium (Ir).
delete The method according to claim 1,
x is greater than 0 and not greater than 0.05.
The method according to claim 1,
Wherein the biogas reforming catalyst is a single phase homogeneous catalyst.
The method according to claim 1,
Wherein the biogas reforming catalyst has no support.
The method according to claim 1,
Wherein the biogas reforming catalyst is a biogas reforming catalyst.
The method according to claim 1,
Wherein the biogas reforming catalyst exhibits a methane conversion of 75% or more during a period of from 50 to 100 hours at 700 to 800 ° C.
The method according to claim 1,
Wherein the biogas reforming catalyst is resistant to carbon deposition.
The method for producing a biogas reforming catalyst according to claim 1,
Preparing a compound represented by Formula 1 by doping a part of chromium (Cr) in a perovskite material represented by LaCrO ₃ with a transition metal to prepare a biogas reforming catalyst .
10. The method of claim 9,
Partially doping and substituting the perovskite material with a transition metal,
Gel method is performed using distilled water or deionized water (DI water) as a solvent for dissolving the perovskite material represented by LaCrO ₃ . A method for producing a catalyst for reforming biogas.
10. The method of claim 9,
After the perovskite material is partially doped and substituted with a transition metal,
1. A method for producing a catalyst for biogas reforming, comprising: activating a catalyst represented by the above formula (1) to at least one selected from the group consisting of hydrogen, nitrogen, helium and argon.
12. The method of claim 11,
Wherein the activation treatment is carried out at a temperature of 750 ° C to 900 ° C using a gas containing hydrogen as an inert gas.

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