KR20130075147A - Copper based catalyst for methane reformation using co2, and the fabrication method thereof - Google Patents

Abstract

PURPOSE: A copper-based catalyst for reforming methane using carbon dioxide and a fabricating method thereof are provided to fabricate synthetic gas with high content of carbon monoxide. CONSTITUTION: A copper-based catalyst for reforming methane using carbon dioxide is represented by chemical formula, a (X)-b (Cu)-c (Y)/Z. In the chemical formula, X is rhodium (Rh) or ruthenium (Ru); Y is manganese (Mn), lanthanum (La), or cerium (Ce); Z, which is a carrier, is silica (SiO2); a, b, and c are respectively the weight% of X, Cu, and Y with respect to Z; and a is 0.1-1.0 weight%, b is 5.0-20.0 weight%, and c is 5.0-20.0 weight%. [Reference numerals] (AA) Conversion rate (%); (BB) Example 3; (CC) CH4 conversion rate (%); (DD) CO2 conversion rate (%); (EE) Time (hr)

Description

Copper based catalyst for methane reforming reaction using carbon dioxide and its preparation method

The present invention relates to a copper catalyst for the reforming reaction of methane using carbon dioxide and a method for producing the same.

As the global warming causes global greenhouse gas reduction proposals to be announced, the government of the Republic of Korea has set the target of reducing greenhouse gas emissions at 30% of the 2020 emission estimate. In particular, it is inevitable that the energy-consuming and export industries, including steel, automobiles, and petrochemicals, will be hit. However, the bigger problem is that domestic companies are already at the world's highest level of energy efficiency, which limits their greenhouse gas reduction. In addition, if the government regulates as a means of reduction, production disruption may also occur due to companies moving their plants overseas or rising costs for greenhouse gas reduction.

As a solution to this problem, rather than reducing carbon dioxide emissions, researches are being made on the use of carbon dioxide emissions to produce carbon dioxide and hydrogen from the synthesis gas, and various high value-added products such as methanol synthesis, oxo synthesis, and Fisher Tropsch synthesis. Processes have been developed for use as synthetic raw materials for chemicals.

The production of such synthesis gas includes a method by coal gasification, steam reforming of hydrocarbons using natural gas, and the like, partial oxidation reforming, and the like.

However, the coal gasification method requires an expensive coal gasification heater and a large-scale plant, and steam reforming and partial oxidation reforming methods use 700 to 1200 ° C. using carbon dioxide, oxygen, steam, or a mixture thereof as a reforming gas. Because of the high temperature endothermic reaction, there is a problem that high heat resistance of the catalyst is required.

Meanwhile, nickel-based catalysts, which are widely known as catalysts for reforming reactions, may exhibit high activity, but there is a problem in that the stability of the catalysts is lowered due to the rapid generation of cokes, and there is an urgent need to develop new catalysts to solve these problems. It's happening.

In the synthesis method of the synthesis gas, the reforming reaction of methane using carbon dioxide can produce a synthesis gas (H ₂ : CO = 1: 1) having a higher carbon monoxide content than other reforming methods, so that the prepared synthesis gas is used as oxo alcohol. (oxoalcohol), dimethyl ether (dimethyl ether, DME), polycarbonate (poly carbonate, PC), acetic acid (acetic acid), such as high value-added chemicals are easy to use in the manufacturing process. The carbon dioxide reforming reaction of the methane is shown in the following scheme.

<Reaction Scheme>

The carbon dioxide reforming reaction of methane is a very strong endothermic reaction, as can be seen from the above equation, and the equilibrium conversion rate, which is the theoretical maximum conversion at a given temperature, increases with increasing temperature so that the reaction occurs at a temperature above 650 ° C. The reaction proceeds at a high temperature of 850 ° C. In addition, the reaction is characterized by a high carbon-to-hydrogen ratio of the reactor body is easy to form carbon thermodynamically, showing excellent activity even at a relatively low temperature, the development of a catalyst resistant to the coke generation and deactivation by sintering This is required.

Looking at the catalyst for the reforming reaction of methane using conventional carbon dioxide,

Chem. Lett. , 1953 (1992)] and Korean Patent Laid-Open Publication No. 10-2001-57530 to modify methane by supporting nickel metal on a magnesium oxide carrier such as magnesium oxide (MgO) and magnesium oxide-alumina (MgO-Al ₂ O ₃ ). The reaction catalyst was prepared,

[J. Chem. Soc., Chem. Commun., 71 (1995) and Inter. J. Hydro. Ene. 28 (2003), 1045, prepared a catalyst by supporting nickel metal on a carrier of lanthanum oxide (La ₂ O ₃ ).

In addition, Korean Patent No. 10-0482646 and [A. catal. A (2005) 200 discloses a catalyst in which nickel metal is supported on a carrier surface composed of cerium zirconium oxide.

Korean Patent No. 10-0912725 discloses a catalyst in which nickel metal is supported on a carrier of tungsten carbide (WC),

Korean Patent No. 10-0336968 discloses a nickel-based reforming catalyst prepared by supporting alkali metals and alkaline earth metals as co-catalysts on a zirconia carrier modified with ZrO ₂ by alkaline earth metals and IIIB or lanthanum group metals. Has been disclosed,

Korean Patent Laid-Open Publication No. 10-1995-5964 discloses an alkali metal alkaline earth metal promoter and a catalyst in which nickel is supported on a silicon-containing carrier such as zeolite, silica, silicate, silica-alumina,

Korean Patent Publication No. 10-2000-30023 discloses a nickel catalyst supported on an alumina airgel carrier.

Furthermore, Korean Patent No. 10-0732729 discloses a triple (mixed gas of carbon dioxide, oxygen and water vapor) reforming catalyst of methane, a mixture containing yttrium which is an essential component metal, and a metal selected from lanthanum-based elements and alkaline earth metal elements. Nickel-based catalysts in which nickel-doped nickel is supported on a zirconia carrier have been disclosed, and have been shown to have an effect of maintaining activity and extending the life of the catalyst.

As described above, in the reforming reaction of methane using carbon dioxide, attempts have been made to develop a high performance nickel supported catalyst which is inexpensive and resistant to carbon deposition similar to steam reforming, but has a short catalyst life of nickel. Due to this, it faces limitations. On the other hand, while the resistance to carbon deposition and activity is better than the nickel-based catalyst, the research on the noble metal-based catalyst that was difficult to apply due to the expensive disadvantage has been actively made.

US Patent No. 5068057 discloses Pt / Al ₂ O ₃ and Pd / Al ₂ O ₃ catalysts, and International Patent Publication No. WO 92 / 11,199 discloses an alumina catalyst carrying precious metals such as iridium, rhodium, ruthenium and the like. It has been suggested to have the effect of showing high activity and long life.

In addition, Japanese Patent Laid-Open No. 11-276893 discloses the reforming reaction of methane by carbon dioxide on a metal oxide catalyst using a hydrotalcite precursor using noble metals (Rh, Pd, Ru) and transition metals (Ni) as active metals. It was initiated. However, despite the use of expensive precious metals, the conversion of methane was more than 90% only at temperatures of 800 ° C. Except for the catalyst containing (about 50% methane conversion), the conversion rate of methane did not exceed 30%.

Furthermore, U. S. Patent No. 5744419 discloses nickel on a carrier such as silica, alumina, zirconia, or the like previously coated with alkaline earth metals according to the presence or absence of precious metals in connection with steam reforming including oxygen reforming and carbon dioxide reforming. Or a catalyst carrying cobalt has been disclosed,

US Patent No. 4026823 discloses a zirconia-supported nickel catalyst in which cobalt is added to nickel as a steam reforming catalyst for hydrocarbons.

Korean Patent No. 10-0526052 discloses the partial oxidation of methane using metal oxides and the production of hydrogen using reduced metal oxides, but to improve the thermal stability and reactivity of iron oxides containing cobalt as the main active ingredient. The use of alumina together to produce hydrogen can cause carbon deposition problems.

As such, researches on noble metal catalysts have been actively conducted, but catalyst studies on catalyst life and activity due to carbon deposition have attracted continuous interest.

Accordingly, the present inventors have been studying a catalyst material exhibiting excellent durability to replace the nickel-based catalyst, which is a commercial catalyst for steam reforming, which is insufficient in durability, and has excellent catalytic activity and stability at low temperatures, and using methane using carbon dioxide. The catalyst for reforming was developed and the present invention was completed.

An object of the present invention is to provide a copper-based catalyst for the reforming reaction of methane using carbon dioxide and a method for producing the same.

In order to achieve the above object,

It provides a copper-based catalyst for the reforming reaction of methane using carbon dioxide represented by the formula (1):

&Lt; Formula 1 >

a (X) -b (Cu) -c (Y) / Z

In Formula 1, X is rhodium (Rh) or ruthenium (Ru);

Y is manganese (Mn), lanthanum (La) or cerium (Ce);

Z (carrier) is silica (SiO ₂ );

a, b and c each represents the weight percentage of X, Cu, Y relative to the Z component;

a is 0.1 to 1.0% by weight, b is 5.0 to 20.0% by weight, c is 5.0 to 20.0% by weight.

In addition,

Supporting the metal precursor solution on a silica carrier to match the composition ratio of Chemical Formula 1 (step 1);

Drying the silica carrier on which the metal precursor solution is supported in step 1 (step 2); And

It provides a method for producing a copper-based catalyst for the reforming reaction of methane using carbon dioxide represented by the formula (1) comprising the step (step 3) calcining the dried silica carrier in step 2.

Copper-based catalyst for the reforming reaction of methane using carbon dioxide according to the present invention and a method for producing the same according to the present invention, in the reforming reaction using carbon dioxide and methane, exhibits excellent stability and catalytic activity at a relatively low temperature than the conventional nickel-based catalyst Syngas having a high content can be produced. In addition, the use of inexpensive copper can be used to produce a catalyst at a low process cost.

1 is an X-ray diffraction graph of the catalyst prepared in Example 3;
2 is a graph showing the conversion rate of methane and carbon dioxide according to the reaction time of the catalyst prepared in Example 3;
3 is a graph showing the conversion of methane and carbon dioxide according to the reaction time of the catalyst prepared in Example 6.

The present invention

It provides a copper-based catalyst for the reforming reaction of methane using carbon dioxide represented by the formula (1):

&Lt; Formula 1 >

a (X) -b (Cu) -c (Y) / Z

In Formula 1, X is rhodium (Rh) or ruthenium (Ru);

Y is manganese (Mn), lanthanum (La) or cerium (Ce);

Z (carrier) is silica (SiO ₂ );

a, b and c each represents the weight percentage of X, Cu, Y relative to the Z component;

a is 0.1 to 1.0% by weight, b is 5.0 to 20.0% by weight, c is 5.0 to 20.0% by weight.

Conventional catalysts used for the reforming of methane using carbon dioxide are known to use transition metals such as cobalt, nickel and zirconia as active ingredients, and alumina, silica and the like as carrier components. However, even if the catalyst uses the same components, it is known that the activity is completely different depending on the mixing ratio of each component, that is, the relative ratio. Accordingly, the present invention provides a three-phase copper-based catalyst in which the active metal is dispersed in the carrier by selectively using copper as the active ingredient and the transition metals, and controlling the content thereof in an optimum ratio.

The copper-based catalyst according to the present invention is excellent in the stability of the catalyst even at low temperatures than the conventional nickel-based reforming catalyst in performing the reforming reaction of methane, it is possible to produce a synthesis gas having a high carbon monoxide content by improving the catalytic activity. At this time, the stability of the catalyst and the improvement of the catalyst activity are not due to the effects of each of the active metals used in the copper-based catalyst according to the present invention, but due to the synergistic effect between each other, such a synergy if any one component is excluded. It can not be effective.

The copper-based catalyst according to the present invention is copper (Cu); A metal of rhodium (Rh) or ruthenium (Ru) belonging to the platinum group; A metal selected from the group consisting of manganese (Mn), lanthanum (La), and cerium (Ce); and includes silica (SiO ₂ ) as a carrier component. After optimizing the content of the active metals, the copper catalyst according to the present invention can be prepared by impregnating and drying each of them in a carrier and firing the carrier impregnated with the active metals.

Meanwhile, in Chemical Formula 1, X is a metal of rhodium (Rh) or ruthenium (Ru), which is a platinum group element, in a range of 0.1 to 1.0 wt%, preferably 0.1 to 0.5 wt% based on the carrier. Used. When the content of X is less than 0.1% by weight, there is a problem in that no active synergistic effect of rhodium or ruthenium is exhibited, and when the content of X is more than 1.0% by weight, no further increase in activity occurs, and thus economical efficiency. There is a problem that occurs.

In addition, the copper is used in the range of 5 to 20% by weight, preferably 5 to 10% by weight relative to the carrier. When the copper content is less than 5% by weight, there is a problem that the catalytic activity effect is lowered. When the copper content is more than 20% by weight, there is a problem that deactivation occurs due to a sudden carbon deposition phenomenon of the catalyst. There is a problem that the life of the catalyst is reduced.

Further, Y is one metal selected from the group consisting of manganese (Mn), lanthanum (La) and cerium (Ce), and is in the range of 5 to 20% by weight, preferably 5 to 10% by weight, based on the carrier. Used as When the content of Y is less than 5% by weight, there is a problem in that the active synergy does not appear, and when the content of Y is more than 20% by weight, the activity of the catalyst is lowered as an excess of the active metal is mixed. There is.

On the other hand, in the copper catalyst according to the present invention, when any one of the metals X and copper (Cu) is pulled out, there is a problem that the activity of the catalyst is considerably lowered or the catalytic reaction does not occur at all. Therefore, the metal X and copper (Cu) must be included and included in an amount consistent with the above range so as to exhibit the optimum catalytic activity capability.

The present invention

Supporting the metal precursor solution on a silica carrier to match the composition ratio of Chemical Formula 1 (step 1);

Drying the silica carrier on which the metal precursor solution is supported in step 1 (step 2); And

It provides a method for producing a copper-based catalyst for the reforming reaction of methane using carbon dioxide represented by the formula (1) comprising the step (step 3) calcining the dried silica carrier in step 2.

Hereinafter, a method for preparing a copper catalyst according to the present invention will be described in detail for each step.

In the method of preparing a copper-based catalyst according to the present invention, step 1 is a step of supporting a metal precursor solution on a silica carrier so as to match the composition ratio of Chemical Formula 1.

In the metal precursor solution, a nitrate such as Cu (NO ₃ ) ₂ .xH ₂ O may be generally used as the copper precursor material including the copper component. In addition, as a manganese precursor material containing a manganese component Mn (NO ₃ ) ₂ 4H ₂ O may be used, and a lanthanum precursor material including a lanthanum component may include LaCl _3, LaCl ₃ · 7H ₂ O, La (OH) _3, La (NO ₃ ) _{3, and} La ( NO ₃ ) ₃ · 6H ₂ O, La ₂ O _3, La ₂ (SO ₄ ) ₃ · 8H ₂ O, LaCl ₃ · 6H ₂ O, and the like, and the lanthanum precursor material may generally be used. have. Furthermore, a nitrate such as Ce (NO ₃ ) ₃ .6H ₂ O may be generally used as the cerium precursor material including the cerium component, and various ruthenium salts may be used as the ruthenium precursor compound including the ruthenium component. In general, Ru (NO) (NO ₃ ) ₃ , RuCl ₃ .xH ₂ O may be used, and as a rhodium precursor material including a rhodium component, Rh (NO ₃ ) ₃ .xH ₂ O, RhCl ₃ .xH ₂ O may be used, but is not limited thereto.

The method of supporting the metal precursor solution on the silica carrier is not particularly limited, and various methods such as heating impregnation method, room temperature impregnation method, vacuum impregnation method, atmospheric pressure impregnation method, evaporation drying method, pore peeling method, and initial wetness method Impregnation, dipping, spraying, ion exchange, or the like can be used.

On the other hand, in the metal precursor solution prepared to match the composition ratio of Formula 1, X is one metal of rhodium (Rh) or ruthenium (Ru), a platinum group element, 0.1 to 1.0% by weight relative to the carrier, preferably Preferably 0.1 to 0.5% by weight. When the content of X is less than 0.1% by weight, there is a problem in that no active synergistic effect of rhodium or ruthenium is exhibited, and when the content of X is more than 1.0% by weight, no further increase in activity occurs, and thus economical efficiency. There is a problem that occurs.

In addition, the copper (Cu) is used in the range of 5 to 20% by weight, preferably 5 to 10% by weight with respect to the carrier. When the copper content is less than 5% by weight, there is a problem that the catalytic activity effect is lowered. When the copper content is more than 20% by weight, there is a problem that deactivation occurs due to a sudden carbon deposition phenomenon of the catalyst. There is a problem that the life of the catalyst is reduced.

Further, Y is one metal selected from the group consisting of manganese (Mn), lanthanum (La) and cerium (Ce), and is in the range of 5 to 20% by weight, preferably 5 to 10% by weight, based on the carrier. Used as When the content of Y is less than 5% by weight, there is a problem in that the active synergy does not appear, and when the content of Y is more than 20% by weight, the activity of the catalyst is lowered as an excess of the active metal is mixed. There is.

On the other hand, in the metal precursor solution, when any one of the metals X and copper (Cu) is pulled out, there is a problem that the activity of the catalyst produced is significantly lowered, or no catalytic reaction occurs at all. Therefore, the metal X and copper (Cu) must be included in the metal precursor solution, and included in an amount consistent with the above range so as to exhibit the optimum catalytic activity capability.

In the method for preparing a copper catalyst according to the present invention, step 2 is a step of drying the silica carrier on which the metal precursor solution is supported in step 1.

At this time, the drying of the silica carrier is preferably carried out for 5 to 48 hours at a temperature of 50 to 110 ℃. If the drying of the silica carrier is carried out at a temperature of less than 50 ℃, there is a problem that the evaporation of moisture is too slow to consume a lot of drying time unnecessarily, the drying of the silica carrier is carried out at a temperature exceeding 150 ℃ In this case, the moisture is evaporated too quickly, which increases the pore size of the catalyst, which is one of the causes of the catalyst deactivation.

In the method for preparing a copper-based catalyst according to the present invention, step 3 is a step of calcining the dried silica carrier in step 2.

At this time, the firing is preferably carried out for 5 to 48 hours at a temperature of 200 to 700 ℃. When the firing is carried out at a temperature of less than 200 ℃, there is a problem that the chemical bond of the catalyst is not made, but a simple dry state, when the firing is performed at a temperature exceeding 700 ℃, oxidation of the catalyst The degree is large, there is a problem that the decomposition of the catalyst to reach the melting point of the metals used in the catalyst.

On the other hand, the catalyst for the reforming reaction of methane using carbon dioxide is generally carried out a reduction reaction through an appropriate pretreatment process before the reaction, thereby enabling the role as a catalyst. Thus, the method for preparing a copper-based catalyst according to the present invention may further include a step of pretreating the catalyst on which the calcination of step 3 is performed. However, the catalyst prepared according to the present invention can prevent carbon deposition, which is the cause of deactivation of the catalyst, due to the oxides present on the surface of the catalyst even without a reduction reaction, thereby keeping the activity of the catalyst stable. Therefore, the pretreatment step may be appropriately selected by the operator in performing the manufacturing method of the present invention, but is not limited thereto.

On the other hand, when the pretreatment is performed, the pretreatment is an atmosphere having a space velocity of 100 to 100,000 ml / g _cat · hr for 10 minutes to 12 hours at a temperature of 100 to 800 ℃ the catalyst prepared by the firing of step 3 It is preferable to carry out under gas. In addition, the atmosphere gas is preferably, but not limited to, using a hydrogen gas, or a mixed gas of at least one inert gas and hydrogen gas selected from the group consisting of nitrogen, helium and argon.

Further,

By using the copper-based catalyst, there is provided a production method for producing a synthesis gas from a gas containing methane and carbon dioxide as shown in the following scheme.

<Reaction Scheme>

As shown in the above reaction scheme, the copper-based catalyst may be used to prepare a synthesis gas containing carbon monoxide and hydrogen from a gas containing methane and carbon dioxide. Synthetic gas produced using carbon dioxide, which is limited in emissions worldwide, has high concentrations such as oxoalcohol, dimethyl ether (DME), polycarbonate (PC), acetic acid, and the like. It can be used in the value-added chemical manufacturing process, reducing the emission cost of carbon dioxide emissions and economic profit from syngas production.

On the other hand, in the production method for producing the synthesis gas, the copper catalyst is carbon monoxide in the reactor of the reaction temperature of 650 to 850 ℃, pressure of 0.01 to 0.1 MPa, and space velocity of 5,000 to 50,000 ml / g _cat · hr And to prepare a synthesis gas containing hydrogen. Compared with the conventional nickel-based catalyst as described above, the relatively low reaction temperature is to prevent carbonization of the catalyst and changes in the properties of the catalyst due to the high temperature reaction, through which the activity of the catalyst can be stably maintained. At this time, when the reaction temperature is less than 650 ℃ there is a problem that the conversion rate is not enough to convert to carbon monoxide and hydrogen, and when the reaction temperature exceeds 850 ℃ carbonization of the catalyst is started and deactivation proceeds quickly There is a problem. In addition, the reaction pressure is not a variable that greatly affects the catalytic reaction, the pressure of 0.1MPa or more has a problem that the initial reactor installation cost is large, it is preferable to maintain the reaction pressure in the above range.

Further, when the space velocity of the mixed gas containing methane and carbon dioxide is less than 5,000 ml / g _cat · hr there is a problem that the reaction productivity is too low, the space velocity of the mixed gas exceeds 50,000 ml / g _cat · hr In this case, since the contact time between the reactants and the catalyst is shortened, there is a problem that the activation of the catalyst is lowered.

In the gas containing methane and carbon dioxide, the mixture ratio of methane and carbon dioxide (CO ₂ / H ₂ ) is preferably a molar ratio of 0.5 to 2.0. When the mixing ratio is out of the above range, it is preferable to maintain the above range because the reaction is inclined only by either conversion and the reaction is inefficient.

In addition, the reactor used for the reforming reaction of methane and carbon dioxide may be used in the art in general, but is not particularly limited to, specifically, gas phase fixed bed reactor, fluidized bed reactor, liquid slurry type reactor, etc. Can be used.

As described above, the copper-based catalyst prepared according to the present invention can produce a synthesis gas having a higher conversion rate, in particular, a high carbon monoxide ratio, compared to the nickel-based catalyst used in the conventional reforming reaction of methane and carbon dioxide.

Hereinafter, the present invention will be described more specifically by way of examples. However, the following examples are intended to illustrate the present invention, but the scope of the present invention is not limited by the following examples.

&Lt; Example 1 >

Mn (NO ₃ ) ₂ .4H ₂ O was dissolved in water in a ratio as shown in Table 1, and then mixed with silica (SiO ₂ ) as a carrier, which was distilled under reduced pressure at a temperature of 60 ° C. to evaporate water. After evaporation of water was completed, the manganese was impregnated into the silica carrier by drying at a temperature of 60 ° C. for 6 hours. After the impregnation of manganese was performed, Cu (NO ₃ ) ₂ .xH ₂ O and Ru (NO). (NO ₃ ) ₃ were impregnated with silica carrier through the same process as Mn (NO ₃ ) ₂ .4H ₂ O. I was. The carrier impregnated with all the components was calcined at a temperature of 400 ° C. for 6 hours, thereby preparing a copper catalyst according to the present invention.

<Examples 2-18>

A copper-based catalyst was prepared in the same manner as in Example 1, except that the catalyst was prepared using the ratios and materials as described in Table 1.

<Comparative Example 1-3>

A copper-based catalyst was prepared in the same manner as in Example 1, except that the catalyst was prepared using the ratios and materials as described in Table 1.

Experimental Example 1 Catalytic Performance Evaluation

In order to compare the performance of the catalysts prepared in Examples 1 to 18 and Comparative Examples 1 to 3 according to the present invention, the reforming reaction of methane and carbon dioxide was carried out in the following manner, and the results are shown in Table 1. .

0.2 g of each of catalysts having a size of 60 to 80 mesh prepared by Examples 1 to 18 and Comparative Examples 1 to 3 were charged into the reactor. As the reactor, a fixed bed tubular reactor with an external heating system was used, and the reactor was quartz material having a length of 400 mm and an inner diameter of 9.25 mm. Catalytic reaction was performed by supplying a methane / carbon dioxide mixed gas having a mixing molar ratio of 1.0 into the reactor at a space velocity of 20,000 ml / g _cat.hr. At this time, the catalytic reaction was carried out under atmospheric pressure and reaction temperature conditions of 700 ℃, the gas discharged after the reaction was analyzed using a thermal conductivity detector of the on-line gas chromatography system.

As shown in Table 1, when using the copper-based catalyst prepared in Examples 1 to 18 according to the present invention, the conversion of CO ₂ was 50 to 70%, the conversion of CH ₄ was 30 to 60%, Syngas having a ratio of carbon monoxide to hydrogen of 1.0 or more was produced. On the other hand, when even one of the catalyst components, such as the catalyst of Comparative Examples 1 to 3 can be confirmed that the conversion is significantly reduced.

division Ingredients and Composition Ratio reaction
Temperature
(℃) CH ₄
Conversion rate
(%) CO ₂
Conversion rate
(%) CO / H ₂
volume
ratio X b (Cu) Y Carrier Z
(100% by weight) ingredient
a content
(weight%) content
(weight%) ingredient
c content
(weight%) Example 1 Ru 0.5 10 Mn 10 SiO ₂ 700 30 50 1.6 Example 2 Ru 0.5 15 La 5 SiO ₂ 700 47 59 1.3 Example 3 Ru 0.5 12 Ce 8 SiO ₂ 700 48 67 1.4 Example 4 Rh 0.8 10 Mn 10 SiO ₂ 700 32 51 1.6 Example 5 Rh 0.8 15 La 5 SiO ₂ 700 48 60 1.3 Example 6 Rh 0.8 12 Ce 8 SiO ₂ 700 61 72 1.2 Example 7 Ru 0.8 10 Mn 10 SiO ₂ 700 32 48 1.5 Example 8 Ru 0.8 15 La 5 SiO ₂ 700 46 60 1.3 Example 9 Ru 0.8 12 Ce 8 SiO ₂ 700 57 60 1.1 Example 10 Ru 0.5 20 Mn 10 SiO ₂ 700 58 62 1.1 Example 11 Ru 0.8 20 Mn 10 SiO ₂ 700 58 61 1.1 Example 12 Ru 1.0 20 Mn 10 SiO ₂ 700 56 59 1.1 Example 13 Ru 0.5 20 La 5 SiO ₂ 700 46 55 1.2 Example 14 Ru 0.8 20 La 5 SiO ₂ 700 44 56 1.3 Example 15 Ru 1.0 20 La 5 SiO ₂ 700 45 55 1.2 Example 16 Ru 0.5 20 Ce 8 SiO ₂ 700 50 53 1.1 Example 17 Ru 0.8 20 Ce 8 SiO ₂ 700 53 55 1.0 Example 18 Ru 1.0 20 Ce 8 SiO ₂ 700 55 60 1.1 Comparative Example 1 - - 15 - - SiO ₂ 700 12 24 2.0 Comparative Example 2 Ru 0.5 - - - SiO ₂ 700 30 40 1.3 Comparative Example 3 Rh 1.0 - - - SiO ₂ 700 32 43 1.3

Experimental Example 2 X-ray Diffraction Analysis

The copper catalyst prepared in Example 6 according to the present invention was analyzed by X-ray diffraction, and the results are shown in FIG. 1.

As shown in FIG. 1, it can be seen that a peak corresponding to copper oxide is detected in the copper-based catalyst prepared in Example 6 according to the present invention. This confirmed that the copper-based catalyst according to the present invention through Example 6 was well prepared.

Experimental Example 3 Analysis of Change in Catalytic Performance Over Time

In order to analyze the change in catalyst performance over time of the copper catalysts prepared in Examples 3 and 6 according to the present invention, the change in catalyst performance over time was analyzed under the same conditions as in Experimental Example 1, and the results 2 and 3 are shown.

As shown in Figures 2 and 3, it can be seen that the copper-based catalyst prepared in Examples 3 and 6 according to the present invention has no significant change in conversion after the initial reaction and after about 40 hours. Through this, the copper-based catalyst according to the present invention can exhibit a high activity of about 70% even at a relatively low temperature of about 700 ℃, it can be seen that it can improve the stability of the catalytic activity by preventing the deactivation of the catalyst have.

Claims (10)

Copper-based catalyst for the reforming reaction of methane using carbon dioxide represented by the formula (1):

&Lt; Formula 1 >
a (X) -b (Cu) -c (Y) / Z

In Formula 1, X is rhodium (Rh) or ruthenium (Ru);
Y is manganese (Mn), lanthanum (La) or cerium (Ce);
Z (carrier) is silica (SiO ₂ );
a, b and c each represents the weight percentage of X, Cu, Y relative to the Z component;
a is 0.1 to 1.0% by weight, b is 5.0 to 20.0% by weight, c is 5.0 to 20.0% by weight.
Supporting the metal precursor solution on the silica carrier so as to match the composition ratio of Chemical Formula 1 (step 1);
Drying the silica carrier on which the metal precursor solution is supported in step 1 (step 2); And
Method for preparing a copper-based catalyst for the reforming reaction of methane using carbon dioxide represented by the formula (1) comprising the step (step 3) of firing the silica carrier dried in step 2;

&Lt; Formula 1 >
a (X) -b (Cu) -c (Y) / Z

In Formula 1, X is rhodium (Rh) or ruthenium (Ru);
Y is manganese (Mn), lanthanum (La) or cerium (Ce);
Z (carrier) is silica (SiO ₂ );
a, b and c each represents the weight percentage of X, Cu, Y relative to the Z component;
a is 0.1 to 1.0% by weight, b is 5.0 to 20.0% by weight, c is 5.0 to 20.0% by weight.
The method of claim 2, wherein the drying of step 2 is carried out for 5 to 48 hours at a temperature of 50 to 110 ℃ method for producing a copper-based catalyst for the reforming reaction of methane using carbon dioxide.
The method of claim 2, wherein the calcination of step 3 is carried out at a temperature of 200 to 700 ℃ method for producing a copper-based catalyst for the reforming reaction of methane using carbon dioxide.
The method of claim 2, further comprising the step of pretreatment of the catalyst prepared by the calcination of step 3, wherein the copper-based catalyst for the reforming reaction of methane using carbon dioxide.
The method of claim 5, wherein the pretreatment is carried out under an atmospheric gas at a space velocity of 100 to 100,000 ml / g _cat · hr for 10 minutes to 12 hours at a temperature of 100 to 800 ℃ the catalyst prepared by the calcination of step 3 Method for producing a copper-based catalyst for the reforming reaction of methane using carbon dioxide.
The copper for reforming methane using carbon dioxide according to claim 6, wherein the atmosphere gas is hydrogen gas or a mixed gas of hydrogen gas or at least one inert gas selected from the group consisting of nitrogen, helium and argon. Method for producing a catalyst.
A method for producing a synthesis gas from a gas containing methane and carbon dioxide using a copper catalyst, as shown in the following scheme.

<Scheme>

The synthesis of claim 8, wherein the copper-based catalyst comprises carbon monoxide and hydrogen in a reactor at a reaction temperature of 650 to 850 ° C., a pressure of 0.01 to 0.1 MPa, and a space velocity of 5,000 to 50,000 ml / g _cat.hr. A manufacturing method characterized by producing a gas.
The method of claim 9, wherein the reactor is a fixed bed reactor, a fluidized bed reactor, or a slurry reactor.

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