JPS60132649A - Catalyst for preparing high calorie gas, its preparation and preparation of high calorie gas - Google Patents

Abstract

PURPOSE:To obtain a catalyst for converting low calorie gas to high calorie one, by combining manganese oxide, a platinum group metal and metal copper and/ or a copper compound with a ferrous metal being a substrate to support the resulting combination by a carrier. CONSTITUTION:As a catalyst for converting low calorie gas to high calorie one, manganese oxide, a platinum group metal and metal copper and/or a copper compound are combined with a ferrous metal such as cobalt or iron as catalyst substrates to be supported by a carrier while the resulting combination is supported by silica and/or alumina used as the carrier. When this catalyst is used, the content of 2-4C hydrocarbon in formed gas is enhanced and high calorie gas is obtained.

Description

Detailed Description of the Invention The present invention provides a catalyst for obtaining high-calorie gas from low-calorie gas, and a gas containing hydrogen and carbon monoxide or a gas containing hydrogen, carbon monoxide, and carbon dioxide using the catalyst. The present invention relates to a method for producing a high-calorie fuel gas containing a hydrocarbon having 1 to 4 carbon atoms.

Traditionally, coke oven gas has been the mainstream source of city gas, but in recent years it has been reviewed from the viewpoints of protecting the living environment, rationalizing supply methods, non-toxic safety, etc., and there is a sudden shift to high-calorie natural gas. Things are progressing on the pitch. For this reason, the use of coke oven gas as city gas is being limited, but it is important to develop effective uses for coke, as a huge amount of coke is produced as a by-product in the production of coke for steelmaking, which is the core industry. However, in order to continue to utilize this coke oven gas as a fuel, it would be necessary to improve its current low-calorie properties and convert it into a high-calorie gas comparable to natural gas. This is one solution to this problem.

The low calorie nature of gasification gases such as coke oven gas, coal, and heavy oil is due to the large amount of hydrogen, carbon oxide, and carbon dioxide they contain, so in order to make them high calorie, The following substances are methane, ethane, ethylene, and propane.

It needs to be converted to hydrocarbons such as propylene and butane. In view of the above-mentioned circumstances, the present inventors completed the present invention as a result of various studies to obtain a fuel gas having a higher calorie content.

That is, to describe the purpose of the present invention more specifically, a gas containing hydrogen and carbon monoxide, or a gas containing hydrogen, carbon monoxide, and carbon dioxide (hereinafter simply referred to as low-calorie gas), for example, coke oven gas, The object of the present invention is to provide a four-component composition catalyst that can convert gas into a gas with a much higher calorie than conventionally known methods, and a method for producing a high calorie gas using the catalyst. That is, the present invention aims at converting a low-calorie gas into a high-calorie gas containing not only methane but also hydrocarbons having 2 to 4 carbon atoms by contacting the above-mentioned catalyst with the low-calorie gas. Note that when low-calorie gas is converted into high-calorie gas containing hydrocarbons, carbon dioxide is generally produced as a by-product, and conventionally this has been separated and removed. Therefore, in the present invention, the above four-component composition system and the three-component composition system described below are used.
By combining two types of catalysts based on the original composition, the aim is to provide a method for simultaneously converting this by-product diuretic hydrogen into hydrocarbons, thereby eliminating the need for carbon dioxide separation operations. This advantage is demonstrated.

The present invention will be explained in further detail. First, the primary substance in the catalyst of the present invention is silica and/or alumina,
Generally commercially available products, for example, those with a specific surface area of 200I
12/g or less can be used. Iron group metals are used as substrates for catalysts supported on such carriers, and these iron group metals include cobalt and iron.
．． 'r preferred. The catalyst of the present invention is a quaternary composition system in which the substrate metal is combined with manganese oxide, platinum group metal, copper metal and/or copper compound (hereinafter simply referred to as copper compound) and supported on the carrier. It is a catalyst. Examples of platinum group metals include ruthenium, rhodium, palladium, platinum, and iridium.

The catalyst of the present invention combines the above-mentioned catalyst components, so that when it is brought into contact with a low-calorie gas,
A high-calorie gas containing a large amount of 2 to C4 hydrocarbons can be obtained. However, the reason why such an effect can be achieved is not clear in detail, but by combining the above-mentioned copper compounds.

The combined effect on iron group metals and platinum group metals, which are catalytic substances, is promoted, CO adsorption increases and carbon polymerization activity moderately increases, and hydrogen adsorption decreases and carbonization of 02 to C4 is promoted. It is presumed that this is due to improved hydrogen production. In the above combination, the supported amount of the iron group metal serving as the catalyst substrate is 3 to 15%, particularly preferably 5 to 12%, based on the total catalyst. The amount of manganese oxide supported is determined by the atomic ratio of iron group metal element to manganese element (5:1) to (5:1).
: The 114 content of the platinum group metal is set so as to satisfy the range of 4), and the atomic ratio of the iron group metal element to the platinum group metal element satisfies the range of (30: l) to (5: 2). It is set as follows. Further, the supporting amount of the copper compound is set so as to satisfy the range of 0.1 to 3.0% of the total catalyst as metallic copper.

In preparing the catalyst of the present invention, a platinum group metal is supported on a carrier made of silica and/or alumina, and then an iron group metal, manganese oxide, and a copper compound are simultaneously added.
Alternatively, a platinum group metal and a copper compound may be supported simultaneously or individually, and then an iron group metal and a manganese oxide may be supported simultaneously or individually.

That is, the catalyst prepared by supporting each catalyst component according to the procedure described in -I-
When converting to high calorie gas containing hydrocarbons,
In particular, the ability to select the production of 02 to C4 components is effectively exhibited. For example, an iron group metal, a manganese oxide, and a copper compound may be supported simultaneously or individually, and then a platinum group metal is supported, or a copper compound is supported, and then manganese oxide and an iron group metal are simultaneously added, and then a platinum group metal is supported. The present inventors have confirmed that the supported catalyst does not exhibit a sufficient composite effect as a four-component composition catalyst, and is disadvantageous for obtaining a high-calorie gas containing 02 to C4 hydrocarbons.

The catalyst of the present invention is produced by the above-mentioned basic structure, but to describe it more specifically, a platinum group metal, an iron group metal, a platinum group metal, an iron group metal,
After impregnating manganese and copper compounds in the form of nitrate aqueous solution or chloride aqueous solution by means such as spraying N, NK, cloth, and dipping, drying, ammonia treatment, thermal decomposition,
A four-component catalyst is prepared by sequentially performing steps such as hydrogen reduction. Note that in this preparation, the ammonia treatment step may be omitted in some cases. A manufacturing example of the catalyst of the present invention will be explained in more detail.

First, a carrier made of silica and/or alumina, or a molded carrier heat-treated at 500 to 1100°C,
It is impregnated with an aqueous solution of platinum group metal nitrate m411 or its chloride in an amount equal to the pore volume, and air-dried at room temperature while gently rolling.

Note that in order to speed up drying, a commercially available dryer adjusted to a temperature of 150°C may be used. Next, the treated product is exposed to an atmosphere containing 10 to 20% ammonia and 1 to 10% water vapor for 2 to 3 minutes.

Thereafter, it is heated to about 350° C. in air to thermally decompose the impregnated platinum group metal nitrate or chloride into an oxide. Hydrogen concentration of 10 diluted with inert gas
The temperature is raised from room temperature to 400° C. in a ~20% air flow, maintained at the same temperature for 30 minutes for reduction, and then cooled to room temperature in the same air flow. Platinum group metal 1 u obtained in this way
The support is simultaneously impregnated with a mixed solution of an iron group metal such as a nitrate aqueous solution, a manganese such as a 1N aqueous solution of nitric acid, and a copper such as a 111 aqueous nitric acid solution by the same impregnation method as described above.

Then, air drying or heating drying, ammonia treatment, and thermal decomposition are performed in the same manner as in the case of supporting the platinum group metal.

A four-component composition catalyst is obtained by performing a treatment such as hydrogen reduction.

In preparing the catalyst of the present invention, the catalyst components may be supported in the following manner and then heat treated in a reducing atmosphere.

By using the catalyst of the present invention, low-calorie gases such as coke oven gas, steam reformed gas of naphtha and heavy oil, as well as water gas and coal gasification gas can be converted into high-calorie gas containing hydrocarbons having 1 to 4 carbon atoms. For example, the conversion can be done as follows. That is, the catalyst obtained as described above is packed into a reaction tower, and the temperature of the catalyst layer is set to 15
0 to 400°C, preferably controlled at 250 to 350°C, 5 to 30 kg/cm G, preferably 10 to 2
1 per catalyst capacity of 141 under a pressure of 0 kg/cm2G
~10 m”/hr, preferably 2-5 m”/hr
c7) By introducing low-calorie scum, a high-calorie gas containing hydrocarbons having 1 to 4 carbon atoms is generated in the catalyst layer, but at that time, the water produced as a by-product is as shown in the following equation 0. , a shift reaction occurs with -carbon oxide in the low-calorie raw material gas to produce carbon dioxide as a by-product.

Further, in some cases, carbon monoxide itself in the low-calorie raw gas may undergo a disproportionation reaction according to formula (2), producing carbon dioxide as a by-product.

CO+H20=CO2+H2(1) 2CO=CO2+C ■ In the present invention, the CZ to C4 scum mixed with by-product carbon dioxide gas from the above hydrocarbonization reaction is treated with silica and/or
Alternatively, the by-product carbon dioxide can also be converted into methane by subsequent contact with a ternary composition catalyst in which nickel, a rare earth element oxide, and a platinum group metal are supported on a carrier made of alumina. It also includes such effects.

To explain the ternary composition catalyst for converting the above-mentioned by-product carbon dioxide into methane, its preparation involves drying granular silica or alumina (commercially available products as necessary) with a particle size of 2 to 4 fflI11, for example. The carrier is used as a carrier. The substrate of the catalyst supported on the carrier is nickel, and the substrate metal includes a rare earth element oxide such as lanthanum, cerium, praseodymium, thorium or samarium oxide and a platinum group metal such as ruthenium, platinum, palladium, etc. It is a combination of l iJ of rhodium or iridium, but when considering the catalytic effect and economic efficiency, lanthanum oxide and cerium oxide are used as the rare earth element oxides.
Furthermore, as the platinum group metal, ruthenium and palladium can be mentioned as the most preferable metals. In the above combination, the amount of nickel supported on the catalyst (1) is in the range of 3 to 12%, particularly preferably 4 to 8%, based on the total catalyst. The atomic ratio of the elements is set to satisfy (2:1) to (10:1), and the platinum group metal is set so that the atomic ratio of nickel element to platinum group metal element is (10:1) to (30:1). ) It is preferable to support each catalyst component in such a way that it satisfies the above range. Note that even if each catalyst component is supported beyond the specified range, the catalytic effect will not be further improved, but rather the pores of the carrier will be This is undesirable because it tends to cause clogging and cause catalyst performance to deteriorate.In producing this ternary composition catalyst, nickel, rare earth elements, and platinum group metals are added to a support made of silica and/or alumina group. For example, in the form of an aqueous nitrate solution, the material is impregnated by means such as spraying, scattering, or immersion, and then air-dried or heated at 60 to 150° C. and then treated with ammonia.

Performs thermal decomposition and hydrogen reduction. In preparing this catalyst, nickel, rare earth element oxides, and platinum group metals may be supported individually in any order or in combination of two or more thereof on a carrier made of silica and/or alumina. is first applied to the carrier,
Catalysts obtained by supporting a platinum group metal and then simultaneously supporting nickel and a rare earth element oxide have particularly excellent conversion properties from carbon dioxide to hydrocarbons.

A specific example of the preparation of the ternary composition catalyst described in section 2 is as follows. That is, a carrier made of silica and/or alumina is impregnated with an aqueous solution of a platinum group metal salt, such as a nitrate or a chloride, only in the pore volume and a sub-portion of the carrier, and then air-dried or dried by heating at 60 to 150°C. At this time, the concentration of platinum group metal nitrates and chlorides is determined so that a predetermined amount of platinum group metal nitrates and chlorides are contained in the impregnating solution, and after drying and ammonia treatment, the impregnated product is heated to 350°C in the atmosphere. and decomposes chlorides. When the platinum group metal support thus obtained is impregnated with a mixed solution of an aqueous solution of nickel inorganic acid 111, such as nitrate, and an aqueous solution of an inorganic acid salt of a rare earth element, such as nitrate, to support the platinum group metal. Dry as well.

Ammonia treatment and thermal decomposition are performed, and then the temperature is raised from room temperature to 400°C in an air stream with a hydrogen concentration of 10 to 20% diluted with an inert gas, and the temperature is maintained at the same temperature for 30 minutes for reduction. The production of the catalyst is completed by cooling it to room temperature in an air stream.

In producing high calorie gas according to the present invention,
A low-calorie gas as a raw material is introduced under the above-mentioned conditions into the reaction tower filled with the quaternary composition catalyst made of the iron group metal-manganese oxide-platinum group metal-copper compound. If the generated sludge contains by-product carbon dioxide, the sludge is subsequently transferred to a second ternary composition compound consisting of nickel-t□earth element oxide-platinum group metal. Alternatively, the two types of catalysts may be introduced into a separate reaction column packed with
Two reaction towers are filled in series, and the low calorie gas is first brought into contact with the first four-component composition catalyst layer of the present invention, and then brought into contact with the second three-component composition catalyst layer. Good too. In this case, the first catalyst volume is the minimum h1-1 second catalyst volume necessary for the conversion rate of carbon monoxide to reach 100%.
The catalyst volume is such that the conversion rate of the carbon dioxide contained is 100%.
The amount required to reach the target is sufficient. Note that, in actual operation, the decomposition of C2~(, Li & hydrogen hydride is reduced by keeping the temperature of the second catalyst tank approximately 30°C lower than the temperature of the first catalyst tank.

When the catalyst of the present invention is brought into contact with a low-calorie gas, "complete utilization of all carbon butyride in the raw I gas", which was not achieved with conventional catalysts, is achieved, and moreover, compared to the conventional catalysts, A high-calorie gas containing more hydrocarbons having 2 to 4 carbon atoms can be obtained. Furthermore, in order to obtain a high-calorie gas containing hydrocarbons having 2 to 4 carbon atoms in addition to methane using the catalyst of the present invention, a second tertiary gas consisting of nickel, a rare 2nd class element oxide, and a platinum group metal is used. By bringing the original composition catalysts together and bringing them into contact, by-product carbon dioxide can be completely methanized, so a carbon dioxide separation and recovery device is not required, which is extremely effective in terms of the process.

Next, the present invention will be explained with reference to examples, but the present invention can be modified in various ways based on the following examples without departing from the gist thereof. In the description, "parts" represent parts by weight.

Example 1 A commercially available alumina carrier having a specific surface area of 200 to 220♂/g was heated in an electric furnace from room temperature to 1060°C over 4 to 6 hours, and then heat-treated by holding the same temperature for 30 minutes. RuCl3.3H2 was added to 20 parts of the heat-treated carrier that had been cooled to room temperature.
The sample was impregnated by spraying with an aqueous solution prepared by dissolving 1.1 part of 0.01. This impregnation was ammonia-treated by exposure for 2 minutes to an atmosphere previously adjusted to a volume concentration of 10 to 11% by volume and 6% by volume of water vapor, and then heated in air to about 350'O. The impregnated Ru metal n1 was thermally decomposed into an oxide. This was placed in an electric furnace, and the temperature was raised from room temperature to 400°C in 1 hour while passing through a nitrogen stream containing 20 volume % hydrogen at 1 fk degree, and after reducing by holding that temperature for 30 minutes, the same air stream was heated. The mixture was cooled to room temperature to obtain 20.5 parts of RuJIj carrier. Next, Co (NO3) 2 .6H201 was added to 21.0 parts of the Ru carrier.
1/2 of a solution of 2.8 parts of Mn(NO3)2.6H205.5 parts and Cu(NO3)2.201.9 parts of Cu(NO3)2.3H in 5 parts of water t3. After impregnating with the same spraying method as above, drying, ammonia treatment, and thermal decomposition are performed, and after cooling, the remaining above solution is further impregnated with the same operation method as above, and drying, ammonia treatment, and thermal decomposition are performed. , reduced by the same method as above to obtain io%C0-6%
Mn203-2%Ru-2%Cu four-component catalyst 25
I got the department.

Example 2 Catalyst obtained by the method of Example 1: A low-calorie test gas having the composition shown in Table 1 was heated at a pressure of 10 kg.
/cm2G, SV5500hr-', temperature 3
When the mixture was passed once at 20° C., a gas having the composition shown in Table 2 was obtained with a CO conversion rate of 100%. For comparison, 3 consisting of 10%C0-6%M n203-2%Ru
The results are shown below when the same low calorie test gas was passed under the same conditions as in this example for a quaternary composition catalyst obtained by obtaining an original composition support and then further supporting 2% Cu compound. Listed in Table 2.

As is clear from the results in Table 1 and Table 2 onwards, when the catalyst of the present invention is used, a high-calorie gas with a high content of 02 to C4 hydrocarbons in the produced gas can be obtained. I understand.

Example 3 Commercially available alumina J with a specific surface area of 200 to 220 m2/g
The +v body was heated in an electric furnace from room temperature to 1060'O over a period of 4 to 6 hours, and maintained at the same temperature for 30 minutes for heat treatment. Cu(NOa) was added to 20 parts of the heat treated carrier cooled to room temperature.
) The impregnated product was impregnated by spraying with an aqueous solution in which 1.9 parts of 2.3H20 was dissolved in 5 parts of water, and then air-dried overnight while gently rolling to leave the impregnated product 1'J. This impregnated material was exposed to an atmosphere preliminarily adjusted to contain 10 to 11% by volume of ammonia and 6% by volume of water vapor for ammonia treatment, and then heated in air to approximately 350°C to impregnate it. Cu metal salt was thermally decomposed to form an oxide.

Next, RuC13.3H20+ was added to 21.1 parts of the Cu carrier.
After impregnation with an aqueous solution in which 1 part was dissolved in water by the same spraying method as described above, it was dried, treated with ammonia, and then thermally decomposed to obtain an oxide. This was placed in an electric furnace, heated from room temperature to 400℃ in 1 hour while passing a nitrogen stream containing hydrogen at a concentration of 20% by volume, and after being reduced by holding that temperature for 30 minutes, in the same air stream. Cool to room temperature and Cu-Ru support 2
2.1 parts were obtained. Next, add 0 to 2000 parts of Cu-Ru support.
0(NO3) 2 ・6H2012, 8 parts, Mn(NO3)
3) After impregnating 1/2 amount of a solution of 5 parts of 2.6H20 dissolved in 5 parts of water by the same spraying method as above,
After drying, ammonia treatment, and thermal decomposition, and cooling, the remaining solution was further impregnated with the same procedure as described above, and drying, ammonia treatment, and thermal decomposition were performed, and reduction treatment was performed in the same manner as above. , 10%C0-6%Mn203-2%
23 parts of a Ru-2% Cu quaternary composition catalyst were obtained.

Example 4 A low-calorie test residue having the composition shown in the ff5I table was placed on the catalyst obtained by the method of Example 3 at a pressure of 10 k.
g/cm2G, SV5500hr-', and a temperature of 320°C, the Co conversion rate was 100.
A gas having the composition shown in Table 2 in % was obtained. For comparison, a ternary composition support consisting of 10%Co-6%Mn20B-2%Cu was obtained, and then a quaternary composition catalyst was further supported with 2% Ru compound, which was the same as in this example. Table 3 shows the results when the same low-calorie test particles were passed under the same conditions (+1 is added).
The conversion rate is only 20%, which is considerably less active than the present invention.

Table 3 Example 5 A commercially available alumina carrier with a specific surface area of 200 to 220 m27g was heated from room temperature to 1060°C in an electric furnace for 4 to 6 hours.
The sample was heated and maintained at the same temperature for 30 minutes for heat treatment. Cu (NO3) was added to 20 parts of the thermally treated carrier cooled to room temperature.
2.3H201, 9 parts and RuC13.3H201,
An aqueous solution prepared by dissolving 1 part in 5 parts of water was impregnated by a spraying method, and then air-dried overnight while gently rolling to obtain an impregnated product. The impregnated material was ammonia-treated by exposing it to an atmosphere previously adjusted to 10-11% ammonia and 6% water vapor by volume for 2 minutes, and then heated in air to about 350'C to impregnate it. The Cu and Ru metal salts were thermally decomposed to form oxides.

This was placed in an electric furnace, and the temperature was raised from room temperature to 400°C in 1 hour while passing a nitrogen stream containing hydrogen at a concentration of 20% by volume, and the temperature was maintained for 30 minutes to reduce the temperature. The mixture was cooled to room temperature to obtain 22.2 parts of a Cu-Ru carrier. Next, 21.0 parts of Cu-Ru support was coated with Co (NO
3)2 War 6H2012, Part 6, Mn (NO3) 2
・1/2 of a solution of 5 parts of 6H205 dissolved in 5 parts of water
After impregnating the amount by the same spraying method as above, drying,
Ammonia treatment and thermal decomposition are performed, and after cooling, the remaining above solution is further impregnated with the above-mentioned rotation method, dried, and ammonia treated J'l! , ! 8 decomposition and reduction treatment in the same manner as above to obtain 10%Co-6%Mn203
-24 parts of a quaternary composition catalyst of -2% Ru-2% Cu were obtained.

Example 6 A low-calorie test gas having the composition shown in Table 1 was poured onto the catalyst obtained by the method of Example 5 at a pressure of 10 kg/
cm2G, SV5500hr-', temperature 32
When the mixture was passed once at 0°C, a gas having the composition shown in Table 2 was obtained with a conversion rate of 100%. For comparison, we first added 2% copper compound, then 10'%C0 and 6%Mn2.
The results are shown in the fourth example when the same low-calorie test gas was passed under the same conditions as in this example for a four-component composition catalyst in which 0a was simultaneously supported and then 2% Ru compound was further supported. Also listed in the table. The conversion rate of carbon monoxide in the comparative example was only 22%, and the activity was considerably inferior to that of the inventive example.

Table 4 Example 7 Commercially available silica carrier 20 with a specific surface area of 50 to 80 m2/H
The sample was impregnated with an aqueous solution prepared by dissolving 1.8 parts of Cu(NO3) 2 13H20 and 1 part of RuCl3.3H20 in 5 parts of water by a spraying method, and then air-dried overnight while gently rolling to obtain an impregnated product. . This impregnated material was ammonia-treated by exposing it for 2 minutes to an atmosphere previously adjusted to have 1o-it volume % ammonia and 6 volume % water vapor, and then heated in air to about 350°C to impregnate it. Cu and Ru metal salts were thermally decomposed into oxides.

This was placed in an electric furnace, and the temperature was raised from room temperature to 400°C in 1 hour while passing a nitrogen stream containing hydrogen at a concentration of 20% by volume. After reducing by holding that temperature for 30 minutes, it was heated in the same air stream. It was cooled to room temperature to obtain 22.2 parts of a Cu-Ru carrier. Next, CO (NO3) was added to 20.0 parts of the Cu-Ru support.
2 ・8 parts of 6H2012, Mn (NO3) 2 After impregnating 1/2 amount of a solution of 5 parts of 6H20 dissolved in 5 parts of water by the same spraying method as above, drying, ammonia treatment, and thermal decomposition. Example 9 One alumina carrier (diameter 0.5
~2 +i+i), 10%C0-6%Mn2O3-2
%Ru-2%Cu (first catalyst) and 7.5%Nf-3.6%L on the same alumina carrier.
a203-(combined with a second catalyst containing 1.5% Ru, a test gas containing hydrogen and carbon monoxide having the same composition as in Example 1 was placed on the first catalyst, and then ff
52 catalyst was passed once. Note that the conditions at this time are SV5500h when passing over the first catalyst.
r-', temperature 310℃, pressure 10kg/crs2G
So, when passing over the second catalyst, 5V1000h
r-' and the temperature was 290°C, and the other conditions were the same as in the case of passing over the first catalyst. As a result, a high-calorie gas having a composition shown in Table 6 with a CO conversion rate of 100% was obtained.

It is clear from the results in Table 6 that the first catalyst of the present invention and the second catalyst are combined and brought into contact with a test gas having the composition shown in Table 1. According to 11.
? 00 kcal/Nm'' can be obtained, and if this principle is applied to increase the calorie of a low-calorie gas fuel, it is understood that a considerably high-calorie dregs fuel can be obtained.

Applicant Tomoyuki Inui Same Yoshinobu Takegami Kansai Thermochemical Co., Ltd.

Claims (1)

[Claims] (1) A catalyst substrate comprising an iron group metal combined with manganese oxide, a platinum group metal, metallic copper and/or a copper compound, and supported on a carrier made of silica and/or alumina. Catalyst for producing high calorie gas. (2) The catalyst for producing a high-calorie gas according to claim 1Jl''i, wherein the iron group metal as a catalyst substrate is either cobalt or iron. (3) The platinum group metal is ruthenium, rhodium, palladium, or platinum. or iridium. The catalyst for producing high-calorie gas according to claim 1 or 2. (4) Claim ff1 in which the copper compound is copper oxide.
The catalyst for producing high-calorie gas according to any one of items 1 to 3. (5) Iron group metal: 3 to 15%, (the meaning of weight %, the same applies hereinafter) Manganese oxide: An amount where the atomic ratio of iron group metal element to Yangan element satisfies (5:1) to (5:4) , an amount in which the atomic ratio of platinum group metal diiron group metal element to platinum group metal element satisfies (30:1) to (5:2), metallic copper and/or copper compound: 0.1 to 3.0% (as metallic copper) The catalyst for producing high-calorie gas according to any one of claims 1 to 4. (6) A carrier made of silica and/or alumina,
Either the platinum group metal is first supported, and then the iron group metal, manganese oxide, and metallic copper and/or copper compound are simultaneously supported, or the platinum group metal, metallic copper and/or
Alternatively, a copper compound may be present at the same time or individually, and then an iron group metal and manganese manganese may be present at the same time or individually.
1. A method for producing a catalyst for producing a high-calorie gas, characterized in that the catalyst has a retention time of 1. (7) The method for producing a catalyst for producing a high-calorie gas according to claim 6, wherein the iron group metal as the catalyst substrate is either conorte or carbon iron. (8) The method for producing a catalyst for producing a high-calorie gas according to claim 6 or 7, wherein the platinum group metal is ruthenium, rhodium, noradium, platinum, or iridium. (8) Claims 6 to 6 in which the copper compound is copper oxide
A method for producing a catalyst for producing high-calorie gas according to any one of Item 8. (10) Iron group metal = 3 to 15%, manganese oxide: an amount that satisfies the atomic ratio of iron group metal element to manganese element (5:1) to (5:4), platinum group metal: iron group metal element A patent claim in which the atomic ratio of the platinum group metal element to the platinum group metal element satisfies (30:t) to (5:2), Metallic copper and/or copper compound: 0.1 to 3.0% (as metal copper) A method for producing a catalyst for producing high-calorie gas according to any one of items 6 to 9. (11) On a catalyst formed by combining an iron group metal as a catalyst substrate with manganese oxide, a platinum group metal, and a metal copper and/or a copper compound and supporting the combination on a carrier made of silica and/or alumina. A method for producing a high-calorie gas, which comprises conducting a gas containing hydrogen and carbon monoxide or a gas containing hydrogen, carbon monoxide, and carbon dioxide. (12) The method for producing a high-calorie gas according to claim 11, wherein the iron group metal as the catalyst substrate is either cobalt or iron. (13) The method for producing a high-calorie gas according to claim 11 or 12, wherein the platinum group metal is ruthenium, rhodium, palladium, platinum, or iridium. (14) Claim 1 in which the copper compound is copper oxide
The high calorie gas production method according to any one of items 1 to 13. (15) Iron group metal: 3 to 15%, manganese oxide: iron group, an amount that satisfies the atomic ratio of metal element to manganese element (5:1) to (5:4), platinum group metal: iron group metal A patent in which the atomic ratio of the element to the platinum group metal element satisfies (30:l) to (5:2), and the amount of metallic copper and/or copper compound 20.1 to 3.0% (as metallic copper) A method for producing high-calorie gas according to any one of claims 11 to 14. (16) A first composition in which an iron group metal consisting of either cobalt or iron as a catalyst substrate is combined with manganese oxide, a platinum group metal, and metallic copper and/or a copper compound and supported on a carrier consisting of silica and/or alumina. A gas containing hydrogen and carbon monoxide or a gas containing hydrogen, carbon monoxide and carbon dioxide is passed over the catalyst, and then nickel as a catalyst substrate is combined with a rare earth element resistor and a platinum group metal, and silica A method for producing a high-calorie gas, characterized in that the gas is conducted over a second catalyst made of alumina and/or alumina. (17) The method for producing a high-calorie gas according to claim 16, wherein the copper compound in the first catalyst is copper oxide. (1 day) Iron group metal: 3 to 15%, Manganese oxide: An amount that satisfies the atomic ratio of iron group metal element to manganese element (5:l) to (5:4), Platinum group metal: Iron group metal A patent in which the atomic ratio of element to platinum group metal element satisfies (30:l) to (5:2), metallic copper and/or copper compound = 0.1 to 3.0% (as metallic copper) A method for producing high-calorie gas according to claim 16 or 17.