JPS59179154A - Catalyst for producing high calory gas and its production and production of high calory gas - Google Patents

Abstract

PURPOSE:To obtain a catalyst having high activity by combining manganese oxide and platinum group metal as well as >=1 kind among an alkali metal oxide, alkaline earth metal oxide and an oxide of rare earth elements with a ferrous metal and depositing the mixture on a carrier. CONSTITUTION:Manganese oxide and platinum group metal as well as oxide of >=1 kind among the oxide of alkali metals, the oxide of alkaline earth metals and the oxide of rare earth elements are combined with a substrate metal which is a ferrous metal such as cobalt, iron or the like, and the mixture is deposited on a carrier of silica and/or alumina having, for example, <=200m<2>/g specific surface area, thereby obtaining a quaternary compsn. catalyst. The amt. of the ferrous metal to be deposited as a catalyst. The amt. of the ferrous metal to be deposited as a catalyst substrate is 3-15%, more particularly preferably 5-12% with respect to the entire catalyst. The amt. of the manganese oxide to be deposited is 5:1-5:4 in the atom ratio between the ferrous group metal and the manganese element.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a catalyst for obtaining high calorie gas from low calorie gas, a method for producing the same, and a method for producing high calorie gas from low calorie gas. The present invention relates to a method for producing a high-calorie fuel gas containing hydrocarbons of numbers 1 to 4.

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 with the production of coke for the core industry of steelmaking,
Because of the enormous amount of by-products produced, developing effective uses for this has become an important issue. However, in order to continue to utilize this coke oven gas as a fuel, it is necessary to improve its current low calorie property and convert it into a high calorie gas comparable to natural gas.

Traditionally, methods for producing alternative natural gas (SNG) include synthesizing methane from gas from coal-based resources, such as coal gasification gas, or adding expensive naphtha or LPG to coke oven gas and catalytically reforming it. Methods have been proposed for converting methane into methane. You can get it here. SNG, which is mainly composed of methane, has a calorie of at most 8,500 kcal/m3 or less, and in order to supply it as city gas comparable to natural gas, it is necessary to add LPG or the like to heat it and grind it.

In view of the above-mentioned circumstances, the present inventors have completed the present invention as a result of various studies in order to obtain a fuel gas having a higher calorie value.

That is, to describe the purpose of the present invention more specifically, gas containing hydrogen and carbon monoxide, or gas containing hydrogen, carbon monoxide, and carbon monoxide (hereinafter academically referred to as low-calorie gas), for example, coke oven gas. An object of the present invention is to provide a four-component catalyst capable of converting into a gas with a much higher calorie content than conventionally known methods, a method for producing the same, and a method for producing a high-calorie gas using the catalyst. It is in.

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 a 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, an object of the present invention is to provide a method for simultaneously converting this by-product carbon dioxide into hydrocarbons by combining two systems of catalysts, the quaternary composition system and the ternary composition system. This provides the advantage that no carbon dioxide operation is required.

The present invention will be explained in further detail. First of all, in the middle of the present invention (the 40 shells are made of silica and/or alumina, or the shells are commercially available, for example, specific surface area or 2
00 m2/g or less can be used. For the catalyst supported on such a phase, an iron group metal is used, and cobalt and iron are particularly preferred as the iron group metal. A quaternary composition in which manganese oxide, a platinum group metal, an oxide of an alkali metal, an oxide of an alkaline earth metal, or an oxide of a rare earth element are combined and the support has JL1. Examples of platinum group metals include ruthenium, rhodium, haladium, platinum, and iridium; examples of alkali metal oxides include potassium,
Examples of oxides of alkaline earth metals include oxides of magnesium, calcium, strontium, and barium; examples of oxides of rare earth elements include lanthanum; Examples include oxides of cerium, praseodymium, or samarium, respectively.

As described above, the catalyst of the present invention is characterized in that it also supports an oxide of any one of an alkali metal, an alkaline earth metal, and a rare earth element as a catalyst component, and a combination of such catalyst components Therefore, when a low calorie gas is brought into contact with this, a high calorie gas containing more 02 to C4 hydrocarbons can be obtained. However, the details of the reason for such an effect are unknown, but
By combining these metal oxides, an appropriate sintering effect on the iron group metal, which is the catalyst substrate, is promoted, and the iron group metal particles grow to an appropriate size.
CO adsorption increases, carbon polymerization activity increases, and hydrogen adsorption decreases.

Therefore, the methanation activity of carbon oxide is low F, but C
The O shift reaction is also suppressed, producing a nerving effect, and 02~
This is thought to be due to improved C4 hydrocarbon 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. In addition, the amount of manganese oxide supported is that the atomic ratio of iron group metal element to manganese element is (5:1).
The amount of platinum group metal supported is set so that the atomic ratio of iron group metal element to platinum group metal element is in the range of (30:1) to (5:2). set to your satisfaction. Furthermore, the supported amounts of alkali metal oxides, alkaline earth metal oxides, and rare earth element infusions are set so that the atomic ratio of these metals satisfies the range of 0.01 to 1.0% with respect to the total catalyst. be done.

In preparing the catalyst of the present invention, when the amount of catalyst supported is small, for example, when the total amount of catalyst supported is 10% or less, the platinum group metal is first supported on a carrier made of silica and/or alumina, and then the platinum group metal is supported on a carrier made of silica and/or alumina. An iron group metal and manganese oxide are simultaneously supported on this, and then an oxide of an alkali metal, an alkaline earth metal, or a rare earth element is further supported.

That is, the catalyst obtained by supporting each catalyst component according to the above procedure is particularly suitable for converting low-calorie scum into high-calorie gas containing C1 to C4 hydrocarbons.
- The ability to select the production of C4 components is effectively demonstrated. Methods other than the above, such as supporting iron group metal and manganese oxide first and then supporting platinum group metal, supporting platinum group metal, manganese oxide, and iron group metal simultaneously, platinum group metal and alkali If a metal moltenide, an alkaline earth metal oxide, or a rare earth element oxide is supported at the same time, the combined effect as a four-component catalyst cannot be sufficiently exhibited, and high-calorie gas containing 02 to C4 hydrocarbons cannot be produced. The present inventors have confirmed that it is extremely difficult to obtain.

In addition, when the amount of supported catalyst components is large, for example, first, an iron group metal, manganese oxide, and any one of an alkali metal oxide, an alkaline earth metal oxide, or an earth element oxide are simultaneously supported, and then In addition, one platinum group metal may be supported, or one of platinum deposit hE, manganese liquefied, anvil metal, and an alkali metal oxide, an alkaline earth metal oxide, or a rare earth element infusate may be supported at the same time. The combined effect is also exhibited by the quaternary composition catalyst, and C
A high calorie gas containing 2 to C4 hydrocarbons can be obtained.

The catalyst of the present invention is produced by the above-mentioned basic structure, or more specifically, a platinum group metal, an iron group metal, or mankan is added to a substance made of silica and/or alumina in an aqueous nitrate solution. Alternatively, after impregnating it in the form of an aqueous chloride solution by spraying, cloth, dipping, etc., processes such as drying, ammonia treatment, thermal decomposition, and hydrogen reduction are performed sequentially to form a ternary introduction system support. Prepare. This is then impregnated with an alkali metal, an alkaline earth metal, or a rare earth element in the form of an aqueous carbonate solution, an aqueous hydroxide solution, an aqueous nitrate solution, an aqueous chloride solution, etc., by a procedure such as spraying, sheathing, or dipping. This is achieved by sequentially performing all or part of treatments such as drying, ammonia treatment, thermal decomposition, and hydrogen reduction to prepare a quaternary composition catalyst, which is then subjected to a final heat treatment. . 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 shaped carrier made of silica and/or alumina,
Alternatively, a molded phase heat-treated at 500-1100°C is impregnated with an aqueous solution of a platinum group metal nitrate or chloride in an amount equal to the pore volume, and air-dried at room temperature while gently rolling.

In addition, to speed up drying, heat at 150'C! A commercially available dryer adjusted to a temperature of Next, the treated product in -1- 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 1 when this is diluted with inert gas
Raise the temperature from room temperature to 400°C in an air flow of 0 to 20%,
The mixture is maintained at the same temperature for 30 minutes for reduction, and then cooled to room temperature in the same air flow. The platinum group metal support thus obtained is impregnated with a mixed solution of an aqueous nitrate solution of an iron group metal, for example, and an aqueous nitrate solution of mankan, by the same impregnation method as described above. Then, as in the case of supporting the platinum group metal, a ternary composition support is obtained by performing treatments such as air drying or heat drying, ammonia treatment, thermal decomposition, and hydrogen reduction.

The ternary composition support supporting the platinum group metal, iron group metal, and manganese oxide obtained as described above is further impregnated with the above-mentioned impregnating methods such as spraying, scattering, and dipping, such as carbonic acid of an alkali metal. Salt solution.

Air-drying or heat-drying, ammonia treatment, thermal decomposition, hydrogen A quaternary composition catalyst is obtained by performing a treatment such as reduction. In addition, when carbonates or hydroxides of alkali metals or alkaline earth metals are used, the desired four-component composition catalyst can be obtained only by air drying or heat drying, so methods such as ammonia treatment and thermal decomposition reduction are not necessary. Can be omitted. In the preparation of the catalyst of the present invention, if the catalyst components are supported as described below and then heat treated in a reducing atmosphere, the catalyst can be modified into a catalyst with excellent heat resistance and a longer life. When these are brought into contact with each other, there is an effect that a high-calorie residue containing more hydrocarbons having 2 to 4 carbon atoms can be obtained. This heat treatment takes 1 to 3 hours in a reducing atmosphere, such as a 100% hydrogen stream, and is heated to a temperature of 500 to 950 degrees at room temperature.
This is carried out by raising the temperature to C and maintaining the same temperature, and then cooling it to room temperature in the same air flow. The reason why the above effects can be obtained by heat treatment is that the ethnic metal that is the catalyst substrate grows into particles of an appropriate size through sintering, and the hydrogen adsorption rate decreases, thereby reducing the methanation of carbon oxide. Although the activity decreases, the residence time of the adsorbed and oxidized carbon on the active surface increases, which promotes carbon polymerization and is presumed to improve the production of hydrocarbons having 2 to 4 carbon atoms.

By using the catalyst of the present invention, low-calorie gases such as coke oven dregs, naphtha, and water sludge reformed gas of Tsumega oil, as well as water gas and coal cassification gas can be converted into high-calorie gases containing hydrocarbons having 1 to 4 carbon atoms. The conversion into caloric gas can be carried out, for example, 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 1.
5-30 kg/cm2G, preferably 1
per liter of catalyst capacity under pressure of 0 to 20 kg/Cm2G,
1-10 m"/hr, preferably 2-5 m"/hr
By introducing the low-calorie scum of r, 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 , a shift reaction occurs with carbon monoxide in the low-calorie raw material gas, producing carbon dioxide as a by-product. Further, in some cases, carbon monoxide itself in the raw material low-calorie gas may cause a disproportionation reaction by Equation 79, and carbon dioxide may be produced as a by-product.

CO+H20=CO2+H2■ 2CO=CO2+C) In the present invention, 01 to C4 gases mixed with by-product carbon dioxide gas from the above hydrocarbonization reaction are combined with silica and/or
Alternatively, the by-product carbon dioxide can also be converted into methane by subsequently contacting a ternary composition catalyst in which a support made of alumina has 10 nickel, a rare earth element diluted compound, and a platinum group metal. 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 mm, for example. water-removed version) is used as a phase. The catalyst supported on the above-mentioned phase has a substrate of nickel, which contains a rare earth element oxide such as lanthanum, cerium, praseodymium, thorium or samarium oxide and a platinum group metal such as ruthenium, platinum, palladium. , rhodium or iridium, or when considering the catalytic effect and economic efficiency, lanthanum oxide or cerium oxide is used as the oxide of the rare earth element, and ruthenium is used as the platinum group metal. and palladium are most preferred. In the above combination,
The number of supporting paths for nickel, which is the catalyst substrate, is 3 to 3 for all catalysts.
12%, particularly preferably in the range 4-8%. In addition, oxides of rare elements are set so that the atomic ratio of nickel element to frosted earth element satisfies (2:1) to (10:1),
Further, it is preferable that the platinum group metals are supported so that the atomic ratio of nickel element to platinum group metal element satisfies (lO:1) to (30:1). In addition, even if each catalyst component is supported beyond the range specified in 1-1, the catalytic effect will be lower than that.
This is not preferable because it tends to cause blockage of the pores of the carrier and deteriorate catalyst performance on the contrary. In the production of this ternary composition catalyst, nickel, rare earth elements, and platinum group metals are applied to a granular support of silica and/or alumina in the form of an aqueous solution of nitrobutyrate by means such as spraying, scattering, or immersion. Impregnated and dried naturally or 60~
After heating and drying at 150'C, ammonia treatment was performed.

Performs thermal decomposition and hydrogen reduction. In preparing this catalyst, nickel, rare earth element oxides, and platinum group metals may be supported on a granular carrier of silica and/or alumina, either separately in any order, or in combination of two or more of them. However, the catalyst obtained by first supporting a platinum group metal on the carrier and then simultaneously supporting nickel and a rare earth element oxide has particularly excellent conversion properties from carbon dioxide to hydrocarbons. ing.

A specific example of the preparation of the above-mentioned ternary composition catalyst is as follows. That is, a granular support of silica and/or alumina is impregnated with an aqueous solution of platinum group metal salts such as nitrates and chlorides in an amount equal to the pore volume of the phase, and dried in the air or heated at 60 to 150''C. At this time, the concentration of nitrates and chlorides of platinum group metals can be determined by heating the impregnated material to 350°C in the air after drying and ammonia treatment so that the impregnating solution contains a predetermined carrier path. Decompose the nitrates and tl compounds.The platinum group metal support thus obtained is impregnated with a mixed solution of an aqueous solution of a nickel inorganic acid salt, such as a nitrate, and an aqueous solution of an inorganic acid salt of a hexaearth element, such as a nitrate. drying, ammonia treatment, and thermal decomposition in the same manner as in the case of supporting the platinum group metal,
Furthermore, this was diluted with inert residue to give a hydrogen concentration of 10 to 20%.
The temperature was raised from room temperature to 400°C in the airflow of
The preparation of the catalyst is completed by holding for 0 minutes for reduction, and then cooling to room temperature in the same air flow.

In producing high calorie gas according to the present invention,
A reaction tower filled with a quaternary composition catalyst comprising any one of the iron group metal-manganese oxide-platinum group metal-alkali metal oxide, alkaline earth metal oxide, or rare earth element oxide. Then, the low-calorie raw material residue is introduced under the above conditions. If the gas produced here contains by-product carbon dioxide, the gas is
A second compound consisting of nickel-rare earth element oxide-platinum group metal
Alternatively, one reaction column may be filled with two kinds of catalysts in series, and the low-calorie gas is first introduced into the above-mentioned ternary composition catalyst of the present invention. 1st
It may be brought into contact with the first four-component composition catalyst layer, and then brought into contact with the second three-component composition catalyst layer. In this case, the first catalyst volume is the minimum amount necessary to reach a conversion rate of 100% of carbon monoxide, and the second catalyst volume is the minimum amount necessary to reach a conversion rate of 100% of the contained carbon dioxide. Any amount is fine. In actual operation, it is easier to completely convert carbon dioxide into hydrocarbons by maintaining the temperature of the second catalyst layer approximately 50° C. higher than the temperature of the first catalyst layer.

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 material gas", which was not achieved with conventional catalysts, is achieved, and moreover, the number of carbon atoms is higher than that of conventional catalysts. A high-calorie gas containing more 2-4 hydrocarbons 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, it is possible to completely methanize the by-product carbon dioxide, so there is no need for a carbon dibutyride separation and recovery device, which is extremely effective in terms of the process.

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

Example 1 A commercially available alumina spherical molded body with a specific surface area of 200 to 220II+2/g was heated from room temperature to 1060°C in an electric furnace for 4 to 1060°C.
The temperature was raised over 6 hours, and the temperature was maintained for 30 minutes for heat treatment. Ru C was added to 20 parts of the heat-treated carrier cooled to room temperature
The sample was impregnated with an aqueous solution prepared by dissolving 1.08 parts of 13-3H in 5 parts of water by a spraying method, and then air-dried overnight while gently rolling to obtain an impregnated product. The impregnated material was ammonia-treated by being exposed for 2 minutes to an atmosphere previously adjusted to have a capacitance of 10 to 11% by volume and water vapor of 6% by volume, and then heated in air to about 350°C. The impregnated Ru metal salt was thermally decomposed to form 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 a nitrogen stream containing hydrogen at a concentration of 20% by volume.
The temperature was maintained for 30 minutes for reduction, and then cooled to room temperature in the same air flow to obtain 20.5 parts of Ru support. Next, Ru
21.0 parts of the support, G O(NO3) 2 ・6H2
0+2.0 parts and Mn (NO3) 2116H20
After impregnating with 1/2 amount of a solution prepared by dissolving 5.3 parts in 5 parts of water by the same spraying method as above, drying, ammonia treatment, thermal decomposition, and cooling, the remaining above solution was further impregnated with the above solution. Impregnation, drying, ammonia treatment, and
Pyrolysis and reduction treatment in the same manner as above to obtain 1
24 parts of a ternary composition carrier of 0% Co-6% Mn2O3-2% Ru was obtained. To 20 parts of this ternary composition carrier, K2
After impregnating with a solution of 30.4 parts of CO dissolved in 5 parts of water by the same spraying method as above, drying, ammonia treatment,
Thermal decomposition was carried out and reduction treatment was carried out in the same manner as described above. The resulting quaternary composition jt1 carrier was heated in a 100% hydrogen stream from room temperature to 850°C over a period of 2 to 3 hours, maintained at the same temperature for 30 minutes, and heat-treated. By cooling to room temperature, the composition ratio becomes 10%C0-6%Mn.
4 of the present invention consisting of 20a-2%Ru-0.1%
20.2 parts of a catalyst based on the original composition was obtained.

Example 2 10%Co-6%Mn203-2%R in Example 1
Add 200,63 parts of La (NO3) 2 .6H instead of K2CO3(7) to 20 parts of the ternary composition support of
The obtained 4
Example 1 The original composition support was placed in an ioo% hydrogen stream.
By performing heat treatment in the same manner as above and cooling to room temperature in the same air flow, the composition ratio was 10%Co-6%M.
20.2 parts of a four-component catalyst of the present invention consisting of n203-2% Ru-0.1% La2O3 was obtained.

Example 3 10% C obtained by a method similar to that described in Example 1
o-6%M n203-2%FI IJ (7) Mg (NO3) instead of K2CO3 in 20 parts of ternary composition system carrier
After impregnating with a solution of 12 parts of 2.6H dissolved in 5 parts of water, drying, ammonia treatment, thermal decomposition and reduction treatment, the resulting quaternary composition support was
% in a hydrogen stream by the same method as in Example 1, and the composition ratio was 10%C0-6%Mn203-
20.2 parts of a four-component composition catalyst of the present invention consisting of 2% Ru-0.1% MgO was obtained.

Example 4 A commercially available silica molded body having a specific surface area of 600 m 2 /g was heated to temperature A from room temperature to 600° C. over 4 to 6 hours in an electric furnace, and was heat-treated by holding the same temperature for 30 minutes. RuC13.3H201,08 was added to 20 parts of the heat-treated carrier cooled to room temperature.
The sample was impregnated with an aqueous solution prepared by dissolving 5 parts of water in 5 parts of water, and then air-dried overnight with gentle rolling to obtain an impregnated product. This impregnated material was ammonia-treated by being exposed for 2 minutes to an atmosphere previously adjusted to be 10-11% by volume of ammonia and 6% by volume of water, and then heated in air to about 350°C. The impregnated Ru metal salt was thermally decomposed to form an oxide. This was placed in an electric furnace and heated to 40°C from room temperature while passing a nitrogen stream containing hydrogen at a concentration of 20% by volume.
The mixture was heated to 0° C. in 1 hour, maintained at this temperature for 30 minutes for reduction, and then cooled to room temperature in the same air stream to obtain 21 parts of a Ru support. Next, C was added to 21 parts of the Ru carrier.

(NO3)2 -6H20+2 parts and Mn(NO3)
2.17 of a solution of 3 parts of 6H205 dissolved in 5 parts of water
The remaining 1-
Impregnate the solution in 6 with the same procedure as in 2, dry, ammonia, and thermally decompose, and reduce in the same manner as above to obtain a ternary composition system of 10%Co-6%M+1203-2%Ru. 24 parts of carrier were obtained. This ternary composition carrier 20
12 parts of Mg (NO3)2-6H202 and 5 parts of water
After impregnation with a solution dissolved in 100% by the same spraying method as above, drying, ammonia treatment, thermal decomposition, and reduction treatment were performed in the same manner as above. The obtained quaternary composition system support was heated in a 100% hydrogen stream from room temperature to 800'C over a period of 2 to 3 hours, maintained at the same temperature for 30 minutes, and heat-treated. By cooling to room temperature, the composition ratio becomes 10%C0-6%Mn203-2%R
Quaternary composition catalyst 2 of the present invention consisting of u-0,1% MgO
0.2 part was obtained.

Example 5 In 20 parts of 10%Co-6%Mn203-2%R,u (7) ternary composition tn carrier in Example 4, La(NO3) was added instead of Mg(NO3)2 ・6H20(7) 2. After impregnating with a solution of 200.83 parts of 6H dissolved in 5 parts of water by spraying, drying, ammonia treatment, thermal decomposition and reduction treatment, the obtained quaternary composition system support was soaked in 100% hydrogen atmosphere. By performing heat treatment in the same manner as in Example 4 and cooling to room temperature in the same air flow, the composition ratio was 10%Co-6%Mn20.
4 of the present invention consisting of 3-2% Ru-0,1% La2O3
20.2 parts of the original composition catalyst is 13.

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 1 at a pressure of 10 kg/c.
m2G, 5V2000hr', temperature 29
When passed once at 0°C, a high-strength gas having the composition shown in Table 2 was produced with a CO conversion rate of 100%.

For comparison, 10%C0-6% in Example 1
A ternary composition catalyst obtained by heat-treating a ternary composition support consisting of Mn2O3-2%Ru in the same manner as in Example 1."Second, the same low-calorie supply was prepared under the same conditions as in this example. Table 2 also shows the results when the test gas was passed through.

As is clear from the results in Table 1 and Table 2 to Table 1-1, when the catalyst of the present invention was used, the 02 to C4 hydrocarbons in the produced residue were lower than when the catalyst of the comparative example was used. It can be seen that the dregs with high content and high calories are tJI.

Example 7 A low-calorie test residue having the same composition as that used in Example 6 was passed once over the catalyst obtained by the method of Example 2 under the same conditions as Example 6. However, C
A high-calorie gas having the composition shown in Table 3 was obtained with an O conversion rate of 100%.

Table 3 Example 8 A low-calorie test gas having the same composition as that used in Example 6 was passed once under the same conditions as Example 6 over the catalyst obtained by the method of Example 4. When I did it, C
A high-calorie gas having the composition shown in Table 4 was obtained with an O conversion rate of 100%. For comparison, a ternary composition catalyst obtained by heat-treating the ternary composition support consisting of 10%Go-6%Mn203-2%Ru in Example 4 in the same manner as in Example 4 was used. Table 4 also shows the results obtained when the same low-calorie test gas was passed under the same conditions as in Example 6.

(Satoshi) As is clear from the results in Table 4, the generated gas is lower when the catalyst of the present invention is used than when the catalyst/iW of the comparative example is used. It can be seen that a high-calorie gas with a high content of 02 to C4 hydrocarbons can be obtained.

Example 9 A silica molded carrier (direction 0.5~
2 mm), 10%C0-6%Mn2O3-2%Ru
-0.1%MgO supported catalyst of the present invention (first catalyst) and 7.5%Ni-3.6% on the same silica molded support.
La203 was combined with a second catalyst carrying 0.5% Ru, and a test gas containing hydrogen and carbon monoxide having the same composition as in Example 8 was added to the first middle part. The second touch was passed once in two. Note that the conditions at this time are SV160 when passing over the first catalyst.
0h r-1, temperature 280°C1 pressure 20 kg/am
When passing over the second catalyst at 2G, 5V100
0 h r-1, temperature 320'O, and other conditions were the same as in the case of passing over the first catalyst. As a result, a gas having a composition shown in Table 5 was obtained with a CO conversion rate of 100%.

As is clear from the results in Table 5 and above, by combining the first catalyst and the second catalyst of the present invention and bringing them into contact with a low-calorie gas containing hydrogen and carbon monoxide, in addition to methane, It can be seen that a high-calorie gas containing hydrocarbons having 2 to 4 carbon atoms and no carbon dioxide can be obtained.

Example 10 The same two catalysts used in Example 9 were combined, and a test gas having the composition shown in Table 6 was applied to the first catalyst.
It was then passed once over a second catalyst. Note that the conditions at this time are S V]E100h r-' on the first catalyst,
When passing at a temperature of 290°C and a pressure of 20 kg/Cl112G, and then passing over the second catalyst, 5V1000
h r-1, temperature 330° C., and other conditions were the same as in the case of passing over the first catalyst. As a result, CO
The conversion rate was 100%, and a gas having the composition shown in Table 7 was obtained.

As is clear from the results shown in Table 6 and Table 7, the first catalyst of the present invention and the second catalyst are combined and brought into contact with the sample gas having the composition shown in Table 6. By this, 10.2
It can be seen that a high calorie gas of 0.00 kcal/Nm3 can be obtained, and that oxygen contained in the sample gas can also be completely removed without affecting the reaction selection in any way.

Applicants Yoshinobu Takegami and Satoshi Inui Kansai Thermal Chemical Co., Ltd. Teito Hikari Amendment (spontaneous) 1. Display of 1 copy 1982 Patent Application No. 54888 2 Name of invention Catalyst for producing high calorie gas and its manufacturing method and manufacturing method for high-calorie cassettes 3. Relationship with the supplementary case Patent applicant Yoshinobu Takekami, 5, Shugakuin Takabe-cho, Sakyo-ku, Kyoto City (2 people) 4. Agent Shinko Building, 2-3-7 Dojima, Kita-ku, Osaka 530, Japan The "Scope of Claims" and "Details of the Invention (1) "Scope of Claims" in the specification will be corrected as shown in the attached sheet.

(2) Correct "high calorie gas" in the bottom 7 lines of page 8 of the statement to "high calorie."

(3) "Methods other than the above..." on page 14, lines 6-12
``at the same time'' is corrected to the following sentence.

[A method other than the above, for example, a platinum group metal, manganese oxide, and an iron group metal are simultaneously supported, and then one of an alkali metal oxide, an alkaline earth metal oxide, or a rare earth element oxide is applied. "(4) At the same time, a platinum group metal, a mankanoxide, an iron group metal, and any one of an alkali metal oxide, an alkaline earth metal oxide, or a rare earth element oxide are supported." In line 4 from 4th line, ``If the supported amount is large'' should be corrected to ``If the total supported amount is 10% or more of the total catalyst''.

(5) “Or platinum group metals,” on page 15, lines 1 and 2,
"Manganese oxide" should be corrected to "Or supporting a platinum group metal," then "manganese oxide J."

(6) In PJ, page 15, line 9, [stated J is corrected to ``state.''

(7) On page 818, line 11, "at the same temperature" is revised to "at the same temperature."

(8) "Silica or alumina" on page 20, lines 12-13 will be corrected to "silica and/or alumina."

(9) On page 25, line 8 from the bottom, “Global molded body j is
I will correct it.

(10) On page 28, line 8 from the bottom, “Molded body J [Carrier J
I will correct it.

(11) "Molding phase J" in line 6 on page 37 is corrected to "carrier."

(12) Replace page 42 with attached pages 42-59.

As is clear from the above results, 10. 2
00kcal/N+a” (7) iA Calo IJ −
It can be seen that scum can be obtained, and # element contained in the sample gas can be completely removed without affecting the reaction selection in any way.

Example 11 A commercially available alumina carrier having a specific surface area of 200 to 220 m2/g was heated in an electric furnace from room temperature to 1060 DEG C. in 4 parts and 6 times, and was heat-treated by holding the same temperature for 30 minutes. RuC13-3H20 was added to 10 parts of the above heat-treated carrier cooled at room temperature.
The impregnated material was impregnated with an aqueous solution prepared by dissolving 0.3 parts in 5 parts of water by a spraying method, and then air-dried overnight with gentle rolling. 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. The Ru metal salt was thermally decomposed to form an oxide. Put this in an electric furnace and add 2 hydrogen
The temperature was raised from room temperature to 400°C in 1 hour while passing through a nitrogen flow containing a concentration of 0% by volume, and the temperature was maintained for 30 minutes for reduction, and then cooled to room temperature in the same airflow to remove Ru. 0.04 part of supported suspension was obtained. Next, 10 parts of Ru carrier,
C.

(NO3) 2 ・6H202, 8 parts and Mn(N
After impregnating with a solution of 200.5 parts of O3)2.6H dissolved in 5 parts of water by the same spraying method as above, drying, ammonia treatment, thermal decomposition, and reduction treatment in the same manner as above, 5%C0-1%M n 203-0.4%R
10.6 parts of a ternary composition carrier of u was obtained. To 10 parts of this ternary composition support, Mg(NO3) 2 #6H200,
After impregnation with a solution dissolved in 5 parts by the same spraying method as described in IF, drying, ammonia treatment, thermal decomposition, and reduction treatment by the above method. The resulting quaternary composition support was heated in a 100% hydrogen stream from room temperature to 600°C over 2 to 3 hours, maintained at the same temperature for 30 minutes for heat treatment, and then heated to 600°C in the same airflow at room temperature. (The composition ratio is 5%C0-1%Mn203-0.4%Ru-0.05%).
10.0 parts of a four-component catalyst of the present invention consisting of MgO was obtained.

Example 12 2012 parts of Co (NO3)2 6H and Mn(NO
3)'2 Fist 6H205, 3 parts and Mg (NO3)
The sample was impregnated with an aqueous solution in which 12 parts of 2.6H20 was dissolved in 5 parts of water 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% by volume ammonia and 6% by volume water vapor for 2 minutes, and then heated in air to about 350°C.
The impregnated Ru metal salt was thermally decomposed to form 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 a nitrogen stream containing hydrogen at a concentration of 20% by volume, and after being reduced by maintaining this temperature for 30 minutes, it was heated in the same air stream. The mixture was cooled to room temperature to obtain 11.6 parts of a carrier. Next, 10 parts of this support was impregnated with a solution of 1.08 parts of RuCl3.3H dissolved in 5 parts of water by the same spraying method, followed by drying, ammonia treatment, thermal decomposition, and reduction treatment by the same method as above. and 10%C0-6%Mn2O3-2%
Ru-0,05% MgO quaternary M1 support 10.
Got 2 copies.

The obtained quaternary composition support was heated from room temperature to 700'C in a 100% hydrogen stream over a period of 2 to 3 hours,
By holding at the same temperature for 30 minutes, heat treatment, and cooling to room temperature in the same air flow, the composition ratio becomes 10%Co-6%
10.2 parts of a four-component composition catalyst of the present invention consisting of Mn203-2% Ru-0.05% MgO was obtained.

Example 13 A low-calorie test gas having the composition shown in Table 1 was added to the catalyst obtained by the method of Example 11 at a pressure of 1.0.
kg/Cm2G, SV5500hr-',
When passed once at a temperature of 270°C, the CO conversion rate was 10.
At 0%, a high calorie gas having the composition shown in Table 1 was obtained. For comparison, 200.3 parts of RuCl3.3H and 3 parts of co(
NO3) 21I6H202, 8 parts, Mn (NO3)
2 ・6H200.05 parts and Mg(NO3)2 ・
An aqueous solution of 200.5 parts of 6H dissolved 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 Ru metal salt was thermally decomposed and oxidized by being exposed to an atmosphere adjusted to have vol.% ammonia and 6 vol.% water vapor for 2 minutes to perform ammonia treatment, and then heating in air to approximately 350°C. It became a thing. This was placed in an electric furnace, and the temperature was raised from room temperature to 400°C in one hour while passing a nitrogen stream containing hydrogen at a concentration of 20% by volume, and this temperature was maintained for 30 minutes to reduce the resulting 5% Co-1%Mr++0
+ - A four-component catalyst consisting of 0.4% Ru and 0.05% MgO. Second, when the same low-calorie test residue was passed under the same conditions as in this example, the CO conversion rate was 70%. The results shown in Table 7 were obtained.

As is clear from the results in Table 7 and above, when the catalyst of the present invention is used, the CO conversion rate is higher than when the catalyst of the comparative example is used, and the content of 02 to C4 hydrocarbons in the generated gas is It can be seen that a high-calorie gas can be obtained.

Example 14 Example 1 onto the catalyst obtained by the method of Example 12
When a low-calorie test gas having the same composition as that used in Example 3 was passed once at a temperature of 300°C and a pressure and Sv under the same conditions as in Example 13, the CO conversion rate was 100%, as shown in Table 8. A high-calorie gas with the composition shown in was obtained.

Table 8 Example 15 A commercially available alumina carrier having a specific surface area of 200 to 220 m/g was heated in an electric furnace from room temperature to 1060' (!) in 4 to 6 hours, and was heat-treated by maintaining the same temperature for 30 minutes. RIJc 13 was added to 20 parts of the heat-treated carrier cooled to room temperature.
- An aqueous solution of 201.08 parts of 3H dissolved in 5 parts of water was impregnated by a spraying method, and then air-dried overnight while gently rolling to obtain an impregnated product. This impregnated material is prepared in advance for 10~
2. In an atmosphere adjusted to have 11% by volume ammonia and 6% by volume water vapor. The impregnated Ru metal salt was thermally decomposed into an oxide by exposure to ammonia for a minute and then heating to about 350° C. in air. 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 20.5 parts of Ru carrier. Next, 20.0 parts of Ru carrier was added with C0(NO3) 2-6H2012,
After impregnating with 172 parts of a solution prepared by dissolving 0 parts of Mn(NO3) 2 .6H, 3 parts of Mn(NO3) 2 . processing, pyrolysis,
After cooling, the remaining solution was impregnated using the same method as above, dried, treated with ammonia, thermally decomposed, and reduced using the method described above to obtain 10%Co-6%Mn20i-2.
%Ru-0.05%MgO quaternary composition system support 23.
I got 3 copies. 20.0 parts of the obtained quaternary composition support was
oo% In a hydrogen stream, the temperature is raised from room temperature to 800°C over 2 to 3 hours, and the composition ratio is 10 %C0-6%Mn203-2%Ru -0,05%
20.0 parts of a four-component catalyst of the present invention consisting of MgO was obtained.

Example 16 20 parts of a commercially available alumina carrier with a specific surface area of 10112/g was mixed with 2012 parts of Co(NO3)2-6H and Mn(NO3).
The sample was impregnated with an aqueous solution prepared by dissolving 4 parts of 2.6H205 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 adjusted in advance to have to-ii volume % ammonia and 6 volume % water vapor, and then in air for about 35
It was heated to 0°C to thermally decompose the impregnated metal salt 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 a nitrogen stream containing hydrogen at a concentration of 20% by volume. After being reduced by maintaining this temperature for 30 minutes, It was cooled to room temperature to obtain 23.2 parts of Co-Mn2O3 support. Next, 1.0 parts of RuC13 3H was added to 20.0 parts of this Co-Mn2O3 support with 5 parts of water.
After being impregnated with the solution dissolved in the remaining part by the same spraying method, drying, ammonia treatment, and thermal decomposition are performed, and after cooling, the remaining solution is further impregnated with the same operation method as the above solution, followed by drying, ammonia treatment, and thermal decomposition. Reduction treatment was performed in the same manner as above to obtain 20.2 parts of a ternary composition carrier of 10% Co-6% Mn2O3-2% Ru. 20 parts of this ternary composition carrier +: I'vfg (NO3) 2116H201,08
A solution prepared by dissolving 5 parts of water in 5 parts of water was impregnated by the same spraying method as above, followed by drying, ammonia treatment, thermal decomposition, and reduction treatment in the same manner as above. The obtained quaternary composition support was heated in a 100% hydrogen stream from room temperature to 800'C over a period of 2 to 3 hours, maintained at the same temperature for 30 minutes, and heat-treated. By cooling to room temperature, the composition ratio becomes 10%Co-6%Mn203-2%Ru
-20.3 parts of a four-component catalyst of the present invention consisting of 0.05% MgO was obtained.

As a comparative example, a four-component composition catalyst was obtained by the following method. That is, 20 parts of a commercially available alumina carrier with a specific surface area of 20 m2/g, 201.08 parts of RuCl3.3H, 2012 parts of Go(NO3)2.6H, Mn (NO3
) An aqueous solution prepared by dissolving 3 parts of 2.6H205 in 5 parts of water was impregnated by a spraying method, and then air-dried overnight while being gently transferred to obtain an impregnated product. This impregnated material was exposed to an atmosphere adjusted in advance to have 10 to 11% by volume of ammonia and 6% by volume of water vapor for ammonia treatment, and then heated in air to about 350°C to impregnate it. The Ru metal salt was thermally decomposed to form 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 a nitrogen stream containing hydrogen at a concentration of 20% by volume, and this temperature was maintained for 30 minutes to reduce to 10%Co-6%. Mn
23.6 parts of a ternary composition support of 203-2% Ru was obtained. Mg (No3) 2 is added to 20 parts of this ternary composition carrier.
- After impregnating with a solution of 12 parts of 6H202 dissolved in 5 parts of water by the same spraying method as above, drying, ammonia treatment, thermal decomposition, and reduction treatment were performed in the same manner as above. The obtained quaternary composition support was heated in 100% hydrogen 51 from room temperature to 800°C over a period of 2 to 3 hours,
By holding at the same temperature for 30 minutes, heat treatment, and cooling to room temperature in the same air flow, the composition ratio becomes 10%C0-6%
20.2 parts of a four-component composition catalyst of the present invention consisting of Mn20+-2%Ru-0.05%MgO was obtained.

Example 17 A low-calorie test gas having the composition shown in Table 1 was applied to the catalyst obtained by the method of Example 15 at a pressure of 10 kg.
/cm2G, SV4000hr-', temperature 2
When the mixture was passed through 90° C. once, a high-calorie scum with a Co conversion rate of 100% and a composition shown in Table 9 was obtained. In addition, 10%C0-6%Mn203-2%Ru-0 of the comparative example
, 1% MgO when the same low-calorie test gas was passed under the same conditions as in this example, and the results are also shown in Table 9.

(Heart) - As is clear from the results in Table 9-1, when the catalyst of the present invention was used, the CO conversion rate was higher than when the catalyst of the comparative example was used. It can be seen that the produced gas has a high content of 02 to C4 hydrocarbons and a high-calorie gas can be obtained.

Example 18 A low-calorie test gas having the composition shown in Table 1 was poured onto the catalyst obtained by the method of Example 16 at a pressure of 10 kg/
Cm G, 5V4000hr-', temperature 290
After one pass through °C, the Co conversion rate was 100% and the first
A high-calorie gas having the composition shown in Table O was obtained.

Table 2, Claims (1) Manganese butyride and platinum group metals as catalyst substrates, including alkali metal oxides, alkaline earth metal oxides or rare earth element infusions. Combining any one type of oxide onto a support made of silica and/or alumina 11! A catalyst for producing high-calorie scum, which is characterized by a high calorie content.

(2) The catalyst for producing high-calorie gas according to claim 1, wherein the iron group metal as the catalyst substrate is either cobal I or iron.

(3) The catalyst for producing high-calorie gas according to claim 1 or 2, wherein the platinum group metal is ruthenium, rhodium, palladium, platinum, or iridium.

(4) The alkali metal oxides are potassium, sodium,
An oxide of any one of lithium, cesium, or rubidium, an oxide of an alkaline earth metal is an oxide of any one of magnesium, calcium, strontium, or lithium, and an oxide of a rare earth element. is a lantern, cerium.

The catalyst for producing high-calorie scum according to any one of claims 1 to 3, which is an oxide of either praseodymium or samarium.

(5) Iron group metal = 3 to 15%, (meaning of weight %, below) Mancan oxide: Star whose atomic ratio of iron group metal element to manganese element satisfies (5:l) 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:]) to (5:2), oxidation of alkali metal oxide, alkaline earth metal oxide or rare earth element Any one of the oxides: 0.
01-1.0% of the catalyst for producing high-calorie gas in one night according to any one of claims 1 to 4.

Then, oxides of alkali metals, alkaline earths (7)
7. The method for producing a catalyst for producing high-calorie gas according to claim 6, wherein the iron group metal as the catalyst substrate is either cobalt or 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, palladium, platinum or iridium.

(9) The alkali metal oxides are potassium, sodium,
An oxide of any one of lithium, cesium, or rubidium, an oxide of an alkaline earth metal such as magnesium, calcium, strontium, or barium, an oxide of a rare earth element, or lanthanum, Seryu 1.

The method for producing a catalyst for producing a high-calorie gas according to any one of claims 6 to 8, wherein the catalyst is an oxide of either praseodymium or samarium.

(10) Iron group metal: 3 to 15%, manganese oxide: iron group metal element to manganese element atomic ratio satisfies (5:l) to (5:4), platinum group metal: iron group metal element Any one of alkali metal oxides, alkaline earth metal oxides, or rare earth element oxides whose atomic ratio of platinum group metal elements to platinum group metal elements satisfies (30:1) to (5:2). Infusion: 0
．． 01 to 1.0%. A method for producing a catalyst for producing a high-calorie gas according to any one of claims 6 to 9.

(11) Manganese oxide, platinum group metal, and any one of an alkali metal oxide, an alkaline earth metal oxide, or a rare earth element oxide as a catalyst substrate for an iron group metal.
A catalyst consisting of a combination of oxides of various species supported on a carrier made of silica and/or alumina is a catalyst in which a gas containing hydrogen and carbon monoxide or a gas containing hydrogen, carbon monoxide and carbon dioxide is passed through the catalyst. Features: A method for producing high-calorie gas.

(12) The method for producing a high-calorie scum 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-9 platinum, or iridium.

(14) The alkali metal oxide is any one of potassium, sodium, lithium, cesium, or rubidium, and the alkaline earth metal oxide is any one of magnesium, calcium, strontium, or barium. Oxides of rare earth elements are lanthanum and cerium.

The method for producing a high-calorie gas according to any one of claims 11 to 13, wherein the oxide is one of praseodymium and samarium.

(15) Iron group metal = 3 to 15%, amount that satisfies the atomic ratio of mankanese diiron group metal element to manganese element (5:I) to (5:4), platinum group metal: iron group metal element An amount in which the atomic ratio of the platinum group metal element to the platinum group metal element satisfies (30:l) to (5:2); any one of alkali metal oxides, alkaline earth metal oxides, or rare earth element oxides; Oxide: 0
．． 01 to 1.0%.

(16) An iron group metal consisting of either cobalt or iron as a catalyst substrate, manganese oxide and a platinum group metal, and any one of an alkali metal oxide, an alkaline earth metal oxide, or a rare earth element oxide. A gas containing hydrogen and carbon monoxide or a gas containing hydrogen, carbon monoxide, and carbon dioxide is passed over the first catalyst, which is a combination of ingots and supported on a carrier made of silica and/or alumina, and then a gas containing hydrogen, carbon monoxide, and carbon dioxide is introduced into the catalyst. A method for producing a high-calorie scum, which comprises combining nickel as a substrate with an oxide of a rare earth element and a platinum group metal, and conducting the mixture over a second catalyst supported on a carrier made of silica and/or alumina.

(17) The alkali metal oxide in the first catalyst is an oxide of potassium, sodium, lithium, cesium or rubidium, and the alkaline earth metal oxide is magnesium, calcium, strontium or barium. 17. The method for producing a high-calorie gas according to claim 16, wherein the rare earth element oxide is an oxide of any one of lanthanum, cerium, praseodymium, and samarium.

(18) Iron group metal: 3-15%.

Manganese oxide: The atomic ratio of iron group metal element to manganese element satisfies (5:l) to (5:4), Platinum group metal: The atomic ratio of iron group metal element to platinum group metal element satisfies (30: Wrinkles satisfying 1) to (5:2), any one oxide among alkali metal oxides, alkaline earth metal oxides, or rare earth element acetides: 0
．． Claim 16 or 1 which is 01 to 1,0%
The method for producing high calorie gas as described in item 7.

- Ding - system supplementary ItE book (spontaneous) 1. Table of G > 1 < 1988 Patent Application No. 54888 2 Name of the invention Catalyst for producing high-calorie gas and method for producing the same and method for producing high-calorie gas 3 Relationship with the Nagisa case to be amended Patent applicant 5 Take, Shugakuin Takabe-cho, Sakyo-ku, Kyoto-shi Nobu Niyoshi (and 2 others) 4. Agent: Shinko Building, 2-3-7 Dojima, Kita-ku, Osaka 530 "Detailed description of the invention" in the specification Each column 6, contents of amendment (1) The specified parts of Shoes #l will be corrected as shown in the attached errata.

True False Group Example 15 Commercially available alumina 11 with a specific surface area of 200 to 220 m”/g
The body was heated in an electric furnace from room temperature to 1060'C over 4 to 6 hours, and then maintained at the same temperature for 30 minutes for heat treatment. RuC13 Fist 3H was added to 20 parts of the heat-treated carrier cooled to room temperature.
The product was impregnated with a water solution prepared by dissolving 201.08 parts 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 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. The Ru metal salt was thermally decomposed to form an oxide. This was placed in an electric furnace, and the temperature was raised from room temperature to 400°C at a rate of 1II1 while passing a nitrogen stream containing hydrogen at a concentration of 20% by volume.
After holding for 0 minutes for reduction, the mixture was cooled to room temperature in the same air flow to obtain 20.5 parts of Ru support. Next, Ru carrier 20
．． In part 0, G.

(NO3) 2116H2012, 0 parts, Mn(NO3
) 2 Reference 6H205, 3 parts and Mg(NO3)2
・172 of a solution of 201.06 parts of 6H 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 -1: solution is impregnated in the same manner as above, dried, ammonia treated, thermally decomposed, and reduced by the above method. Co-6%Mn203-2%Ru -0,05
23.3 parts of a quaternary composition support of %MgO was obtained. 20.0 parts of the obtained quaternary composition support in a 100% hydrogen stream,
The composition ratio is 10%Co-6%Mn by raising the temperature from room temperature to 800℃ over 2 to 3 hours, holding it at the same temperature for 30 minutes, performing heat treatment, and cooling it to room temperature in the same air flow.
20.0 parts of a four-component catalyst of the present invention consisting of 203-2% Ru and 0.05% MgO was obtained.

As a comparative example, a four-component composition catalyst was obtained by the following method. That is, RuCl3*3H201, RuCl3*3H201,
08 part, Co, (NO3) 2.6H2012 part, M
An aqueous solution prepared by dissolving 3 parts of 6H205 in 5 parts of water was impregnated by a spraying method, and then air-dried overnight while gently rolling to obtain an impregnated product. This impregnated material was exposed for 2 minutes to an atmosphere adjusted to have 10-11% ammonia and 6% water vapor by volume for ammonia treatment, and then heated in air to about 350°C to impregnate. The resulting Ru metal salt was thermally decomposed to form 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 a nitrogen stream containing hydrogen at a concentration of 20% by volume, and this temperature was maintained for 30 minutes.
23.6 parts of a ternary composition support of %Co-6%Mn2O3-2%Ru was obtained. Mg is added to 20 parts of this ternary composition support.
(NO3) 2.6 H202,12'? After impregnation with a solution prepared by dissolving B in 5 parts of water by the same spraying method as above, drying, ammonia treatment, thermal decomposition, and reduction treatment were performed in the same manner as above. The resulting quaternary composition carrier was 10
The composition ratio is increased to 10% by raising the temperature from room temperature to 80°C over 2 to 3 hours in a 0% hydrogen stream, holding it at the same temperature for 30 minutes for heat treatment, and cooling it to room temperature in the same air stream. co-6%Mn203-2%Ru-0,1%M
20.2 parts of a quaternary composition catalyst of the present invention consisting of gO was obtained.

Example 16 In Example 15, a low-calorie test gas having the composition shown in Table 1 was heated to a pressure of 10 k to the catalyst thus obtained.
g/cm2G, 5V4000hr"", temperature 2
When the mixture was passed through 90° C. once, a high-calorie gas having a composition shown in Table 10 was obtained with a co conversion rate of 100%.

Note that the four-component composition catalyst of the comparative example obtained in Example 15 (10%Co-6%Mn203-2%Ru-0,
The results when the same low calorie test gas was passed through 1%Mg0)J2 under the same conditions as in this example are also listed in the $10 table.

Table 10 As is clear from the above results, when the catalyst of the present invention is used, the CO conversion rate is higher than when the catalyst of the comparative example is used, and the content of 02 to C4 hydrocarbons in the generated sludge is lower. It can be seen that a high-calorie gas can be obtained.

Example 17 20 parts of a commercially available alumina carrier with a specific surface area of Low2/g was
o (NO3)2 ・6H2012 parts, Mn(NO3)
The sample was impregnated by a spraying method with an aqueous solution of 4 parts of 2.6H205 dissolved in 5 parts of water, and then gently rolled and air-dried at night to obtain an impregnated product.

This impregnated material was placed in an atmosphere adjusted in advance to have 10 to 11 volume ψ% ammonia and 6 volume % water vapor.
ammonia treatment by exposure for 30 minutes, then in air for approximately 3 hours.
It was heated to 50°C to thermally decompose the impregnated metal salt 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 a nitrogen stream containing hydrogen at a concentration of 20% by volume, and this temperature was maintained for 30 minutes for reduction.

It was cooled to room temperature in the same air flow to obtain "Co-Mn20311" Special Holiday 23, 2JR. Next, this Co-Mn20
After impregnating 20.0 parts of the 31-molecular weight carrier with a solution of 1.0 parts of RuC13.3H dissolved in 5 parts of water using the same spraying method, drying, ammonia treatment, and thermal decomposition were performed, and after cooling, the remaining ]- Impregnate with the same procedure as the above solution, dry,
Ammonia treatment, thermal decomposition, and reduction treatment were performed in the same manner as above to obtain 10%Co-6%Mn2O3-2%Ru.
20.2 parts of a carrier based on the original composition was obtained. 20 parts of this ternary composition support was impregnated with a solution of 1.08 parts of Mg(NC):+)2-6H dissolved in 5 parts of water by the same spraying method as above, followed by drying, ammonia treatment, and thermal decomposition. and reduction treatment was carried out in the same manner as above. The obtained quaternary composition support was heated in a 100% hydrogen stream from room temperature to 800°C over 2 parts and 3 days, and then heat-treated by keeping it at the same temperature for 30 minutes. By cooling to room temperature, the composition ratio becomes 10%Co-6%Mr++Oa-2%Ru
- Quaternary composition catalyst 2 of the present invention consisting of 0.05% MgO
0.3 parts were obtained.

Example 18 A low-calorie test residue having the composition shown in Table 1 was added to the catalyst obtained by the method of Example 17 at a pressure of 10 kg.
/cm2G, SV4000hr-”, temperature (y
When passed once at 290°C, CO conversion rate was 100%.
A high calorie gas having the composition shown in Table 11 was obtained.

Claims (1)

[Scope of Claims] (1) An iron group metal as a catalyst substrate is oxidized with manganese in solution, a platinum group metal, and any one of an alkali metal oxide, an alkaline earth metal oxide, or a rare earth element oxide. 1. A catalyst for producing a high-calorie gas, characterized in that it is made of a combination of substances and maintained on a carrier made of silica and/or alumina for J months. (2) The catalyst for producing high-calorie gas according to claim 1, wherein the iron group metal as the catalyst substrate is either cobalt or iron. (3) The catalyst for producing high-calorie gas according to claim 1 or 2, wherein the platinum group metal is ruthenium, rhodium, palladium, platinum, or iridium. (4) The alkali metal liquefied substances are potassium, sodium,
The oxide of any one of lithium, cesium or rubidium is an oxide of any one of alkaline earth metals, the oxide of an alkaline earth metal is an oxide of any one of magnesium, calcium, strontium or barium, and the oxide of an earth element is an oxide of any one of magnesium, calcium, strontium or barium. Lantern, cerium. The catalyst for producing high-calorie gas according to any one of claims 1 to 3, which is an oxide of praseodymium or samarium I&I. (5) Iron group metal = 3 to 15% (meaning of weight a%, same below), manganese oxide: atomic ratio of iron group metal element to manganese element satisfies (5:1) to (5:4) Kuniji, Platinum group metal: an amount in which the atomic ratio of iron group metal element to platinum group metal element satisfies (30:I) to (5:2), alkali metal oxide, alkaline earth metal moltenide, or rare earth element Any one type of oxide among the oxides: 0
．． 5. The catalyst for producing high-calorie residue according to any one of claims 1 to 4, wherein the content is 01 to 1.0%. (6) A carrier made of silica and/or alumina,
First, a platinum group metal is supported, then an iron group metal and a manganese oxide are simultaneously supported, and then, among oxides of alkali metals, infusions of alkaline earth metals, and oxides of secondary elements, A method for producing a catalyst for producing high-calorie gas, characterized by supporting any one type of oxide. (7) The method for producing a catalyst for producing a high-calorie gas according to claim 6, wherein the iron group metal as the substrate is either cobalt or 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, palladium, platinum or iridium. (9) The alkali metal oxides are potassium, sodium,
The oxide of any one of lithium, cesium, or rubidium, the oxide of the alkaline earth metal is an oxide of any one of magnesium, calcium, strontium, or barium, and the oxide of the rare earth element is lanthanum, cerium. The method for producing a catalyst for producing a high-calorie gas according to any one of claims 6 to 8, wherein the catalyst is an oxide of praseodymium or samarium. (lO) Iron group metal: 3-15%. Manganese oxide: A star whose atomic ratio of iron group metal elements to manganese elements satisfies (5:I) to (5:4), Platinum group metal: A star whose atomic ratio of iron group metal elements to platinum group metal elements satisfies (30: 1) to (5:2), any one oxide among alkali metal oxides, alkaline earth metal oxides, and rare earth element oxides: 0
．． The method for producing a catalyst for producing high-calorie gas according to any one of claims 6 to 9, wherein the content is 01 to 1.0%. (11) An iron group metal as a catalyst substrate is combined with manganese oxide, a platinum group metal, and any one of an alkali metal oxide, an alkaline earth metal oxide, or a rare earth element oxide, and silica and/or or a catalyst supported on a carrier made of alumina. (12) The method for producing a high-calorie scum 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 scum according to claim 11 or 12, wherein the platinum group metal is ruthenium, rhodium, palladium, platinum, or iridium. (14) The alkali metal oxide is any one of potassium, thorium, lithium, cesium or rubidium, and the alkaline earth metal oxide is any one of magnesium, calcium, strontium or barium. Oxides of rare earth elements include lanthanum and cerium. The method for producing a high-calorie gas according to any one of claims 11 to 13, wherein the oxide is one of praseodymium and samarium. (15) Iron group metal = 3 to 15%, Nogan 7 oxide: an amount that satisfies the original ratio of iron group metal element to manganese element (5:1) to (5:4), platinum group metal: iron group metal An amount in which the atomic ratio of metal element to platinum group metal element satisfies (30:1) to (5:2), any one of alkali metal oxide, alkaline earth metal oxide, or rare earth element oxide Oxide of: 0.
01 to 1.0%. (1B) An iron group metal consisting of either cobalt or iron as a catalyst substrate, manganese oxide and a platinum group metal, an alkali metal oxide, an alkaline earth metal oxide or an oxide of an earth element. A gas containing hydrogen and carbon monoxide, or a gas containing hydrogen, carbon monoxide, and carbon dioxide is added to the first catalyst, which is a combination of one of the above oxides and supported on a carrier made of silica and/or alumina. conduction, and then conduction over a second catalyst made of nickel as a catalyst substrate, a combination of a diluted compound of a rare class 2 element and a platinum group metal, and supported on a carrier made of silica and/or alumina. A method for producing high calorie gas. (17) The alkali metal oxide in the first catalyst is any one of potassium, sodium, lithium, cesium, or rubidium, and the alkaline earth metal oxide is magnesium, calcium, strontium, or barium. The method for producing a high-calorie gas according to claim 16, wherein the oxide of the hexaearth element is an oxide of any one of lanthanum, cerium, praseodymium, or samarium. . (18) Iron group metal: 3 to 15%, manganese oxide: an amount that satisfies the atomic ratio of iron group metal element to manganese element (5:I) to (5:4), platinum group metal: iron group metal element An amount in which the atomic ratio of the platinum group metal element to the platinum group metal element satisfies (30:l) to (5:2), oxidation of any one of alkali metal oxides, alkaline earth metal oxides, or rare earth element oxides. Things: 0.
Claim 16 or 17 which is 01 to 1.0%.
2. Method for producing high calorie gas as described in Section 1.