阅读说明：本技术 除草剂中间体的制造方法 (Process for producing herbicide intermediate ) 是由 永田大贵 箕轮宣人 中西希 志村胜也 藤谷忠博 于 2018-07-05 设计创作，主要内容包括：本申请公开一种甲基二氯膦的制造方法,其包括如下步骤：在存在添加剂的情况下使用金属化合物及载持在载体上的金属化合物的至少任一种使甲烷和三氯化磷进行反应。(The application discloses a method for preparing methyldichlorophosphine, which comprises the following steps: methane and phosphorus trichloride are reacted with at least either one of a metal compound and a metal compound supported on a carrier in the presence of an additive.)

1. A method for producing methyldichlorophosphine is characterized by comprising the following steps: methane and phosphorus trichloride are reacted with at least either one of a metal compound and a metal compound supported on a carrier in the presence of an additive.

2. The method of claim 1, wherein the additive is at least 1 selected from the group consisting of oxygen and chlorine.

3. The method according to any one of claims 1 to 2, wherein the metal compound is at least 1 selected from the group consisting of metal halides, metal oxides, metal borides, metal carbides, alloys, and elemental metals.

4. The method of claim 3, wherein the metal halide is at least 1 selected from the group consisting of indium chloride, cesium chloride, rubidium chloride, chromium chloride, calcium chloride, lanthanum chloride, lithium chloride, potassium chloride, barium chloride, cerium chloride, ferric chloride, sodium chloride, nickel chloride, holmium chloride, strontium chloride, cobalt chloride, gadolinium chloride, ytterbium chloride, cadmium chloride, nickel fluoride, and nickel bromide.

5. The method of claim 3, wherein the metal oxide is at least 1 selected from the group consisting of strontium oxide, indium oxide, cobalt oxide, palladium oxide, and nickel oxide.

6. The method of claim 3 wherein the metal boride is at least 1 selected from the group consisting of zirconium boride, titanium boride, nickel boride, lanthanum boride, aluminum boride and tantalum boride.

7. The method of claim 3, wherein the metal carbide is at least 1 selected from the group consisting of titanium carbide, zirconium carbide, niobium carbide, tantalum carbide, chromium carbide, and silicon carbide.

8. The method of claim 3, wherein the alloy is at least 1 selected from the group consisting of a nickel-iron alloy and a nickel-yttrium alloy.

9. The method of claim 3, wherein the elemental metal is at least 1 selected from the group consisting of nickel and iron.

10. The method according to any one of claims 1 to 9, wherein the carrier is at least 1 selected from the group consisting of activated carbon, alumina, magnesia, ceria, titania, silica gel, silica alumina, zirconia, zeolite, hydrotalcite, diatomaceous earth, and cordierite.

11. The method according to claim 1, wherein the carrier of the metal compound supported on the carrier is at least 1 selected from the group consisting of alumina, silica gel and silica alumina, and the metal compound is at least 1 selected from the group consisting of lithium chloride, potassium chloride, barium chloride, calcium chloride, indium chloride, cerium chloride, cesium chloride, ferric chloride, sodium chloride and nickel chloride.

Technical Field

The present invention relates to a process for producing methyldichlorophosphine which is useful as an intermediate for production of 2-amino-4- (hydroxymethylphosphinyl) butanoic acid and L-2-amino-4- (hydroxymethylphosphinyl) butanoic acid, which are herbicides.

Background

Methyldichlorophosphine is known to be useful as a useful production intermediate of 2-amino-4- (hydroxymethylphosphinyl) butanoic acid and L-2-amino-4- (hydroxymethylphosphinyl) butanoic acid having herbicidal activity (see, for example, patent document 1).

As a method for producing methyldichlorophosphine, for example, known are: a reaction in the presence of aluminum chloride (for example, see patent document 2); a method of using a highly toxic compound such as phosgene or carbon tetrachloride (see, for example, patent documents 3 to 5); a method using thionyl chloride or sulfuryl chloride (for example, see patent document 6); a method using ultraviolet rays (for example, see patent document 7); a method of using oxygen as an additive (for example, see patent document 8 and non-patent document 1); and a method using a composite perovskite catalyst (for example, see non-patent documents 2 to 4).

However, the method of patent document 2 requires an amount of aluminum chloride equal to or greater than that required, and thus has a problem in terms of economy or a problem in that a large amount of metal waste is generated.

The methods of patent documents 3 to 5 have the following problems: highly toxic compounds such as phosgene or carbon tetrachloride are used, and these compounds themselves are changed to generate many by-products. In addition, there are also problems as follows: these compounds have a boiling point close to that of methyldichlorophosphine as a product, and therefore, distillation and purification are difficult, and high-grade facilities and excessive heat energy are required. Further, there are problems as follows: the reaction tube may be clogged because of the generation of solid by-products.

The method of patent document 6 has the following problems: since the compound used is changed, a large amount of by-products is produced. Further, these compounds have a boiling point close to that of methyldichlorophosphine as a product, and similarly, it is difficult to perform distillation purification, and a high-level facility and excessive heat energy are required.

The method of patent document 7 uses ultraviolet rays, but has a problem of low yield of the product.

The methods of patent document 8 and non-patent document 1 use oxygen as an additive, but have the following problems: the yield of the product is low, and by-products such as methyldichlorophosphonic acid are produced, which causes problems such as corrosion of equipment and generates additional waste.

The methods of non-patent documents 2 to 4 synthesize methyldichlorophosphine using a composite perovskite catalyst, but have problems of low yield and corrosion of the catalyst.

Disclosure of Invention

[ problems to be solved by the invention ]

The present invention is to solve the above problems and achieve the following object. That is, an object of the present invention is to provide a method for producing methyldichlorophosphine which is useful as an intermediate of herbicides and the like with excellent yield, while reducing the burden on the environment due to the production of waste products and suppressing the production of by-products.

[ means for solving problems ]

The present inventors have found that when methane and phosphorus trichloride are reacted with at least either one of a metal compound and a metal compound supported on a carrier in the presence of an additive, the production of waste and by-products produced by the reaction can be suppressed, and methyldichlorophosphine can be produced with an excellent yield, thereby completing the present invention.

Means for solving the problems are as follows. That is to say that the position of the first electrode,

the preparation method of < 1 > methyl dichlorophosphine is characterized by comprising the following steps: methane and phosphorus trichloride are reacted with at least either one of a metal compound and a metal compound supported on a carrier in the presence of an additive.

[ Effect of the invention ]

The present invention can solve the above problems and provide a method for producing methyldichlorophosphine which is useful as an intermediate of herbicides and the like with excellent yield, while reducing the burden on the environment due to the production of waste products and suppressing the production of by-products.

Drawings

FIG. 1 is a graph showing the spectral data of gas chromatography-mass spectrometry of the reaction solution of example 15.

FIG. 2 is a graph showing the spectral data of the reaction solution of example 22 by gas chromatography-mass spectrometry.

FIG. 3 is a graph showing the spectral data of gas chromatography-mass spectrometry of the reaction solution of example 25.

FIG. 4 is a graph showing the spectral data of gas chromatography-mass spectrometry of the reaction solution of example 29.

FIG. 5 is a graph showing the spectral data of a sample of methyldichlorophosphonic acid by gas chromatography-mass spectrometry.

Detailed Description

(Process for producing methyldichlorophosphine)

The process for producing methyldichlorophosphine of the present invention comprises at least a reaction step of reacting methane and phosphorus trichloride with at least either one of a metal compound and a metal compound supported on a carrier in the presence of an additive, and further comprises other steps as required.

< reaction step >

Additives-

In the present invention, the additive is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include oxygen gas, chlorine gas and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

The form of the oxygen gas may be a form containing only oxygen, or a form containing oxygen such as air.

The additive is preferably oxygen or chlorine.

At least one of a metal compound and a metal compound supported on a carrier

At least either one of the metal compound and the metal compound supported on the carrier may be used, or two of them may be used. The metal compound and the metal compound supported on the carrier are preferably compounds having low toxicity.

The amount of at least one of the metal compound and the metal compound supported on the carrier is not particularly limited, and may be appropriately selected according to the purpose.

Metal compound- -

The metal compound used for the metal compound or the metal compound supported on the carrier is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include: metal halides, metal nitrates, metal nitrites, metal sulfates, metal sulfites, metal oxides, composite metal oxides, metal peroxides, metal halide complexes, zeolites, metal borides, metal silicides, metal nitrides, metal sulfides, metal phosphides, metal antimonides, metal selenides, metal carbides, metal chlorates, metal perchlorates, metal bromates, metal perbromates, metal iodates, metal periodates, metal oxalates, metal carbonates, metal phosphates, metal phosphites, metal hypophosphites, metal borates, metal chromates, metal silicates, metal arsenates, metal permanganates, metal simple substances, alloys, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination. Of these, metal halides, metal oxides, metal borides, metal carbides, alloys, and simple metals are preferable.

The metal compound may be used either directly in the reaction or after a pretreatment for activation.

In the present invention, metal means a metal element and a semimetal element. Examples of the semimetal element include boron, silicon, germanium, arsenic, antimony, tellurium, selenium, polonium, and astatine.

In the present invention, the halogen element means an element of group 17 of the periodic table. Examples of the halogen element include fluorine, chlorine, bromine, and iodine.

Metal halides

In the present invention, the metal halide means a compound in which an element having a lower electronegativity than a halogen element and the halogen element are bonded to each other through an ionic bond or a covalent bond. Examples of the metal halide include: lithium fluoride, beryllium fluoride, sodium fluoride, magnesium fluoride, aluminum fluoride, potassium fluoride, calcium fluoride, scandium fluoride, titanium fluoride, vanadium fluoride, chromium fluoride, manganese fluoride, iron fluoride, cobalt fluoride, nickel fluoride, copper fluoride, zinc fluoride, gallium fluoride, germanium fluoride, arsenic fluoride, selenium fluoride, rubidium fluoride, strontium fluoride, yttrium fluoride, zirconium fluoride, niobium fluoride, molybdenum fluoride, ruthenium fluoride, rhodium fluoride, palladium fluoride, silver fluoride, cadmium fluoride, indium fluoride, tin fluoride, antimony fluoride, tellurium fluoride, cesium fluoride, barium fluoride, lanthanum fluoride, hafnium fluoride, tantalum fluoride, tungsten fluoride, rhenium fluoride, osmium fluoride, iridium fluoride, platinum fluoride, gold fluoride, mercury fluoride, thallium fluoride, lead fluoride, bismuth fluoride, cerium fluoride, praseodymium fluoride, neodymium fluoride, samarium fluoride, europium fluoride, gadolinium fluoride, terbium fluoride, dysprosium fluoride, holmium fluoride, erbium fluoride, thulium fluoride, ytterbium fluoride, lutetium fluoride, lithium chloride, lithium fluoride, and lithium fluoride, Beryllium chloride, sodium chloride, magnesium chloride, aluminum chloride, potassium chloride, calcium chloride, scandium chloride, titanium chloride, vanadium chloride, chromium chloride, manganese chloride, iron chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, gallium chloride, germanium chloride, arsenic chloride, selenium chloride, rubidium chloride, strontium chloride, yttrium chloride, zirconium chloride, niobium chloride, molybdenum chloride, ruthenium chloride, rhodium chloride, palladium chloride, silver chloride, cadmium chloride, indium chloride, tin chloride, antimony chloride, tellurium chloride, cesium chloride, barium chloride, lanthanum chloride, hafnium chloride, tantalum chloride, tungsten chloride, rhenium chloride, osmium chloride, iridium chloride, platinum chloride, gold chloride, mercury chloride, thallium chloride, lead chloride, bismuth chloride, cerium chloride, praseodymium chloride, neodymium chloride, samarium chloride, europium chloride, gadolinium chloride, terbium chloride, dysprosium chloride, holmium chloride, erbium chloride, thulium chloride, ytterbium chloride, lutetium chloride, calcium chloride, lithium bromide, lithium chloride, copper chloride, zinc chloride, gallium chloride, germanium chloride, lithium chloride, Beryllium bromide, sodium bromide, magnesium bromide, aluminum bromide, potassium bromide, calcium bromide, scandium bromide, titanium bromide, vanadium bromide, chromium bromide, manganese bromide, iron bromide, cobalt bromide, nickel bromide, copper bromide, zinc bromide, gallium bromide, germanium bromide, arsenic bromide, selenium bromide, rubidium bromide, strontium bromide, yttrium bromide, zirconium bromide, niobium bromide, molybdenum bromide, ruthenium bromide, rhodium bromide, palladium bromide, silver bromide, cadmium bromide, indium bromide, tin bromide, antimony bromide, tellurium bromide, cesium bromide, barium bromide, lanthanum bromide, hafnium bromide, tantalum bromide, tungsten bromide, rhenium bromide, osmium bromide, iridium bromide, platinum bromide, gold bromide, mercury bromide, thallium bromide, lead bromide, bismuth bromide, cerium bromide, praseodymium bromide, neodymium bromide, samarium bromide, europium bromide, gadolinium bromide, terbium bromide, dysprosium bromide, holmium bromide, erbium bromide, thulium bromide, ytterbium bromide, lutetium bromide, lithium iodide, beryllium iodide, lithium iodide, beryllium bromide, lithium iodide, lithium bromide, and the like, Sodium iodide, magnesium iodide, aluminum iodide, potassium iodide, calcium iodide, scandium iodide, titanium iodide, vanadium iodide, chromium iodide, manganese iodide, iron iodide, cobalt iodide, nickel iodide, copper iodide, zinc iodide, gallium iodide, germanium iodide, arsenic iodide, selenium iodide, rubidium iodide, strontium iodide, yttrium iodide, zirconium iodide, niobium iodide, molybdenum iodide, ruthenium iodide, rhodium iodide, palladium iodide, silver iodide, cadmium iodide, indium iodide, tin iodide, antimony iodide, tellurium iodide, cesium iodide, barium iodide, lanthanum iodide, hafnium iodide, tantalum iodide, tungsten iodide, rhenium iodide, osmium iodide, iridium iodide, platinum iodide, gold iodide, mercury iodide, thallium iodide, lead iodide, bismuth iodide, cerium iodide, praseodymium iodide, neodymium iodide, samarium iodide, europium iodide, gadolinium iodide, terbium iodide, dysprosium iodide, holmium iodide, erbium iodide, thulium iodide, ytterbium iodide, lutetium iodide, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination. Of these, nickel chloride, holmium chloride, strontium chloride, cobalt chloride, gadolinium chloride, ytterbium chloride, cadmium chloride, nickel fluoride, nickel bromide, indium chloride, cesium chloride, rubidium chloride, chromium chloride, calcium chloride, lanthanum chloride, lithium chloride, potassium chloride, barium chloride, cerium chloride, iron chloride, and sodium chloride are preferable.

Metal nitrate

In the present invention, the metal nitrate means a compound in which a group 1 to group 16 element and a nitrate ion are bonded. Examples of the metal nitrate include: lithium nitrate, beryllium nitrate, sodium nitrate, magnesium nitrate, aluminum nitrate, potassium nitrate, calcium nitrate, scandium nitrate, titanium nitrate, vanadium nitrate, chromium nitrate, manganese nitrate, iron nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, gallium nitrate, germanium nitrate, arsenic nitrate, selenium nitrate, rubidium nitrate, strontium nitrate, yttrium nitrate, zirconium nitrate, niobium nitrate, molybdenum nitrate, ruthenium nitrate, rhodium nitrate, palladium nitrate, silver nitrate, cadmium nitrate, indium nitrate, tin nitrate, antimony nitrate, tellurium nitrate, cesium nitrate, barium nitrate, lanthanum nitrate, hafnium nitrate, tantalum nitrate, tungsten nitrate, rhenium nitrate, osmium nitrate, iridium nitrate, platinum nitrate, gold nitrate, mercury nitrate, thallium nitrate, lead nitrate, bismuth nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate, promethium nitrate, samarium nitrate, europium nitrate, gadolinium nitrate, terbium nitrate, dysprosium nitrate, holmium nitrate, erbium nitrate, thulium nitrate, ytterbium nitrate, lutetium nitrate, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal nitrite

In the present invention, the metal nitrite means a compound in which a group 1 to group 16 element and a nitrite ion are bonded. Examples of the metal nitrite include: lithium nitrite, beryllium nitrite, sodium nitrite, magnesium nitrite, aluminum nitrite, potassium nitrite, calcium nitrite, scandium nitrite, titanium nitrite, vanadium nitrite, chromium nitrite, manganese nitrite, iron nitrite, cobalt nitrite, nickel nitrite, copper nitrite, zinc nitrite, gallium nitrite, germanium nitrite, arsenic nitrite, selenium nitrite, rubidium nitrite, strontium nitrite, yttrium nitrite, zirconium nitrite, niobium nitrite, molybdenum nitrite, ruthenium nitrite, rhodium nitrite, palladium nitrite, silver nitrite, cadmium nitrite, indium nitrite, tin nitrite, antimony nitrite, tellurium nitrite, cesium nitrite, barium nitrite, lanthanum nitrite, hafnium nitrite, tantalum nitrite, tungsten nitrite, rhenium nitrite, osmium nitrite, iridium nitrite, platinum nitrite, gold nitrite, mercury nitrite, thallium nitrite, lead nitrite, bismuth nitrite, cerium nitrite, bismuth nitrite, titanium nitrite, chromium nitrite, praseodymium nitrite, neodymium nitrite, promethium nitrite, samarium nitrite, europium nitrite, gadolinium nitrite, terbium nitrite, dysprosium nitrite, holmium nitrite, erbium nitrite, thulium nitrite, ytterbium nitrite, lutetium nitrite, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal sulfate- -

In the present invention, the metal sulfate means a compound in which a group 1 to group 16 element and a sulfate ion are bonded. Examples of the metal sulfate include: lithium sulfate, beryllium sulfate, sodium sulfate, magnesium sulfate, aluminum sulfate, potassium sulfate, calcium sulfate, scandium sulfate, titanium sulfate, vanadium sulfate, chromium sulfate, manganese sulfate, ferric sulfate, cobalt sulfate, nickel sulfate, copper sulfate, zinc sulfate, gallium sulfate, germanium sulfate, arsenic sulfate, selenium sulfate, rubidium sulfate, strontium sulfate, yttrium sulfate, zirconium sulfate, niobium sulfate, molybdenum sulfate, ruthenium sulfate, rhodium sulfate, palladium sulfate, silver sulfate, cadmium sulfate, indium sulfate, tin sulfate, antimony sulfate, tellurium sulfate, cesium sulfate, barium sulfate, lanthanum sulfate, hafnium sulfate, tantalum sulfate, tungsten sulfate, rhenium sulfate, osmium sulfate, iridium sulfate, platinum sulfate, gold sulfate, mercury sulfate, thallium sulfate, lead sulfate, bismuth sulfate, cerium sulfate, praseodymium sulfate, neodymium sulfate, promethium sulfate, samarium sulfate, europium sulfate, gadolinium sulfate, terbium sulfate, dysprosium sulfate, holmium sulfate, erbium sulfate, thulium sulfate, ytterbium sulfate, lutetium sulfate, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal sulfites-

In the present invention, the metal sulfite means a compound in which a group 1 to group 16 element and sulfite ion are bonded. Examples of the metal sulfite include: lithium sulfite, beryllium sulfite, sodium sulfite, magnesium sulfite, aluminum sulfite, potassium sulfite, calcium sulfite, scandium sulfite, titanium sulfite, vanadium sulfite, chromium sulfite, manganese sulfite, ferric sulfite, cobalt sulfite, nickel sulfite, copper sulfite, zinc sulfite, gallium sulfite, germanium sulfite, arsenic sulfite, selenium sulfite, rubidium sulfite, strontium sulfite, yttrium sulfite, zirconium sulfite, niobium sulfite, molybdenum sulfite, ruthenium sulfite, rhodium sulfite, palladium sulfite, silver sulfite, cadmium sulfite, indium sulfite, tin sulfite, antimony sulfite, tellurium sulfite, cesium sulfite, barium sulfite, lanthanum sulfite, hafnium sulfite, tantalum sulfite, tungsten sulfite, rhenium sulfite, osmium sulfite, iridium sulfite, platinum sulfite, gold sulfite, mercury sulfite, thallium sulfite, lead sulfite, bismuth, cerium sulfite, chromium sulfite, iron, zinc sulfite, iron, Praseodymium sulfite, neodymium sulfite, promethium sulfite, samarium sulfite, europium sulfite, gadolinium sulfite, terbium sulfite, dysprosium sulfite, holmium sulfite, erbium sulfite, thulium sulfite, ytterbium sulfite, lutetium sulfite, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal oxides-

In the present invention, the metal oxide means a compound in which a group 1 to group 16 metal element and oxygen are bonded. Examples of the metal oxide include: silver oxide, boron oxide, barium oxide, dibismuth trioxide, calcium oxide, cadmium oxide, cerium oxide, cobalt oxide, cobaltous oxyhydroxide, cobaltosic oxide, chromium trioxide, cuprous oxide, copper oxide, dysprosium oxide, erbium oxide, europium oxide, ferrous oxide, ferric oxide, ferroferric oxide, gallium oxide, gadolinium oxide, germanium dioxide, hafnium oxide, mercury oxide, holmium oxide, indium oxide, lanthanum oxide, lithium oxide, lutetium oxide, magnesium oxide, manganese dioxide, manganese sesquioxide, trimanganese tetroxide, molybdenum dioxide, molybdenum trioxide, niobium monoxide, niobium dioxide, niobium trioxide, niobium pentoxide, neodymium oxide, nickel monoxide, lead dioxide, trilead tetroxide, palladium oxide, praseodymium oxide, platinum dioxide, platinum oxide, rhenium oxide, ruthenium oxide, antimony trioxide, antimony tetroxide, antimony trioxide, cobalt oxide, cobalt trioxide, cobalt oxide, cobalt oxyhydroxide, chromium oxide, lanthanum oxide, lithium oxide, lead oxide, antimony pentoxide, scandium oxide, silicon monoxide, silicon dioxide, samarium oxide, stannous oxide, tin dioxide, strontium oxide, tantalum pentoxide, terbium oxide, tellurium dioxide, tellurium trioxide, titanium monoxide, titanium dioxide, titanium sesquioxide, thallium oxide, thallium trioxide, thulium oxide, vanadium trioxide, vanadium dioxide, vanadium pentoxide, vanadium tetraoxide, tungsten dioxide, tungsten trioxide, yttrium oxide, ytterbium oxide, zinc oxide-aluminum oxide, zirconium oxide, silicon monoxide, silicon dioxide, quartz, glass, quartz sand, quartzite, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination. Of these, nickel oxide, strontium oxide, indium oxide, cobalt oxide, and palladium oxide are preferable.

Complex metal oxide

In the present invention, the complex metal oxide means an oxide containing 2 or more metal elements among the metal elements of groups 1 to 16 and oxygen. As the composite metal oxide, as for a composite oxide containing 2 kinds of metals, for example, there can be mentioned: a composite oxide of a group 1 element and a group 1 element, a composite oxide of a group 1 element and a group 2 element, a composite oxide of a group 1 element and a group 3 element, a composite oxide of a group 1 element and a group 4 element, a composite oxide of a group 1 element and a group 5 element, a composite oxide of a group 1 element and a group 6 element, a composite oxide of a group 1 element and a group 7 element, a composite oxide of a group 1 element and a group 8 element, a composite oxide of a group 1 element and a group 9 element, a composite oxide of a group 1 element and a group 10 element, a composite oxide of a group 1 element and a group 11 element, a composite oxide of a group 1 element and a group 12 element, a composite oxide of a group 1 element and a group 13 element, a composite oxide of a group 1 element and a group 14 element, a composite oxide of a group 1 element and a group 15 element, A composite oxide of a group 1 element and a group 16 element, a composite oxide of a group 2 element and a group 2 element, a composite oxide of a group 2 element and a group 3 element, a composite oxide of a group 2 element and a group 4 element, a composite oxide of a group 2 element and a group 5 element, a composite oxide of a group 2 element and a group 6 element, a composite oxide of a group 2 element and a group 7 element, a composite oxide of a group 2 element and a group 8 element, a composite oxide of a group 2 element and a group 9 element, a composite oxide of a group 2 element and a group 10 element, a composite oxide of a group 2 element and a group 11 element, a composite oxide of a group 2 element and a group 12 element, a composite oxide of a group 2 element and a group 13 element, a composite oxide of a group 2 element and a group 14 element, a composite oxide of a group 2 element and a group 15 element, A composite oxide of a group 2 element and a group 16 element, a composite oxide of a group 3 element and a group 3 element, a composite oxide of a group 3 element and a group 4 element, a composite oxide of a group 3 element and a group 5 element, a composite oxide of a group 3 element and a group 6 element, a composite oxide of a group 3 element and a group 7 element, a composite oxide of a group 3 element and a group 8 element, a composite oxide of a group 3 element and a group 9 element, a composite oxide of a group 3 element and a group 10 element, a composite oxide of a group 3 element and a group 11 element, a composite oxide of a group 3 element and a group 12 element, a composite oxide of a group 3 element and a group 13 element, a composite oxide of a group 3 element and a group 14 element, a composite oxide of a group 3 element and a group 15 element, a composite oxide of a group 3 element and a group 16 element, A composite oxide of a group 4 element and a group 4 element, a composite oxide of a group 4 element and a group 5 element, a composite oxide of a group 4 element and a group 6 element, a composite oxide of a group 4 element and a group 7 element, a composite oxide of a group 4 element and a group 8 element, a composite oxide of a group 4 element and a group 9 element, a composite oxide of a group 4 element and a group 10 element, a composite oxide of a group 4 element and a group 11 element, a composite oxide of a group 4 element and a group 12 element, a composite oxide of a group 4 element and a group 13 element, a composite oxide of a group 4 element and a group 14 element, a composite oxide of a group 4 element and a group 15 element, a composite oxide of a group 4 element and a group 16 element, a composite oxide of a group 5 element and a group 5 element, a composite oxide of a group 5 element and a group 6 element, a composite oxide of a group 4 element and a group 6 element, A composite oxide of a group 5 element and a group 7 element, a composite oxide of a group 5 element and a group 8 element, a composite oxide of a group 5 element and a group 9 element, a composite oxide of a group 5 element and a group 10 element, a composite oxide of a group 5 element and a group 11 element, a composite oxide of a group 5 element and a group 12 element, a composite oxide of a group 5 element and a group 13 element, a composite oxide of a group 5 element and a group 14 element, a composite oxide of a group 5 element and a group 15 element, a composite oxide of a group 5 element and a group 16 element, a composite oxide of a group 6 element and a group 6 element, a composite oxide of a group 6 element and a group 7 element, a composite oxide of a group 6 element and a group 8 element, a composite oxide of a group 6 element and a group 9 element, a composite oxide of a group 6 element and a group 10 element, A composite oxide of a group 6 element and a group 11 element, a composite oxide of a group 6 element and a group 12 element, a composite oxide of a group 6 element and a group 13 element, a composite oxide of a group 6 element and a group 14 element, a composite oxide of a group 6 element and a group 15 element, a composite oxide of a group 6 element and a group 16 element, a composite oxide of a group 7 element and a group 7 element, a composite oxide of a group 7 element and a group 8 element, a composite oxide of a group 7 element and a group 9 element, a composite oxide of a group 7 element and a group 10 element, a composite oxide of a group 7 element and a group 11 element, a composite oxide of a group 7 element and a group 12 element, a composite oxide of a group 7 element and a group 13 element, a composite oxide of a group 7 element and a group 14 element, a composite oxide of a group 7 element and a group 15 element, A composite oxide of a group 7 element and a group 16 element, a composite oxide of a group 8 element and a group 8 element, a composite oxide of a group 8 element and a group 9 element, a composite oxide of a group 8 element and a group 10 element, a composite oxide of a group 8 element and a group 11 element, a composite oxide of a group 8 element and a group 12 element, a composite oxide of a group 8 element and a group 13 element, a composite oxide of a group 8 element and a group 14 element, a composite oxide of a group 8 element and a group 15 element, a composite oxide of a group 8 element and a group 16 element, a composite oxide of a group 9 element and a group 9 element, a composite oxide of a group 9 element and a group 10 element, a composite oxide of a group 9 element and a group 11 element, a composite oxide of a group 9 element and a group 12 element, a composite oxide of a group 9 element and a group 13 element, A composite oxide of a group 9 element and a group 14 element, a composite oxide of a group 9 element and a group 15 element, a composite oxide of a group 9 element and a group 16 element, a composite oxide of a group 10 element and a group 10 element, a composite oxide of a group 10 element and a group 11 element, a composite oxide of a group 10 element and a group 12 element, a composite oxide of a group 10 element and a group 13 element, a composite oxide of a group 10 element and a group 14 element, a composite oxide of a group 10 element and a group 15 element, a composite oxide of a group 10 element and a group 16 element, a composite oxide of a group 11 element and a group 11 element, a composite oxide of a group 11 element and a group 12 element, a composite oxide of a group 11 element and a group 13 element, a composite oxide of a group 11 element and a group 14 element, a composite oxide of a group 11 element and a group 15 element, a composite oxide of a group 9 element and a group 16 element, a composite oxide of a group 10 element and a group 13 element, a composite oxide of a group 11 element, A composite oxide of a group 11 element and a group 16 element, a composite oxide of a group 12 element and a group 12 element, a composite oxide of a group 12 element and a group 13 element, a composite oxide of a group 12 element and a group 14 element, a composite oxide of a group 12 element and a group 15 element, a composite oxide of a group 12 element and a group 16 element, a composite oxide of a group 13 element and a group 13 element, a composite oxide of a group 13 element and a group 14 element, a composite oxide of a group 13 element and a group 15 element, a composite oxide of a group 13 element and a group 16 element, a composite oxide of a group 14 element and a group 14 element, a composite oxide of a group 14 element and a group 15 element, a composite oxide of a group 15 element and a group 16 element, a composite oxide of a group 14 element and a group 15 element, A compound oxide of a group 16 element and a group 16 element, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination. Among these, a composite oxide of a group 2 element and a group 8 element, a composite oxide of a group 6 element and a group 7 element, a composite oxide of a group 7 element and a group 8 element, a composite oxide of a group 8 element and a group 9 element, a composite oxide of a group 8 element and a group 10 element, a composite oxide of a group 8 element and a group 11 element, a composite oxide of a group 13 element and a group 14 element, and a composite oxide of a group 14 element and a group 15 element are preferable, and examples thereof include cobalt iron oxide, copper iron oxide, indium tin oxide, magnesium iron oxide, manganese-chromium oxide, manganese-iron oxide, nickel-iron oxide, and the like.

Examples of the composite metal oxide containing 3 or more metals include composite metal oxides in which 3 or more of the following simple metals, that is, 3 or more of lithium, beryllium, sodium, magnesium, aluminum, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, rubidium, strontium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, cesium, barium, lanthanum, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium are combined. These may be used alone in 1 kind, or 2 or more kinds may be used in combination. More specifically, examples thereof include lead-lanthanum-zirconium-titanium oxide, lead-zirconium-titanium oxide, tin-antimony oxide, strontium titanate-niobium pentoxide, and the like.

Metal peroxides

In the present invention, the metal peroxide means a peroxide containing 2 or more metal elements selected from the group consisting of group 1 to group 16 metal elements and oxygen. Examples of the metal peroxide include: lithium peroxide, beryllium peroxide, sodium peroxide, magnesium peroxide, aluminum peroxide, potassium peroxide, calcium peroxide, scandium peroxide, titanium peroxide, vanadium peroxide, chromium peroxide, manganese peroxide, iron peroxide, cobalt peroxide, nickel peroxide, copper peroxide, zinc peroxide, gallium peroxide, germanium peroxide, arsenic peroxide, selenium peroxide, rubidium peroxide, strontium peroxide, yttrium peroxide, zirconium peroxide, niobium peroxide, molybdenum peroxide, ruthenium peroxide, rhodium peroxide, palladium peroxide, silver peroxide, cadmium peroxide, indium peroxide, tin peroxide, antimony peroxide, tellurium peroxide, cesium peroxide, barium peroxide, lanthanum peroxide, hafnium peroxide, tantalum peroxide, tungsten peroxide, rhenium peroxide, osmium peroxide, iridium peroxide, platinum peroxide, gold peroxide, mercury peroxide, thallium peroxide, lead peroxide, bismuth peroxide, cerium peroxide, bismuth peroxide, magnesium peroxide, aluminum peroxide, potassium peroxide, calcium peroxide, scandium peroxide, titanium peroxide, vanadium peroxide, chromium peroxide, manganese peroxide, iron peroxide, cobalt peroxide, nickel peroxide, praseodymium peroxide, neodymium peroxide, promethium peroxide, samarium peroxide, europium peroxide, gadolinium peroxide, terbium peroxide, dysprosium peroxide, holmium peroxide, erbium peroxide, thulium peroxide, ytterbium peroxide, lutetium peroxide, silver peroxide, barium peroxide, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal halide complex

In the present invention, the metal halide complex means a compound in which a metal ion is present in the center of the molecule and which contains a halide ion as a ligand. Examples of the metal halide complex include: calcium hexaflourosilicate (IV), ammonium hexafluorozirconate (IV), potassium heptafluorotantalate (V), ammonium hexafluorotitanate (IV), potassium hexafluorotitanate (IV), ammonium tetrafluoroberyllium (II), potassium tetrafluoroberyllium (II), lithium tetrafluoroborate (III), potassium pentachlorohydrochloride (III), potassium pentaamlodipine iridate (III) chloride, cis-tetraaminodichlorocobalt (III) chloride, pentaamlodipine cobaltate (III) chloride, diamminedichloropalladium (II), pentaamlodipine iridate (III) chloride, trans-diamminedichloroplatinum (II), cis-diamminedichloroplatinum (II), potassium tetrachlorozinc (II), lithium tetrachloroaluminate (III), ammonium hexachloroiridate (III), potassium hexachloroiridate (III), sodium hexachloroiridate (III), ammonium hexachloroiridate (IV), potassium hexachloroiridate (IV), sodium hexachloroiridate (IV), potassium hexachloroiridate (III), Ammonium hexachloroosmium (IV), potassium hexachloroosmium (IV), sodium hexachloroosmium (IV), ammonium tetrachlorogallium (III), potassium tetrachloroaurate (III), sodium tetrachloroaurate (III), lithium tetrachloroaurate (III), ammonium tetrachloromercuric (II), ammonium hexachlorostannate (IV), potassium hexachlorotitanium (IV), potassium dichlorotetranitroiridium (III), potassium pentachlorothioyl ruthenium (III), ammonium tetrachloroplatinate (II), potassium tetrachloroplatinate (II), sodium tetrachloroplatinate (II), ammonium hexachloroplatinate (IV), potassium hexachloroplatinate (IV), sodium hexachloroplatinate (IV), ammonium tetrachloropalladium (II), potassium tetrachloropalladium (II), sodium tetrachloropalladium (II), lithium tetrachloropalladium (II), potassium hexachloropalladium (IV), ammonium hexachlororuthenium (III), ammonium pentachlorothruthenate (III), potassium hexachlororuthenium (IV), sodium hexachloro-chloride (IV), ammonium tetrachloro-2-chloro-potassium (IV), potassium hexachloro-mercury (II), Potassium hexachlororhenium (III), potassium hexachlororhenium (IV), ammonium hexachlororhodium (III), potassium hexachlororhodium (III), sodium hexachlororhodium (III), potassium hexabromoiridium (IV), potassium hexabromoosmium (III), potassium tetrabromoaurate (III), sodium tetrabromoaurate (III), potassium hexabromoplatinate (IV), potassium tetrabromoadallate (II), potassium hexabromopalladate (IV), potassium hexabromoruthenate (III), potassium hexabromoruthenate (IV), potassium hexaiodoiridium (III), rubidium triiodosilver (I) acid, potassium tetraiodomercury (II), sodium tetraiodomercury (II), potassium hexaiodoplatinum (IV), potassium hexaiodoruthenium (III), and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Zeolite-zeolite

In the present invention, zeolite is a clay mineral, which means an aqueous aluminosilicate containing an alkali or alkaline earth metal and having an anionic framework with voids in the crystal structure, and examples of the zeolite include A-type, ferrierite, MCM-22, ZSM-5, mordenite, L-type, Y-type, X-type, β -type, and 1 kind of these may be used alone or 2 or more kinds may be used in combination.

Metal boride compounds

Examples of the metal boride include: lithium boride, beryllium boride, sodium boride, magnesium boride, aluminum boride, potassium boride, calcium boride, scandium boride, titanium boride, vanadium boride, chromium boride, manganese boride, iron boride, cobalt boride, nickel boride, copper boride, zinc boride, gallium boride, germanium boride, arsenic boride, selenium boride, rubidium boride, strontium boride, yttrium boride, zirconium boride, niobium boride, molybdenum boride, ruthenium boride, rhodium boride, palladium boride, silver boride, cadmium boride, indium boride, tin boride, antimony boride, tellurium boride, cesium boride, barium boride, lanthanum boride, hafnium boride, tantalum boride, tungsten boride, rhenium boride, osmium boride, iridium boride, platinum boride, gold boride, mercury boride, thallium boride, lead boride, bismuth, cerium boride, praseodymium boride, neodymium boride, promethium boride, samarium boride, europium boride, gadolinium, terbium boride, dysprosium boride, holmium boride, erbium boride, thulium boride, ytterbium boride, lutetium boride, lead boride, bismuth boride, cerium boride, and the like, Silicon boride and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination. Among these, zirconium boride, titanium boride, nickel boride, lanthanum boride, aluminum boride, and tantalum boride are preferable.

Metal silicide

Examples of the metal silicide include: lithium silicide, beryllium silicide, sodium silicide, magnesium silicide, aluminum silicide, potassium silicide, calcium silicide, scandium silicide, titanium silicide, vanadium silicide, chromium silicide, manganese silicide, iron silicide, cobalt silicide, nickel silicide, copper silicide, zinc silicide, gallium silicide, germanium silicide, arsenic silicide, selenium silicide, rubidium silicide, strontium silicide, yttrium silicide, zirconium silicide, niobium silicide, molybdenum silicide, ruthenium silicide, rhodium silicide, palladium silicide, silver silicide, cadmium silicide, indium silicide, tin silicide, antimony silicide, tellurium silicide, cesium silicide, barium silicide, lanthanum silicide, hafnium silicide, tantalum silicide, tungsten silicide, rhenium silicide, osmium silicide, iridium silicide, platinum silicide, gold silicide, mercury silicide, thallium silicide, lead silicide, bismuth silicide, cerium silicide, praseodymium silicide, neodymium silicide, promethium silicide, samarium silicide, europium silicide, gadolinium silicide, terbium silicide, dysprosium silicide, holmium silicide, erbium silicide, thulium silicide, ytterbium silicide, lutetium silicide, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal nitride

Examples of the metal nitride include: lithium nitride, beryllium nitride, sodium nitride, magnesium nitride, aluminum nitride, potassium nitride, calcium nitride, scandium nitride, titanium nitride, vanadium nitride, chromium nitride, manganese nitride, iron nitride, cobalt nitride, nickel nitride, copper nitride, zinc nitride, gallium nitride, germanium nitride, arsenic nitride, selenium nitride, rubidium nitride, strontium nitride, yttrium nitride, zirconium nitride, niobium nitride, molybdenum nitride, ruthenium nitride, rhodium nitride, palladium nitride, silver nitride, cadmium nitride, indium nitride, tin nitride, antimony nitride, tellurium nitride, cesium nitride, barium nitride, lanthanum nitride, hafnium nitride, tantalum nitride, tungsten nitride, rhenium nitride, osmium nitride, iridium nitride, platinum nitride, gold nitride, mercury nitride, thallium nitride, lead nitride, bismuth nitride, cerium nitride, praseodymium nitride, neodymium nitride, promethium nitride, samarium nitride, europium nitride, gadolinium nitride, terbium nitride, dysprosium nitride, holmium nitride, erbium nitride, thulium nitride, ytterbium nitride, lutetium nitride, neodymium nitride, and indium nitride, Silicon nitride, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal sulfides- -

Examples of the metal sulfide include: lithium sulfide, beryllium sulfide, sodium sulfide, magnesium sulfide, aluminum sulfide, potassium sulfide, calcium sulfide, scandium sulfide, titanium sulfide, vanadium sulfide, chromium sulfide, manganese sulfide, iron sulfide, cobalt sulfide, nickel sulfide, copper sulfide, zinc sulfide, gallium sulfide, germanium sulfide, arsenic sulfide, selenium sulfide, rubidium sulfide, strontium sulfide, yttrium sulfide, zirconium sulfide, niobium sulfide, molybdenum sulfide, ruthenium sulfide, rhodium sulfide, palladium sulfide, silver sulfide, cadmium sulfide, indium sulfide, tin sulfide, antimony sulfide, tellurium sulfide, cesium sulfide, barium sulfide, lanthanum sulfide, hafnium sulfide, tantalum sulfide, tungsten sulfide, rhenium sulfide, osmium sulfide, iridium sulfide, platinum sulfide, gold sulfide, mercury sulfide, thallium sulfide, lead sulfide, bismuth sulfide, cerium sulfide, praseodymium sulfide, neodymium sulfide, promethium sulfide, samarium sulfide, europium sulfide, gadolinium sulfide, terbium sulfide, dysprosium sulfide, holmium sulfide, erbium sulfide, thulium sulfide, ytterbium sulfide, lutetium sulfide, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal phosphide

Examples of the metal phosphide include: lithium phosphide, beryllium phosphide, sodium phosphide, magnesium phosphide, aluminum phosphide, potassium phosphide, calcium phosphide, scandium phosphide, titanium phosphide, vanadium phosphide, chromium phosphide, manganese phosphide, iron phosphide, cobalt phosphide, nickel phosphide, copper phosphide, zinc phosphide, gallium phosphide, germanium phosphide, arsenic phosphide, selenium phosphide, rubidium phosphide, strontium phosphide, yttrium phosphide, zirconium phosphide, niobium phosphide, molybdenum phosphide, ruthenium phosphide, rhodium phosphide, palladium phosphide, silver phosphide, cadmium phosphide, indium phosphide, tin phosphide, cesium phosphide, barium phosphide, lanthanum phosphide, hafnium phosphide, tantalum phosphide, tungsten phosphide, rhenium phosphide, osmium phosphide, iridium phosphide, platinum phosphide, gold phosphide, thallium phosphide, cerium phosphide, praseodymium phosphide, neodymium phosphide, promethium phosphide, samarium phosphide, europium phosphide, gadolinium phosphide, terbium phosphide, dysprosium phosphide, holmium phosphide, erbium phosphide, thulium phosphide, ytterbium phosphide, cobalt phosphide, copper phosphide, iron phosphide, gallium phosphide, indium phosphide, gallium phosphide, germanium phosphide, arsenic phosphide, indium phosphide, lead phosphide, Dimanganese phosphide, nickelous phosphide, trinickel phosphide, trizinc phosphide, silicon phosphide and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal antimonide-

Examples of the metal antimonide include aluminum antimonide, bismuth antimonide, iron antimonide, indium antimonide, manganese antimonide, tetrazinc antimonide, and zinc antimonide. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal selenides

Examples of the metal selenides include: lithium selenide, beryllium selenide, sodium selenide, magnesium selenide, aluminum selenide, potassium selenide, calcium selenide, scandium selenide, titanium selenide, vanadium selenide, chromium selenide, manganese selenide, iron selenide, cobalt selenide, nickel selenide, copper selenide, zinc selenide, gallium selenide, germanium selenide, arsenic selenide, rubidium selenide, strontium selenide, yttrium selenide, zirconium selenide, niobium selenide, molybdenum selenide, ruthenium selenide, rhodium selenide, palladium selenide, silver selenide, cadmium selenide, indium selenide, tin selenide, antimony selenide, tellurium selenide, cesium selenide, barium selenide, lanthanum selenide, hafnium selenide, tantalum selenide, tungsten selenide, rhenium selenide, osmium selenide, iridium selenide, platinum selenide, gold selenide, mercury selenide, thallium selenide, lead selenide, bismuth selenide, cerium selenide, praseodymium selenide, neodymium selenide, promethium selenide, samarium selenide, europium selenide, gadolinium selenide, terbium selenide, dysprosium selenide, holmium selenide, erbium selenide, thulium selenide, ytterbium selenide, lutetium selenide, silicon selenide, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal carbide-

Examples of the metal carbide include: lithium carbide, beryllium carbide, sodium carbide, magnesium carbide, aluminum carbide, potassium carbide, calcium carbide, scandium carbide, titanium carbide, vanadium carbide, chromium carbide, manganese carbide, iron carbide, cobalt carbide, nickel carbide, copper carbide, zinc carbide, gallium carbide, germanium carbide, arsenic carbide, selenium carbide, rubidium carbide, strontium carbide, yttrium carbide, zirconium carbide, niobium carbide, molybdenum carbide, ruthenium carbide, rhodium carbide, palladium carbide, silver carbide, cadmium carbide, indium carbide, tin carbide, antimony carbide, tellurium carbide, cesium carbide, barium carbide, lanthanum carbide, hafnium carbide, tantalum carbide, tungsten carbide, rhenium carbide, osmium carbide, iridium carbide, platinum carbide, gold carbide, mercury carbide, thallium carbide, lead carbide, bismuth carbide, cerium carbide, praseodymium carbide, neodymium carbide, promethium carbide, samarium carbide, europium carbide, gadolinium carbide, terbium carbide, dysprosium carbide, holmium carbide, erbium carbide, thulium carbide, ytterbium carbide, lutetium carbide, and the like, Silicon carbide, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination. Of these, titanium carbide, zirconium carbide, niobium carbide, tantalum carbide, chromium carbide, and silicon carbide are preferable.

Metal chlorate-containing compounds

Examples of the metal chlorate include sodium chlorate, potassium chlorate, calcium chlorate, barium chlorate, zinc chlorate, and silver chlorate. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal perchlorates-

Examples of the metal perchlorate include potassium perchlorate, barium perchlorate, magnesium perchlorate, and lithium perchlorate. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal bromate salt-

Examples of the metal bromate include potassium bromate, sodium bromate, and aluminum bromate. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal perbromate salt

Examples of the metal perbromate include sodium perbromate, potassium perbromate and calcium perbromate. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal iodate salts

Examples of the metal iodate include sodium iodate, silver iodate, and calcium iodate. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal periodate salts

Examples of the metal periodate include sodium periodate, potassium periodate, rubidium periodate, and cesium periodate. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal oxalate salts

Examples of the metal oxalate include: lithium oxalate, beryllium oxalate, sodium oxalate, magnesium oxalate, aluminum oxalate, potassium oxalate, calcium oxalate, scandium oxalate, titanium oxalate, vanadium oxalate, chromium oxalate, manganese oxalate, iron oxalate, cobalt oxalate, nickel oxalate, copper oxalate, zinc oxalate, gallium oxalate, germanium oxalate, arsenic oxalate, selenium oxalate, rubidium oxalate, strontium oxalate, yttrium oxalate, zirconium oxalate, niobium oxalate, molybdenum oxalate, ruthenium oxalate, rhodium oxalate, palladium oxalate, silver oxalate, cadmium oxalate, indium oxalate, tin oxalate, antimony oxalate, tellurium oxalate, cesium oxalate, barium oxalate, lanthanum oxalate, hafnium oxalate, tantalum oxalate, tungsten oxalate, rhenium oxalate, osmium oxalate, iridium oxalate, platinum oxalate, gold oxalate, mercury oxalate, thallium oxalate, lead oxalate, bismuth oxalate, cerium oxalate, praseodymium oxalate, neodymium oxalate, promethium oxalate, samarium oxalate, europium oxalate, gadolinium oxalate, terbium oxalate, dysprosium oxalate, holmium oxalate, erbium oxalate, thulium oxalate, ytterbium oxalate, lutetium oxalate, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal carbonates

Examples of the metal carbonate include: lithium carbonate, beryllium carbonate, sodium carbonate, magnesium carbonate, aluminum carbonate, potassium carbonate, calcium carbonate, scandium carbonate, titanium carbonate, vanadium carbonate, chromium carbonate, manganese carbonate, iron carbonate, cobalt carbonate, nickel carbonate, copper carbonate, zinc carbonate, gallium carbonate, germanium carbonate, arsenic carbonate, selenium carbonate, rubidium carbonate, strontium carbonate, yttrium carbonate, zirconium carbonate, niobium carbonate, molybdenum carbonate, ruthenium carbonate, rhodium carbonate, palladium carbonate, silver carbonate, cadmium carbonate, indium carbonate, tin carbonate, antimony carbonate, tellurium carbonate, cesium carbonate, barium carbonate, lanthanum carbonate, hafnium carbonate, tantalum carbonate, tungsten carbonate, rhenium carbonate, osmium carbonate, iridium carbonate, platinum carbonate, gold carbonate, mercury carbonate, thallium carbonate, lead carbonate, bismuth carbonate, cerium carbonate, praseodymium carbonate, neodymium carbonate, promethium carbonate, samarium carbonate, europium carbonate, gadolinium carbonate, terbium carbonate, dysprosium carbonate, holmium carbonate, erbium carbonate, thulium carbonate, ytterbium carbonate, lutetium carbonate, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal phosphates-

Examples of the metal phosphate include: lithium orthophosphate, beryllium orthophosphate, sodium orthophosphate, magnesium orthophosphate, aluminum orthophosphate, potassium orthophosphate, calcium orthophosphate, scandium orthophosphate, titanium orthophosphate, vanadium orthophosphate, chromium orthophosphate, manganese orthophosphate, iron orthophosphate, cobalt orthophosphate, nickel orthophosphate, copper orthophosphate, zinc orthophosphate, gallium orthophosphate, germanium orthophosphate, arsenic orthophosphate, selenium orthophosphate, rubidium orthophosphate, strontium orthophosphate, yttrium orthophosphate, zirconium orthophosphate, niobium orthophosphate, molybdenum orthophosphate, ruthenium orthophosphate, rhodium orthophosphate, palladium orthophosphate, silver orthophosphate, cadmium orthophosphate, indium orthophosphate, tin orthophosphate, antimony orthophosphate, tellurium orthophosphate, cesium orthophosphate, barium orthophosphate, lanthanum orthophosphate, hafnium orthophosphate, tantalum orthophosphate, tungsten orthophosphate, rhenium orthophosphate, osmium orthophosphate, iridium orthophosphate, platinum orthophosphate, gold orthophosphate, mercury orthophosphate, lead orthophosphate, bismuth orthophosphate, cerium orthophosphate, lead orthophosphate, bismuth orthophosphate, lead orthophosphate, Praseodymium orthophosphate, neodymium orthophosphate, promethium orthophosphate, samarium orthophosphate, europium orthophosphate, gadolinium orthophosphate, terbium orthophosphate, dysprosium orthophosphate, holmium orthophosphate, erbium orthophosphate, thulium orthophosphate, ytterbium orthophosphate, lutetium orthophosphate, lithium polyphosphate, beryllium polyphosphate, sodium polyphosphate, magnesium polyphosphate, aluminum polyphosphate, potassium polyphosphate, calcium polyphosphate, scandium polyphosphate, titanium polyphosphate, vanadium polyphosphate, chromium polyphosphate, manganese polyphosphate, iron polyphosphate, cobalt polyphosphate, nickel polyphosphate, copper polyphosphate, zinc polyphosphate, gallium polyphosphate, germanium polyphosphate, arsenic polyphosphate, selenium polyphosphate, rubidium polyphosphate, strontium polyphosphate, yttrium polyphosphate, zirconium polyphosphate, niobium polyphosphate, molybdenum polyphosphate, ruthenium polyphosphate, rhodium polyphosphate, palladium polyphosphate, silver polyphosphate, cadmium polyphosphate, indium polyphosphate, tin polyphosphate, antimony polyphosphate, cesium polyphosphate, barium, lanthanum polyphosphate, yttrium polyphosphate, lithium polyphosphate, hafnium polyphosphate, tantalum polyphosphate, tungsten polyphosphate, rhenium polyphosphate, osmium polyphosphate, iridium polyphosphate, platinum polyphosphate, gold polyphosphate, mercury polyphosphate, thallium polyphosphate, lead polyphosphate, bismuth polyphosphate, cerium polyphosphate, praseodymium polyphosphate, neodymium polyphosphate, promethium polyphosphate, samarium polyphosphate, europium polyphosphate, gadolinium polyphosphate, terbium polyphosphate, dysprosium polyphosphate, holmium polyphosphate, erbium polyphosphate, thulium polyphosphate, ytterbium polyphosphate, lutetium polyphosphate, lithium metaphosphate, beryllium metaphosphate, sodium metaphosphate, magnesium metaphosphate, aluminum metaphosphate, potassium metaphosphate, calcium metaphosphate, scandium metaphosphate, titanium metaphosphate, vanadium metaphosphate, chromium metaphosphate, manganese metaphosphate, cobalt metaphosphate, nickel metaphosphate, copper metaphosphate, zinc metaphosphate, gallium metaphosphate, germanium metaphosphate, arsenic metaphosphate, selenium metaphosphate, rubidium metaphosphate, strontium metaphosphate, yttrium metaphosphate, zirconium metaphosphate, niobium metaphosphate, Molybdenum metaphosphate, ruthenium metaphosphate, rhodium metaphosphate, palladium metaphosphate, silver metaphosphate, cadmium metaphosphate, indium metaphosphate, tin metaphosphate, antimony metaphosphate, tellurium metaphosphate, cesium metaphosphate, barium metaphosphate, lanthanum metaphosphate, hafnium metaphosphate, tantalum metaphosphate, tungsten metaphosphate, rhenium metaphosphate, osmium metaphosphate, iridium metaphosphate, platinum metaphosphate, gold metaphosphate, mercury metaphosphate, thallium metaphosphate, lead metaphosphate, bismuth metaphosphate, cerium metaphosphate, praseodymium metaphosphate, neodymium metaphosphate, promethium metaphosphate, samarium metaphosphate, europium metaphosphate, gadolinium metaphosphate, terbium metaphosphate, dysprosium metaphosphate, erbium metaphosphate, thulium metaphosphate, ytterbium metaphosphate, lutetium metaphosphate, etc. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal phosphites

Examples of the metal phosphite include: lithium phosphite, beryllium phosphite, sodium phosphite, magnesium phosphite, aluminum phosphite, potassium phosphite, calcium phosphite, scandium phosphite, titanium phosphite, vanadium phosphite, chromium phosphite, manganese phosphite, iron phosphite, cobalt phosphite, nickel phosphite, copper phosphite, zinc phosphite, gallium phosphite, germanium phosphite, arsenic phosphite, selenium phosphite, rubidium phosphite, strontium phosphite, yttrium phosphite, zirconium phosphite, niobium phosphite, molybdenum phosphite, ruthenium phosphite, rhodium phosphite, palladium phosphite, silver phosphite, cadmium phosphite, indium phosphite, tin phosphite, antimony phosphite, tellurium phosphite, cesium phosphite, barium phosphite, lanthanum phosphite, hafnium phosphite, tantalum phosphite, tungsten phosphite, rhenium phosphite, osmium phosphite, iridium phosphite, platinum phosphite, gold phosphite, mercury phosphite, thallium phosphite, lead phosphite, bismuth phosphite, cerium phosphite, Praseodymium phosphite, neodymium phosphite, promethium phosphite, samarium phosphite, europium phosphite, gadolinium phosphite, terbium phosphite, dysprosium phosphite, holmium phosphite, erbium phosphite, thulium phosphite, ytterbium phosphite, lutetium phosphite, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal hypophosphite salts

Examples of the metal hypophosphite include: lithium hypophosphite, beryllium hypophosphite, sodium hypophosphite, magnesium hypophosphite, aluminum hypophosphite, potassium hypophosphite, calcium hypophosphite, scandium hypophosphite, titanium hypophosphite, vanadium hypophosphite, chromium hypophosphite, manganese hypophosphite, iron hypophosphite, cobalt hypophosphite, nickel hypophosphite, copper hypophosphite, zinc hypophosphite, gallium hypophosphite, germanium hypophosphite, arsenic hypophosphite, selenium hypophosphite, rubidium hypophosphite, strontium hypophosphite, yttrium hypophosphite, zirconium hypophosphite, niobium hypophosphite, molybdenum hypophosphite, ruthenium hypophosphite, rhodium hypophosphite, palladium hypophosphite, silver hypophosphite, cadmium hypophosphite, indium hypophosphite, tin hypophosphite, antimony hypophosphite, tellurium hypophosphite, cesium hypophosphite, barium hypophosphite, lanthanum hypophosphite, hafnium hypophosphite, tantalum hypophosphite, tungsten hypophosphite, rhenium hypophosphite, osmium hypophosphite, iridium hypophosphite, platinum hypophosphite, gold hypophosphite, mercury hypophosphite, lead hypophosphite, bismuth hypophosphite, cerium hypophosphite, bismuth hypophosphite, manganese hypophosphite, cobalt hypophosphite, nickel hypophosphite, copper hypophosphite, zinc hypophosphite, gallium hypophosphite, germanium hypophosphite, arsenic hypophosphite, selenium hypophosphite, rubidium hypophosphite, strontium hypophosphite, yttrium hypophosphite, lead hypophosphite, bismuth, lead hypophosphite, and the like, Praseodymium hypophosphite, neodymium hypophosphite, promethium hypophosphite, samarium hypophosphite, europium hypophosphite, gadolinium hypophosphite, terbium hypophosphite, dysprosium hypophosphite, holmium hypophosphite, erbium hypophosphite, thulium hypophosphite, ytterbium hypophosphite, lutetium hypophosphite, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal borates

Examples of the metal borate include: lithium orthoborate, beryllium orthoborate, sodium orthoborate, magnesium orthoborate, aluminum orthoborate, potassium orthoborate, calcium orthoborate, scandium orthoborate, titanium orthoborate, vanadium orthoborate, chromium orthoborate, manganese orthoborate, iron orthoborate, cobalt orthoborate, nickel orthoborate, copper orthoborate, zinc orthoborate, gallium orthoborate, germanium orthoborate, arsenic orthoborate, selenium orthoborate, rubidium orthoborate, strontium orthoborate, yttrium orthoborate, zirconium orthoborate, niobium orthoborate, molybdenum orthoborate, ruthenium orthoborate, rhodium orthoborate, palladium orthoborate, silver orthoborate, cadmium orthoborate, indium orthoborate, tin orthoborate, antimony orthoborate, tellurium orthoborate, cesium orthoborate, barium orthoborate, lanthanum orthoborate, hafnium orthoborate, tantalum orthoborate, tungsten orthoborate, rhenium orthoborate, osmium orthoborate, iridium orthoborate, platinum orthoborate, gold orthoborate, mercury orthoborate, bismuth orthoborate, lead orthoborate, bismuth orthoborate, cerium orthoborate, thallium orthoborate, Praseodymium orthoborate, neodymium orthoborate, promethium orthoborate, samarium orthoborate, europium orthoborate, gadolinium orthoborate, terbium orthoborate, dysprosium orthoborate, holmium orthoborate, erbium orthoborate, thulium orthoborate, ytterbium orthoborate, lutetium orthoborate, lithium metaborate, beryllium metaborate, sodium metaborate, magnesium metaborate, aluminum metaborate, potassium metaborate, calcium metaborate, scandium metaborate, titanium metaborate, vanadium metaborate, chromium metaborate, manganese metaborate, iron metaborate, cobalt metaborate, nickel metaborate, copper metaborate, zinc metaborate, gallium metaborate, germanium metaborate, arsenic metaborate, selenium metaborate, rubidium metaborate, strontium metaborate, yttrium metaborate, zirconium metaborate, niobium metaborate, molybdenum metaborate, ruthenium metaborate, rhodium metaborate, palladium metaborate, silver metaborate, cadmium metaborate, indium metaborate, tin metaborate, antimony metaborate, tellurium, cesium, lanthanum metaborate, metaborate, Hafnium metaborate, tantalum metaborate, tungsten metaborate, rhenium metaborate, osmium metaborate, iridium metaborate, platinum metaborate, gold metaborate, mercury metaborate, thallium metaborate, lead metaborate, bismuth metaborate, cerium metaborate, praseodymium metaborate, neodymium metaborate, promethium metaborate, samarium metaborate, europium metaborate, gadolinium metaborate, terbium metaborate, dysprosium metaborate, holmium metaborate, erbium metaborate, thulium metaborate, ytterbium metaborate, lutetium metaborate, lithium tetraborate, beryllium tetraborate, sodium tetraborate, magnesium tetraborate, aluminum tetraborate, potassium tetraborate, calcium tetraborate, scandium tetraborate, titanium tetraborate, vanadium tetraborate, chromium tetraborate, manganese tetraborate, iron tetraborate, cobalt tetraborate, nickel tetraborate, copper tetraborate, zinc tetraborate, gallium tetraborate, germanium tetraborate, arsenic tetraborate, selenium tetraborate, rubidium tetraborate, strontium tetraborate, zirconium tetraborate, niobium tetraborate, yttrium tetraborate, zirconium tetraborate, niobium tetraborate, ruthenium tetraborate, zirconium tetraborate, ruthenium tetraborate, strontium tetraborate, Molybdenum tetraborate, ruthenium tetraborate, rhodium tetraborate, palladium tetraborate, silver tetraborate, cadmium tetraborate, indium tetraborate, tin tetraborate, antimony tetraborate, tellurium tetraborate, cesium tetraborate, barium tetraborate, lanthanum tetraborate, hafnium tetraborate, tantalum tetraborate, tungsten tetraborate, rhenium tetraborate, osmium tetraborate, iridium tetraborate, platinum tetraborate, gold tetraborate, mercury tetraborate, thallium tetraborate, lead tetraborate, bismuth tetraborate, cerium tetraborate, praseodymium tetraborate, neodymium tetraborate, promethium tetraborate, samarium tetraborate, europium tetraborate, gadolinium tetraborate, terbium tetraborate, dysprosium tetraborate, holmium tetraborate, erbium tetraborate, thulium tetraborate, ytterbium tetraborate, lutetium tetraborate, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal chromates

Examples of the metal chromate include: lithium chromate, beryllium chromate, sodium chromate, magnesium chromate, aluminum chromate, potassium chromate, calcium chromate, scandium chromate, titanium chromate, vanadium chromate, chromium chromate, manganese chromate, iron chromate, cobalt chromate, nickel chromate, copper chromate, zinc chromate, gallium chromate, germanium chromate, arsenic chromate, selenium chromate, rubidium chromate, strontium chromate, yttrium chromate, zirconium chromate, niobium chromate, molybdenum chromate, ruthenium chromate, rhodium chromate, palladium chromate, silver chromate, cadmium chromate, indium chromate, tin chromate, antimony chromate, tellurium chromate, cesium chromate, barium chromate, lanthanum chromate, hafnium chromate, tantalum chromate, tungsten chromate, rhenium chromate, osmium chromate, iridium chromate, platinum chromate, gold chromate, mercury chromate, lutetium chromate, lead chromate, bismuth chromate, cerium chromate, praseodymium chromate, neodymium chromate, promethium chromate, samarium chromate, terbium chromate, gadolinium chromate, yttrium chromate, lead chromate, yttrium chromate, lead chromate, yttrium chromate, lead chromate, yttrium chromate, lithium dichromate, beryllium dichromate, sodium dichromate, magnesium dichromate, aluminum dichromate, potassium dichromate, calcium dichromate, scandium dichromate, titanium dichromate, vanadium dichromate, chromium dichromate, manganese dichromate, iron dichromate, cobalt dichromate, nickel dichromate, copper dichromate, zinc dichromate, gallium dichromate, germanium dichromate, arsenic dichromate, selenium dichromate, rubidium dichromate, strontium dichromate, yttrium dichromate, zirconium dichromate, niobium dichromate, molybdenum dichromate, ruthenium dichromate, rhodium dichromate, palladium dichromate, silver dichromate, cadmium dichromate, indium dichromate, tin dichromate, antimony dichromate, tellurium dichromate, cesium dichromate, barium dichromate, lanthanum dichromate, hafnium dichromate, tantalum dichromate, tungsten dichromate, rhenium dichromate, osmium dichromate, iridium dichromate, lead dichromate, Praseodymium dichromate, neodymium dichromate, promethium dichromate, samarium dichromate, europium dichromate, gadolinium dichromate, terbium dichromate, dysprosium dichromate, holmium dichromate, erbium dichromate, thulium dichromate, ytterbium dichromate, lutetium dichromate, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal silicates

Examples of the metal silicate include: lithium silicate, beryllium silicate, sodium silicate, magnesium silicate, aluminum silicate, potassium silicate, calcium silicate, scandium silicate, titanium silicate, vanadium silicate, chromium silicate, manganese silicate, iron silicate, cobalt silicate, nickel silicate, copper silicate, zinc silicate, gallium silicate, germanium silicate, arsenic silicate, selenium silicate, rubidium silicate, strontium silicate, yttrium silicate, zirconium silicate, niobium silicate, molybdenum silicate, ruthenium silicate, rhodium silicate, palladium silicate, silver silicate, cadmium silicate, indium silicate, tin silicate, antimony silicate, tellurium silicate, cesium silicate, barium silicate, lanthanum silicate, hafnium silicate, tantalum silicate, tungsten silicate, rhenium silicate, osmium silicate, iridium silicate, platinum silicate, gold silicate, mercury silicate, thallium silicate, lead silicate, bismuth silicate, cerium silicate, praseodymium silicate, neodymium silicate, promethium silicate, samarium silicate, europium silicate, gadolinium silicate, terbium silicate, dysprosium silicate, holmium silicate, erbium silicate, thulium silicate, ytterbium silicate, lutetium silicate, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal arsenate-

Examples of the metal arsenate include: lithium arsenate, beryllium arsenate, sodium arsenate, magnesium arsenate, aluminium arsenate, potassium arsenate, calcium arsenate, scandium arsenate, titanium arsenate, vanadium arsenate, chromium arsenate, manganese arsenate, ferric arsenate, cobalt arsenate, nickel arsenate, copper arsenate, zinc arsenate, gallium arsenate, germanium arsenate, arsenic arsenate, selenium arsenate, rubidium arsenate, strontium arsenate, yttrium arsenate, zirconium arsenate, niobium arsenate, molybdenum arsenate, ruthenium arsenate, rhodium arsenate, palladium arsenate, silver arsenate, cadmium arsenate, indium arsenate, tin arsenate, antimony arsenate, tellurium arsenate, cesium arsenate, barium arsenate, lanthanum arsenate, hafnium arsenate, tantalum arsenate, tungsten arsenate, rhenium arsenate, osmium arsenate, iridium arsenate, platinum arsenate, gold arsenate, mercury arsenate, thallium arsenate, lead arsenate, bismuth arsenate, cerium arsenate, praseodymium arsenate, neodymium arsenate, promethium arsenate, samarium arsenate, europium arsenate, gadolinium arsenate, terbium arsenate, dysprosium arsenate, holmium arsenate, erbium arsenate, thulium arsenate, ytterbium arsenate, lutetium arsenate, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal permanganates

Examples of the metal permanganates include: lithium permanganate, beryllium permanganate, sodium permanganate, magnesium permanganate, aluminum permanganate, potassium permanganate, calcium permanganate, scandium permanganate, titanium permanganate, vanadium permanganate, chromium permanganate, manganese permanganate, iron permanganate, cobalt permanganate, nickel permanganate, copper permanganate, zinc permanganate, gallium permanganate, germanium permanganate, arsenic permanganate, selenium permanganate, rubidium permanganate, strontium permanganate, yttrium permanganate, zirconium permanganate, niobium permanganate, molybdenum permanganate, ruthenium permanganate, rhodium permanganate, palladium permanganate, silver permanganate, cadmium permanganate, indium permanganate, tin permanganate, antimony permanganate, tellurium permanganate, cesium permanganate, barium permanganate, lanthanum permanganate, hafnium permanganate, tantalum permanganate, tungsten permanganate, rhenium permanganate, osmium permanganate, iridium permanganate, thallium permanganate, bismuth permanganate, gold permanganate, mercury permanganate, bismuth permanganate, manganese permanganate, Praseodymium permanganate, neodymium permanganate, promethium permanganate, samarium permanganate, europium permanganate, gadolinium permanganate, terbium permanganate, dysprosium permanganate, holmium permanganate, erbium permanganate, thulium permanganate, ytterbium permanganate, lutetium permanganate, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Metal simple substance-

Examples of the simple metal include: lithium, beryllium, sodium, magnesium, aluminum, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, rubidium, strontium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, cesium, barium, lanthanum, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination. Of these, nickel and iron are preferable.

Alloys-

As the alloy, as an alloy containing 2 kinds of metals, for example, there can be mentioned: an alloy of a group 1 element and a group 1 element, an alloy of a group 1 element and a group 2 element, an alloy of a group 1 element and a group 3 element, an alloy of a group 1 element and a group 4 element, an alloy of a group 1 element and a group 5 element, an alloy of a group 1 element and a group 6 element, an alloy of a group 1 element and a group 7 element, an alloy of a group 1 element and a group 8 element, an alloy of a group 1 element and a group 9 element, an alloy of a group 1 element and a group 10 element, an alloy of a group 1 element and a group 11 element, an alloy of a group 1 element and a group 12 element, an alloy of a group 1 element and a group 13 element, an alloy of a group 1 element and a group 14 element, an alloy of a group 1 element and a group 15 element, an alloy of a group 1 element and a group 16 element, an alloy of a group 2 element and a group 2 element, an alloy of a group 2 element and a group 3 element, An alloy of a group 2 element and a group 4 element, an alloy of a group 2 element and a group 5 element, an alloy of a group 2 element and a group 6 element, an alloy of a group 2 element and a group 7 element, an alloy of a group 2 element and a group 8 element, an alloy of a group 2 element and a group 9 element, an alloy of a group 2 element and a group 10 element, an alloy of a group 2 element and a group 11 element, an alloy of a group 2 element and a group 12 element, an alloy of a group 2 element and a group 13 element, an alloy of a group 2 element and a group 14 element, an alloy of a group 2 element and a group 15 element, an alloy of a group 2 element and a group 16 element, an alloy of a group 3 element and a group 3 element, an alloy of a group 3 element and a group 4 element, an alloy of a group 3 element and a group 5 element, an alloy of a group 3 element and a group 6 element, an alloy of a group 3 element and a group 7 element, An alloy of a group 3 element and a group 8 element, an alloy of a group 3 element and a group 9 element, an alloy of a group 3 element and a group 10 element, an alloy of a group 3 element and a group 11 element, an alloy of a group 3 element and a group 12 element, an alloy of a group 3 element and a group 13 element, an alloy of a group 3 element and a group 14 element, an alloy of a group 3 element and a group 15 element, an alloy of a group 3 element and a group 16 element, an alloy of a group 4 element and a group 4 element, an alloy of a group 4 element and a group 5 element, an alloy of a group 4 element and a group 6 element, an alloy of a group 4 element and a group 7 element, an alloy of a group 4 element and a group 8 element, an alloy of a group 4 element and a group 9 element, an alloy of a group 4 element and a group 10 element, an alloy of a group 4 element and a group 11 element, an alloy of a group 4 element and a group 12 element, An alloy of a group 4 element and a group 13 element, an alloy of a group 4 element and a group 14 element, an alloy of a group 4 element and a group 15 element, an alloy of a group 4 element and a group 16 element, an alloy of a group 5 element and a group 5 element, an alloy of a group 5 element and a group 6 element, an alloy of a group 5 element and a group 7 element, an alloy of a group 5 element and a group 8 element, an alloy of a group 5 element and a group 9 element, an alloy of a group 5 element and a group 10 element, an alloy of a group 5 element and a group 11 element, an alloy of a group 5 element and a group 12 element, an alloy of a group 5 element and a group 13 element, an alloy of a group 5 element and a group 14 element, an alloy of a group 5 element and a group 15 element, an alloy of a group 5 element and a group 16 element, an alloy of a group 6 element and a group 6 element, an alloy of a group 6 element and a group 7 element, An alloy of a group 6 element and a group 8 element, an alloy of a group 6 element and a group 9 element, an alloy of a group 6 element and a group 10 element, an alloy of a group 6 element and a group 11 element, an alloy of a group 6 element and a group 12 element, an alloy of a group 6 element and a group 13 element, an alloy of a group 6 element and a group 14 element, an alloy of a group 6 element and a group 15 element, an alloy of a group 6 element and a group 16 element, an alloy of a group 7 element and a group 7 element, an alloy of a group 7 element and a group 8 element, an alloy of a group 7 element and a group 9 element, an alloy of a group 7 element and a group 10 element, an alloy of a group 7 element and a group 11 element, an alloy of a group 7 element and a group 12 element, an alloy of a group 7 element and a group 13 element, an alloy of a group 7 element and a group 14 element, an alloy of a group 7 element and a group 15 element, An alloy of a group 7 element and a group 16 element, an alloy of a group 8 element and a group 8 element, an alloy of a group 8 element and a group 9 element, an alloy of a group 8 element and a group 10 element, an alloy of a group 8 element and a group 11 element, an alloy of a group 8 element and a group 12 element, an alloy of a group 8 element and a group 13 element, an alloy of a group 8 element and a group 14 element, an alloy of a group 8 element and a group 15 element, an alloy of a group 8 element and a group 16 element, an alloy of a group 9 element and a group 9 element, an alloy of a group 9 element and a group 10 element, an alloy of a group 9 element and a group 11 element, an alloy of a group 9 element and a group 12 element, an alloy of a group 9 element and a group 13 element, an alloy of a group 9 element and a group 14 element, an alloy of a group 9 element and a group 15 element, an alloy of a group 9 element and a group 16 element, An alloy of a group 10 element and a group 10 element, an alloy of a group 10 element and a group 11 element, an alloy of a group 10 element and a group 12 element, an alloy of a group 10 element and a group 13 element, an alloy of a group 10 element and a group 14 element, an alloy of a group 10 element and a group 15 element, an alloy of a group 10 element and a group 16 element, an alloy of a group 11 element and a group 11 element, an alloy of a group 11 element and a group 12 element, an alloy of a group 11 element and a group 13 element, an alloy of a group 11 element and a group 14 element, an alloy of a group 11 element and a group 15 element, an alloy of a group 11 element and a group 16 element, an alloy of a group 12 element and a group 12 element, an alloy of a group 12 element and a group 13 element, an alloy of a group 12 element and a group 14 element, an alloy of a group 12 element and a group 15 element, an alloy of a group 12 element and a group 16 element, An alloy of a group 13 element and a group 13 element, an alloy of a group 13 element and a group 14 element, an alloy of a group 13 element and a group 15 element, an alloy of a group 13 element and a group 16 element, an alloy of a group 14 element and a group 14 element, an alloy of a group 14 element and a group 15 element, an alloy of a group 14 element and a group 16 element, an alloy of a group 15 element and a group 15 element, an alloy of a group 15 element and a group 16 element, an alloy of a group 16 element and a group 16 element, and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination. More specifically, for example, there may be mentioned: 42 alloy, KS steel, Amalgam (Amalgam), aluminum alloy, Alumel alloy, Inconel (Inconel), Invar (Invar), Widia alloy, Wood's alloy, Elinvar (Elinvar), dammaral (Kanthal), GaIntin (Galinstan), Cunifel (Cunife), chrome molybdenum steel, Chromel alloy, silicon steel, Kovar), constantan (Konstatan), Sun platinum (Sun platinum), Duranil (Duranickel), Duralumin (Duralumin), Aluminol, Standard pure silver (Stesilverer), Stellite (Stellite), stainless steel, specular iron (Spiegelesen), Sendust (Sendust), titanium alloy, Tobanton brass (Tombac), sodium-potassium alloy, Nichrom, North-European Stellite, platinum (Perwold), Bakelite (platinum), lead Bakelite (Pentium), lead Baumly (Pentium, lead alloy), platinum (platinum), platinum (alloy), platinum (alloy), sodium-nickel (alloy), sodium-potassium alloy, White tin (platinum), platinum (platinum, Magnesium alloys, maraging steel, manganese molybdenum steel, Misch metal (Misch metal), Monel (Monel), andel, brass, hard lead, steel, bronze, red copper, brass, cemented carbide, cupronickel, nickel silver, hydrogen storage alloys, nickel-iron alloys, nickel-yttrium alloys, and the like. Of these, nickel-iron alloy and nickel-yttrium alloy are preferable.

Examples of the alloy containing 3 or more metals include an alloy in which 3 or more simple metals shown below are combined, that is, an alloy in which 3 or more simple metals selected from lithium, beryllium, sodium, magnesium, aluminum, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, rubidium, strontium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, cesium, barium, lanthanum, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium are combined. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

A metal compound supported on a carrier

In the present invention, the metal compound supported on the carrier means a metal compound in which the metal compound is supported on at least a part of the surface of the carrier.

The mass of the metal compound supported on the carrier is not particularly limited, and may be appropriately selected according to the purpose, and is preferably in the range of 0.1 to 50% by mass, and more preferably in the range of 1 to 40% by mass. The mass of the metal compound supported on the carrier (hereinafter, sometimes referred to as "% support") can be determined by the following equation.

% support { (mass of metal compound)/(mass of metal compound + mass of support) } × 100

A support

The carrier is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include: activated carbon, alumina, magnesia, ceria, titania, silica gel (silica gel), silica alumina (silica alumina), zirconia, zeolite, hydrotalcite, diatomaceous earth, cordierite, and the like.

The carrier of the metal compound supported on the carrier is not particularly limited, and may be appropriately selected according to the purpose, and is preferably alumina, silica gel, or silica alumina.

The metal compound in the metal compound supported on the carrier is not particularly limited and may be appropriately selected according to the purpose, and lithium chloride, potassium chloride, barium chloride, calcium chloride, indium chloride, cerium chloride, cesium chloride, ferric chloride, sodium chloride, and nickel chloride are preferable.

The metal compound supported on the carrier is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include: lithium chloride supported on silica gel (hereinafter sometimes referred to as "lithium chloride/silica gel"), lithium chloride supported on silica alumina (hereinafter sometimes referred to as "lithium chloride/silica alumina"), lithium chloride supported on zirconia (hereinafter sometimes referred to as "lithium chloride/zirconia"), lithium chloride supported on tungstic zirconia (hereinafter sometimes referred to as "lithium chloride/tungstic zirconia"), lithium chloride supported on titania (hereinafter sometimes referred to as "lithium chloride/titania"), lithium chloride supported on alumina (hereinafter sometimes referred to as "lithium chloride/alumina"), lithium chloride supported on ceria (hereinafter sometimes referred to as "lithium chloride/ceria"), lithium chloride supported on magnesia (hereinafter sometimes referred to as "lithium chloride/magnesia"), lithium chloride supported on hydrotalcite (hereinafter sometimes referred to as "lithium chloride/hydrotalcite"), strontium chloride supported on silica gel (hereinafter sometimes referred to as "strontium chloride/silica gel"), strontium chloride supported on silica alumina (hereinafter sometimes referred to as "strontium chloride/silica alumina"), strontium chloride supported on zirconia (hereinafter sometimes referred to as "strontium chloride/zirconia"), strontium chloride supported on tungstic zirconia (hereinafter sometimes referred to as "strontium chloride/tungstic zirconia"), strontium chloride supported on titania (hereinafter sometimes referred to as "strontium chloride/titania"), strontium chloride supported on alumina (hereinafter sometimes referred to as "strontium chloride/alumina"), strontium chloride supported on ceria (hereinafter sometimes referred to as "strontium chloride/ceria"), strontium chloride supported on magnesium oxide (hereinafter, sometimes referred to as "strontium chloride/magnesium oxide"), strontium chloride supported on hydrotalcite (hereinafter, sometimes referred to as "strontium chloride/hydrotalcite"), potassium chloride supported on alumina (hereinafter, sometimes referred to as "potassium chloride/alumina"), and the like. These may be used alone in 1 kind, or 2 or more kinds may be used in combination. Among these, lithium chloride/alumina, lithium chloride/silica gel, lithium chloride/silica alumina, and potassium chloride/alumina are preferable.

Reaction-

The reaction step may be carried out either in an open system or a closed system, and a closed system is preferable in terms of no toxicity problem.

The reaction apparatus (hereinafter, also referred to as "reaction tube") used in the reaction step is not particularly limited, and may be appropriately selected according to the purpose.

The reaction temperature in the reaction step is not particularly limited, and may be appropriately selected depending on the purpose, and is preferably in the range of 300 to 750 ℃, more preferably in the range of 350 to 700 ℃, still more preferably in the range of 400 to 650 ℃, and particularly preferably in the range of 420 to 630 ℃.

The molar ratio (mol: mol) of methane to phosphorus trichloride is not particularly limited and may be appropriately selected according to the purpose, and is preferably 20: 1-1: 1, more preferably 18: 1-1: 1, particularly preferably 15: 1-1.5: 1, in the above range.

The reaction pressure in the reaction step is not particularly limited and may be appropriately selected according to the purpose, and is preferably in the range of 500mbar to 25bar, and particularly preferably in the range of 900mbar to 10 bar.

The speed at which the methane, the phosphorus trichloride, and the additive pass through the reaction tube (hereinafter, sometimes referred to as "linear speed") is not particularly limited, and may be appropriately selected according to the purpose, and is preferably in the range of 10 cm/min to 5,000 cm/min, more preferably in the range of 50 cm/min to 3,000 cm/min, further preferably in the range of 100 cm/min to 2,000 cm/min, and particularly preferably in the range of 800 cm/min to 1,800 cm/min, in terms of the total linear speed of the methane, the phosphorus trichloride, and the additive.

The additive may be introduced into the mixed gas of methane and phosphorus trichloride.

The concentration of the additive to the methane (additive concentration (%) ═ number of moles of additive/number of moles of methane × 100) is not particularly limited, and may be appropriately selected depending on the purpose, and is preferably in the range of 0.05% to 10%, more preferably in the range of 0.1% to 7%, and still more preferably in the range of 0.2% to 5%.

< other step >

The other step is not particularly limited as long as the effect of the present invention is not impaired, and may be appropriately selected according to the purpose, and for example, a recovery step of recovering a reactant which has passed through the reaction step and then exited from the reaction apparatus may be mentioned.

The method for the recovery is not particularly limited, and a known method can be appropriately selected.

In the recovery step, a raw material may be recovered in addition to the reactant. At this time, the reactant and the raw material can be separated by, for example, distillation treatment or the like, and the obtained raw material can be used again in the < reaction step >.