WO2005021437A1

WO2005021437A1 - Porous material and method for producing same

Info

Publication number: WO2005021437A1
Application number: PCT/JP2004/010455
Authority: WO
Inventors: Heng-Dao Quan; Hui-E Yang; Masanori Tamura; Akira Sekiya
Original assignee: National Institute Of Advanced Industrial Science And Technology
Priority date: 2003-08-27
Filing date: 2004-07-23
Publication date: 2005-03-10
Also published as: CN1798703B; JP2005067983A; JP4231921B2; CN1798703A

Abstract

A material composition is disclosed which is preferably used for synthesizing a porous metal fluoride which has a large surface area and is stable in a corrosive environment. A porous metal fluoride obtained by subjecting such a material composition to hydrogen fluoride treatment has a larger surface area and is stable in a corrosive environment, and thus can be used as a fluorination catalyst.

Description

Specification

Porous material and method for producing the same

Technical field

The present invention relates to a raw material composition for synthesizing a porous metal fluoride, a porous metal fluoride obtained by fluorinating the raw material, a fluorine catalyst containing the porous metal fluoride, and a fluorine-containing catalyst. The present invention relates to a method for producing a fluoro compound using a catalyst.

Background art

[0002] Porous materials having micro and meso-sized pores are widely used for catalysts, selective separation, selective reactions, sensors, and the like (Non-Patent Document 1). However, most of such porous materials are silicates or metal oxides (Non-Patent Documents 2, 3). Since these silicates and metal oxides react and corrode themselves in a corrosive atmosphere such as in the presence of hydrogen fluoride, and at high temperatures the pore structure is destroyed. It has the disadvantage that it cannot be used stably.

[0003] On the other hand, porous aluminum fluoride (Non-Patent Documents 4 and 5), porous magnesium fluoride (Non-Patent Document 6), and porous calcium fluoride (Non-Patent Documents) are stable porous materials. 7), porous chromium fluoride (Patent Document 1) is known.

However, these surface areas are about 75 m ² / g for porous aluminum fluoride, about 60 m ² / g for porous calcium fluoride, and about 47 m ² / g for porous magnesium fluoride. It's just Porous chromium fluoride is useful as a gas-phase fluorination reaction catalyst, and is used in the production of hydrofluorocarbons, such as in refrigerants. , Its surface area is only about 70 m ² / g, known force (Patent Document 2)

For example, porous chromium fluoride is usually made by fluorinating chromium oxide, but the catalytic activity of the chromium fluoride catalyst is affected by the surface area of the precursor chromium oxide, and the surface area of chromium oxide is reduced. It is reported that as the size increases, the catalytic activity of fluorination improves (Patent Document 3). As described above, porous materials having a large surface area are expected to have excellent properties such as high catalytic activity. However, there has been a demand for the development of a stable porous material.

[0004] Non-patent document 1: Yunfeng Lu, et al., Nature, 389 (25), 364 (1997)

Non-Patent Document 2: Hui-suk Yun, et al "Adv. Mater., 13 (18), 1377 (2001)

Non-Patent Document 3: Hong Yang, et al., Nature, 379 (22), 703 (1996)

Non-Patent Document 4: H.D.Quan, et al "J. Fluorine Chem" 99, 176 (1999)

Non-Patent Document 5: H.D.Quan, et al "Tetrahedron, 57, 4111 (2001)

Non-Patent Document 6: M. Wojciechowska, et al "Catal. Lett., 66, 147 (2000)

Non-Patent Document 7: 0. (311 & 11, et al "J. Fluorine Chem., 116, 65 (2002)

Patent Document 1: US Pat. No. 3,258,500

Patent Document 2: International Publication No. 98/10862 pamphlet

Patent Document 3: European Patent Application No. 0514932

Disclosure of the invention

Problems to be solved by the invention

[0005] A first object of the present invention is to provide a raw material composition suitably used for synthesizing a porous metal fluoride having a large surface area and being stable even in a corrosive atmosphere or the like. The second object is to provide a porous metal fluoride which has a large surface area by fluorinating the raw material composition and is stable even in a corrosive atmosphere, and the third object is to provide the porous metal fluoride. A fourth object is to provide a fluorination catalyst containing a fluoride, and to provide an efficient method for producing a fluoro compound using the fluorination catalyst.

Means for solving the problem

[0006] The present inventor has conducted intensive studies to solve the above-mentioned problems, and as a result, the raw material composition containing a silicon compound in a metal compound which is a precursor of a porous metal fuzzy object is subjected to a fluorination treatment. As a result, they have found that a porous metal fluoride having a large surface area and stable even in a corrosive atmosphere or the like can be provided, and the present invention has been completed.

(1) A method for producing a porous metal fluoride, which comprises introducing a silicon-containing compound into a metal salt and then subjecting the metal salt to hydrogen fluoride treatment.

(2) Raw material composition for synthesizing porous metal fluoride comprising metal compound containing silicon compound object.

(3) Silicon compounds containing silicon dioxide (SiO 2), hydrofluoric acid (H SiF), and caustic acid (

H SiO), meta-silicic acid (H SiO), orthodicarboxylic acid (H Si 0), meta-di-acid (H Si 0), meta-tri-acid (H Si 0), and metal salts of these various silicic acids The raw material composition according to the above (2), which is at least one selected from the group consisting of:

(4) The raw material composition according to the above (2) or (3), wherein the silicon-containing compound is contained in the metal compound by a coprecipitation method, an impregnation method or direct mixing.

(5) The raw material composition as described in any of (2) to (4) above, wherein the coprecipitation method is a method using ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate. .

(6) The above (2) to (5), wherein the metal salt is at least one metal compound selected from chromium, cobalt, anorenium, calcium, magnesium, nickele, titanium, zinc, indium and iron. The raw material composition according to any one of the above.

(7) 90m has a surface area of chromium fluoride, cobalt fluoride having a surface area of ^{^{110m 2 / g- 300m 2 / g}} , 80m 2 / g- 300m 2 / g with a surface area of ^² / g- 500m ² / g Anodium fluoride, 100m ² / g—Calcium fluoride with a surface area of 300m ² / g, 70m ² / g Magnesium fluoride with a surface area of 300m ² / g, 5m ² / g—300m ² / g surface area nickel fluoride with, titanium fluoride having a surface area of 5m ^² / g- 300m ² / g, zinc fluoride having a surface area of 5m ^² / g- 300m ² / g, of 5m ^² / g- 300m ² / g At least one porous metal fluoride selected from indium fluoride having a surface area and 5 m ² / g—iron fluoride having a surface area of 300 m ² / g.

(8) Porous chromium fluoride characterized by a surface area of 90m ² Zg—200m ² / g

(9) A porous metal fluoride obtained by subjecting the raw material composition according to any of (2) to (6) to a hydrogen fluoride treatment.

(10) Porous metal fluoride power Selected from chromium fluoride, cobalt fluoride, aluminum fluoride, calcium fluoride, magnesium fluoride, nickel fluoride, titanium fluoride, zinc fluoride, indium fluoride and iron fluoride The porous metal fluoride according to the above (9), which is at least one kind selected from the group consisting of: (11) chromium fluoride having a surface area of porous metal fluoride force ^{^{90m 2 / g- 500m 2 / g}} , cobalt fluoride having a surface area of ^{^{110m 2 / g- 300m 2 / g}} , 80m 2 / g- 300m 2 magnesium fluoride having a surface area of aluminum fluoride, full Tsu of calcium having a surface area of ^{^{100m 2 / g- 300m 2 / g}} , 70m 2 / g- 300m 2 / g with a surface area of / g, 5m ² / g- nickel fluoride having a surface area of 300m ² / g, titanium fluoride having a surface area of 5m ^² Zg 300m ² Zg, zinc fluoride having a surface area of 5m ^² / g 300m ² Zg, of 5 m ² Zg one 300 meters ² / g The porous metal fluoride according to the above (10), which is indium fluoride having a surface area and iron fluoride having a surface area of 5 m ² Zg and 300 m ² Zg.

(12) The porous metal fluoride according to the above (11), wherein the porous metal fluoride is a porous metal chromium having a surface area of 90 m ² / g to 200 m ² / g.

(13) A fluorination catalyst comprising the porous metal fluoride according to any one of (7) to (12).

(14) A chromium salt, a cobalt salt, an iron salt, a zinc salt, a magnesium salt, a silver salt, a nickel salt, an indium salt, an antimony salt, Fluorination catalyst obtained by adding at least one metal salt selected from radium salts and platinum salts

(15) A process for producing a fluoro compound, which comprises reacting a hydrogen or fluorine compound with hydrogen fluoride in the presence of the fluorination catalyst according to (13) or (14).

(16) The method for producing a fluoro compound according to the above (15), wherein the halogen compound is a halogenated hydrocarbon.

(17) The method for producing a fluoro compound according to the above (16), wherein the halogen hydrocarbon is dichloromethane.

The invention's effect

The raw material composition according to the present invention comprising a metal compound and a silicon compound is often porous and amorphous, and its surface area may be 400 m ² / g or more depending on the case. In addition, the chemical composition turns into a fluoride of the metal by a reaction with hydrogen fluoride. Because of these characteristics, fluorination treatment gives a porous metal fluoride with a much larger surface area than conventional products and is stable even in corrosive atmospheres. . Further, the obtained porous metal fluoride has excellent fluorination catalytic activity, and when used as a catalyst for producing a fluoro compound by reacting a halide with hydrogen fluoride, it can be used in a high yield. Can be obtained.

BEST MODE FOR CARRYING OUT THE INVENTION

[0008] The raw material composition for synthesizing a porous metal fluoride of the present invention comprises a metal compound containing a silicon compound.

The metal compound containing a silicon compound is not particularly limited as long as it gives a porous metal fluoride by hydrogen fluoride treatment, but chromium, cobalt, aluminum, calcium, magnesium, nickel, titanium, zinc, Indium, iron salts, or mixtures thereof are preferred. More preferably, these oxides, hydroxides, or mixtures thereof are preferred. More preferred are chromium oxides and hydroxides and salts containing these.

[0009] The silicon compound is not particularly limited as long as it can be applied to the present production method, but is preferably silicon dioxide (SiO 2), caustic hydrofluoric acid (H SiF), and orthocaic acid (H SiO 2). , Metasilicic acid (H SiO), ortho-dicarboxylic acid (H Si 0), meta-di-acid (H Si 0), meta-tri-carboxylic acid (H Si 0)

Ii), metal salts of these various keic acids, or mixtures thereof.

[0010] The content of silicon when the silicon compound is added to the metal compound is 0.1 to 20% by weight, preferably 115 to 5% by weight. If the content of silicon is too large, the structure may be destroyed during the treatment with hydrogen fluoride, which is not preferable.

The method for incorporating the silicon compound into the precursor is not particularly limited, and examples thereof include a coprecipitation method, an impregnation method, and a method of directly mixing the precursor and the silicon compound.

In the case of the coprecipitation method, an aqueous solution of a metal salt, a silicon-containing compound and a base are mixed to precipitate a metal hydroxide containing the silicon-containing compound. The base used at this time is not particularly limited as long as a hydroxide precipitate can be obtained by this method, but examples thereof include ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. The pH at the time of precipitation is 6-9, preferably 7-8. The precipitate obtained is filtered and washed with water, preferably with deionized water.

The precursor into which the silicon-containing compound has been introduced is fired if necessary. The temperature is 300-600 ° C, preferably 400-500 ° C, and firing in air may be used, but firing in a nitrogen atmosphere is preferable.

[0012] The raw material composition (hereinafter also referred to as a precursor) obtained as described above is often porous and amorphous, and its surface area may be 400 m ² / g or more in some cases. is there. In addition, as for the chemical composition, the metal becomes a fluoride of the metal by the reaction with hydrogen fluoride. Due to these characteristics, the surface area measured by the BET method by fluorination treatment has a larger surface area, for example, 90 m ² / g—200 m ² / g, and is stable even in a corrosive atmosphere. Provides a porous metal fluoride. In this way, the fluorinated chromium having a surface area of 90m ^² Zg 500m ² Zg as suitably obtained porous metal fluoride, cobalt fluoride having a surface area of ^{^{110 m 2 / g 300m 2 Zg}} , 80m 2 / g — Aluminum fluoride with a surface area of 300 m ² / g, 100 m ² / g— Futani calcium with a surface area of 300 m ² / g, 70 m ² / g— Magnesium fluoride with a surface area of 300 m ² / g, 5 m ² nickel fluoride having a surface area of Zg one 300m ² / g, titanium fluoride to have a surface area of ^{^{5m 2 / g- 300m 2 / g}} , zinc fluoride having a surface area of ^{^{5m 2 / g- 300m 2 / g}} , 5m such as iron fluoride having a surface area of indium fluoride and 5m ^² / g- 300m ² / g with a surface area of ^² / g- 3 00m ² / g can be mentioned. Among them, chromium fluoride having a surface area of 90 m ² / g to 500 m ² / g, particularly porous chromium fluoride having a surface area of 90 m ² / g to 200 m ² / g is preferable.

[0013] The hydrogen fluoride treatment may be performed by bringing the precursor into contact with hydrogen fluoride or hydrogen fluoride diluted with a diluent gas such as nitrogen gas or argon gas. The temperature of the hydrogen fluoride treatment is from room temperature to 500 ° C, preferably from 50 ° C to 350 ° C. There is no particular limitation on the amount of hydrogen fluoride. The remaining hydrogen fluoride can be removed by flowing a nitrogen stream.

The reason why the hydrogen fluoride treatment can provide a stable porous metal fluoride even in a corrosive atmosphere with a large surface area is not clear, but when the precursor is fluorinated, the silicon contained in the precursor is not included. Is reacted with hydrogen fluoride to form gaseous silicon tetrafluoride and is removed.Therefore, it is presumed that this is partly because pores are formed there and a large surface area is obtained. You.

[0014] The porous metal fluoride according to the present invention is obtained by fluorinating a halogen compound such as carbon black. It can be suitably used as a catalyst for producing a fluoro compound by fluorination with hydrogen fluoride. Further, a chromium salt, a cobalt salt, an iron salt, a zinc salt, a magnesium salt, a silver salt, a nickel salt, an indium salt, or a mixture thereof may be added to the porous metal fluoride. As for the method of addition, it may be added to the porous fluorinated product, or may be added to the precursor by an impregnation method or a coprecipitation method, and then subjected to a hydrogen fluoride treatment. The amount of addition is 1: 1 to 100: 1, preferably 3: 1 10: 1, in a molar ratio of the metal of the porous fluoride to the metal of the additive.

[0015] Examples of the halogen compound which is a starting material for producing a fluoro compound include halogenated hydrocarbons such as chlorocarbons, fluorofluorocarbons, hydrochlorofluorocarbons, and chloroolefins.

Specific columns include chloromethane, dichloromethane, trichloromethane, tetrachloromethane, chlorofluoromethane, dichlorofluoromethane, chlorodifluoromethane, chloromethane, 1,1-dichloromethane, 1,2-dichloroethane, 1,1,1_trichloroethane, 1,1,2_trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, 1_black mouth 1, 1, 1-difluoro- 1, 2-difluoro-, 1_ 2, 2, 2-difluoro-, 1, 1-dichloro- 1-fluoro-, 1, 1-dichloro-2- 2-fluoro-, 1 1,2-dichloroethylene, 1,2-dichloroethylene, 1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, 1,1-dichloro-2,2-dichloro-1,2-dichloroethylene Norre Oroechiren, like Torifuruorokuro port ethylene.

[0016] The hydrogen fluoride used in these catalytic fluorination reactions is advantageously used in an excess amount with respect to the starting halogen compound, usually in an amount of 1 to 30 equivalents, preferably 3 to 10 equivalents. Preferably, it is used. In this case, hydrogen fluoride diluted with a diluent gas such as nitrogen gas or argon gas can also be used.

[0017] The reaction temperature of the fluorination is usually 200 ° C, 450 ° C, preferably 230 ° C, 400 ° C. The reaction can be carried out in either a batch system or a flow system.

[0018] Examples of the fluoro compound obtained by the fluorination reaction of the present invention include fluoromethane, difluoromethane, trifluoromethane, tetrafluoromethane, fluoroethane, 1,1-difluoroethane, 1,2-difluoroethane, 1,1,1, and 1_Trifluoroetan, 1,1,2—Trifluoroethan, 1,1,1,2—Tetrafluoroeethane, 1,1,2,2-Tetrafluore Lohetan and pentafunolelohetan can be mentioned.

Example

Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Example 1

[0020] Sodium silicate (NaSiO, 3g) was dissolved in 28% aqueous ammonia (114ml), and added to an aqueous solution of chromium trichloride (chromium content: about 10%, 240g) with vigorous stirring. The pH after mixing was about 7. The precipitate was collected by filtration, washed with deionized water, dried, and calcined at 450 ° C. under a nitrogen stream to obtain a chromium salt of a precursor containing silicon. The specific surface area by BET method is 36 6m / g.

Example 2

[0021] The precursor prepared in Example 1 was treated with hydrogen fluoride diluted with nitrogen (hydrogen fluoride Z nitrogen = 1/3) for 4 hours at room temperature, and the temperature was further increased. , And treated only with hydrogen fluoride to obtain porous chromium fluoride. The specific surface area by the BET method was 176 m ² / g. Example 3

[0022] Gas phase fluorination of dichloromethane was carried out using the porous chromium fluoride prepared in Example 2 as a catalyst. Dichloromethane (0.1 Sg / min) and hydrofluoric anhydride (300 ml Zmin) were vaporized and allowed to react by flowing over a catalyst. The product was washed with water, dried over soda lime, and analyzed by gas chromatography. Difluoromethane (CH F) and chlorofluoromethane at each reaction temperature

Table 1 shows the yield of (CH C1F).

[Table 1]

Replacement form (Rule 26) Example 4

[0024] A precursor and porous chromium fluoride were prepared in the same manner as in Examples 1 and 2, except that 9 g of sodium silicate was used. The specific surface areas determined by the BET method were 470 and 169 m ² / g, respectively, for the precursor and the porous chromium fluoride. Next, the porous chromium fluoride obtained here was used, and the gas phase fluorination of dichloromethane was carried out in the same manner as in Example 3. Table 2 shows the results.

[Table 2]

Example 5

[0026] A precursor and porous chromium fluoride were prepared in the same manner as in Examples 1 and 2, except that 9 g of sodium silicate was used and the firing temperature was 400 ° C. The specific surface areas by the BET method were 407 and 187 m ² / g for the precursor and the porous chromium fluoride, respectively. Next, using the porous chromium fluoride obtained here, gas phase fluorination of dichloromethane was carried out in the same manner as in Example 3. Table 3 shows the results.

[Table 3]

Example 6

Replacement form (Rule 26) [0028] A precursor and porous chromium fluoride were prepared in the same manner as in Examples 1 and 2, except that 15 g of sodium silicate was used and the sintering temperature was 400 ° C. The specific surface areas by the BET method were 355 and 152 m ² / g for the precursor and the porous chromium fluoride, respectively. Next, the porous chromium fluoride obtained here was used, and the gas phase fluorination of dichloromethane was carried out in the same manner as in Example 3. Table 4 shows the results.

[0029] 4]

Example 7

[0030] A precursor and porous chromium fluoride were prepared in the same manner as in Examples 1 and 2, except that 0.9 g of sodium silicate was used. The specific surface areas determined by the BET method were 395 and 110 m ² / g, respectively, for the precursor and the porous chromium fluoride.

Example 8

[0031] Sodium silicate (9g) was dissolved in 28% aqueous ammonia (114ml), and this was dissolved in an aqueous solution of chromium trichloride (chromium content about 10%, 240g) and an aqueous solution of cobalt dichloride (cobalt content about 15%, 32g) Was added with vigorous stirring. Subsequent operations were performed in the same manner as in Examples 1 and 2, to obtain a precursor and porous chromium fluoride containing cobalt. The specific surface areas by the BET method were 356 and 134 m ² / g, respectively, for the precursor and the porous chromium fluoride containing cobalt. Next, the porous chromium fluoride containing cobalt obtained here was used, and the gas phase fluorination of dichloromethane was carried out in the same manner as in Example 3. Table 5 shows the results.

[Table 5]

Replacement form (Rule 26) Reaction temperature: (o. Light (%):.

CH ₂ C

242 71 11

273 71 12

300 74 12

329 74 13

355 74.13 Comparative Example 1

A porous chromium fluoride was prepared in the same manner as in Examples 1 and 2, except that sodium silicate was not used. The specific surface area by the BET method was 253 and 90 m ² / g for the precursor and the porous chromium fluoride, respectively. Next, using the porous chromium fluoride obtained here, gas phase fluorination of dichloromethane was carried out in the same manner as in Example 2. Table 6 shows the results.

[0034] [Table 6]

When compared in the same reaction temperature range, the yield of difluoroethane was lower than when sodium silicate was used (Examples 3 to 6).

Replacement form (Rule 26)

Claims

The scope of the claims

[1] A method for producing a porous metal fluoride, which comprises introducing a silicon-containing compound into a metal salt and then subjecting the metal salt to hydrogen fluoride treatment.

[2] A raw material composition for synthesizing a porous metal fluoride, comprising a metal salt containing a silicon compound.

[3] Silicon-containing compounds include silicon dioxide (SiO 2), hydrofluoric acid (H SiF), and caustic acid (H

Selected from SiO 2), metasilicic acid (H SiO), orthodicarboxylic acid (H Si 0), metadicarboxylic acid (H Si 0), metatrisilic acid (H Si 0) and metal salts of these various silicic acids 3. The raw material composition according to claim 2, wherein the raw material composition is at least one selected from the group consisting of:

4. The raw material composition according to claim 2, wherein the silicon-containing compound is contained in the metal compound by a coprecipitation method, an impregnation method, or direct mixing.

[5] The raw material composition according to any one of claims 2 to 4, wherein the coprecipitation method is a method using ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate.

[6] The metal salt according to any one of claims 2 to 5, wherein the metal salt is at least one metal salt selected from chromium, cobalt, anorenium, calcium, magnesium, nickel, titanium, zinc, indium and iron. A raw material composition according to item 1.

[7] 90m ² / g- 500m has a surface area of cobalt ^{^{fluoride, 80m 2 / g- 300m 2 /}} g with a surface area of chromium ^{^{fluoride, 110m 2 / g- 300m 2 /}} g with a surface area of ² / g having a surface area of hydrofluoric Kaa Noreminiumu, calcium fluoride having a surface area of ^{^{100m 2 / g- 300m 2 / g}} , magnesium fluoride having a surface area of 70m ² / g one ^{^{300m 2 / g, 5m 2 Zg}} 300m 2 / g Nickel fluoride, 5 m ² Zg Titanium fluoride with a surface area of 300 m ² Zg, 5 m ² / g—Zinc fluoride with a surface area of 300 m ² / g, 5 m ² Zg Indium fluoride with a surface area of 300 m ² Zg and 5 m ² Zg At least one kind of porous metal fluoride selected from iron fluoride having a surface area of 300 m ² Zg.

[8] Porous chromium fluoride characterized by a surface area of 90m ² / g—200m ² / g

[9] A porous metal fluoride obtained by subjecting the raw material composition according to any one of claims 2 to 6 to hydrogen fluoride treatment.

[10] Porous metal fluoride power Chromium fluoride, cobalt fluoride, aluminum fluoride, fluorinated power 10. The porous metal foil according to claim 9, wherein the porous metal foil is at least one selected from the group consisting of norem, magnesium fluoride, nickel fluoride, titanium fluoride, zinc fluoride, indium fluoride, and iron fluoride. monster.

[11] chromium fluoride having a surface area of porous metal fluoride force 90m ^² Zg- 500m ² / g, cobalt fluoride having a surface area of ^{^{11 0m 2 / g 300m 2 Zg}} , 80m 2 / g- 300m 2 / g magnesium fluoride having a surface area of aluminum fluoride, Futsui spoon calcium having a surface area of ^{^{100m 2 / g- 300m 2 / g}} , 70m 2 / g- 300m 2 / g with a table area, 5 m ² Zg one 300 meters ² / Nickel fluoride with a surface area of 5 g ² , 5 m ² / g Titanium fluoride with a surface area of 300 m ² Zg, 5 m ² / g—zinc fluoride with a surface area of 300 m ² / g, 5 m ² Zg 300 m ² / g 11. The porous metal fluoride according to claim 10, wherein the porous metal fluoride is indium fluoride having a surface area of 5 m ² Zg and iron fluoride having a surface area of 300 m ² Zg.

12. The porous metal fluoride according to claim 11, wherein the porous metal fluoride is a porous chromium fluoride having a surface area of 90 m ² / g to 200 m ² / g.

[13] A fluorination catalyst comprising the porous metal fluoride according to any one of claims 7 to 12.

[14] The porous metal fluoride according to any one of claims 7 to 12, wherein chromium salt, cobalt salt, iron salt, zinc salt, magnesium salt, silver salt, nickel salt, indium salt, antimony salt, palladium salt, platinum are used. Fluorination catalyst obtained by adding at least one metal salt selected from salts

[15] A method for producing a fluoro compound, comprising reacting a halogen compound with hydrogen fluoride in the presence of the fluorination catalyst according to claim 13 or 14.

[16] The method for producing a fluoro compound according to claim 15, wherein the halogenated compound is a halogenated hydrocarbon.

[17] The method for producing a fluoro compound according to claim 16, wherein the halogen hydrocarbon is dichloromethane.