JPH07126197A - Production of fluorinated hydrocarbon - Google Patents

Abstract

PURPOSE:To obtain a fluorinated hydrocarbon useful as a foaming agent, refrigerant, cleaning agent, etc., with prolonged catalytic life in a high yield and selectivity by reducing a chlorofluorinated hydrocarbon with hydrogen in the presence of a specific catalyst. CONSTITUTION:The compound such as a compound of the formula II ((p) is x+y+2 when x+y+z=2n and is x+y when x+y+z=2n+2) is produced by reducing (A) a chlorofluorinated hydrocarbon such as a compound of the formula I ((n) is 1-6; (x) is O to 2n; (y) and (z) are 1 to 2n+1; x+y+z is 2n or 2n+2) with hydrogen in the presence of (B) a catalyst containing palladium and bismuth as essential components.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a foaming agent such as polyolefin foam, polystyrene foam, polyurethane foam and polyisocyanurate foam, a refrigerant such as an air conditioner, a refrigerator and a chiller unit, a cleaning solvent such as flux and oil and fat, a reaction solvent and the like. To a method for producing a fluorinated hydrocarbon useful as various solvents, and a hydrogen reduction catalyst used therefor.

[0002]

2. Description of the Related Art As a method for producing fluorinated hydrocarbons, hydrogen is added to corresponding unsaturated fluorinated hydrocarbons, reduction of chlorinated fluorinated hydrocarbons, fluorination of chlorinated fluorinated hydrocarbons, chlorinated carbonization. Methods such as fluorination of hydrogen are known.

For example, as a method for producing 1,1-difluoroethane (hereinafter referred to as HFC152a),
Fluorination of acetylene with hydrogen fluoride (German Patent 2
139993, German 2105478, French 1604142, French 1570306
, Etc.), fluorination of vinyl chloride with hydrogen fluoride (German Patent No. 2215019, etc.), and fluorination of 1,1-dichloroethane with hydrogen fluoride using an antimony pentachloride catalyst (Journal of the Society of Chemical Ind.
ustry Vol.66 P.430-433 (1947)), 1-chlor-
Reduction of 1,1-difluoroethane (hereinafter referred to as HCFC142b) with hydrogen (JP-A-3-83940)
Etc. have been proposed.

However, with respect to (1), the raw materials are not readily available, and the catalyst is significantly deteriorated because the reaction is carried out at a relatively high temperature. For antimony pentachloride used as a catalyst, the catalyst is significantly deteriorated and a regeneration operation is required. In addition to that, a palladium-based catalyst is used, but it has a drawback such as a short catalyst life.

As a method for producing fluorinated propanes, for example, in the case of 1,1,2,2,3-pentafluoropropane (hereinafter referred to as HFC245ca),
Reduction of 1-chloro-1,2,2,3,3-pentafluoropropane with hydrogen using a palladium catalyst supported on activated carbon (JP-A-2-204443), 1,1,3-trichloro-2,2-difluoropropane Fluorination with potassium fluoride (JP-A-2-207038) has been proposed.

[0006] However, with respect to, the target selectivity and the yield of HCFC245ca are low, and there is a drawback as an industrial production method. Furthermore, 1,1,
As a method for producing 1,4,4,4-hexafluorobutane, a method of hydrogenating 2-chloro-1,1,1,4,4,4-hexafluorobutene-2 as a raw material in a gas phase ( JP-A-5-155788) has been proposed. However, since this method produces about 5% by-products, a more industrially advantageous production method is desired.

[0007]

Therefore, the present invention provides a catalyst having high reaction activity, long life and high selectivity in a method for producing a fluorinated hydrocarbon by reducing a corresponding chlorinated fluorinated hydrocarbon with hydrogen. To provide.

[0008]

[Means for Solving the Problems] In view of the above problems of the prior art, the present inventors have made earnest studies on a method of reducing chlorinated fluorinated hydrocarbons with hydrogen in the presence of a catalyst. It was found that palladium is excellent in catalytic activity, and when a catalyst obtained by adding bismuth to palladium is used, the catalyst life is long, the desired fluorinated hydrocarbon is selectively produced in high yield, and the present invention has been achieved. It was done.

That is, the present invention is a method for producing a fluorinated hydrocarbon by reducing a chlorinated fluorinated hydrocarbon with hydrogen in the presence of a catalyst, which comprises a catalyst containing palladium or palladium and bismuth as essential components. It is a method for producing a fluorinated hydrocarbon characterized by using, more preferably, the chlorinated fluorinated hydrocarbon represented by the following formula (1) is reduced with hydrogen in the presence of a catalyst to obtain the following formula (2 ) A method for producing a fluorinated hydrocarbon represented by the formula (1), wherein a catalyst containing palladium or palladium and bismuth as an essential component is used.

C _n H _x Cl _y F _z
(1) C _n H _p F _z (2) [(1) and (2), n is an integer of 1 to 6, and x is 0.
˜2n, y and z are integers from 1 to 2n + 1, x + y + z
= 2n + 2 or 2n, and x + y + z = 2n + 2
, P = x + y, and x + y + z = 2n, p
= X + y + 2. The chlorinated fluorinated hydrocarbon referred to in the present invention is a saturated or unsaturated aliphatic hydrocarbon which may have a branch, a cyclic hydrocarbon which is a compound having chlorine and fluorine. When reducing such a chlorinated fluorinated hydrocarbon, it is possible to reduce only the chlorine atom without reducing the fluorine atom. Further, it is easily expected that the method of the present invention can be applied to hydrocarbons having other halogen atoms such as bromine and iodine, which are usually observed in such a reduction reaction.

Examples of the chlorinated fluorocarbon having 1 carbon atom to which the method of the present invention can be applied include chlorotrifluoromethane, chlorodifluoromethane, chlorofluoromethane,
Dichlorodifluoromethane, dichlorofluoromethane,
Examples thereof include chlorofluoromethane. These chlorinated fluorinated hydrocarbons may be obtained by any method, and the mixture may be directly used in the method of the present invention.

The chlorinated fluorohydrocarbon having 2 carbon atoms to which the method of the present invention can be applied is represented by the following formula (3): C ₂ H _x Cl _y F _z (3) [wherein x is 0 to 4, y And z are integers from 1 to 5 and x + y + z = 6 or 4. ] A chlorinated fluorinated ethane or ethylene represented by, for example, chloropentafluoroethane, 1,1-dichlorotetrafluoroethane, 1,2-dichlorotetrafluoroethane,
1,1,1-trichlorotrifluoroethane, 1,1,
2-trichlorotrifluoroethane, 1-chloro-1,
1-difluoroethane, 2-chloro-1,1,1-trifluoroethane, 2,2-dichloro-1,1,1-trifluoroethane, chlorotrifluoroethylene, 1,1
-Dichlorodifluoroethylene, 1,2-dichlorodifluoroethylene, trichlorofluoroethylene, 2-chloro-1,1-difluoroethylene, 1,2-dichloro-1-fluoroethylene, 1,1-dichloro-2-fluoroethylene, 1-chloro-1-fluoroethylene, 1
-Chloro-2-fluoroethylene and its isomers, and the like, 1,1-dichlorotetrafluoroethane, 1,1,1-trichlorofluoroethane, 1-
Chloro-1,1-difluoroethane, 2,2-dichloro-1,1,1-trifluoroethane, chlorotrifluoroethylene and the like are particularly preferable.

The chlorinated fluorocarbon having 3 carbon atoms to which the method of the present invention can be applied is represented by the following formula (4): C ₃ H _x Cl _y F _z (4) [where x is 0 to 6, y And z are integers from 1 to 7 and x + y + z = 8 or 6. ] It is a chlorinated fluorinated propane or propene represented by, for example,
1,1,3-trichloro-1,2,2,3,3-pentafluoropropane, 1,3-dichloro-1,1,2,
2,3,3-hexafluoropropane, 1,1,1-trichloro-2,2,3,3,3-pentafluoropropane, 1,1-dichloro-1,2,2,3,3,3- Hexafluoropropane, 1-chloro-1,1,2,2
3,3,3-heptafluoropropane, 1,1,1,2
-Tetrachloro-2,3,3,3-tetrafluoropropane, 1,1,2-trichloro-1,2,3,3,3-
Pentafluoropropane, 1,2-dichloro-1,1,
2,3,3,3-hexafluoropropane, 1,1,
1,3-tetrachloro-2,2,3,3-tetrafluoropropane, 1,1,2,3-tetrachloro-1,2,
3,3-tetrafluoropropane, 1,2,3-trichloro-1,1,2,3,3-pentafluoropropane,
1,1,3,3-tetrachloro-1,2,3,3-tetrafluoropropane, 1,1,3-trichloro-1,
2,3,3,3-pentafluoropropane, 1,1,
1,3,3-pentachloro-2,2,3-trifluoropropane, 1,1,3,3-tetrachloro-1,2,
2,3-tetrafluoropropane, 1,3,3-trichloro-1,1,2,2,3-pentafluoropropane,
1,1,1,2,3-pentachloro-2,3,3-trifluoropropane, 1,1,2,3-tetrachloro-
1,2,3,3-tetrafluoropropane, 1,2,3
-Trichloro-1,1,2,3,3-pentafluoropropane, 3-chloropentafluoropropene-1,2-
Chloropentafluoropropene-1,1-chloropentafluoropropene-1,1,1-dichlorotetrafluoropropene-1,1,2-dichlorotetrafluoropropene-1,1,3-dichlorotetrafluoropropene-
1,3,3,3-trichlorotrifluoropropene-
1,1,1,3-trichlorotrifluoropropene-
1,1,1,2-trichlorotrifluoropropene-1
And its isomers.

Further, a compound obtained by substituting a part of chlorine in the above-exemplified compounds with hydrogen, for example, 3,3-dichloro-
1,1,1,2,2-pentafluoropropane, 1,3
-Dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1,2,2,3,3-pentafluoropropane, 1-chloro-1,2,2,3,3 −
Pentafluoropropane, 1-chloro-2,2,3,
3,3-pentafluoropropane, 1-chloro-1,
1,2,2,3-pentafluoropropane, 1-chloro-2,3,3-tetrafluoropropene-1,1,1-
Dichloro-3,3,3-trifluoropropene-1,
1,3-dichloro-2,3,3-trifluoropropene-1,1,2-dichloro-3,3,3-trifluoropropene-1, and the like, or mixtures of these with the compounds exemplified above. Suitable as a raw material.

The chlorinated fluorinated hydrocarbon having 4 carbon atoms to which the method of the present invention can be applied is represented by the following formula (5) C ₄ H _x Cl _y F _z (5) [wherein x is 0 to 8 and y And z are integers from 1 to 9 and x + y + z = 10 or 8. ] Fluorinated chlorinated butanes and butenes represented by, for example, chlorononafluorobutane, 1,1-dichlorooctafluorobutane, 2,2-dichlorooctafluorobutane,
2,3-dichlorooctafluorobutane, 2,2,3-
Trichloroheptafluorobutane, 1,2,4-trichloroheptafluorobutane, 2,2,3,3-tetrachlorohexafluorobutane, 1,2,3,4-tetrachlorohexafluorobutane, 1,2,2 3-tetrachlorohexafluorobutane, 1,1,3,4-tetrachlorohexafluorobutane, 1,1,1,3,3-pentachloropentafluorobutane, 1,1,3,3,4-
Pentachloropentafluorobutane, 1,1,1,3
3,3-hexachlorotetrafluorobutane, 1,2,
2,3,3,4-hexachlorotetrafluorobutane,
1,1,2,3,4,4-hexachlorotetrafluorobutane, 1,1,1,3,3,4-hexachlorotetrafluorobutane, 1,1,1,2,2,3,3-heptachloro Trifluorobutane, 1,1,2,2,3,3,3
4-heptachlorotrifluorobutane, 1,1,1,
2,2,4,4,4-octachlorodifluorobutane,
1,1,1,2,2,3,3,4-octachlorodifluorobutane, 2-chloroheptafluorobutene-2,
2,3-dichloro-1,1,1,4,4,4-hexafluorobutene-2,1,4-dichloro-1,1,2,
3,4,4-hexafluorobutene-2,4,4-dichloro-1,1,2,3,3,4-hexafluorobutene-2,3,4-dichloro-1,1,2,3 4,4-hexafluorobutene-2,2,4,4-trichloropentafluorobutene-2,2,2,3-trichloropentafluorobutane, 1,3,4,4-tetrachlorotetrafluorobutene-1, 2,2,4,4-tetrachlorotetrafluorobutene-1 and its isomers can be mentioned.

Further, a compound obtained by substituting a part of chlorine of the above exemplified compounds with hydrogen, for example, 1-chloro-1,
1,2,2,3,3,4,4-octafluorobutane,
1,1-dichloro-2,2,3,3,4,4,4-heptafluorobutane, 2,2,3-trichloro-1,1,
1,3,3,3-hexafluorobutane, 3,3,3-
Trichloro-1,1,1-trifluoro-1-trifluoromethylpropane, 1,1,2,2,3,3,4-heptachloro-4,4-difluorobutane, 1-chloro-
2,2,3,3,4,4,4-heptafluorobutane,
1,2-dichloro-2,3,3,4,4,4-hexafluorobutane, 2,3-dichloro-1,1,1,4
4,4-hexafluorobutane, 1,1,1-trichloro-2,2,4,4,4-pentafluorobutane, 1,
1,1,2,2-pentafluoro-4,4,4-trifluorobutane, 2-chloro-1,1,1,4,4,4-
Hexafluorobutane, 1,3-dichloro-1,1,
4,4,4-pentafluorobutane, 1,1,1-trichloro-2,2,3,3-tetrafluorobutane, 2-
Chloro-1,1,1,4,4,4-hexafluorobutene-2,4-chloro-1,1,2,3,3,4-hexafluorobutene-1,1,3,4-trichloro- 1,
3,4,4-tetrafluorobutene-1,1,1,1,
2-tetrachloro-1,1,1-trifluorobutene-
2, etc., or a mixture of these with the compounds exemplified above is also suitable as a raw material.

The chlorinated fluorinated hydrocarbon having 5 carbon atoms to which the method of the present invention can be applied is represented by the following formula (6): C ₅ H _x Cl _y F _z (6) [wherein x is 0 to 10 and y And z are integers from 1 to 11 and x + y + z = 12 or 10. ] Fluorinated chlorinated pentanes and pentenes represented by, for example, 1-chloroundecafluoropentane, 1,1,
3-trichloro-1,2,2,3,4,4,5,5,5
-Nonafluoropentane, 1,1,1.2,2,4
4,5,5,5-decachloro-3,3-difluoropentane, 2,3-dichlorooctafluoropentene-1,
3,4, dichloro-2-trifluoromethylpentafluorobutene-1, etc., or 1-chloro-1,1,
Compounds having hydrogen, such as 2,2,3,3,4,4,5,5-decafluoropentane, may be mentioned. Alternatively, a mixture of these and the compounds exemplified above is also suitable as a raw material.

The chlorinated fluorohydrocarbon having 6 carbon atoms to which the method of the present invention can be applied is represented by the following formula (7): C ₆ H _x Cl _y F _z (7) [wherein x is 0 to 12, y And z are integers from 1 to 13 and x + y + z = 14 or 12. ] Fluorinated chlorinated hexane and hexene represented, for example, 1-chlorotridecafluorohexane, 3,4-
Dichlorodecafluorohexane, 2,5-dichlorodecafluorohexane, 1,5-dichlorodecafluorohexane, 1,1,1-trichloroundecafluorohexane, 2,3,4,5,6,7-hexachlorooctafluorohexane Examples thereof include hexane, 1,1,1,3,4,6,6,6-octachlorohexafluoroethane and isomers thereof.

Further, a compound obtained by substituting a part of chlorine in the above exemplified compounds with hydrogen, for example, 1-chloro-1,
1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane, 1-chloro-2,2,3,3,4
4,4,5,5,6,6,6-undecafluorohexane and the like, or mixtures of these with the compounds exemplified above are also suitable as raw materials.

The method of the present invention can be applied to the above-mentioned various chlorinated fluorinated hydrocarbons, but it is particularly preferable to produce fluorinated hydrocarbons having more fluorine atoms than carbon atoms.

The raw material chlorinated fluorinated hydrocarbon may be produced by any method. For example, 1,3
-Dichloro-1,1,2,2,3-pentafluoropropane (hereinafter referred to as HCFC225cb) is a substance listed as an alternative to specific CFCs, and is an addition compound of tetrafluoroethylene and carbon tetrachloride ( CClF ₂ CC
F ₂ CCl ₃ ) after being fluorinated with hydrogen fluoride (CC
1F ₂ CCF ₂ CCl ₂ F) can be produced by a method of reducing with hydrogen. HCFC225cb is an addition compound of tetrafluoroethylene and trichlorofluoromethane (CF ₃ CC
F ₂ CCl ₃ ) can be produced by a method of reducing with hydrogen. Further, the method of the present invention can be applied to chlorinated fluorinated propane which is an intermediate product thereof.

Further, 2,3-dichloro-1,1,1,
Although 4,4,4-hexafluorobutene-2 may be produced by any method, for example, it is synthesized by a coupling reaction of 1,1,1-trichloro-2,2,2-trifluoroethane. (US Pat. No. 4,264,040), which was synthesized by fluorinating 1,1,1,2,3,4,4,4-octachlorobutene-2 (USP2).
554,857) and the like. In addition, 2,3-dichloro-1,1,1,4, which is an intermediate of this reaction,
A compound in which a part or all of chlorine in 4,4-hexafluorobutene-2 is replaced with hydrogen can also be used as a raw material. Although these raw materials have cis and trans isomers, the reaction of the present invention can be applied to any isomer or a mixture of these isomers. The same applies to the compounds exemplified above.

The palladium or the catalyst containing palladium of the present invention can be used in various forms of a simple substance of metal, for example, powder, metal black, wire mesh, sol, etc., but it is usually used as a supported catalyst, and its carrier is activated carbon, alumina,
Aluminum fluoride, partially fluorinated alumina, zirconia, partially fluorinated zirconia, calcium fluoride, silica, partially fluorinated silica, silica-alumina, titania, partially fluorinated Various carriers such as titania can be used, and activated carbon, alumina, aluminum fluoride, partially fluorinated alumina and calcium fluoride are preferable, and activated carbon is particularly recommended. The supported amount of palladium is 0.01 with respect to the weight of the carrier.
% To 20% by weight, preferably 0.1 to 10% by weight
A weight% range is recommended. If it is less than 0.01% by weight, the volume of the catalyst bed must be increased, and if it is 20% by weight.
As described above, it is difficult to support palladium in a uniformly dispersed state.

The palladium or the catalyst containing palladium of the present invention has a higher activity, a higher selectivity, and a longer life, and therefore, other than palladium, 1a group, 2a group, 3b group, 4b group and 5b group.
Tribe, 6b family, 7b family, 8 family, 1b family, 2b family, 3a family,
Group 4a, group 5a, group 6a, preferably group 3a, 4a
One or more elements of group 5a, for example Tl, In,
Ga, Sn, Pb, Bi can be added, in particular bismuth or a combination of bismuth and one or more of the other elements mentioned above is recommended.

Other one or more of the above elements include W, Re, Ta, Os, Mo, Ir, and
Ru, Nb, Hf, etc., and T for the purpose of enhancing selectivity.
l, Sn, Cu, In, Cd, Ag, Pd, Hg, H
It is also preferable to use f, Zr, Mg, La, Ce or the like together.

Therefore, specifically, Pd / Bi / W
, Pd / Bi / Re, Pd / Bi / Ta, Pd / Bi
/ Os, Pd / Bi / Mo, Pd / Bi / Ir, Pd /
Bi / Ru, Pd / Bi / Nb, Pd / Bi / Hf, P
d / Bi / Tl, Pd / Bi / Sn, Pd / Bi / C
u, Pd / Bi / In, Pd / Bi / Cd, Pd / Bi
/ Ag, Pd / Bi / Pd, Pd / Bi / Hg, Pd /
Bi / Zr, Pd / Bi / Mg, Pd / Bi / La, P
A ternary catalyst such as d / Bi / Ce can be mentioned. It is also possible to use the above-mentioned elements in combination with these ternary catalysts.

When bismuth is added to the palladium catalyst of the present invention, the composition ratio of palladium and bismuth is preferably 0.5 to 200 parts by weight, more preferably 5 to 150 parts by weight, relative to 100 parts by weight of palladium. And 20
˜100 parts by weight is more suitable. If the amount of bismuth is 0.5 parts by weight or less, the effect of achieving a high yield, the effect of preventing catalyst deterioration, and the effect of facilitating the temperature control of the reactor due to the addition of bismuth are not observed. It is not preferable because the activating activity is reduced.

Further, when the above-mentioned element is added as the third component, it is added in an amount of 0.5 to 100 parts by weight of palladium.
200 parts by weight are suitable, 5 to 150 parts by weight are more suitable and 20 to 100 parts by weight are even more suitable. When the amount of the third component is 0.5 parts by weight or less, the catalyst deterioration preventing effect or the selectivity improving effect due to the addition of the third component is not recognized, and when the amount of bismuth is 200 parts by weight or more, the hydrogenation activity decreases, which is not preferable.

The method of supporting palladium on the carrier in the catalyst of the present invention can be adopted from the conventionally known production methods. For example, a palladium-supported catalyst can be produced by immersing a carrier in a solution containing a palladium compound, air-drying and heating to dry. In this case, the final temperature is 200 to 500 ° C, preferably 250 to 400 ° C.
Bake at. When adding the second component or the third component such as bismuth, it is necessary to immerse the palladium-supported catalyst prepared in advance in a solution containing the second component, for example, the bismuth compound or the third component, and air dry and heat dry. It can be manufactured repeatedly. Also in this case, finally, the firing is performed at 200 to 500 ° C, preferably 250 to 400 ° C. When the second or third component such as bismuth is added, the palladium-supported catalyst prepared in advance is dipped in a solution containing the second component, for example, the bismuth compound and the third component, and air-dried and heat-dried. It can be manufactured. Even in this case, finally 2
Firing is performed at 00 to 500 ° C, preferably 250 to 400 ° C. Further, the carrier is immersed in a solution containing two or more kinds of catalyst components such as a palladium compound and a bismuth compound, and air-dried and heat-dried to produce a supported catalyst containing palladium and other components by one dipping operation. You can also Also in this case, finally, the firing is performed at 200 to 500 ° C, preferably 250 to 400 ° C.

The metal used for supporting is not particularly limited as long as it is a compound capable of forming a solution, but the palladium compound includes palladium chloride, palladium nitrate, palladium sulfate, sodium tetrachloropalladate, palladium acetate, acetylacetonato palladium. Allyl palladium chloride, tetrakis (triphenylphosphine) palladium, etc., and the bismuth compound is preferably bismuth chloride, bismuth nitrate, bismuth sulfate, etc., and other elements are almost always chloride, nitrate, acetate, sulfate or Compounds such as oxides can be used, and those that dissolve in the solvent of the immersion liquid are selected.

Examples of the solvent used for preparing the catalyst include water or aqueous solutions of ammonia, hydrochloric acid, nitric acid, sulfuric acid and the like, and organic solvents such as methanol, ethanol, acetone, methylene chloride, chloroform and benzene. Further, water, an aqueous solution or a mixture of organic solvents can be used.

Before the reaction is started, the reaction is carried out in a hydrogen atmosphere or in the presence of a reducing agent such as hydrazine in an amount of 200 to 200%.
It is necessary to reduce the supported metal at 500 ° C, preferably 300 to 500 ° C. If the temperature is 200 ° C or lower, reduction sufficiently occurs, and if it is 500 ° C or higher, the sintering of the catalyst may be promoted, which is not preferable.

The reaction of the present invention can be carried out in a gas phase or a liquid phase, but when it is carried out in a gas phase, the reaction pressure is not particularly limited, but it is carried out at 1 to 10 kg / cm ² . 1k
If it is less than g / cm ² , the shape of the reactor becomes large, which is not preferable, and if it is 10 kg / cm ² or more, it is not particularly preferable in terms of the strength of the apparatus. When the reaction is carried out in the gas phase, the contact time may be in the range of 0.5 to 200 seconds, preferably 1 to 100 seconds, more preferably 2 to 60 seconds.
It is in the range of seconds. The contact time must be adjusted and printed according to the reaction temperature, but if the contact time is shorter than 0.5 seconds, a sufficient reaction rate cannot be obtained, and if it is longer than 200 seconds, overhydrogenation tends to occur, which is not preferable.

In the present invention, the molar ratio of the hydrogen gas and the raw material gas differs depending on the raw material organic substance, but the formula C _n H _x Cl _y F _z (1) [(1) and (2), n is 1 to 6). Integer, x is 0
˜2n, y and z are integers from 1 to 2n + 1, x + y + z
= 2n + 2 or 2n. ], Y: 1 to
20y: 1, preferably y: 1 to 15y: 1,
y: 1-10y: 1 is more preferable, and y: 1-5y: 1.
Is more preferable. . If the amount of hydrogen is excessive, there will be problems in hydrogen recovery. On the other hand, since hydrogen gas also has a function of regenerating the catalyst, it is particularly preferable that hydrogen is 1.0y to 4.0y mole times when the starting material is a saturated compound and 1.5y to 5.0y mole times when the starting material is an unsaturated compound. is there. If desired, the reaction system may be diluted with an inert gas such as nitrogen, argon or helium.

The reaction temperature is related to the reaction rate, the catalyst life and the boiling point of the raw material compound. Generally, for a raw material compound having a boiling point of 70 ° C. or lower, 70 to 400 ° C., preferably 90 to 350 ° C., more preferably 100. ~ 300
C., more preferably in the range 100 to 250.degree. C. is recommended. When the temperature is lower than 70 ° C or the boiling temperature of the starting compound, a special device such as a decompression reaction device is required to completely vaporize the starting material. When the temperature exceeds 400 ° C, the sintering of the catalyst is promoted, so the catalyst life is extended. Is reduced.

When the reaction of the method of the present invention is carried out in the liquid phase, it is in the presence or absence of a solvent inert to the hydrogenation reaction, for example, water, diethyl ether, tetrahydrofuran, methanol, ethanol, isopropanol and the like. To do. In this case, the reaction pressure is not particularly limited, but is 1 to 100 kg / cm ² . 1 kg / cm ²
If it is less than 100 g / cm ² , the shape of the reactor becomes large, and if it is 100 kg / cm ² or more, it is not particularly preferable from the viewpoint of the strength of the apparatus. The reaction temperature is related to the reaction rate and the catalyst life, but is 20 to 200 ° C., more preferably 30.
A range of ~ 150 ° C is recommended. If the temperature is 20 ° C or lower, the reaction takes time, and if it is 200 ° C or higher, perhydrogenation occurs, which is not preferable. The reaction time is about 30 minutes to 10 hours, but is not particularly limited. The reaction system may be either a batch system or a flow system, but the reaction conditions are naturally slightly different.

[0037]

The present invention will be described in detail below with reference to examples, but the invention is not limited thereto.

Preparation Example 1 0.10 g of bismuth nitrate pentahydrate was dissolved in 200 cc of pure water, and 200 cc of commercially available 0.5% palladium-supported activated carbon (manufactured by NE Chemcat) was immersed in this solution for 20 hours. After that, the water was evaporated to dryness using an evaporator. The catalyst was air-dried and then calcined at 300 ° C. for 2.5 hours to prepare a catalyst (bismuth corresponds to 10% by weight of palladium).

Preparation Example 2 A catalyst was prepared in the same manner as in Preparation Example 1 except that the amount of bismuth nitrate pentahydrate was 0.05 g (bismuth corresponds to 5% by weight of palladium).

Preparation Example 3 A solution A was prepared by adding 20.2 g of bismuth nitrate pentahydrate and 100 cc of 35% hydrochloric acid to 100 cc of pure water kept at 70 ° C. Similarly, in 100 cc of pure water kept at 70 ° C., 33.8 g of palladium chloride and 100% of 35% hydrochloric acid were added.
Solution c was added and stirred well to prepare solution B. In addition, 405 g of activated carbon (3I manufactured by JGC Chemical Co., Ltd.) was placed in a flask containing 1100 cc of pure water and soaked all day and night, and then a mixture of solution A and solution B, which had been premixed and well stirred, was poured into the flask and thoroughly stirred After leaving it for a whole day and night again, the water content was evaporated to dryness using an evaporator. This was further dried with a warm air dryer at 120 ° C. for 2 hours and calcined at 300 ° C. for 3 hours to prepare a catalyst. Palladium is 5% by weight of activated carbon and bismuth is 43% by weight of palladium.

Preparation Example 4 A solution A was prepared by adding 2.02 g of bismuth nitrate pentahydrate and 10 cc of 35% hydrochloric acid into 10 cc of pure water kept at 70 ° C. Similarly, 3.38 g of palladium chloride and 10 cc of 35% hydrochloric acid were added to 100 cc of pure water kept at 70 ° C. and well stirred to prepare a liquid B. Further, 40.5 g of activated carbon (manufactured by JGC Kagaku Co., Ltd. 3I) was placed in a round bottom flask containing 110 cc of pure water and immersed for a whole day and night, and then a mixture of solution A and solution B which had been premixed and well stirred was injected. After stirring well and leaving it for a whole day and night again, the water was evaporated with an evaporator to dryness. This was further dried with a warm air dryer at 120 ° C for 2 hours and calcined at 300 ° C for 3 hours to prepare a bismuth-palladium / activated carbon catalyst. Palladium is 5% by weight of activated carbon and bismuth is 43% by weight of palladium.

Preparation Example 5 Palladium chloride was added to 10 cc of pure water kept at 70.degree.
125 g and 35% hydrochloric acid (10 cc) were added and well stirred to prepare a solution B. Also, after putting 15 g of activated carbon (3I manufactured by JGC Chemicals Co., Ltd.) in a round bottom flask containing 50 cc of pure water and immersing it all day and night, inject the solution B into the flask and stir it well.
After allowing it to stand for a whole day and night again, water was evaporated to dryness with an evaporator. This was further dried with a warm air dryer at 120 ° C. for 2 hours and calcined at 300 ° C. for 3 hours to prepare a palladium / activated carbon catalyst. Palladium is 0.5 of activated carbon weight
%.

Preparation Example 6 A solution A was prepared by adding 0.20 g of bismuth nitrate pentahydrate and 10 cc of 35% hydrochloric acid into 10 cc of pure water kept at 70 ° C. Similarly, 0.34 g of palladium chloride and 1 cc of 35% hydrochloric acid were added to 10 cc of pure water kept at 70 ° C. and well stirred to prepare a liquid B. Similarly, maintained at 70 ℃ 10c
0.15 g of hafnium chloride and 35% hydrochloric acid in pure water of c
cc was added and well stirred to prepare a liquid C. Further, 40.5 g of activated carbon (manufactured by JGC Chemical Co., Ltd. 3I) was placed in a round-bottomed flask containing 110 cc of pure water and immersed for a whole day and night, and then the mixture of solution A, solution B, and solution C was stirred well in advance and well stirred. Was poured, and the mixture was thoroughly stirred, allowed to stand for a whole day and night, and then evaporated to dryness with an evaporator. This one more
A hafnium-bismuth-palladium / activated carbon catalyst was prepared by drying in a warm air dryer at 20 ° C for 2 hours and calcining at 300 ° C for 3 hours. Palladium is 0.5% by weight of activated carbon. Bismuth and hafnium each make up 43% by weight of palladium.

Preparation Examples 7 to 10 In place of hafnium chloride in Preparation Example 6, niobium chloride, magnesium chloride, zirconium chloride and molybdenum oxide were used to prepare three-way catalysts in the same manner as in Preparation Example 6. In each case, palladium is 0.5% by weight of activated carbon, and the metals replacing bismuth and hafnium are 43% by weight of palladium, respectively.

Preparative Example 11 Palladium chloride was added to 10 cc of pure water kept at 70.degree.
34 g and 10 cc of 35% hydrochloric acid were added and well stirred to prepare a palladium chloride solution. In addition, activated carbon (3 manufactured by JGC Chemical Co., Ltd.
I) 40.5 g was put in a flask containing 110 cc of pure water and soaked for a whole day and night, then a palladium chloride solution was poured into the flask, stirred well and left for a whole day and night, and then water was evaporated using an evaporator. Allowed to dry. This is further dried in a hot air dryer at 120 ° C for 2 hours,
A catalyst was prepared by calcining at 0 ° C. for 3 hours. Palladium is 0.5% by weight of activated carbon.

Preparation Example 12 A Pd / Zr-based catalyst was prepared in the same manner as in Preparation Example 6 except that zirconium chloride was used instead of hafnium chloride in Preparation Example 6 and the bismuth chloride solution (solution A) was not used. did.
In each case, palladium is 0.5% by weight of activated carbon and zirconium is 43% by weight of palladium.

Example 1 2.5 cm inner diameter and 40 c length equipped with an external tubular electric furnace
m of the quartz reaction tube was filled with 50 cc of the catalyst prepared in Preparation Example 1, and the temperature was raised while flowing hydrogen. After reducing the catalyst with hydrogen at 400 ° C. for 2 hours at a hydrogen flow rate of 80 cc / min, the catalyst was cooled to 320 ° C. which is the reaction temperature, and the HCFC1
42b and hydrogen were introduced into the reaction tube at flow rates of 20 cc / min and 80 cc / min, respectively. The contact time was 30 seconds.
The results of gas chromatograph analysis of the gas flowing out of the reaction tube at 2 hours after the start of the reaction are shown in Table 1. In addition, as a result of examining the catalyst life, HCFC1
42b reaction rate is 78%, HFC152a selectivity is 8
It was 6%, and no catalyst deterioration was observed.

[0048]

[Table 1]

Example 2 A reaction test was conducted under the same operations and conditions as in Example 1 except that the reaction temperature was 300 ° C. The results are shown in Table 1.

Example 3 The amount of HCFC 142b and the amount of hydrogen supplied were each 20 cc /
A reaction test was conducted under the same operation and conditions as in Example 1 except that the time was 60 minutes / minute and the contact time was 38 seconds.
The results are shown in Table 1.

Example 4 Using the catalyst prepared in Preparation Example 2, a reaction test was conducted under the same operations and conditions as in Embodiment 1. The results are shown in Table 1.

Comparative Example 1 A reaction test was conducted under the same operations and conditions as in Example 1 except that the commercially available 0.5% palladium-supported activated carbon used in Preparation Example 1 was used as the catalyst. The results are shown in Table 1. As a result of examining the catalyst life, although the selectivity of HFC152a does not change to 80% after 10 hours,
The reaction rate of HCFC142b decreased to 30%, and catalyst deterioration was observed.

Example 5 Inner diameter 2.5 cm, length 40 c, equipped with external tubular electric furnace
m of the quartz reaction tube was filled with 50 cc of the catalyst prepared in Preparation Example 1, and the temperature was raised while flowing hydrogen. After reducing the catalyst with hydrogen at a flow rate of hydrogen of 80 cc / min for 2 hours at 400 ° C., it was cooled to 320 ° C. which is a reaction temperature, and
25 cb and hydrogen were introduced into the reaction tube at flow rates of 20 cc / min and 80 cc / min, respectively. The contact time was 30 seconds. Table 2 shows the results of gas chromatograph analysis of the gas flowing out from the reaction tube at 2 hours after the start of the reaction.

[0054]

[Table 2]

Example 6 A reaction test was conducted under the same operations and conditions as in Example 5 except that the reaction temperature was 300 ° C. The results are shown in Table 2.

Example 7 HCFC 225cb and hydrogen supply amounts of 20 cc each
/ Min, 60 cc / min, and the contact time was 38 seconds, and the reaction test was conducted under the same operations and conditions as in Example 5. The results are shown in Table 2.

Example 8 Using the catalyst prepared in Preparation Example 2, a reaction test was conducted under the same operations and conditions as in Example 1. The results are shown in Table 2.

Comparative Example 2 A reaction test was conducted under the same operations and conditions as in Example 5 except that the commercially available 0.5% palladium-supported activated carbon used in Preparation Example 1 was used as the catalyst. The results are shown in Table 2. As a result of examining the catalyst life, although the selectivity of HFC245cb did not change to 80% after 10 hours, the reaction rate of HCFC225cb decreased to 30%, and catalyst deterioration was observed.

Example 9 Inner diameter 3.7 cm, length 110 with external tubular electric furnace
cm in a quartz reaction tube 900c prepared in Preparation Example 3
c was charged, and the temperature rise was started while flowing hydrogen. 400
After reducing the catalyst with hydrogen at a flow rate of 2000 cc / min for 2 hours at ℃, the reaction temperature was cooled to 240 ℃, H
CFC225cb and hydrogen 0.96 mol / H, respectively
r was introduced into the reaction tube through a vaporizer and a mixer at a flow rate of 3.86 mol / Hr. The contact time was 30 seconds. Table 3 shows the results of gas chromatographic analysis of the gas flowing out from the reaction tube at the time when the gas reached a substantially steady state.

Examples 10 to 15 Following Example 9, the reaction conditions were changed as shown in Table 3, and the gas flowing out from the reaction tube at the time when the reaction conditions became almost steady was analyzed by gas chromatography. Table 3
It was shown to.

[0061]

[Table 3]

Example 16 Inner diameter 3.7 cm, length 110 with external tubular electric furnace
cm in a quartz reaction tube 900c prepared in Preparation Example 3
c was charged, and the temperature rise was started while flowing hydrogen. 400
After reducing the catalyst with hydrogen at a flow rate of 2000 cc / min for 2 hours at ℃, cool the reaction tube to 240 ℃,
225 cb and hydrogen 1.49 mol / Hr, respectively.
It was introduced into the reaction tube through a vaporizer and a mixer at a flow rate of 02 mol / Hr, and then the temperature of the electric furnace was adjusted so that the reaction temperature was kept at 280 ° C. The contact time was 19 seconds. Table 3 shows the results of gas chromatograph analysis of the gas flowing out of the reaction tube 102 hours after the start of the reaction. The reaction product composition, the HCFC225cb conversion rate, and the HFC245ca selectivity were almost the same as those immediately after the start of the reaction.

Example 17 Inner diameter 2.5 cm, length 40 c, equipped with external tubular electric furnace
m of the quartz reaction tube was filled with 50 cc of the catalyst prepared in Preparation Example 1, and the temperature was raised while flowing hydrogen. The catalyst was hydrogen-reduced at a hydrogen flow rate of 80 cc / min at 400 ° C. for 2 hours, then cooled to a reaction temperature of 250 ° C., and 3,3-dichloro-1,1,1,2,2-pentafluoropropane (hereinafter, HCFC225ca) and hydrogen were introduced into the reaction tube at flow rates of 20 cc / min and 80 cc / min, respectively. The contact time was 30 seconds. Table 4 shows the results of gas chromatographic analysis of the gas flowing out of the reaction tube at 2 hours after the start of the reaction.

Example 18 A reaction test was conducted under the same operations and conditions as in Example 17 except that the reaction temperature was 230 ° C. The results are shown in Table 4.

Comparative Example 3 A reaction test was conducted under the same operations and conditions as in Example 17, except that the commercially available 0.5% palladium-supported activated carbon used in Preparation Example 1 was used as the catalyst. The results are shown in Table 4.

[0066]

[Table 4]

Example 19 Inner diameter 1.4 cm, length 50 c equipped with external tubular electric furnace
m in a stainless steel reaction tube and the catalyst 40 prepared in Preparation Example 4
cc was charged, and the temperature rise was started while flowing hydrogen. 40
After reducing the catalyst with hydrogen at 0 ° C for 2 hours at a hydrogen flow rate of 100 cc / min, the reaction tube was cooled to 260 ° C, and 1,3-
Dichloro-1,1,2,2,3,3-hexafluoropropane and hydrogen were introduced into the reaction tube through a vaporizer and a mixer at flow rates of 20 cc / min and 60 cc / min, respectively, and then the reaction temperature was 280 ° C. The temperature of the electric furnace was adjusted so that The contact time was 30 seconds. Table 5 shows the results of gas chromatograph analysis of the gas flowing out from the reaction tube at the time when the gas reached a substantially steady state.

Comparative Example 4 Using the catalyst prepared in Preparation Example 11, a reaction was carried out under the same conditions as in Example 19. The results are shown in Table 5.

Examples 20 to 22 Subsequent to Example 19, the reaction conditions (reaction temperature, starting material, flow rate of starting material, hydrogen flow rate, contact time) were changed to those shown in Table 5 to bring them to a substantially steady state. The gas flowing out from the reaction tube at that time was analyzed by gas chromatography. The results are shown in Table 5.

[0070]

[Table 5]

Example 23 Inner diameter 1.4 cm, length 50 c with external tubular electric furnace
m in a stainless steel reaction tube and the catalyst 40 prepared in Preparation Example 4
cc was charged, and the temperature rise was started while flowing hydrogen. 40
After hydrogen reduction of the catalyst for 2 hours at 0 ° C. and a hydrogen flow rate of 100 cc / min, the reaction tube was cooled to 280 ° C.
3-Trichloro-1,2,2,3,3-pentafluoropropane and hydrogen were introduced into the reaction tube through the vaporizer and the mixer at flow rates of 20 cc / min and 60 cc / min, respectively, and then the reaction temperature was 280 ° C. The temperature of the electric furnace was adjusted so that The contact time was 30 seconds. Table 6 shows the results of gas chromatograph analysis of the gas flowing out of the reaction tube at the time when the gas reached a substantially steady state.

Comparative Example 5 Using the catalyst prepared in Preparation Example 11, a reaction was carried out under the same conditions as in Example 23. The results are shown in Table 6.

Examples 24 to 26 Subsequent to Example 23, the reaction conditions (reaction temperature, starting material, flow rate of starting material, hydrogen flow rate, contact time) were changed to those shown in Table 6 to bring them to a substantially steady state. The gas flowing out from the reaction tube at that time was analyzed by gas chromatography. The results are shown in Table 6.

[0074]

[Table 6]

Example 27 Inner diameter 1.4 cm, length 50 c equipped with external tubular electric furnace
m in a stainless steel reaction tube and the catalyst 40 prepared in Preparation Example 4
cc was charged, and the temperature rise was started while flowing hydrogen. 40
After hydrogen reduction of the catalyst at 0 ° C. for 2 hours at a hydrogen flow rate of 100 cc / min, the reaction temperature was cooled to 200 ° C.,
2,3-dichloro-1,1,1,4,4,4-hexafluorobutene-2 and hydrogen at 10 cc / min and 70, respectively
It was introduced into the reaction tube after passing through a vaporizer and a mixer at a flow rate of cc / min. The contact time was 30 seconds. The composition of the reaction product was almost stable 2 hours after the start of the reaction, and the gas chromatographic analysis results of the gas flowing out from the reaction tube at this time are shown in Table 7.

[0076]

[Table 7]

Examples 28 to 36 Subsequent to Example 27, the reaction conditions (reaction temperature, organic substance (2,3-dichloro-1,1,1,4,4,4-hexafluorobutene-2) flow rate, contact) The time) was changed as shown in Table 7, and the gas flowing out from the reaction tube at the time when each of the conditions became almost steady was analyzed by gas chromatography. The results are shown in Table 7.

Example 37 Subsequent to Example 36, reaction conditions (reaction temperature, organic substance (2,3-dichloro-1,1,1,4,4,4-hexafluorobutene-2) flow rate, contact time) Was the same as in Example 7 and the reaction was carried out again for 50 hours. The reaction was carried out for about 100 hours in total, and the reaction results at this time are shown in Table 1. As is clear from Table 7, no catalyst deterioration was observed.

Example 38 Inner diameter 1.4 cm, length 50 c equipped with external tubular electric furnace
m of the reaction tube made of stainless steel, the catalyst 40 prepared in Preparation Example 5
cc was charged, and the temperature rise was started while flowing hydrogen. 40
After hydrogen reduction of the catalyst at 0 ° C. with a hydrogen flow rate of 100 cc / min for 2 hours, the reaction temperature was cooled to 110 ° C.,
2,3-dichloro-1,1,1,4,4,4-hexafluorobutene-2 and hydrogen at 40 cc / min and 28, respectively
It was introduced into the reaction tube after passing through a vaporizer and a mixer at a flow rate of 0 cc / min. The contact time was 7.5 seconds. The gas flowing out from the reaction tube at the time when it reached a substantially steady state was analyzed by a gas chromatograph. The results are shown in Table 7.

Examples 39-40 Following Example 37, the reaction temperature was changed as shown in Table 7, and the gas flowing out from the reaction tube at the time when the reaction conditions became almost steady was analyzed by gas chromatography. Table 7
It was shown to.

Example 41 Inner diameter 2.8 cm, length 16c equipped with external tubular electric furnace
m in a stainless steel reaction tube and the catalyst 10 prepared in Preparation Example 6
0 cc was filled and the temperature rise was started while flowing hydrogen. Four
After hydrogen reduction of the catalyst at 00 ° C. with a hydrogen flow rate of 100 cc / min for 2 hours, the reaction tube was cooled to 300 ° C. and HCF was added.
C225cb and hydrogen 40cc / min, 160c respectively
It was introduced into the reaction tube through a vaporizer and a mixer at a flow rate of c / min, and then the temperature of the electric furnace was adjusted so that the reaction temperature was maintained at 330 ° C. The contact time was 30 seconds. Table 8 shows the results of gas chromatographic analysis of the gas flowing out from the reaction tube at the time when the gas reached a substantially steady state.

[0082]

[Table 8]

Examples 42 to 46 The catalysts prepared in Preparation Examples 7 to 11 were changed to the reaction temperatures shown in Table 8, and the same experiment as in Example 41 was conducted. The results are shown in Table 8.

Reference Example 1 The same experiment as in Example 41 was conducted, except that the catalyst prepared in Preparation Example 12 was changed to the reaction temperature shown in Table 8. The results are shown in Table 8.

[0085]

As is apparent from the results of the examples, according to the method of the present invention, in the method for producing a corresponding fluorinated hydrocarbon by hydrogen reduction of a chlorinated fluorinated hydrocarbon,
It is clear that when a palladium or a composite system containing palladium and bismuth is used as a catalyst, it has a high reaction rate, a high selectivity and a long life. Therefore, the present invention can provide an industrially advantageous method for producing a fluorinated hydrocarbon.

Continuation of front page (31) Priority claim number Japanese Patent Application No. 5-199711 (32) Priority date 5 (1993) August 11 (33) Priority claim country Japan (JP)

Claims (10)

[Claims] 1. A chlorinated fluorinated hydrocarbon in the presence of a catalyst,
A method for producing a fluorinated hydrocarbon by reduction with hydrogen, which comprises using a catalyst containing palladium and bismuth as essential components. 2. A method for producing a fluorinated hydrocarbon represented by the following formula (2) by reducing chlorinated fluorinated hydrocarbon represented by the following formula (1) with hydrogen in the presence of a catalyst. And a catalyst containing palladium and bismuth as essential components is used. _{C n H x Cl y F z} (1) C n H p F z (2) [(1), in (2), n is an integer from 1 to 6, x is 0
˜2n, y and z are integers from 1 to 2n + 1, x + y + z
= 2n + 2 or 2n, and x + y + z = 2n + 2
, P = x + y, and x + y + z = 2n, p
= X + y + 2. ] 3. The method for producing a fluorinated hydrocarbon according to claim 2, wherein the chlorinated fluorinated hydrocarbon and the fluorinated hydrocarbon are n = 2 to 4. 4. A chlorinated fluorinated hydrocarbon is 1-chloro-
1,1-difluoroethane, 1,3-dichloro-1,
1,2,2,3-pentafluoropropane, 3,3-dichloro-1,1,1,2,2-pentafluoropropane, 1,3-dichloro-1,1,2,2,3,3- Hexafluoropropane, 1,1,3-trichloro-1,
2,2,3,3-hexafluoropropane or 2,3
-The method for producing a fluorinated hydrocarbon according to claim 1, which is dichloro-1,1,1,4,4,4-hexafluorobutene-2. 5. A chlorinated fluorinated hydrocarbon in the presence of a catalyst,
A catalyst containing palladium and bismuth as essential components used in a method for producing a fluorinated hydrocarbon by reduction with hydrogen. 6. The catalyst according to claim 5, wherein the catalyst is supported on a carrier. 7. The catalyst according to claim 5, wherein the carrier is activated carbon. 8. The amount of palladium supported on the carrier is 0.0.
The catalyst according to claim 5, which is 1 to 20% by weight. 9. The weight ratio of bismuth to palladium of the catalyst is
The catalyst according to claim 5, which is 0.5 to 200: 100. 10. 2,3-Dichloro-1,1,1,4
A method for producing 1,1,4,4,4-hexafluorobutane by reducing 4,4-hexafluorobutene-2 with hydrogen in the presence of a catalyst, wherein a catalyst containing palladium as an essential component is used. 1, 1, 4, 4, 4-
Method for producing hexafluorobutane.