JP2001261593A - Method for producing hydrogen-containing fluorinated hydrocarbon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new and economical method for producing a hydrogen- containing fluorinated hydrocarbon without causing the corrosion of the reactor by reacting hydrogen fluoride with one or more kinds of halogenated hydrocarbons in the presence of a fluorination catalyst and provide a reactor for the production method. SOLUTION: The objective method for the production of a hydrogen- containing fluorinated hydrocarbon by the reaction of hydrogen fluoride (HG) with a halogenated hydrocarbon in the presence of a fluorination catalyst comprises a step to introduce HF into the gap between an inner reactor made of a material resistant to the reaction and an outer vessel placed outside of the inner reactor and made of a material resistant to HF, a step to introduce HF into the inner reactor, a step to introduce the halogenated hydrocarbon into the inner reactor and a reaction step to react the HF with the halogenated hydrocarbon in the inner reactor in the presence of the fluorination catalyst to obtain the hydrogen-containing fluorinated hydrocarbon.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a hydrogen-containing fluorinated hydrocarbon and an apparatus therefor. still,
Throughout this specification the term "hydrogen containing fluorinated hydrocarbon"
A compound in which part of the hydrogen atoms of a hydrocarbon is replaced with fluorine atoms and contains at least one hydrogen atom, and may or may not have a chlorine element. For example, the hydrogen-containing fluorinated hydrocarbon means a hydrogen-containing fluorinated alkane and a hydrogen-containing fluorinated alkene.

[0002]

2. Description of the Related Art Hitherto, chlorofluorocarbon generally known as chlorofluorocarbon has been used as a foaming agent, a cleaning agent, or a refrigerant due to its stability and thermal properties. The chlorofluorocarbon is a simple alkane, such as methane or ethane, where all hydrogens have been replaced by chlorine or fluorine. In recent years, chlorofluorocarbons have been regulated because of their property of depleting the ozone layer.

[0003] For this reason, there is an increasing demand for hydrogen-containing fluorinated hydrocarbons having little or no effect on the ozone layer, and their development has been promoted. Hydrogen-containing fluorinated hydrocarbons include, for example, 2,2-dichloro-
1,1,1-trifluoroethane (“HCFC-12
3) and 1,1,1,3,3-pentafluoropropane (also referred to as "HFC-245fa"). This HCFC-
123 is a refrigerant for a centrifugal chiller or 2-chloro-1,1,1,2-tetrafluoroethane (“HCF
Compounds useful as intermediate materials such as C-124 "and pentafluoroethane (also referred to as" HCFC-125 "). Also, HFC-245fa is
It is a compound useful as a foaming agent that does not have the risk of destroying the ozone layer.

In order to produce such a hydrogen-containing fluorinated hydrocarbon, trichlorofluoromethane ("CFC-1") is used.
1)), dichlorodifluoromethane (“CFC
-12) and 1,1,2-trichlorotrifluoroethane (also referred to as "CFC-113") such as a conventional method for producing a chlorofluorocarbon that does not contain a hydrogen atom. As a conventional method for producing chlorofluorocarbon, a method is known in which chlorinated alkenes and / or chlorinated alkanes are reacted with hydrogen fluoride in the presence of a fluorination catalyst to produce chlorofluorocarbons.

[0005]

In the above-mentioned method for producing chlorofluorocarbon, the reaction mixture is corrosive due to the interaction between the fluorination catalyst and hydrogen fluoride. When such a method is applied to the production of hydrogenated fluorinated hydrocarbons and the reaction conditions are adapted, the reaction mixture becomes very corrosive. Therefore, when a conventional apparatus material, for example, a stainless steel material is used as a material for a reactor for performing a fluorination reaction for producing a hydrogen-containing fluorinated hydrocarbon, the reactor is significantly corroded and consumed. become. For this reason, there is a problem that the life of the reactor is short and the equipment cost is high.

Considering the high corrosiveness of the reaction mixture, the following reactors have been proposed for use in the fluorination reaction. (1) Gold, platinum, palladium, molybdenum, rhenium,
Consisting of a composite material containing one or more corrosion-resistant metals selected from the group consisting of
(JP-A-501550) (2) Reactor made of fluororesin or lined with a fluororesin (JP-A-7-233102) (3) Reactor having a corrosion-resistant metal material containing aluminum on its inner surface (JP-A-10-120602) (4) Reactor (WO99 / 26720) which is disposed inside a metal container and has at least an inner surface covered with a fluororesin

However, these reactors (1) to (4) have drawbacks, and are not always optimal as reactors used for producing hydrogen-containing fluorinated hydrocarbons. More specifically, among the corrosion-resistant metal materials used in the reactor of (1), gold, platinum, palladium, and rhenium are not suitable for large-scale production because of their high cost. Molybdenum and tungsten have the drawback that the joints become very brittle due to the effects of impurities mixed in a very small amount during welding and the effect of welding heat, and that sufficient mechanical strength cannot be maintained. Further, molybdenum and tungsten are very hard and brittle metals, and therefore have very poor workability.
Therefore, it is practically impossible to construct a reactor on an industrial scale using these materials. In addition, when a resin is used as in the reactors of (2) and (4), the thermal conductivity of the resin material is lower than that of the metal material. It is very difficult to sufficiently supply, and it is difficult to control the reaction temperature especially when a large-capacity reactor is used. In addition, the reactor (3) exhibits high corrosion resistance under anhydrous conditions, but corrosion of the reactor progresses remarkably due to the incorporation of a small amount of water. Extremely difficult.

[0008] Therefore, an object of the present invention is to provide hydrogen fluoride and 1
As a reaction raw material (hereinafter referred to as “hydrogen fluoride reaction raw material” and “halogenated hydrocarbon reaction raw material”) in the presence of a fluorination catalyst to obtain a reaction product A process for producing a hydrogen-containing fluorinated hydrocarbon, which obtains a reaction mixture containing a hydrogen-containing fluorinated hydrocarbon, wherein the above-mentioned problems of the prior art are improved, an economical and novel production method, and a reaction therefor. It is to provide a device.

[0009]

According to the present invention, there is provided a method for producing a hydrogen-containing fluorinated hydrocarbon, comprising the steps of: reacting a hydrogen fluoride with one or more halogens selected from the group consisting of chlorinated alkenes and hydrogen-containing alkane chlorides; A reaction mixture containing a fluorinated hydrocarbon as a reaction product by reacting a fluorinated hydrocarbon reaction raw material with a fluorinated catalyst in the presence of a fluorination catalyst. Gap between an inner reactor made of a material which is chemically resistant and an outer container which is arranged outside the inner reactor and is made of a material which is substantially resistant to at least one (or first) reactant. Supplying the one (the first) reactant to the inner reactor; and supplying the other (or the second) reactant to the inner reactor. Feed to inner reactor Step a; both (first and second
A) reacting the reaction raw materials in the inner reactor in the presence of a fluorination catalyst to obtain a reaction product containing a hydrogen-containing fluorinated hydrocarbon, whereby the above-mentioned problem is solved. In the method of the present invention, the one (the first)
The reactants are fed, for example, from the gap or one of the (the first
) Can be supplied to the inner reactor from a source of the reactants (described below with reference to FIG. 1).

In one embodiment of the present invention, the one reactant may be a hydrogen fluoride reactant and the other reactant may be a halogenated hydrocarbon reactant. In another embodiment of the present invention, the one reactant may be a halogenated hydrocarbon reactant and the other reactant may be a hydrogen fluoride reactant.

Specifically, one embodiment of the process of the present invention comprises an inner reactor made of a material that is substantially resistant to the reaction, and a hydrogen fluoride reactant disposed outside the inner reactor. Supplying a hydrogen fluoride reaction raw material to a gap with an outer container made of a material substantially resistant to water; supplying a hydrogen fluoride reaction raw material to an inner reactor; and a halogenated hydrocarbon reaction raw material. Supplying hydrogen to the inner reactor; reacting the hydrogen fluoride reaction raw material with the halogenated hydrocarbon reaction raw material in the inner reactor in the presence of a fluorination catalyst to produce a reaction containing hydrogen-containing fluorinated hydrocarbons And a reaction step of obtaining a product.

Another embodiment of the process of the present invention comprises an inner reactor made of a material substantially resistant to the reaction, and a halogenated hydrocarbon reaction disposed outside the inner reactor. Supplying a halogenated hydrocarbon reaction raw material to a gap between an outer container made of a material substantially resistant to the raw material; supplying the halogenated hydrocarbon reaction raw material to an inner reactor; and hydrogen fluoride. Supplying the reaction raw material to the inner reactor; and reacting the hydrogen fluoride reaction raw material and the halogenated hydrocarbon reaction raw material in the inner reactor in the presence of a fluorination catalyst to contain a hydrogen-containing fluorinated hydrocarbon. And a reaction step of obtaining a reaction product.

In accordance with the present invention, a highly corrosive reaction mixture (ie, a mixture containing unreacted raw materials, catalyst, and reaction products) is held in an inner reactor. Even if a part of the reaction mixture leaks into the gap between the inner reactor and the outer vessel, the reaction mixture is diluted by the one reactant supplied to the gap to weaken the corrosiveness. Therefore, since the inner reactor does not require a strict sealing property against leakage and does not require complicated processing, a material having substantially resistance to the reaction as the material of the inner reactor is processed. It is possible to choose regardless of gender. For example, even if it is a metal material for which it is difficult to secure the sealability by welding or the like,
Any material that is substantially resistant to the reaction can be used as the inner reactor material.

[0014] The gap between the inner reactor and the outer vessel may be maintained at a pressure higher than the pressure inside the inner reactor. In this case, a positive differential pressure (based on the pressure in the inner reactor) only needs to exist between the gap and the inner reactor, and it is not necessary to respond according to the absolute pressure of the inner reactor. Having the gap have a positive differential pressure with respect to the inner reactor further reduces leakage of the reaction mixture retained in the inner reactor into the gap. Further, unnecessary vaporization of the raw material existing in the gap can be suppressed.

In the present invention, the term "material having substantial resistance to the reaction" means a material whose corrosion amount is acceptable when the above-mentioned fluorination reaction is carried out on an industrial scale. . For example, those skilled in the art can easily select such a material by exposing a test piece of the intended material to the reaction conditions assumed when applying the present invention and measuring the amount of corrosion. .

In a preferred embodiment of the invention, the material which is substantially resistant to the reaction, ie the material of the inner reactor, is a corrosion-resistant metal comprising at least one metal selected from the group consisting of molybdenum and tungsten. It is. For example, an alloy containing Mo or W and further containing other components may be mentioned. Further, some high melting point metals having corrosion resistance, such as Mo and W, may be used.

Since the inner reactor does not require strict sealing as described above, it can be easily manufactured using a commercially available plate material by a method such as crimping or bolting.

Further, according to the present invention, since the inner reactor is located inside the outer vessel, the differential pressure between the reaction pressure and the ambient pressure is substantially applied to the outer vessel, and the inner reactor is substantially free of pressure. It doesn't matter. Therefore, the inner reactor does not need to have high pressure resistance, and the thickness of the inner reactor can be reduced.

Further, according to the present invention, the highly corrosive reaction mixture is retained in the inner reactor and the outer vessel is not exposed to the highly corrosive reaction mixture. Therefore, the outer container does not need to have high corrosion resistance, and may be made of a material that is held in the gap and that is substantially resistant to the one reaction raw material that comes into contact with the outer container. Therefore, it is possible to select a material having high workability as the material of the outer container. In the present invention, the “material having substantially resistance to one reaction raw material” is the same as the above “material having substantially resistance to reaction” on an industrial scale. When the reaction raw material is held in the gap, it means a material whose corrosion amount is acceptable. For example, those skilled in the art can easily select such a material by exposing a test piece of the intended material to a holding condition assumed when applying the present invention and measuring the amount of corrosion. .

Preferably, the material substantially resistant to the one reaction raw material, that is, the outer container material includes nickel such as Hastelloy (trade name), Inconel (trade name) and Monel (trade name). Alloys, stainless materials, and metal materials such as iron. The metal material has high thermal conductivity, so that the amount of heat required to remove the hydrogen-containing fluorinated hydrocarbon generated by the fluorination reaction in a gaseous state can be sufficiently supplied from the outside to the outside via the outer container. This has the advantage that the temperature can be easily controlled.

The present invention can be carried out in any of a continuous system and a batch system. Specifically, in the case of the batch type, (i) both the reaction materials are supplied to the inner reactor while the one reaction material is held in the gap, and fluorination is performed in the presence of the fluorination catalyst. Perform the reaction. On the other hand, in the case of the continuous type, while the one reaction material is held in the gap, both or any one of the reaction materials is continuously supplied to the inner reactor, and the fluorination is performed in the presence of the fluorination catalyst. Perform the reaction. In the case of the continuous type, the method of continuously supplying the one reaction raw material to the inner reactor includes (ii) a method of continuously supplying the one reaction raw material directly to the inner reactor from outside the reactor (in this case, (Iii) the one reaction material in the gap is maintained and held) and (iii) continuously transferring the one reaction material held in the gap to the inner reactor, and There are two methods of continuously supplying the one reaction material to the gap so as to compensate for the reduced amount of the material.

According to the present invention, if the inner reactor is not completely sealed and some of the reaction mixture can leak into the gap, the reaction mixture leaking from the inner reactor is retained in the gap. The corrosiveness is reduced by dilution with the one reactant being treated, preferably to a degree that is substantially non-corrosive to the outer reactor material. However, when the present invention is carried out by the above methods (i) and (ii), as the operation time becomes longer, the liquid retained in the gap contains the reaction mixture leaked from the inner reactor. Over time, it can accumulate and become more corrosive.
For this reason, it is preferable that the liquid in the gap is at least partially replaced by the new one reactant as necessary. On the other hand, in the case of the above (iii), it is possible to eliminate the necessity of replacing the liquid held in the gap by suitably selecting the reaction conditions and the supply amount of the reaction raw material to the gap. .

In a preferred embodiment of the method of the present invention,
Using the method (iii) above, the step of supplying the one reaction material to the gap is continuously performed, and the step of supplying the one reaction material to the inner reactor is performed by the step of supplying the one reaction material to the gap. It is carried out continuously by feeding one of the reactants to the inner reactor. According to this aspect, the reaction mixture that has leaked into the gap can then be returned to the inner reactor. The supply of the one reaction raw material supplied to the gap to the inner reactor can be performed by overflow described later with reference to FIG. Alternatively, the one reactant can be transferred from the gap to the inner reactor using a pump. In this case, a valve may be provided as needed.

Further, the method of the present invention may further include a step of supplying heat to the reaction mixture to remove a fraction containing a gasified reaction product. Thereby, a reaction product can be selectively taken out from the reaction mixture.

The fluorination catalyst used in the present invention is a halide of at least one element selected from the group consisting of antimony, niobium, and tantalum, and is preferably a chlorinated compound, a fluorinated compound, or a chlorinated fluorinated compound. It is.
The fluorination catalyst may be a mixture of two or more halides having different elements and / or different halogens. Further, the fluorination catalyst has a different valence (ie, other than pentavalent) in addition to the pentavalent halide as described above.
It may further comprise one or more of antimony halides (eg, SbF ₃ which is a trivalent antimony halide as described above), and halides of elements such as titanium and tin. The fluorination catalyst is more preferably SbF ₅ , SbCl ₅ , SbCl
₂ F ₃ , NbClF ₄ , NbF ₅ , TaCl ₅ , TaF
_{And at} least one compound selected from the group consisting of TaClF ₄ .

As the starting material, one or more halogenated hydrocarbon reacting materials selected from the group consisting of chlorinated alkenes and hydrogen-containing chlorinated alkanes are used. Throughout this specification the term "chlorinated alkene" refers to a compound in which at least one of the hydrogen atoms of the alkene has been replaced with a chlorine atom, which may or may not have a hydrogen atom, and which has a fluorine atom. It may or may not have. Further, the term "hydrogenated chlorinated alkane" refers to a compound in which part of a hydrogen atom of a saturated hydrocarbon is replaced with a chlorine atom and has at least one hydrogen atom. It is not necessary. These chlorinated alkenes and hydrogen-containing chlorinated alkanes are preferably 1
-6, more preferably 1-4. It should be understood that throughout this specification, chlorinated alkenes and hydrogen-containing chlorinated alkanes include partially fluorinated compounds of these compounds. The term "partially fluorinated" refers to a chlorinated compound in which some (but not all) of the chlorine atoms have been replaced with fluorine atoms.

Specifically, the chlorinated alkene preferably contains chlorinated ethylene (more preferably, tetrachloroethylene, trichloroethylene), chlorinated propene, chlorinated butene, and partially fluorinated products thereof. The hydrogen-containing chlorinated alkane preferably contains hydrogen-containing chlorinated methane (more preferably, dichloromethane), hydrogen-containing chlorinated ethane, hydrogen-containing chlorinated propane, and partially fluorinated products thereof.

The chlorinated ethylene can be represented by the following general formula _{(1): C 2 H a} F b Cl c (1) ( wherein, a, b and c, a + b + c = 4 , a ≧ 0,
b ≧ 0 and c ≧ 1).

The water Motoshio iodination methane can be represented by the following general formula _{(2): CH d F e} Cl f (2) ( wherein, d, e and f, d + e + f = 4 , d ≧ 1,
e ≧ 0 and an integer satisfying f ≧ 1).

The water Motoshio hydrogenation ethane has the following general formula _{(3): C 2 H g} F h Cl i (3) ( wherein, g, h and i, g + h + i = 6 , g ≧ 1,
h ≧ 0 and i ≧ 1).

The water Motoshio iodination propane has the following general formula _{(4): C 3 H j} F k Cl l (4) ( wherein, j, k and l, j + k + l = 8 , j ≧ 1,
k ≧ 0 and an integer satisfying l ≧ 1).

The chlorination propene has the following general formula _{(5): C 3 H m} F n Cl o (5) ( wherein, m, n and o, m + n + o = 6 , m ≧ 0,
n ≧ 0 and an integer satisfying o ≧ 1).

The chlorination butadiene, the following general formula _{(6): C 4 H p} F q Cl r (6) ( wherein, p, q and r, p + q + r = 6 , p ≧ 0,
q ≧ 0 and an integer satisfying r ≧ 1).

The hydrogenated fluorinated hydrocarbon as the target product is obtained by substituting a part or all of the chlorine atoms of the halogenated hydrocarbon starting material with fluorine atoms, or optionally, at least one of the chlorinated alkenes. A compound having at least one hydrogen atom in which the number of double bonds is reduced by a fluorine atom and a hydrogen atom bonded to a double bond by an addition reaction. Therefore, the target product produced by the fluorination reaction differs depending on the halogenated hydrocarbon as the starting material. Combinations of starting materials and preferred end products are shown below.

When the starting halogenated hydrocarbon reacting material is chlorinated ethylene represented by the above general formula (1), the preferred hydrogen-containing fluorinated hydrocarbon as the target product is represented by the following general formula: _{(7): C 2 H a} + 1 F b + w + 1 Cl c-w (7) ( wherein, a, b, c and w are, a + b + c = 4 , a ≧
0, an integer satisfying b ≧ 0, c ≧ 1 and 0 ≦ w ≦ c). More specifically,
In this case, preferred combinations of the starting material / target substance, that is, the halogenated hydrocarbon / hydrogen-containing fluorinated hydrocarbon include:
Tetrachloroethylene / 2,2-dichloro-1,1,1
-Trifluoroethane, trichloroethylene / 2-chloro-1,1,1-trifluoroethane, vinylidene chloride / 1,1,1-trifluoroethane, vinyl chloride / 1,
1-difluoroethane, 1,1,1-trichloroethane / 1,1,1,1-trifluoroethane and the like are included.

When the halogenated hydrocarbon reaction raw material as the starting material is the hydrogenated chlorinated methane represented by the above general formula (2), the preferred hydrogenated fluorinated hydrocarbon as the target product is as follows: General formula (8): CH _{d Fe + x} Cl _fx (8) (where d, e, f and x are d + e + f = 4, d ≧
1, e ≧ 0, f ≧ 1, and an integer satisfying 1 ≦ x ≦ f)
And hydrogen-containing fluorinated methane represented by More specifically, preferred combinations of halogenated hydrocarbons / hydrogen containing fluorinated hydrocarbons in this case include dichloromethane / difluoromethane and the like.

When the halogenated hydrocarbon reacting raw material which is the starting material is hydrogenated chlorinated ethane represented by the above general formula (3), the preferred hydrogenated fluorinated hydrocarbon as the target product is as follows: formula _{(9): C 2 H g} F h + y Cl i-y (9) ( wherein, g, h, i and y, g + h + i = 6 , g ≧
1, h ≧ 0, i ≧ 1, and an integer satisfying 1 ≦ y ≦ i)
And hydrogen-containing fluorinated ethane represented by the formula: More specifically, preferred combinations of halogenated hydrocarbons / hydrogen-containing fluorinated hydrocarbons in this case include 1,1,1,2-tetrachloroethane / 1,1,1-trifluoro-2-chloroethane and the like. included.

When the halogenated hydrocarbon reaction raw material as the starting material is the hydrogenated chlorinated propane represented by the above general formula (4), the preferred hydrogenated fluorinated hydrocarbon as the target product is as follows: General formula (10): C ₃ H _j F _{k + z} Cl _l-z (10) (where j, k, l and z are j + k + 1 = 8, j ≧
1, an integer satisfying k ≧ 0, l ≧ 1, and 1 ≦ z ≦ l)
It is a hydrogen-containing fluorinated propane represented by these. More specifically, preferred combinations of halogenated hydrocarbons / hydrogen-containing fluorinated hydrocarbons in this case include 1,1,1,3,3-
One or more substituted propane / 1,1,1 selected from the group consisting of pentachloropropane and its partially fluorinated compounds
1,3,3-pentafluoropropane and the like are included.

Here, the partially fluorinated product of 1,1,1,3,3-pentachloropropane is 1,1,1,3,3
-Pentachloropropane in which a part of chlorine atoms are substituted by fluorine atoms, for example, 1,1,3,3-tetrachloro-1-fluoropropane, 1,3,3-trichloro-1,1- Difluoropropane, 3,3-dichloro-1,1,1-trifluoropropane, 3-chloro-
1,1,1,3-tetrafluoropropane and the like can be mentioned.

When the starting halogenated hydrocarbon reaction raw material is a chlorinated propene represented by the above general formula (5), the preferred hydrogen-containing fluorinated hydrocarbon as the target product is represented by the following general formula: (11): C ₃ H _{m + 1} F _{n + u + 1} Cl _ou (11) (where m, n, o and u are m + n + o = 6, m ≧
0, n ≧ 0, o ≧ 1, and an integer satisfying 0 ≦ u ≦ o)
It is a hydrogen-containing fluorinated propane represented by these. More specifically, preferred combinations of halogenated hydrocarbons / hydrogen-containing fluorinated hydrocarbons in this case include 1,1,1,2,3,
One or more substituted propene / 2,2 selected from the group consisting of 3-hexachloropropene and its partially fluorinated compounds
3-dichloro-1,1,1,3,3-pentafluoropropane and the like are included.

Here, the partially fluorinated 1,1,1,2,3,3-hexachloropropene is 1,1,1,1
It refers to 2,3,3-hexachloropropene in which some of the chlorine atoms have been replaced with fluorine atoms.
3-trichloro-1,1,1-trifluoropropene,
Examples thereof include 1,2,3,3-tetrachloro-1,1-difluoropropene and 1,1,2,3,3-pentachloro-1-fluoropropene.

When the starting halogenated hydrocarbon reaction raw material is a chlorinated butadiene represented by the above general formula (6), a hydrogen-containing fluorinated hydrocarbon preferred as a target product is represented by the following general formula: (12): C ₄ H _{p + 1} F _{q + v + 1} Cl _rv (12) (where p, q, r and v are p + q + r = 6, p ≧
0, q ≧ 0, r ≧ 1, and an integer satisfying 0 ≦ v ≦ r)
Is a hydrogen-containing fluorinated butene represented by the formula: More specifically, preferred combinations of halogenated hydrocarbons / hydrogen-containing fluorinated hydrocarbons in this case include 1,1,2,3,4,
4-hexachlorobutadiene / 2-chloro-1,1,1
1,4,4,4-hexafluorobutene and the like are included.

As the amounts of the halogenated hydrocarbon and hydrogen fluoride as the reaction raw materials and the fluorination catalyst, any suitable amounts can be used. The molar ratio of hydrogen fluoride to the halogenated hydrocarbon supplied as a reaction raw material is not less than the stoichiometric ratio, that is, excluding hydrogen fluoride existing in the gap between the outer vessel and the inner reactor, that is, hydrogen fluoride is Preferably, it is in an excessive state. In general, considering the efficiency of the reaction vessel and the loss during the recovery of unreacted hydrogen fluoride, 1
The supply molar ratio of hydrogen fluoride to halogenated hydrocarbon in the range of 10 to 10 moles, particularly 1 to 5 moles is preferable.

The fluorination reaction step is preferably carried out under the condition that at least one of the reactants supplied to the gap is liquid. This fluorination reaction is usually performed under normal pressure or under pressure. The reaction pressure, that is, the pressure in the reactor is preferably a gauge pressure of 0 to 20 kgf.
/ Cm ² (0 to 1.96 MPa), more preferably 5 to 5 cm
It is 15 kgf / cm ² (0.49 to 1.47 MPa). The reaction temperature, that is, the temperature of the reaction mixture is 0 to 175 ° C.
And more preferably 20 to 120 ° C. These reaction pressures and temperatures are exemplary only, and are not intended to limit the present invention to the above ranges.

The reaction step is generally carried out using a reaction raw material or a reaction product as a reaction solvent. To obtain a target product with a high selectivity, hydrogen fluoride as a reaction raw material is reacted with the reaction solvent. It is particularly preferred to use

According to another aspect of the present invention, there is provided a reactor comprising an inner reactor for reacting one reactant and the other reactant, and an outer container disposed outside the inner reactor. An inner reactor made of a material substantially resistant to the reaction, and an outer vessel made of a material substantially resistant to the one reaction raw material. Apparatus arranged with a gap to hold the raw materials, further comprising means for supplying the one reaction raw material to the inner reactor, and means for supplying the other reactive raw material to the inner reactor Is provided. This apparatus can be suitably used to carry out the above-described method for producing a hydrogen-containing fluorinated hydrocarbon of the present invention.

In one embodiment of the reactor of the present invention,
Means for supplying the one reaction material to the inner reactor may be, for example, as described later with reference to FIG.
An overflow structure or a pump means for supplying the one reaction material from the gap to the inner reactor may be used.

In one embodiment of the reactor of the present invention, the means for supplying the other reactant to the inner reactor may be, for example, an inner reactor as described later with reference to FIG. It may be a plug-in tube reaching the interior of the.
According to this aspect, the reaction mixture held in the inner reactor can be stirred without requiring additional means, and higher reaction efficiency can be obtained.

In a preferred embodiment, the reactor of the present invention may further include means for supplying heat to the reaction mixture to gasify a fraction containing the reaction product. This means may be, for example, a jacketed heat exchanger as described below with reference to FIG. Also,
The reactor of the present invention may be connected to a condensing means (such as a condenser) to liquefy the gasified and extracted fraction. Furthermore, if necessary, in order to separate the fraction containing the reaction product taken out of the reaction apparatus into each component, or to separate the target reaction product,
This fraction may be subjected to a distillation operation.

[0050]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the present invention will be described below with reference to the drawings. FIG. 1 shows a reactor according to one embodiment of the present invention. Using this reactor, the method for producing a hydrogen-containing fluorinated hydrocarbon of the present invention is performed. In the embodiment shown in FIG. 1, liquid hydrogen fluoride (HF) is used as the one reaction material, and halogenated hydrocarbon is used as the other reaction material.

The reactor 20 includes an inner reactor 2 for reacting one reactant and the other reactant, and an outer vessel 1 arranged outside the inner reactor. The inner reactor 2 is made of a material which is substantially resistant to the reaction (or to the reaction mixture under the reaction conditions), for example a corrosion-resistant metal, while the outer vessel 1 is And a substantially resistant material, for example a metal. The inner reactor 2 is fixed to the outer vessel 1 with a support 7,
A gap 3 is provided between the outer vessel 1 and the inner reactor 2 for holding the one reaction material.

The outer vessel 1 and the inner reactor 2 serve as means for supplying the one reactant to the inner reactor 2 so that the one reactant flows into the inner reactor 2 from the gap 3 (FIG. 1). (Inflows in the direction indicated by the dotted arrows). The means for supplying the one reaction material to the inner reactor 2 is not limited to the overflow structure, and a pump means "P" or the like schematically shown by a dashed line in the figure may be used. It is possible. Alternatively, while holding the one reactant, a new one reactant is supplied to its source (eg,
It may be supplied directly to the inner reactor from outside the reactor such as a tank.

As shown in FIG. 1, the outer container 1 has an inlet pipe 4 for supplying the one reaction raw material to the gap 3 and an outlet (or discharge pipe) 6 for taking out a reaction product. Is provided. As means for supplying the other reaction material to the inner reactor 2, an insertion pipe (introduction pipe)
5 penetrates the outer vessel 1 and reaches the interior of the inner reactor 2. A jacket heat exchanger having a heat medium inlet 9 and a heat medium outlet 10 is provided outside the outer container 1 as means for supplying heat to the reaction mixture and gasifying a fraction containing a reaction product. 8 is attached.

The other reactant supplied from the insertion tube 5 may be liquid or gaseous. Plug-in tube 5
By supplying the other reaction raw material into the reaction mixture 11 by using, the reaction mixture 11 can be stirred, and the reaction efficiency can be improved. Alternatively, a stirrer or mixer may be provided inside the inner reactor to stir or mix the reaction mixture 11.

Next, a method for continuously producing hydrogen-containing fluorinated hydrocarbons using such a reactor 20 will be described below. First, a fluorination catalyst (not shown) is previously charged into the inner reactor 2, and liquid hydrogen fluoride (HF) is supplied to the lower part of the gap 3 between the outer vessel 1 and the inner reactor 2 through the introduction pipe 4. The supplied hydrogen fluoride overflows as shown by a dotted arrow in FIG. 1 and flows into the inner reactor 2. On the other hand, the halogenated hydrocarbon reactant is fed directly into the inner reactor 2 via the plug-in tube 5.

The one reaction material (hydrogen fluoride in this embodiment) and the other reaction material (halogenated hydrocarbon in this embodiment) thus introduced are combined with each other.
The fluorination reaction is performed in the inner reactor 2 in the presence of a fluorination catalyst to obtain a reaction mixture containing a hydrogen-containing fluorinated hydrocarbon as a reaction product. Heat is supplied to the reaction mixture 11 containing at least the reaction product generated by the fluorination reaction by using the jacket heat exchanger 8. The fraction containing the reaction product gasified by the heat supply is taken out from the outlet 6 provided in the outer container 1, whereby the desired reaction product, that is, the hydrogen-containing fluorinated hydrocarbon can be obtained. .

In the embodiment shown in FIG. 1, heat is supplied to the reaction mixture by the heat medium inlet 9 of the jacket heat exchanger 8.
From the heat medium to the heat medium outlet 10, whereby heat released from the heat exchanger 8 is conducted to the external vessel 1 and the one reaction raw material held in the gap 3 and transmitted to the reaction mixture. This is done by: Therefore, the outer container 1
And preferably, the material of the inner reactor 2 is preferably a metal material having high thermal conductivity as described above.

The fluorination reaction itself is known, and those skilled in the art can easily select the reaction conditions (temperature, pressure, supply amounts of the catalyst and the reaction raw materials, etc.). For example, "ADVANCES IN FLUORI
NE CHEMISTRY vol. 3 "(1963)
Year).

The reactor of the present invention as described above is suitably used for carrying out the method for producing a hydrogen-containing fluorinated hydrocarbon as described above, but is not limited thereto. It can also be used to carry out other reactions which have a very high corrosiveness.

Next, a method of joining the inner reactor when molybdenum is used as the material of the inner reactor 2 will be described with reference to FIGS. FIG. 2 is a perspective view of the inner reactor, and FIG. 3 is a cross-sectional view of the junction of the inner reactor shown in FIG.
It is a partial expanded sectional view along X 'line. The inner reactor 2 of FIG. 2 is manufactured by joining using a commercially available molybdenum plate 12. In FIG. 2, plate members 12 are joined to each other at a joint 13. As a joining method, a bolt fixing method as shown in FIG. 3 is used. The molybdenum plate 12 is joined to each other by bolts 13 and nuts 14.
A seal member 15 is provided between each plate member 12 and the bolts 13 and nuts 14 to enhance the sealing performance at the joint. The inner reactor produced by such a joining method is a plate material 1
Although there is no strict sealing because the two spaces are not sealed, as described above, even if the reaction mixture leaks into the gap outside the inner reactor, the reaction mixture is not The outer reactor does not need to have high corrosion resistance because it is diluted.

[0061]

EXAMPLE 1 In a reactor 20 having the structure described above with reference to FIGS. 1 to 3, a capacity 500 in which the material of the inner reactor 2 was molybdenum and the material of the outer vessel 1 was iron.
A 1 liter reactor 20 was used. This reactor device 20
SbCl ₅ 30 as a fluorination catalyst in the inner reactor 2
kg (1 × 10 ² mol) is placed in a gap 3 between the outer vessel 1 and the inner reactor 2 in 200 liters of liquid hydrogen fluoride (1 × 1
0 ⁴ mol) was previously introduced.

The temperature of the reaction mixture 11 in the inner reactor 2;
That is, while maintaining the reaction temperature at 80 ° C. and the pressure in the reactor 20, that is, the reaction pressure at 1.1 MPa (gauge pressure),
16. Liquid hydrogen fluoride is introduced through the introduction pipe (insertion pipe) 5.
Liquid 1,1,1,3,3-pentachloropropane was supplied as a halogenated hydrocarbon reaction raw material at a rate of 7 kg / hour through the introduction pipe 4 at a rate of 30 kg / hour to progress the liquid phase fluorination reaction.

As described above, a fraction containing gaseous reaction products (including unreacted HF and HCl as a by-product) was obtained from the outlet 6. This fraction is a hydrogen-containing fluorohydrocarbon (corresponding to about 18 kg / hour)
Containing 99% as a main product in a hydrogen-containing fluorohydrocarbon.
Mol% or more of 1,1,1,3,3-pentafluoropropane, and trace amounts (less than 1 mol%) of 1,1,1,3-tetrafluoro-3-chloropropane and 1, 1,1-trifluoro-3,3-dichloropropane was included.

After operating for 500 hours under the above conditions, corrosion of the outer container 1 was visually inspected, but no corrosion of the outer container was observed.

(Example 2) The same reaction apparatus as that used in Example 1 was used. Hereinafter, unless otherwise specified, it is the same as the first embodiment, and the same applies to the following third to fifth embodiments.

As a fluorination catalyst, TaCl ₅ 36 kg
(1 × 10 ² mol) was introduced in advance, and 200 liters (1 × 10 ⁴ mol) of liquid hydrogen fluoride was supplied as in Example 1. Next, while maintaining the reaction temperature at 80 ° C. and the reaction pressure at 1.1 MPa (gauge pressure) in the same manner as in Example 1, the liquid hydrogen fluoride was passed through the introduction pipe (insertion pipe) 5 for 3 hours.
At 9.2 kg / hour, liquid 1,1,1,2,3,3-hexachloropropene is supplied as a halogenated hydrocarbon reaction raw material at a rate of 34.5 kg / hour through the introduction pipe 4 to advance the liquid phase fluorination reaction. I let it.

As described above, a fraction containing a hydrogen-containing fluorinated hydrocarbon (corresponding to about 27.5 kg / hour) was obtained. In this fraction, 99 mol% or more of 1,1,1,3,
It contains 3-pentafluoro-2,3-dichloropropane, and traces (less than 1 mol%) of 1,1, as a by-product.
1,3-tetrafluoro-2,3,3-trichloropropane was included.

After operating for 500 hours under the above conditions, corrosion of the external container was visually inspected. In this example, no corrosion of the external container was observed at all.

Example 3 As in Example 1, 30 kg (1 × 10 ² mol) of SbCl ₅ and 200 liters of liquid hydrogen fluoride (1 × 10 ⁴ mol) were used as a fluorination catalyst.
l) was previously introduced. Next, as in Example 1, the reaction temperature was set to 80 ° C., and the reaction pressure was maintained at 1.1 MPa (gauge pressure).
At 1 kg / hour, liquid trichlorene, ie, trichloroethylene, was supplied as a halogenated hydrocarbon reaction raw material at 18.2 kg / hour through an introduction pipe (insertion pipe) 5 to advance the liquid phase fluorination reaction.

As described above, a fraction containing a hydrogen-containing fluorinated hydrocarbon (corresponding to about 15.9 kg / hour) was obtained. This fraction contains 99% by mole or more of 1,1,1-trifluoro-2-chloroethane as the main product in the hydrogen-containing fluorohydrocarbon, and traces (less than 1% by mole) as the by-product. 1,1-difluoro-1,2-
Dichloroethane was included.

After operating for 500 hours under the above conditions, the corrosion of the external container was visually inspected. In this example, no corrosion of the external container was observed at all.

Example 4 As in Example 1, 30 kg (1 × 10 ² mol) of SbCl ₅ and 200 liters of liquid hydrogen fluoride (1 × 10 ⁴ mol) were used as a fluorination catalyst.
l) was previously introduced. Next, the reaction temperature was set to 100 ° C.
While maintaining the reaction pressure at 1.5 MPa (gauge pressure), 14.8 liquid hydrogen fluoride was introduced through the inlet pipe (insertion pipe) 5.
Liquid perfluorin, ie, tetrachloroethylene, was supplied as a halogenated hydrocarbon reaction raw material at a rate of 23.0 kg / hour at a rate of 23.0 kg / hour at a rate of 23.0 kg / hour to progress the liquid phase fluorination reaction.

As described above, a fraction containing a hydrogen-containing fluorinated hydrocarbon (corresponding to about 19.8 kg / hour) was obtained. This fraction contains 99% by mole or more of 1,1,1-trifluoro-2,2-dichloroethane as a main product in a hydrogen-containing fluorohydrocarbon, and a trace amount (less than 1% by mole) as a by-product. 1,1-Difluoro-)
2,3-dichloroethane was included.

After operating for 500 hours under the above conditions, corrosion of the external container was visually inspected. In this example, no corrosion of the external container was observed at all.

Example 5 As in Example 1, 30 kg (1 × 10 ² mol) of SbCl ₅ and 200 liters (1 × 10 ⁴ mol) of hydrogen fluoride were used as a fluorination catalyst.
Was introduced in advance. Next, while maintaining the reaction temperature at 100 ° C. and maintaining the reaction pressure at 1.1 MPa (gauge pressure), 22.0 kg of liquid hydrogen fluoride was passed through the introduction pipe (insertion pipe) 5.
/ Hour, liquid 1,
1,2,3,4,4-Hexachlorobutadiene was supplied at a rate of 36.2 kg / hour through the introduction pipe 4 to advance the liquid phase fluorination reaction.

As described above, a fraction containing a hydrogen-containing fluorinated hydrocarbon (corresponding to about 26.9 kg / hour) was obtained. In this fraction, 98 mol% or more of 1,1,1,4,
4,4-hexafluoro-2-chlorobutene,
A small amount (less than 2 mol%) of butenes whose fluorination had not progressed was contained as a by-product.

After operating for 500 hours under the above conditions, corrosion of the external container was visually inspected. In this example, no corrosion of the external container was observed at all.

[0078]

According to the present invention, a reaction product of hydrogen fluoride and one or more halogenated hydrocarbons in the presence of a fluorination catalyst is used to contain a hydrogen-containing fluorinated hydrocarbon as a reaction product. Disclosed is a method for producing a hydrogen-containing fluorinated hydrocarbon for obtaining a reaction mixture, which is an economical and novel production method in which the problem of reactor corrosion is improved, and a reaction apparatus which can be suitably used in this method. You.

[Brief description of the drawings]

FIG. 1 is a schematic vertical sectional view illustrating one embodiment of the present invention.

FIG. 2 is a perspective view of the inner reactor illustrating a junction of the inner reactor used in one embodiment of the present invention.

FIG. 3 is a partially enlarged cross-sectional view taken along line XX ′ of a junction of the inner reactor of FIG. 2;

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Outer container 2 Inner reactor 3 Gap 4 Introducing pipe 5 Introducing pipe (insertion pipe) 6 Outlet part 7 Post 8 Jacket type heat exchanger 9 Heat medium inlet 10 Heat medium outlet 11 Reaction mixture 12 Plate material 13 Bolt 14 Nut 15 Sealing material 20 reactor

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C07B 61/00 300 C07B 61/00 300 (72) Inventor Shun Shibanuma No. 1 Nishiichitsuya, Settsu-shi, Osaka No. 1 Daikin Industries, Ltd. Yodogawa Works F term (reference) 4H006 AA02 AC30 BA12 BA13 BA37 BD83 BE01 EA02 EA03 4H039 CA51 CF10 CL60

Claims (24)

[Claims] 1. A material selected from the group consisting of a hydrogen fluoride reaction raw material and a chlorinated alkene and a hydrogen-containing alkane chloride.
A process for producing a hydrogenated fluorinated hydrocarbon, comprising reacting at least one halogenated hydrocarbon reactant in the presence of a fluorination catalyst to obtain a reaction mixture containing the hydrogenated fluorinated hydrocarbon as a reaction product: In the gap between the inner reactor made of a material substantially resistant to the reaction and the outer container arranged outside the inner reactor and made of a material substantially resistant to at least one reaction raw material. Supplying the one reactant; supplying the one reactant to the inner reactor; supplying the other reactant to the inner reactor; and supplying both reactants in the inner reactor. Reacting in the presence of a fluorination catalyst to obtain a reaction product containing a hydrogen-containing fluorinated hydrocarbon. 2. The step of supplying the one reactant to the gap is continuously performed, and the step of supplying the one reactant to the inner reactor includes the step of supplying the one reactant supplied to the gap to the inner side. The method of claim 1, wherein the method is performed continuously by feeding to a reactor. 3. The method according to claim 1, further comprising the step of supplying heat to the reaction mixture to remove a fraction containing the gasified reaction product. 4. The method according to claim 1, wherein said one reactant is a hydrogen fluoride reactant, and said other reactant is a halogenated hydrocarbon reactant. 5. The method according to claim 1, wherein said one reactant is a halogenated hydrocarbon reactant and said other reactant is a hydrogen fluoride reactant. 6. The fluorination catalyst is SbF ₅ , SbC
_{l 5, SbCl 2 F 3,} NbClF 4, NbF 5, Ta
Cl _5, TaF _5, and TaClF is one or more compounds selected from the group consisting of _4, The method according to claim 1. 7. A halogenated hydrocarbon reaction raw material of the general formula _{(1): C 2 H a} F b Cl c (1) ( wherein, a, b and c, a + b + c = 4 , a ≧ 0,
The method according to any one of claims 1 to 6, wherein the chlorinated ethylene is represented by the following formula: b ≥ 0 and c ≥ 1. 8. halogenated hydrocarbon reaction raw material of the general formula _{(2): CH d F e} Cl f (2) ( wherein, d, e and f, d + e + f = 4 , d ≧ 1,
The method according to any one of claims 1 to 6, wherein the chlorinated methane is a hydrogen-containing methane represented by an integer satisfying e ≧ 0 and f ≧ 1). 9. halogenated hydrocarbon reaction raw material of the general formula _{(3): C 2 H g} F h Cl i (3) ( wherein, g, h and i, g + h + i = 6 , g ≧ 1,
The method according to any one of claims 1 to 6, which is a hydrogen-containing chlorinated ethane represented by the following formula: h ≥ 0 and i ≥ 1. 10. A halogenated hydrocarbon reaction raw material of the general formula _{(4): C 3 H j} F k Cl l (4) ( wherein, j, k and l, j + k + l = 8 , j ≧ 1,
The method according to any one of claims 1 to 6, which is a hydrogen-containing chlorinated propane represented by the formula (1): k ≧ 0 and l ≧ 1). 11. halogenated hydrocarbon reaction raw material of the general formula _{(5): C 3 H m} F n Cl o (5) ( wherein, m, n and o, m + n + o = 6 , m ≧ 0,
The method according to any one of claims 1 to 6, which is a chlorinated propene represented by the following formula: n ≧ 0 and an integer satisfying o ≧ 1). 12. halogenated hydrocarbon reaction raw material of the general formula _{(6): C 4 H p} F q Cl r (6) ( wherein, p, q and r, p + q + r = 6 , p ≧ 0,
The method according to any one of claims 1 to 6, which is a chlorinated butadiene represented by the following formula: q≥0 and r≥1). 13. The halogenated hydrocarbon reaction raw material is tetrachloroethylene, and the hydrogen-containing fluorinated hydrocarbon produced by the reaction is 2,2-dichloro-1,1,1-trifluoroethane. the method of. 14. The method according to claim 7, wherein the halogenated hydrocarbon reactant is trichloroethylene, and the hydrogen-containing fluorinated hydrocarbon produced by the reaction is 2-chloro-1,1,1-trifluoroethane. . 15. The method according to claim 8, wherein the halogenated hydrocarbon reaction raw material is dichloromethane, and the hydrogen-containing fluorinated hydrocarbon produced by the reaction is difluoromethane. 16. The halogenated hydrocarbon reaction raw material is 1,
One or more substituted propanes selected from the group consisting of 1,1,3,3-pentachloropropane and partially fluorinated compounds thereof, wherein the hydrogen-containing fluorinated hydrocarbon produced by the reaction is 1,1,1,3,3. The method according to claim 10, which is 3-pentafluoropropane. 17. The halogenated hydrocarbon reaction raw material is 1,
One or more substituted propenes selected from the group consisting of 1,1,2,3,3-hexachloropropene and partially fluorinated compounds thereof, wherein the hydrogen-containing fluorinated hydrocarbon produced by the reaction is 2,3-dichloro- The method according to claim 11, which is 1,1,1,3,3-pentafluoropropane. 18. The halogenated hydrocarbon reacting raw material is 1,
1,2,3,4,4-hexachlorobutadiene,
The method according to claim 12, wherein the hydrogen-containing fluorinated hydrocarbon produced by the reaction is 2-chloro-1,1,1,4,4,4-hexafluorobutene. 19. A reactor comprising an inner reactor for reacting one reactant and the other reactant, and an outer vessel disposed outside the inner reactor, wherein the reactor is substantially free of reaction. An inner reactor made of a material that is chemically resistant, and an outer container made of a material that is substantially resistant to the one reaction material are used to hold the one reaction material therebetween. An apparatus arranged with a gap, further comprising: means for supplying the one reactant to the inner reactor; and means for supplying the other reactant to the inner reactor. 20. The means for supplying the one reactant to the inner reactor is an overflow structure or a pump means for supplying the one reactant held in the gap to the inner reactor from the gap. Item 20. The device according to Item 19. 21. The apparatus according to claim 19, further comprising means for supplying heat to the reaction mixture to gasify a fraction containing the reaction product. 22. Apparatus according to claim 19, wherein the means for supplying the other reactant to the inner reactor is a bayonet tube reaching the interior of the inner reactor. 23. The method according to claim 1, wherein the method according to claim 19 is used. 24. The material according to claim 19, wherein the material substantially resistant to the reaction is a corrosion-resistant metal containing at least one metal selected from the group consisting of molybdenum and tungsten. Equipment.