WO2020218340A1 - Method for producing hydrochlorofluorocarbon, method for producing 1-chloro-2,3,3-trifluoropropene, and method for producing 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene - Google Patents

Abstract

The present invention provides a method for producing HCFC, the method being capable of producing HCFC at high selectivities. A method for producing hydrochlorofluorocarbon according to the present invention is characterized by producing a hydrochlorofluorocarbon given by formula (2) by the reaction, in the presence of a catalyst, of hydrogen chloride with a hydrofluorocarbon given by formula (1): X-L-Y formula (1), and X-L-Z formula (2), where X represents -CH_aF_(3-a), Y represents -CH_bF_(3-b), and Z represents -CH_bCl_cF_(3-b-c).

Description

Production method of hydrochlorofluorocarbon, production method of 1-chloro-2,3,3-trifluoropropene, production of 1-chloro-2,3,3,4,5,5-heptafluoro-1-pentene Method

The present invention is a method for producing hydrochlorofluorocarbon, a method for producing 1-chloro-2,3,3-trifluoropropene, 1-chloro-2,3,3,4,5,5-heptafluoro-1. -Regarding the manufacturing method of pentene.

In recent years, hydrochlorofluoroolefins (HCFOs) have attracted attention as compounds that have little impact on the global environment and can be used in various applications such as cleaning agents, refrigerants, working fluids, propellants, heat media, foaming agents, and solvents. Among HCFO, high nonflammable, as compounds having excellent above applications 1-chloro-2,3,3,3-tetrafluoropropene _{(CF 3 -CF = CClH, HCFO} -1224yd) and 1-chloro-2, HCFOs in which a chlorine atom is bonded to the terminal carbon of a carbon-carbon double bond, such as 3,3-trifluoropropene (CF ₂ H-CF = CCLH, HCFO-1233yd), are known.
In the present specification, for halogenated hydrocarbons, the abbreviation of the compound is described in parentheses after the compound name, but in the present specification, the abbreviation is used instead of the compound name as necessary. Further, as an abbreviation, only the number after the hyphen (−) and the lowercase alphabetic part (for example, “1233yd” in “HCFO-1233yd”) may be used.

International Publication No. 1990/0087754

The present inventors have carbon-carbon as long as it is a hydrochlorofluorocarbon (hereinafter, also referred to as “HCFC”) having a specific structure (-CF _2- CH _b Cl _c F _(3-bc) ) described later. It was found that HCFO in which a chlorine atom is bonded to the terminal carbon of a double bond can be efficiently synthesized.
As a method for producing an HCFC having the specific structure, for example, Patent Document 1 describes a method of reacting an HCFC having a difluoromethylene group with hydrogen fluoride to fluorinate the HCFC. However, with the production method described in Patent Document 1, it is difficult to control the fluorination reaction, and it is difficult to selectively obtain HCFC having the above specific structure, and a method capable of obtaining HCFC with a higher selectivity is desired. Was there.
As described above, a more efficient method is desired for the production of HCFC. In particular, from an industrial point of view, it is desirable that HCFCs can be produced with a high selectivity from hydrofluorocarbons, which are relatively easy to synthesize.
An object of the present invention is to provide a method for producing HCFC, which can produce HCFC with a high selectivity.
Further, the present invention relates to a method for producing 1-chloro-2,3,3-trifluoropropene, and 1-chloro-2,3,3,4,5,5-heptafluoro-1-pentene. Providing a manufacturing method is also an issue.

As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by the following configuration.

(1) In the presence of a catalyst, hydrofluorocarbon represented by the formula (1) described later is reacted with hydrogen chloride to produce hydrochlorofluorocarbon represented by the formula (2) described later. A method for producing hydrochlorofluorocarbons.
(2) The production method according to (1), wherein the catalyst is a metal-containing catalyst.
(3) The catalyst contains one or more selected from metal oxides, partial halides of metal oxides and metal halides, and the metal oxides, partial halides of metal oxides and metal halides are respectively. The production method according to (1) or (2), which comprises at least one selected from Cr and Al.
(4) The production method according to (3), wherein the catalyst contains a partially halide of a metal oxide.
(5) L _{is, -CF 2 -, - CF 2} CF 2 -, - CF 2 -CF 2 -CF 2 -, - CF 2 -CHF-CF 2 - or _{-CF 2 -CH} 2 _-CF 2 - with The production method according to any one of (1) to (4).
(6) The production method according to any one of (1) to (5), wherein a is 1, b is 2, and c is 1.
(7) The production method according to any one of (1) to (6), wherein the hydrofluorocarbon represented by the formula (1) and hydrogen chloride are reacted in a gas phase.
(8) The production method according to any one of (1) to (7), wherein the reaction temperature is 100 to 450 ° C.
(9) The production method according to any one of (1) to (8), wherein the molar ratio of hydrogen chloride to the hydrofluorocarbon represented by the formula (1) is 0.5 to 2.0.
(10) A reaction is carried out using a raw material composition containing hydrofluorocarbon represented by the formula (1) and hydrogen chloride, and the water content of the raw material composition is 5000 mass ppm or less, (1) to (1). The manufacturing method according to any one of 9).
(11) The production method according to (10), wherein the water content is 400 mass ppm or less.
(12) The hydrofluorocarbon represented by the formula (1) is 1,1,2,2,3-pentafluoropropane.
The production method according to any one of (1) to (11), wherein the hydrochlorofluorocarbon represented by the formula (2) is 3-chloro-1,1,2,2-tetrafluoropropane.
(13) 3-Chloro-1,1,2,2-tetrafluoropropane produced by the method according to (12) is subjected to a hydrogen fluoride reaction to 1-chloro-2,3,3-trifluoropropene. A method for producing 1-chloro-2,3,3-trifluoropropene, which comprises producing 1-chloro-2,3,3-trifluoropropene.
(14) The hydrofluorocarbon represented by the formula (1) is 1,1,2,2,3,3,4,5-nonafluoropentane.
Described in any of (1) to (11), wherein the hydrochlorofluorocarbon represented by the formula (2) is 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane. Manufacturing method.
(15) 5-Chloro-1,1,2,2,3,3,4,5-octafluoropentane produced by the method according to (14) is subjected to a hydrogen fluoride reaction to 1-chloro-2. , 3,3,4,5,5-Heptafluoro-1-pentene, 1-chloro-2,3,3,4,5,5-Heptafluoro-1 -Pentene manufacturing method.

According to the present invention, it is possible to provide a method for producing HCFC, which can produce HCFC with a high selectivity.
Further, according to the present invention, a method for producing 1-chloro-2,3,3-trifluoropropene and 1-chloro-2,3,3,4,5,5-heptafluoro-1-. A method for manufacturing pentene can be provided.

It is a schematic diagram which shows the reaction apparatus.

The method for producing a hydrochlorofluorocarbon of the present invention (hereinafter, also simply referred to as “the production method of the present invention”) is a hydrofluorocarbon represented by the formula (1) described later (hereinafter, “Compound 1”) in the presence of a catalyst. It is also described as) and hydrogen chloride to react to produce hydrochlorofluorocarbon represented by the formula (2) (hereinafter, also referred to as “Compound 2”). That is, the production method of the present invention is a method of producing compound 2 by contacting compound 1 with hydrogen chloride in the presence of a catalyst.
In the following, first, the components used in the production method of the present invention will be described in detail, and then the procedure of the production method will be described in detail.
As the description of the components, compound 1 and compound 2 will be described in detail first.

Compound 1 is a compound represented by the formula (1).
Equation (1) XLY
X represents −CH _a F _(3-a) .
a represents 0 or 1.

Y represents -CH _b F _(3-b) .
b represents 1 or 2.
However, when a is 0, b represents 1 or 2, and when a is 1, b represents 2.
That is, examples of the compound 1 include CF _3- L-CHF ₂ , CF _3- L-CH ₂ F, and CHF _2- L-CH ₂ F.

L _{is, -CF 2 -, - CF 2} CF 2 -, or carbon atoms, which may at least part of the hydrogen atoms are substituted by fluorine atoms is a fluoroalkylene group having 3 to 6 carbon atoms 3 All of the ends of the fluoroalkylene groups of to 6 are -CF _2- .
Even -CF 2 Any terminus of the fluoroalkylene group _- and, -CF 2 at both ends in the fluoroalkylene group _- is meant to position, for example, as the fluoroalkylene group having a carbon number of 3 _{is, -CF 2 -CF 2 -CF 2 -} , - CF 2 -CH 2 -CF 2 -, - CF 2 -CFH-CF 2 - and the like.
The _{L, -CF 2 -, - CF} 2 CF 2 -, - CF 2 -CF 2 -CF 2 -, - CF 2 -CHF-CF 2 - and _{-CF 2 -CH} 2 _-CF 2 - are preferred, _-CF 2 is a perfluoroalkylene group -, - _{CF 2 CF} 2 - and _-CF 2 _-CF 2 -CF ₂ - is more preferable.

The compound produced from compound 1 as a raw material is a compound represented by the formula (2).
Equation (2) XLZ
Z represents -CH _b Cl _c F _(3-bc) .
b represents 1 or 2.
c represents 1 or 2.
However, when b is 1, c represents 1 or 2, and when b is 2, c represents 1.
That is, as the _{Z, -CHClF, -CHCl 2, -CH} 2 Cl and the like.

The relationship between a, b, and c is expressed as shown in Table 1 below. In Table 1, "X", "Y", and "Z" correspond to "X", "Y", and "Z" in the above-mentioned equations (1) and (2).
Further, the "X", "Y", and "Z" columns in Table 1 represent the numerical values that can be taken by a, b, and c, and the structure in that case. For example, "(a = 0) CF ₃ " means that when a is 0, X represents CF ₃ .

In the production method of the present invention, by reacting compound 1 with hydrogen chloride in the presence of a catalyst, the fluorine atom bonded to the carbon atom located at the terminal of compound 1 can be replaced with a chlorine atom. At that time, the fluorine atom substituted with the terminal carbon atom having a small number of substitutions of the fluorine atom among both ends can be selectively substituted with the chlorine atom. In the production method of the present invention, when X and Y in the formula (1) are compared, the number of substitutions of fluorine atoms in Y is smaller, and the substitution of fluorine atoms and chlorine atoms proceeds at the position of Y.
Further, the number of substitutions of fluorine atoms to chlorine atoms can be controlled by adjusting the reaction conditions and the like. For example, as shown in Table 1, when Y is CHF ₂ , one fluorine atom is replaced with a chlorine atom to form CHClF, or two fluorine atoms are replaced with a chlorine atom to form CHCl _2. Will be done.
More specifically, the relationship of a, b, and c described above represents the case of aspects 1 to 4 in Table 1 above. For example, in the case of "Aspect 4", Compound 1 than the "X" column and "Y" column is _CHF 2 -L-CH ₂ F, "X" column and "Z" column from compound 2 CHF ₂ - It means that it becomes L-CH ₂ Cl.
That is, in the production method of the present invention, a, b, and c can take the following four aspects.
(Aspect 1) a is 0, b is 1, and c is 1.
(Aspect 2) a is 0, b is 1, and c is 2.
(Aspect 3) a is 0, b is 2, and c is 1.
(Aspect 4) a is 1, b is 2, and c is 1.
The production method of the present invention can be particularly preferably used for a reaction in which only one fluorine atom of compound 1 is replaced with a chlorine atom. For example, when 1,1,2,2,3-pentafluoropropane is used as compound 1, 3-chloro-1,1,2,2-tetrafluoropropane (HCFC-244ca) can be produced as compound 2. Further, for example, when 1,1,2,2,3,3,4,5-nonafluoropentane (HFC-449pccc) is used as compound 1, 5-chloro-1,1,2 as compound 2 , 2,3,3,4,5-octafluoropentane (HCFC-448occc) can be produced.

In the production method of the present invention, compound 1 contributes to the reaction as described above. A raw material composition containing compound 1 may be used as a raw material. The compound 1 may be two or more kinds.
The raw material composition may contain impurities in addition to compound 1. Examples of impurities include raw materials for producing compound 1, by-products generated in addition to compound 1 when producing compound 1, water, and the like. When the raw material composition contains the above impurities, by-products generated from the impurities may be removed by known means such as distillation, extraction distillation, azeotropic distillation, membrane separation, two-layer separation, and adsorption. .. The impurities are preferably compounds that are inert under the reaction conditions of the present invention.

The raw material composition is preferably dehydrated before being used in the reaction because the conversion rate of compound 1 is more excellent. That is, in the reaction, it is preferable to use a raw material composition that has been dehydrated.
The water content (water content) of the raw material composition used in the reaction is preferably 5000 mass ppm or less, more preferably 2000 mass ppm or less, further preferably 400 mass ppm or less, and particularly preferably 200 mass ppm or less. The lower limit is 0 mass ppm.
Here, ppm represents parts per million.
The water content is measured using a Karl Fischer moisture meter. A trace moisture measuring device (manufactured by Mitsubishi Chemical Analytech Co., Ltd., CA-200 type) is used as a Karl Fischer moisture meter, and a liquefied gas vaporizer (manufactured by the same company, model number: VG-200 type) is connected to the sample introduction part. , The raw material composition after the dehydration treatment in a preset amount is vaporized and automatically injected into the moisture meter.

Compound 1 is contained as a main component in the raw material composition used for the reaction. The main component means that the content of the compound 1 is 50% by mass or more, preferably 60% by mass or more, and more preferably 75% by mass or more, based on the total mass of the raw material composition. The upper limit is 100% by mass.

The method for dehydrating the raw material composition is not particularly limited, and examples thereof include distillation and a method using a dehydrating agent. When a dehydrating agent is used, the dehydrating agent is brought into contact with the raw material composition to reduce the water content in the raw material composition.
Examples of the dehydrating agent include zeolite, molecular sieve, alumina, calcium chloride, magnesium sulfate, sodium sulfate, calcium sulfate, and potassium carbonate.

Hydrogen chloride is a gas at normal temperature and pressure. Hydrogen chloride may be used by dissolving it in water at the time of handling.
In the reaction, it is preferable to use hydrogen chloride that has been dehydrated.

As the catalyst in the production method of the present invention, a metal-containing catalyst is preferable. Specific examples of the metal-containing catalyst include simple metals, metal oxides, partial halides of metal oxides, and metal halides. The partial halide of the metal oxide is a compound in which a part of the metal oxide is halogenated (F, Cl, Br, I, etc.). The metal halide is a compound composed of a metal and a halogen. The partial halide and the metal halide of the metal oxide may contain only one kind of halogen, or may contain two or more kinds of halogens.
As the catalyst, two or more kinds may be used in combination.

As the partial halide of the metal oxide, a partial fluoride of the metal oxide in which the metal oxide is fluorinated is preferable. In this case, the partial fluoride of the metal oxide may contain a halogen other than fluorine.
Further, as the metal halide, metal fluoride is preferable. The metal fluoride may contain halogens other than fluorine.

The metal elements contained in the elemental metal, the metal oxide, and the metal halide include Li, Na, K, Cs, Mg, Ca, Sr, Ba, Al, Cr, and Zr in terms of improving the reactivity. , Fe, Ni, Co, Zn, Mn, Sb, Nb, and Ta are preferred, and at least one selected from Al, Zn, Cr, Mg, Ca, K, Zr, and Li. Is more preferable, and at least one selected from Al, Zn, Cr, Mg, and Zr is further preferable.

Among them, the catalyst contains one or more selected from metal oxides, partial halides of metal oxides, and metal halides from the viewpoint that compound 2 can be produced with a higher selectivity. It is preferable that the partially halide of the metal oxide and the metal halide each contain at least one metal element selected from Cr and Al (hereinafter, also referred to as "metal A"). That is, the catalyst preferably contains one or more selected from a metal oxide containing a metal A, a partial halide of the metal oxide containing the metal A, and a metal halide containing the metal A. The metal oxide, a partial halide of the metal oxide, and the metal halide may contain both Cr and Al.
Among them, the catalyst more preferably contains a partial halide of a metal oxide containing a metal A.

Among the catalysts containing the metal A, a metal oxide containing Cr, a partial halide of the metal oxide containing Cr, or a metal halide containing Cr is used because the conversion rate of compound 1 is higher. preferable.

When a metal oxide containing metal A, a partial halide of the metal oxide, or a metal halide is used as the catalyst, the catalyst uses a metal other than metal A for various purposes such as improving durability. It may be included.
Specific examples of other metals include Na, K, Mg, Ca, Zr, Fe, Zn, Ni, Co and Mn. Of these, Na, K, Mg, Zn, or Mn is preferable, and Mg or Zn is even more preferable, from the viewpoint of increasing the physical and chemical durability of the catalyst and producing the compound 2 more efficiently.
When the catalyst contains a metal other than metal A, the conversion rate of compound 1 is more excellent. As the other metal, Na, K, Mg, Zn, or Mn is preferable, and Mg or Zn is more preferable, from the viewpoint of further improving the conversion rate.

When Cr is contained in the catalyst, the Cr content is preferably 1% by mass or more based on the total mass (100% by mass) of the metal contained in the catalyst from the viewpoint of improving the conversion rate of Compound 1. More than% by mass is more preferable, and 10% by mass or more is further preferable. The upper limit is 100% by mass.
When Al is contained in the catalyst, the Al content is preferably 5% by mass or more, preferably 5% by mass or more, based on the total mass (100% by mass) of the metal contained in the catalyst, from the viewpoint of improving the conversion rate of Compound 1. It is more preferably mass% or more, and further preferably 50% by mass or more. The upper limit is 100% by mass.
When the catalyst contains a metal other than the metal A, the content of the metal A is preferably 90 to 99.9% by mass, more preferably 95 to 99% by mass, based on the total mass of the metal (100% by mass). preferable. On the other hand, the metal other than the metal A is preferably 0.1 to 10% by mass, more preferably 1 to 5% by mass, based on the total mass of the metal (100% by mass).

The water content of the catalyst used in the reaction is preferably low. Specifically, the catalyst is placed in the reactor, N ₂ is supplied into the reactor so as to be 3.94 NmL / min per 1 g of the catalyst, and the water content in the gas obtained from the reactor outlet is 100. The volume is preferably ppm or less, and more preferably 50 volume ppm or less.

Specific examples of the catalyst include a partially fluorinated chromium-zinc composite oxide (partial fluoride of the chromium-zinc composite oxide) and a partially fluorinated chromium-aluminum-magnesium composite oxide (of the chromium-aluminum-magnesium composite oxide). (Partial fluoride), partially fluorinated alumina (partial fluoride of alumina), and partially fluorinated chromium oxide (partial fluoride of chromium oxide). Among them, the partially fluorinated chromium-zinc composite oxide (partial fluoride of the chromium-zinc composite oxide) and the partially-fluorinated chromium oxide (of the chromium oxide) because the conversion rate of the compound 1 is excellent. Partial fluoride) is preferred.

The catalyst may be molded into pellets and used, or may be supported on a carrier and used in order to improve the reactivity.
Examples of the carrier include carbon materials such as activated carbon, carbon black and carbon fiber, and oxide materials such as alumina, silica, titania, zirconia, alkali metal oxide and alkaline earth metal oxide, and activated carbon, alumina, silica and the like. Zirconia, alkali metal oxides, and alkaline earth metal oxides are preferred. Among these, activated carbon, alumina, and zirconia are more preferable because they have a large specific surface area and can easily support a catalyst.

Examples of the method for molding the catalyst into pellets include a method in which the catalyst is crushed into powder and molded by a locking machine or the like.
As the pellet-shaped catalyst, for example, a columnar catalyst having a diameter of about 3.0 mm and a height of about 4.0 mm can be used. In addition, a binder may be mixed with the catalyst, if necessary. The amount of the binder used is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 10 parts by mass or less with respect to 100 parts by mass of the catalyst. In this case, a pellet-shaped catalyst can be molded from a mixture of the catalyst and the binder by a locking machine or the like.
Specific examples of the binder include carbon, cellulose, alumina, and silica.

The catalyst is preferably pre-dried in an inert atmosphere (eg, in a nitrogen stream) in order to improve reactivity. From the viewpoint of simplifying the operation and improving the work efficiency, the catalyst may be dried in the same manner as described above while being contained in the reactor.
Alternatively, the catalyst may be dried before being pre-contained in the reactor.

The specific surface area of the catalyst depends on the type of each catalyst. Generally, the smaller the specific surface area, the lower the conversion rate, and the larger the specific surface area, the lower the selectivity and the faster the deterioration.
For example, when the binder is not used, the specific surface area of the metal oxide and the partial halide of the metal oxide is preferably 10 to 400 m ² / g, and the specific surface area of the metal halide is 3 to 300 m ² / g. preferable.
When the above binder is used, it cannot be said unconditionally because it depends on the specific surface area of the binder. For example, when a carbon binder having a high specific surface area is used, the specific surface area of the mixture of the catalyst and the carbon binder is 20 to 20 to. About 1200 m ² / g is preferable.
In this specification, the specific surface area is a value measured by the BET method.

Further, the catalyst is preferably subjected to an activation treatment in advance from the viewpoint of improving reactivity (particularly, improving the conversion rate of compound 1). Examples of the activation treatment method include a method in which the catalyst is brought into contact with the activation treatment agent under heating or non-heating. Examples of the activating treatment agent include halogen-containing compounds, and specific examples thereof include hydrogen chloride, hydrogen fluoride, chlorocarbon, fluorocarbon, chlorofluorocarbon, hydrochlorocarbon, hydrofluorocarbon, hydrochlorofluorocarbon, chloroolefin, and fluoroolefin. , Chlorofluoroolefin, hydrofluoroolefin, hydrochloroolefin, hydrochlorofluoroolefin and the like. Moreover, you may use compound 1 which is a raw material as a halogen-containing compound.
By subjecting the metal oxide to the above activation treatment, a partial halide of the metal oxide can be produced.

The catalyst may be activated before being contained in the reactor, but it is preferable to perform the activation treatment in the state of being contained in the reactor because the operation is simple and the work efficiency is good. Therefore, it is preferable to introduce the activation treatment agent into the reactor containing the catalyst to perform the activation treatment. The activating treatment agent may be introduced into the reactor at room temperature, but it is preferable to adjust the temperature by heating or the like when introducing the activating treatment agent into the reactor from the viewpoint of efficient activation treatment. When introducing the activation treatment agent, an inert gas (diluted gas) may be introduced together. Specific examples of the diluent gas include nitrogen, carbon dioxide, helium, and argon.
Further, in order to increase the efficiency of the activation treatment, it is preferable to carry out the activation treatment in a state where the inside of the reactor is heated. At that time, the temperature of the reactor when supplying the activation treatment agent is preferably 50 to 500 ° C, more preferably 100 to 400 ° C, and even more preferably 150 to 350 ° C. The residence time of the activating treatment agent is preferably 1 to 1000 seconds, more preferably 2 to 500 seconds.

Further, the catalyst can be reactivated in addition to the above-mentioned activation treatment before the reaction. In particular, when the activity of the catalyst decreases and the conversion rate of compound 1 decreases, the catalyst can be reactivated. As a result, the activity of the catalyst can be regenerated and the catalyst can be reused.

Examples of the reactivation treatment method include a method in which the catalyst is brought into contact with a treatment agent (reactivation treatment agent) for the reactivation treatment under heating or non-heating, as in the activation treatment before use. Be done. Specific examples of the reactivation treatment agent include oxygen, chlorine, hydrogen fluoride, hydrogen chloride, halogen-containing hydrocarbons, and perhalogenated carbon.
In addition, in the reactivation treatment, in order to dilute the reactivation treatment agent, nitrogen, carbon dioxide, rare gas (helium, etc.), water vapor, etc. are inert from the viewpoint of suppressing side reactions and improving the durability of the catalyst. Gas can be used.

When the activity of the catalyst is reduced to the extent that it cannot be reactivated, or when the production of compound 2 is stopped, the catalyst may be taken out from the reactor and refilled. When the catalyst is extracted, it is preferable to purge the reactor with an inert gas in advance in order to remove organic substances and acids remaining in the reactor or adhering to the catalyst. Specific examples of the inert gas used include nitrogen and helium. Purging with air may not be preferable because it may form harmful substances such as hexavalent chromium in the catalyst.

In the above reactions (liquid phase reaction, gas phase reaction), the molar ratio of hydrogen chloride used to compound 1 used (molar amount of hydrogen chloride / molar amount of compound 1) is higher in selectivity for compound 2. From the viewpoint of production, 0.01 to 100 is preferable, 0.1 to 10 is more preferable, 0.3 to 5 is further preferable, and 0.5 to 2 is particularly preferable. 0.75 to 1.5 is more particularly preferable, and 0.8 to 1.2 is most preferable, from the viewpoint of suppressing the production of by-products and improving the volumetric efficiency of the reactor.
Above all, when the molar ratio is 0.75 or more, the conversion rate of compound 1 is more excellent.

The above reaction is carried out using a reactor.
The shape and structure of the reactor are not particularly limited. For example, in the case of a gas phase reaction described later, a cylindrical vertical reactor capable of filling a catalyst inside may be mentioned. As the cylindrical vertical reactor, a multi-tube reactor is preferable.
Specific examples of the material of the reactor include glass, iron, nickel, stainless steel, iron or an alloy containing nickel as a main component.
The reactor may be provided with a heating unit such as an electric heater inside. The reactor may have a sheath tube into which a thermometer for measuring the temperature inside is inserted.
When a multi-tube reactor is used as the reactor, the pressure loss of each reactor is preferably within ± 20% and within ± 15% of the average value of the pressure loss of all the reactors. It is more preferable, and it is further preferable that it is within ± 10%. The difference in pressure loss between reaction tubes can be reduced by adjusting the catalyst filling amount in each reaction tube to be constant.

The reaction between compound 1 and hydrogen chloride in the production method of the present invention may be either a liquid phase reaction or a gas phase reaction.
The liquid phase reaction means that compound 1 and hydrogen chloride are each reacted in a liquid state.
The gas phase reaction means that compound 1 and hydrogen chloride are reacted in a gaseous state, respectively.
The above reaction may be carried out by a batch type, a semi-continuous type or a continuous distribution type.

The liquid phase reaction will be described in detail.
As a specific procedure of the liquid phase reaction, for example, compound 2 produced by the reaction by continuously or discontinuously supplying hydrogen chloride into a reactor in which a mixture of the liquid compound 1 and the catalyst exists. The procedure for extracting the compound from the reactor continuously or discontinuously can be mentioned.
The reaction temperature in the liquid phase reaction is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, further preferably 50 ° C. or higher, preferably 250 ° C. or lower, and more preferably 200 ° C. or lower from the viewpoint of reaction yield and production efficiency. , 150 ° C. or lower is more preferable.
The reaction time in the liquid phase reaction is preferably 0.1 to 100 hours, more preferably 0.2 to 50 hours, still more preferably 0.5 to 20 hours from the viewpoint of reaction yield and production efficiency. The reaction time means the residence time of the raw material in the reactor.
The liquid phase reaction may be carried out in the presence of a solvent, if necessary. Specific examples of the solvent include a linear perfluoroalkyl compound having 5 to 8 carbon atoms represented by CF ₃ (CF ₂ ) _m CF ₃ (where _{m in} the formula represents an integer of 3 to 6). Can be mentioned.

Next, the gas phase reaction will be described in detail.
As a specific procedure of the gas phase reaction, compound 1 and hydrogen chloride, which are raw materials heated to the gas state, are continuously supplied into the reactor, and the catalyst filled in the reactor and the gas state are used. Examples thereof include a procedure for contacting compound 1 with hydrogen chloride to obtain compound 2.
A gas (diluted gas) inert to the above reaction may be supplied to the reactor because it is effective in adjusting the flow rate, suppressing by-products, suppressing catalyst deactivation, and the like. Specific examples of the diluent gas include nitrogen, carbon dioxide, helium, and argon.

The reaction temperature (temperature in the reactor) in the gas phase reaction is preferably 100 to 450 ° C., more preferably 120 to 380 ° C., further preferably 140 to 360 ° C., and 160 to 160, from the viewpoint that the compound 2 can be produced more efficiently. ~ 340 ° C. is particularly preferable.
When the reaction temperature is 100 ° C. or higher (preferably 180 ° C. or higher, more preferably 225 ° C. or higher), the conversion rate of compound 1 increases. Further, when the reaction temperature is 450 ° C. or lower (preferably 360 ° C. or lower), the selectivity of compound 2 increases.
The temperature inside the reactor can be controlled by adjusting the temperature and pressure of the raw materials supplied to the reactor. If necessary, the inside of the reactor can be supplementarily heated by an electric heater, a microwave generator, or the like.

The reaction time in the gas phase reaction is preferably 0.1 to 1000 seconds, more preferably 1 to 800 seconds, still more preferably 5 to 600 seconds.
The reaction time corresponds to the residence time of the raw material in the reactor, and can be controlled by adjusting the supply amount (flow rate) of the raw material to the reactor.

The pressure of the reaction system (pressure in the reactor) in the gas phase reaction is preferably 0 to 2.0 MPa, more preferably 0 to 1.5 MPa. Negative pressure may be used. The pressure in the reactor is more preferably 0 to 1.0 MPa from the viewpoint of handleability. In the present specification, pressure indicates gauge pressure unless otherwise specified.

The content of by-products in the product is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the product. The lower limit of the content of the by-product is usually 0% by mass. Here, the product means a halogenated hydrocarbon produced by the reaction of Compound 1 with hydrogen chloride.
When the product contains impurities, a treatment for separating the compound 2 from the obtained product may be carried out. Examples of the separation treatment include known methods such as distillation.

Next, a more detailed aspect of the gas phase reaction will be described with reference to FIG. The reactor 20 shown in FIG. 1 is an example of a reactor used for a gas phase reaction.
The reactor 20 includes a reactor 1. A supply line 2 for compound 1, a supply line 3 for hydrogen chloride, and a supply line 4 for nitrogen, which is a diluting gas, are connected to the reactor 1.
The reactor 1 preferably includes a heating unit such as an electric heater.
The supply line 2 of the compound 1 and the hydrogen chloride supply line 3 may be separately connected to the reactor 1, or may be connected in front of the reactor 1 and connected to the reactor 1. For example, as shown in FIG. 1, the supply line 2 of compound 1, the supply line 3 of hydrogen chloride, and the supply line 4 of nitrogen are connected. As a result, the mixture of compound 1, hydrogen chloride and nitrogen is supplied to the reactor 1 via the mixture supply line 5.

In the reaction apparatus 20 shown in FIG. 1, the preheaters (preheaters) 2a and 3a provided with electric heaters and the like are provided in the compound 1 supply line 2, the hydrogen chloride supply line 3, and the nitrogen supply line 4, respectively. And 4a are provided. It is preferable that the compound 1, hydrogen chloride and nitrogen supplied to the reactor 1 are preheated to predetermined temperatures by the preheaters 2a, 3a and 4a, respectively, and then supplied to the reactor 1. As a result, compound 1, hydrogen chloride and nitrogen can be efficiently raised to a predetermined reaction temperature inside the reactor 1. Preheaters 2a, 3a and 4a are not essential, but are preferably installed.

An outlet line 7 is connected to the outlet of the reactor 1 via a cooling unit 6 such as a heat exchanger. Further, a water vapor and acidic liquid recovery tank 8, an alkaline cleaning device 9, and a dehydration tower 10 are connected to the outlet line 7 in this order.
Acidic substances such as hydrogen chloride and hydrogen fluoride, water vapor, and water are removed from the reaction mixture taken out from the reactor 1 by the treatment from the outlet line 7 onward. The gas thus obtained is hereinafter referred to as "outlet gas". Each component in the outlet gas is analyzed and quantified by an analyzer 11 such as gas chromatography (GC).

Compound 2 is contained in the outlet gas. Examples of the compound other than the compound 2 contained in the outlet gas include compound 1 which is an unreacted raw material, hydrogen chloride, and hydrogen fluoride.

The components other than compound 2 contained in the outlet gas can be removed to a desired degree by a known means such as distillation.
In the reactor 20, the unreacted raw material can be separated from the reaction mixture and the outlet gas discharged from the reactor 1 by distillation or the like and returned to the reactor as a part of the raw material. Thereby, the productivity of compound 2 can be improved.

In the production method of the present invention, when compound 1 is 1,1,2,2,3-pentafluoropropane (245ca), compound 2 is 3-chloro-1,1,2,2-tetrafluoropropane (244ca). ) Is obtained.
Hereinafter, the case where 245ca is used as the raw material will be described in detail.

245ca can be produced by a known method, for example, by the method described in International Publication No. 1994/27939.

When 244ca is produced by a vapor phase reaction using 245ca as a raw material, 244ca can be obtained as a component of crude gas. In addition to 244ca, unreacted 245ca, 2-chloro-1,3,3-trifluoropropene (1233xe), 1-chloro-2,3,3-trifluoropropene (1233yd), 1 , 2-Dichloro-3,3-difluoropropene (1232xd), 1,3-dichloro-2,3-difluoropropene (1232yd), 2,3-dichloro-1,3-difluoropropene (1232xe), 1,2 , 3-Trichloro-3-fluoropropene (1231xd), 2,3,3-trichloro-1-fluoropropene (1231xe), 1,3,3-trichloro-2-fluoropropene (1231yd), 1,2,3 , 3-Tetrachloropropene (1230xd), unreacted hydrogen chloride, hydrogen fluoride, etc. may be included.
The components other than the above 244ca can be removed to a desired extent by known means such as distillation, extraction distillation, azeotropic distillation, membrane separation, bilayer separation and adsorption.

In the present specification, when a compound name or an abbreviation of a compound is used without particular mention, at least one selected from Z-form and E-form is shown, and more specifically, Z-form or E-form. Alternatively, an arbitrary proportion mixture of Z-form and E-form is shown. When (E) or (Z) is added after the compound name or the abbreviation of the compound, the (E) form or the (Z) form of each compound is indicated. For example, 1233yd (Z) indicates a Z form and 1233yd (E) indicates an E form.

The obtained 244ca may be subjected to a hydrogen fluoride reaction to produce 1233yd.
Examples of the procedure for the defluorinated hydrogen reaction include known methods such as International Publication No. 2016/136744.

The above-mentioned 244ca defluorinated hydrogen reaction may be either a liquid phase reaction or a gas phase reaction. The liquid phase reaction means that 244ca in a liquid state or dissolved in a liquid is subjected to a hydrogen fluoride reaction. Further, the gas phase reaction means that 244ca in a gaseous state is subjected to a hydrogen fluoride reaction.

Further, in the production method of the present invention, when compound 1 is HFC-449pccc, HCFC-448occc can be obtained as compound 2.
Hereinafter, the case where 449 pccc is used as a raw material will be described in detail.

449 pccc can be produced by a known method, for example, RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 5 No. 7 2002 pp. It can be produced by the method described in 1162-1165.

When 448 occc is produced by a vapor phase reaction using 449 pcs cc as a raw material, 448 occc can be obtained as a component of a crude gas. In addition to 448 occc, the crude gas may contain unreacted 449 pccc, C ₅ H ₂ F _(7-x) Cl _{(1 + x)} (x represents 0 to 7), and the like.
The components other than 448occc can be removed to a desired extent by known means such as distillation, extraction distillation, azeotropic distillation, membrane separation, bilayer separation and adsorption.

The obtained 448 occc may be subjected to a hydrogen fluoride reaction to produce 1-chloro-2,3,3,4,5,5-heptafluoro-1-pentene (HCFO-1437 dycc). In particular, it is preferable to produce (Z) -1-chloro-2,3,3,4,5,5-heptafluoro-1-pentene (HCFO-1437dycc (Z)).
Examples of the procedure for the defluorination hydrogen reaction include known methods such as Zhurnal Organicheskoi Kimii, (Russia), 1988, Vol. 24, No. 8, pp. 1626-1633.

The 448 occc defluorinated hydrogen reaction may be either a liquid phase reaction or a gas phase reaction. The liquid phase reaction means that 448 occc dissolved in a liquid state or a liquid is defluorinated by a hydrogen fluoride reaction. Further, the gas phase reaction means that 448 occc in a gaseous state is subjected to a hydrogen fluoride reaction.

The present invention will be described in more detail below by way of example, but the present invention is not limited thereto. Examples 1 to 19 described later correspond to Examples.

<Gas chromatograph conditions>
In the production of the following various compounds, the composition analysis of the obtained product was performed using a gas chromatograph (GC). As the column, DB-1301 (length 60 m × inner diameter 250 μm × thickness 1 μm, manufactured by Agilent Technologies Co., Ltd.) was used.

<Catalyst preparation>
The catalyst used for the reaction described later was prepared as follows.
As the reaction device used in each preparation example, the same reaction device as the reaction device 20 described with reference to FIG. 1 was used. As the reactor 1, a tubular reactor made of SUS304 having an inner diameter of 16.1 mm and a length of 15 cm was used.

(Catalyst Preparation Example 1)
The reactor was filled with 38.1 g of a chromium-zinc composite oxide (PRICAT62-3M, Johnson Massey), and the temperature inside the reactor was raised to 300 ° C. while flowing nitrogen (N ₂ ) at 150 Nml / min. While maintaining the inside of the reactor at atmospheric pressure, the filled catalyst was dried until the water content in the gas obtained from the reactor outlet became 5 volume ppm or less. Then, the temperature of the reactor was raised to 350 ° C., trifluoromethane (HFC-23) was supplied at a flow rate of 21.9 Nml / min and N ₂ at a flow rate of 43.7 NmL / min for 16 hours, and the mixture was partially fluorinated in the reactor. A chromium-zinc composite oxide was prepared. The obtained catalyst corresponds to a partial fluoride of a metal oxide.
The Cr content in the chromium-zinc composite oxide (PRICAT62-3M) is 97.0% by mass with respect to the total mass of the metal contained in the catalyst, and the Zn content is contained in the catalyst. It was 2.9% by mass with respect to the total mass of the metal.

(Catalyst Preparation Example 2)
The procedure is the same as (Catalyst Preparation Example 1) except that the chromium-zinc composite oxide (PRICAT62-3M, manufactured by Johnson Massey) is changed to 33.6 g of the chromium-aluminum-magnesium composite oxide (N401AG, manufactured by Nikki Catalyst Kasei). To obtain a partially fluorinated chromium-aluminum-magnesium composite oxide. The obtained catalyst corresponds to a partial fluoride of a metal oxide.
The Cr content in the chromium aluminum-magnesium composite oxide (N401AG) is 20.3% by mass with respect to the total mass of the metal contained in the catalyst, and the Al content is the metal contained in the catalyst. It was 76.6% by mass with respect to the total mass, and the Mg content was 3.0% by mass with respect to the total mass of the metal contained in the catalyst.

(Catalyst Preparation Example 3)
Fluorination treatment according to the same procedure as (Catalyst Preparation Example 1) except that the chromium-zinc composite oxide (PRICAT62-3M, manufactured by Johnson Massey) was changed to 25.5 g of alumina (N612N, manufactured by Nikki Catalyst Kasei Co., Ltd.). Was carried out to obtain partially fluorinated alumina. The obtained catalyst corresponds to a partial fluoride of a metal oxide.

(Catalyst Preparation Example 4)
A partially fluorinated chromium-zinc composite oxide was prepared according to the same procedure as in (Catalyst Preparation Example 1) except that the temperature of the reactor was changed from 350 ° C. to 320 ° C.

(Catalyst Preparation Example 5)
1100g of Cr a _{(NO 3) 3 · 9H 2} O was dissolved in a 2.5 liter water was added an aqueous solution 2000g of ammonium hydroxide 28% by weight. While stirring 4 L of heated water, the aqueous solution obtained above was added to the water to obtain a hydroxide precipitate. Then, the precipitate was filtered off, and the obtained solid content was washed with pure water and dried, and the obtained product was crushed to obtain an oxide powder. Graphite was mixed with the obtained oxide powder in an amount of 3% by mass, molded into a cylindrical shape having a diameter of 5 mm and a height of 5 mm by a tableting molding machine, and calcined in nitrogen at 420 ° C. for 5 hours to prepare a chromium oxide. ..
Partially fluorinated chromium according to the same procedure as (Catalyst Preparation Example 1) except that the chromium-zinc composite oxide (PRICAT62-3M, manufactured by Johnson Massey) was changed to 36.6 g of the chromium oxide obtained above. An oxide was obtained.

(Catalyst Preparation Example 6)
The reactor was filled with 38.1 g of a chromium-zinc composite oxide (PRICAT62-3M, Johnson Massey), and the temperature inside the reactor was raised to 300 ° C. while flowing nitrogen (N ₂ ) at 150 Nml / min. While maintaining the inside of the reactor at atmospheric pressure, the filled catalyst was dried until the water content in the gas obtained from the reactor outlet became 5 volume ppm or less.

<Example 1>
Catalyst Preparation The reactor temperature was set to 250 ° C. while flowing N ₂ through the reactor containing the catalyst prepared in Example 1 at a flow rate of 15.6 NmL / min. After the reactor temperature was stabilized, 245ca was supplied to the reactor at a flow rate of 0.047 g / min and hydrogen chloride was supplied at a flow rate of 0.013 g / min. The crude gas at the outlet of the reactor was washed with water and then passed through an alkaline washing part and a molecular sieve 4A to remove the acid content and obtain a dried product. In addition, each component of the crude gas at the outlet of the reactor was analyzed by gas chromatography. Table 2 shows the analysis results of the crude gas 10 hours after the start of supply of 245ca and hydrogen chloride.
As the 245ca, a dehydrated product was used. Specifically, a molecular sieve 4A (genuine) as a dehydrating agent is placed in a closed container filled with the raw material composition 1 containing 245ca (content of 245ca in the raw material composition 1: 99.9% by mass or more) (1 kg). 100 g (manufactured by Chemical Co., Ltd.) was added and allowed to stand for 3 days to perform dehydration treatment, and the raw material composition 2 after dehydration treatment was used as the above 245ca.
The water content of the raw material composition 2 was 20 mass ppm.
The water content was measured using a Karl Fischer moisture meter. A trace moisture measuring device (manufactured by Mitsubishi Chemical Analytech Co., Ltd., CA-200 type) is used as a Karl Fischer moisture meter, and a liquefied gas vaporizer (manufactured by the same company, model number: VG-200 type) is connected to the sample introduction part. , The preset amount of the raw material composition 2 was vaporized and automatically injected into the moisture meter.

<Example 2>
As shown in Table 2, a product was obtained according to the same procedure as in Example 1 except that the supply amounts of hydrogen chloride and N ₂ were changed.

<Example 3>
As shown in Table 2, a product was obtained according to the same procedure as in Example 1 except that the type of catalyst was changed.

<Example 8>
As shown in Table 2, a product was obtained according to the same procedure as in Example 1 except that the supply amounts of hydrogen chloride and N ₂ were changed.

<Example 9>
As shown in Table 2, the reaction temperature, and, 245ca, except for changing the supply amount of hydrogen chloride and N _2, in accordance with the same procedure as in Example 1 to give the product.

<Example 10>
As shown in Table 2, the reaction temperature, and, 245ca, except for changing the supply amount of hydrogen chloride and N _2, in accordance with the same procedure as in Example 1 to give the product.

<Example 11>
As shown in Table 2, 245ca, except for changing the supply amount of hydrogen chloride and N _2, in accordance with the same procedure as in Example 1 to give the product.

<Example 12>
Catalyst Preparation The reactor temperature was set to 330 ° C. while flowing N ₂ through the reactor containing the catalyst prepared in Example 4 at a flow rate of 81.5 NmL / min. After the reactor temperature was stabilized, 245ca was supplied to the reactor at a flow rate of 0.244 g / min and hydrogen chloride was supplied at a flow rate of 0.066 g / min. The crude gas at the outlet of the reactor was washed with water and then passed through an alkaline washing part and a molecular sieve 4A to remove the acid content and obtain a dried product. In addition, each component of the crude gas at the outlet of the reactor was analyzed by gas chromatography. Table 2 shows the analysis results of the crude gas 10 hours after the start of supply of 245ca and hydrogen chloride.
As the 245ca, the one subjected to the same dehydration treatment as in Example 1 was used.

<Example 13>
As shown in Table 2, a product was obtained according to the same procedure as in Example 12, except that the reaction temperature and the supply amounts of 245ca, hydrogen chloride and N ₂ were changed.

<Example 14>
As shown in Table 2, a product was obtained according to the same procedure as in Example 12, except that the reaction temperature and the supply amounts of 245ca, hydrogen chloride and N ₂ were changed.

<Example 15>
The product was obtained according to the same procedure as in Example 1 except that the catalyst was changed to the catalyst prepared in (Catalyst Preparation Example 5).

<Example 16>
The reactor temperature was set to 300 ° C. while flowing N ₂ at a flow rate of 85.7 NmL / min through the reactor containing the catalyst prepared in Catalyst Preparation Example 6. After the reactor temperature was stabilized, 245ca was supplied to the reactor at a flow rate of 0.256 g / min and hydrogen chloride was supplied at a flow rate of 0.070 g / min. The crude gas at the outlet of the reactor was washed with water and then passed through an alkaline washing part and a molecular sieve 4A to remove the acid content and obtain a dried product. In addition, each component of the crude gas at the outlet of the reactor was analyzed by gas chromatography. Table 2 shows the analysis results of the crude gas 5 hours after the start of supply of 245ca and hydrogen chloride.

<Example 17>
As shown in Table 2, the reaction temperature, and, 245ca, except for changing the supply amount of hydrogen chloride and N _2, in accordance with the same procedure as in Example 16 to give the product.

In Table 2, the conversion rate represents the ratio (unit:%) of the molar amount of 245ca consumed in the reaction to the molar amount of 245ca used in the reaction.
The 244ca selectivity represents the ratio (unit:%) of the molar amount of 244ca in the product to the molar amount of 245ca consumed in the reaction.
The 1233 yd (Z) selectivity represents the ratio (unit:%) of the molar amount of 1233 yd (Z) in the product to the molar amount of 245 ca consumed in the reaction.
The other selectivity represents the ratio (unit:%) of the molar amount of components other than the above components in the product to the molar amount of 245 ca consumed in the reaction.
In Examples 1 to 3, 8 to 10, 14 to 15, the reaction pressure (pressure in the reactor) was 0 MPaG, and the residence time was 30 seconds. In Examples 11 to 13 and 16 to 17, the reaction pressure (pressure in the reactor) was 0 MPaG, and the residence time was 5 seconds. Further, in Example 4 described later, the reaction pressure (pressure in the reactor) was 0 MPaG, and the residence time was 30 seconds.

As shown in Table 2, according to the production method of the present invention, HCFC could be produced with a high selectivity.
When the catalyst obtained in Catalyst Preparation Example 3 was used instead of the catalyst obtained in Catalyst Preparation Example 1 of Example 1, a predetermined HCFC could be obtained (Example 4), but the conversion rate was high. It was lower than that of Example 3, and the selectivity was about 70%, which was slightly inferior.
From the comparison of Examples 1 to 4, it was confirmed that the effect was more excellent when the catalyst contained Cr.

From the comparison between Example 1 and Example 8, it was confirmed that the conversion rate was more excellent when the molar ratio of hydrogen chloride to compound 1 was 0.75 or more.
From the comparison between Examples 1 and 9 to 10, it was confirmed that the conversion rate was more excellent when the reaction temperature was 180 ° C. (preferably 225 ° C.) or higher.
From the comparison of Examples 11 to 14, it was confirmed that the selectivity was more excellent when the reaction temperature was 360 ° C. or lower.
From the comparison between Examples 12 and 16 to 17, it was confirmed that the conversion rate was more excellent when the activation treatment was carried out (in other words, when a partial halide of the metal oxide was used).

<Example 5>
Catalyst Preparation The reactor temperature was set to 250 ° C. while flowing N ₂ through the reactor containing the catalyst prepared in Example 1 at a flow rate of 15.6 NmL / min. After the reactor temperature was stabilized, 449 pccc was supplied to the reactor at a flow rate of 0.082 g / min and hydrogen chloride at a flow rate of 0.013 g / min. The crude gas at the outlet of the reactor was washed with water and then passed through an alkaline washing part and a molecular sieve 4A to remove the acid content and obtain a dried product. In addition, each component of the crude gas at the outlet of the reactor was analyzed by gas chromatography. As a result of analyzing the crude gas 10 hours after the start of supply of 449 pccc and hydrogen chloride, the conversion rate of 449 pccc was 63.4%, the selectivity of 448 occc was 94.8%, and the selectivity of 1437 dycc (Z) was 0.1%. there were.
The conversion rate represents the ratio (unit:%) of the molar amount of 449 pccc consumed in the reaction to the molar amount of 449 pccc used in the reaction.
The 448 occc selectivity represents the ratio (unit:%) of the molar amount of 448 occc in the product to the molar amount of 449 pccc consumed in the reaction.
The 1437 dycc (Z) selectivity represents the ratio (unit:%) of the molar amount of 1437 dycc (Z) in the product to the molar amount of 449 pccc consumed in the reaction.

<Example 6>
In a 2-liter four-necked flask equipped with a stirrer and a Dimroth condenser, 251.31 g of 244ca obtained in Example 1 and 2.51 g of tetra-n-butylammonium chloride (TBAC) were placed, and the flask was placed at 50 ° C. Heated to. The reaction temperature was maintained at 50 ° C., and 631.55 g of a 34 mass% potassium hydroxide (KOH) aqueous solution was added dropwise over 5 minutes. Then, stirring was continued for 30 hours, and the organic layer was recovered. The organic layer recovered above was washed with water and then distilled to obtain purified 1233 yd containing 1233 yd (E) and 1233 yd (Z). The selectivity of 1233yd (E) was 8.9%, and the selectivity of 1233yd (Z) was 91.0%.

<Example 7>
In a 0.2 liter four-necked flask equipped with a stirrer and a Dimroth condenser, 100.7 g of 448 occc obtained in Example 5 and 1.0 g of tetra-n-butylammonium bromide (TBAB) as a phase transfer catalyst. And the flask was cooled to 10 ° C. The reaction temperature was maintained at 10 ° C., and 153.9 g of a 34 mass% potassium hydroxide (KOH) aqueous solution was added dropwise over 30 minutes. Then, stirring was continued for 38 hours. The obtained reaction solution was separated into an organic phase and an aqueous phase, and the organic phase was recovered. The recovered organic phase was purified to obtain 78.6 g of an isomer mixture of 1437 dycc (Z) and 1437 dycc (E) having a purity of 99.5%. The mass ratio (1437 dycc (Z) / 1437 dycc (E)) of 1437 dycc (Z) and 1437 dycc (E) in the isomer mixture was 99/1.

<Example 17>
As shown in Table 3, a product was obtained according to the same procedure as in Example 1 except that the water content of the raw material composition 2 was 198 mass ppm.

<Example 18>
As shown in Table 3, a product was obtained according to the same procedure as in Example 1 except that the water content of the raw material composition 2 was 395 mass ppm.

<Example 19>
As shown in Table 3, a product was obtained according to the same procedure as in Example 1 except that the water content of the raw material composition 2 was 1995 mass ppm.

In Table 3, the "water content [mass ppm]" column represents the water content of the raw material composition 2.

As shown in Table 3, according to the production method of the present invention, the effect is excellent when the water content of the raw material composition 2 is 2000 mass ppm or less (preferably 400 mass ppm or less, more preferably 200 mass ppm or less). It was confirmed that.
The entire contents of the specification, claims, abstract and drawings of Japanese Patent Application No. 2019-084111 filed on April 25, 2019 are cited here as disclosure of the specification of the present invention. It is something to incorporate.

1: Reactor 2: Compound 1 supply line 2a: Preheater 3: Hydrogen chloride supply line 3a: Preheater 4: Nitrogen supply line 4a: Preheater 5: Mixture supply line 6: Cooling unit 7: Outlet line 8 : Water vapor and acidic liquid recovery tank 9: Alkaline cleaning device 10: Dehydration tower 11: Analyzer 20: Reaction device

Claims (15)

1. Production of hydrochlorofluorocarbon, which comprises reacting hydrofluorocarbon represented by the formula (1) with hydrogen chloride in the presence of a catalyst to produce hydrochlorofluorocarbon represented by the formula (2). Method.
   Equation (1) XLY
   Equation (2) XLZ
   X represents −CH _a F _(3-a) .
   Y represents -CH _b F _(3-b) .
   Z represents -CH _b Cl _c F _(3-bc) .
   L _{is, -CF 2 -, - CF 2} CF 2 -, or carbon atoms, which may at least part of the hydrogen atoms are substituted by fluorine atoms is a fluoroalkylene group having 3 to 6 carbon atoms 3 All of the ends of the fluoroalkylene groups of to 6 are -CF _2- .
   a represents 0 or 1.
   b represents 1 or 2.
   c represents 1 or 2.
   However, when a is 0, b represents 1 or 2, and when a is 1, b represents 2.
   When b is 1, c represents 1 or 2, and when b is 2, c represents 1.
2. The production method according to claim 1, wherein the catalyst is a metal-containing catalyst.
3. The catalyst comprises one or more selected from metal oxides, partial halides of metal oxides, and metal halides.
   The production method according to claim 1 or 2, wherein the metal oxide, a partial halide of the metal oxide, and the metal halide contain at least one selected from Cr and Al, respectively.
4. The production method according to claim 3, wherein the catalyst contains a partially halide of the metal oxide.
5. Wherein L is _{-CF 2 -, - CF 2 CF} 2 -, - CF 2 -CF 2 -CF 2 -, - CF 2 -CHF-CF 2 - or _{-CF 2 -CH} 2 _-CF 2 - is, according Item 8. The production method according to any one of Items 1 to 4.
6. The production method according to any one of claims 1 to 5, wherein the a is 1, the b is 2, and the c is 1.
7. The production method according to any one of claims 1 to 6, wherein the hydrofluorocarbon represented by the formula (1) and the hydrogen chloride are reacted in a gas phase.
8. The production method according to any one of claims 1 to 7, wherein the reaction temperature is 100 to 450 ° C.
9. The production method according to any one of claims 1 to 8, wherein the molar ratio of hydrogen chloride to the hydrofluorocarbon represented by the formula (1) is 0.5 to 2.0.
10. The reaction was carried out using a raw material composition containing a hydrofluorocarbon represented by the formula (1) and hydrogen chloride.
    The production method according to any one of claims 1 to 9, wherein the water content of the raw material composition is 5000 mass ppm or less.
11. The production method according to claim 10, wherein the water content is 400 mass ppm or less.
12. The hydrofluorocarbon represented by the formula (1) is 1,1,2,2,3-pentafluoropropane.
    The production method according to any one of claims 1 to 11, wherein the hydrochlorofluorocarbon represented by the formula (2) is 3-chloro-1,1,2,2-tetrafluoropropane.
13. 1-Chloro-2,3,3-trifluoropropene is produced by subjecting 3-chloro-1,1,2,2-tetrafluoropropane produced by the method according to claim 12 to a hydrogen fluoride reaction. A method for producing 1-chloro-2,3,3-trifluoropropene, which is characterized by the above.
14. The hydrofluorocarbon represented by the formula (1) is 1,1,2,2,3,3,4,5-nonafluoropentane.
    According to any one of claims 1 to 11, the hydrochlorofluorocarbon represented by the formula (2) is 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane. The manufacturing method described.
15. 5-Chloro-1,1,2,2,3,3,4,5-octafluoropentene produced by the method according to claim 14 is subjected to a hydrogen fluoride reaction to 1-chloro-2,3. Of 1-chloro-2,3,3,4,5,5,5-heptafluoro-1-pentene, which comprises producing 3,4,4,5,5-heptafluoro-1-pentene. Production method.

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