JP6032085B2 - Method for producing 3,3,3-trifluoropropyne - Google Patents

Description

  The present invention relates to a method for producing 3,3,3-trifluoropropyne (hereinafter sometimes referred to as “TFPy”).

  Since TFPy has a trifluoromethyl group and a triple bond in the molecule and has unique properties, many studies have been conducted on single use and derivatives thereof. As a method for producing TFPy, for example, in Non-Patent Document 1-3, a method obtained from 2,3-dibromo-1,1,1-trifluoropropene, and in Non-Patent Document 4, 1,1,2-trichloro-3 is used. A method of deriving from 1,3,3-trifluoropropene is disclosed.

In Non-Patent Document 5, 1-iodo-3,3,3-trifluoropropene is reacted with potassium fluoride (KF). In Non-Patent Document 6, acetylene carboxylic acid (HC≡CCOOH) and tetrafluoride are reacted. A method for reacting sulfur (SF ₄ ) has been reported.

  Patent Document 1 discloses a method of reacting 1-halogeno-3,3,3-trifluoropropene with a base such as potassium hydroxide in the presence of a solvent.

The method described in Non-Patent Document 1-3 is a method for producing TFPy using 3,3,3-trifluoropropene as a starting material, as shown in the following reaction formula.

  However, this method is complicated because it generally requires multiple steps. Furthermore, since the highly corrosive bromine is used, a reaction vessel that can withstand corrosion is required, and it is difficult to employ industrially.

  In the method of Non-Patent Document 4, since a zinc compound is used for 1,1,2-trichloro-3,3,3-trifluoropropene, the treatment of zinc waste liquid becomes a problem.

  Further, in the method of Non-Patent Document 5, since the raw material is expensive, a large amount of by-products are produced together with the target product, and the target product has an extremely low yield (20%), an industrial method is used. As it is difficult to adopt.

  The method of Non-Patent Document 6 is not necessarily an industrial method because acetylene carboxylic acid as a raw material is expensive and sulfur tetrafluoride that is difficult to handle is used.

  Although the method of Patent Document 1 can efficiently produce TFPy under mild conditions, the solvent can be reused on the industrial scale, while the salt remaining in the reaction system can be separated. And a distillation operation of the solvent are required, which requires additional equipment costs and is not necessarily an economical production method. Moreover, although the said literature also discloses the manufacturing method which does not use a solvent, the yield may become low compared with the case where a solvent is used.

  Therefore, the industrial production method employed for mass production of TFPy is not necessarily a satisfactory method, and it has been desired to establish a production method of TFPy that is industrially simple and economically feasible.

JP 2008-285471 A

Journal of the American Chemical Society, 1951, 73, 1042-3. Journal of the Chemical Society, 1951, 2495-504. Journal of the Chemical Society, 1952,3483-90. Journal of Organic Chemistry, 1963, 28, 1139-40. Journal of Fluorine Chemistry, 1978, 12 (4), 321-4. Journal of the American Chemical Society, 1959, 81, 3165-6.

  Provided is a method for producing TFPy on an industrial scale and economically easy to implement.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, (Z) -1-chloro-3,3,3-trifluoropropene (hereinafter sometimes referred to as “1233Z”) is continuously formed with an alkali metal hydroxide in the presence of water. When TFPy was produced by reacting continuously or semi-continuously, it was found that TFPy can be obtained more efficiently than the prior art by continuously extracting the generated TFPy from the reaction system, and the present invention has been completed. .

  That is, the present invention is as follows.

[Invention 1]
(Z) -1-Chloro-3,3,3-trifluoropropene formed in contact with an alkali metal hydroxide in the presence of water, formed continuously or semi-continuously. A method for producing 3,3,3-trifluoropropyne, wherein 3-trifluoropropyne is continuously extracted from the reaction system.

[Invention 2]
(Z) -1-Chloro-3,3,3-trifluoropropene formed in contact with an alkali metal hydroxide in the presence of water, formed continuously or semi-continuously. A method for producing 3,3,3-trifluoropropyne, wherein 3-trifluoropropyne is continuously extracted from the reaction system,
In the reaction, 1.0 to 2.5 mol of alkali metal hydroxide is used with respect to 1 mol of (Z) -1-chloro-3,3,3-trifluoropropene, and 0.1 A process for producing 3,3,3-trifluoropropyne, which is carried out at ~ 0.5 MPaG and 40-60 ° C.

[Invention 3]
Invention 1 or Invention 2 characterized in that an aqueous solution of an alkali metal hydroxide is dropped into contact with (Z) -1-chloro-3,3,3-trifluoropropene charged in the reactor. Of 3,3,3-trifluoropropyne.

[Invention 4]
Invention 1 or Invention 2, wherein (Z) -1-chloro-3,3,3-trifluoropropene is dropped and brought into contact with an alkali metal hydroxide and water charged in the reactor. Of 3,3,3-trifluoropropyne.

[Invention 5]
(Z) -1-chloro-3,3,3-trimethyl produced by a method for producing (Z) -1-chloro-3,3,3-trifluoropropene comprising the following first to third steps: The method for producing 3,3,3-trifluoropropyne according to any one of inventions 1 to 4, wherein fluoropropene is used.

First step:
1,1,1,3,3-pentachloropropane or 1,3,3,3-tetrachloropropene is reacted with hydrogen fluoride to give (A) (E) -1-chloro-3,3,3 -Trifluoropropene and (B) 3-chloro-1,1,1,3-tetrafluoropropane, 2-chloro-1,1,1,3,3-pentafluoropropane, and 1-chloro-1 , 1,4,4,4-pentafluoro-2-butene, a step of obtaining a first composition comprising at least one compound selected from the group consisting of:

Second step:
From the first composition obtained in the first step, 3-chloro-1,1,1,3-tetrafluoropropane, 2-chloro-1,1,1,3,3-pentafluoropropane, and 1 -A compound comprising at least one selected from chloro-1,1,4,4,4-pentafluoro-2-butene is removed by distillation to obtain (E) -1-chloro-3,3,3-tri Obtaining a second composition comprising fluoropropene.

(3) Third Step (E) -1-Chloro-3,3,3-trifluoropropene contained in the second composition obtained in the second step is isomerized, and (Z) -1-chloro- Obtaining a third composition comprising 3,3,3-trifluoropropene.

[Invention 6]
(Z) -1-chloro-3,3,3-trifluoropropene, characterized by reacting 1,3,3,3-tetrafluoropropene with hydrogen chloride in the gas phase in the presence of a catalyst The 3,3,3-trifluoropropyne according to any one of Inventions 1 to 4, wherein (Z) -1-chloro-3,3,3-trifluoropropene produced by the production method is used. Production method.

[Invention 7]
Reacting a raw material containing at least (E) -1-chloro-3,3,3-trifluoropropene or (Z) -1-chloro-3,3,3-trifluoropropene in the presence of a radical; An isomerization step in which the ratio of (E) -1-chloro-3,3,3-trifluoropropene to (Z) -1-chloro-3,3,3-trifluoropropene is changed (Z 1) to 1), characterized in that (Z) -1-chloro-3,3,3-trifluoropropene produced by the method for producing 1-chloro-3,3,3-trifluoropropene is used. The method for producing 3,3,3-trifluoropropyne according to any one of Inventions 4.

[Invention 8]
3,3,3-trifluoropropyne obtained by the production method of any one of inventions 1 to 7.

  According to the present invention, TFPy can be produced in a high yield by an industrial scale and economical method for producing TFPy.

4 is a schematic view of a gas phase reactor used in Example 3. FIG.

Hereinafter, in this specification,
(E) -1-chloro-3,3,3-trifluoropropene may be represented as “1233E”;
3-chloro-1,1,1,3-tetrafluoropropane may be represented as “244fa”,
1,1,1,3,3-pentachloropropane may be represented as “240fa”,
1,1,1,3,3-pentafluoropropane may be represented as “245fa”,
2-chloro-1,1,1,3,3-pentafluoropropane may be represented as “235da”,
2-chloro-1,3,3,3-tetrafluoropropene may be represented as “1224”,
1,1,1,4,4,4-hexafluoro-2-butene may be represented as “1336”.

  1-Chloro-3,3,3-trifluoropropene includes cis-trans isomers (Z) -1-chloro-3,3,3-trifluoropropene and (E) -1-chloro-3, 3,3-trifluoropropene exists, the cis isomer may be expressed as “1233Z”, the trans isomer as “1233E”, and the isomer may not be considered or the mixture may be expressed as “1233”.

  There is a cis-trans isomer in 1,3,3,3-tetrafluoropropene. The cis isomer is represented by “1234Z”, the trans isomer is represented by “1234E”, and the isomer is not considered or a mixture is represented by “1234”. Sometimes.

  There are cis-trans isomers in 2-chloro-1,3,3,3-tetrafluoropropene. The cis isomer is “1224Z”, the trans isomer is “1224E”, the isomer is not considered, and the mixture is “ 1224 ".

  There are cis-trans isomers in 1,1,1,4,4,4-hexafluoro-2-butene. The cis isomer is “1336Z”, the trans isomer is “1336E”, and the isomer is not considered. The mixture may be represented as “1336”.

  Configurations and combinations thereof in the following embodiments are examples, and additions, omissions, substitutions, and other modifications of the configurations can be made without departing from the spirit of the present invention. Further, the present invention is not limited by the embodiments, and is limited only by the scope of the claims.

The present invention is a method for producing TFPy by contacting 1233Z with an alkali metal hydroxide as a base in the presence of water continuously or semi-continuously, wherein the produced TFPy is: A method for producing TFPy, wherein the method is continuously extracted from a reaction system. The reaction formula is shown below.

  In the present invention, “continuously contacting” means that 1233Z and an alkali metal hydroxide are continuously introduced and contacted.

  “Semi-continuously contacting” means that 1233Z and an alkali metal hydroxide are charged together and contacted.

  Here, as shown in a comparative example to be described later, in the batch-type reaction, the target product is obtained, but TFPy produced in the reaction system further reacts with a base (an alkali metal hydroxide in the present invention). In addition, by-products are likely to be generated, resulting in a decrease in the yield of TFPy and an increase in the amount of alkali metal hydroxide used. “Batch type” means that after introduction of 1233Z, water and alkali metal hydroxide, 1233Z, water or alkali metal hydroxide is not newly introduced, and the reaction product is extracted during the reaction. It shows the method of performing the reaction without doing.

  Therefore, by continuously extracting the generated TFPy from the reaction system, this side reaction can be suppressed, and not only can TFPy be produced efficiently, but also the amount of base used can be reduced. Furthermore, the amount of waste generated by the side reaction can also be reduced.

  A method for producing TFPy according to the present invention will be described below.

  A predetermined reactor is used for the production of TFPy. The reactor is provided with a predetermined condenser, and the condenser and a predetermined collector are connected via a predetermined extraction pipe, and the extraction pipe is connected to the inside of the reactor. An extraction valve for adjusting the pressure is provided.

  The reactor is provided with a predetermined stirring blade, and may further be provided with a pressure gauge.

  In the present invention, in the case of “continuously contacting”, 1233Z is added to the reactor, and an aqueous solution of an alkali metal hydroxide is added at a predetermined internal temperature and a predetermined pressure while stirring with the stirring blade. React with. The aqueous solution of the alkali metal hydroxide is dropped into the reaction system over a predetermined time using a predetermined dropping device. TFPy (boiling point: −47 ° C.) produced by the reaction exists as a gas at normal temperature and normal pressure. The reaction pressure is adjusted to a predetermined pressure by the extraction valve, and TFPy vapor generated in the reaction is circulated through the condenser cooled to a predetermined temperature from the start of the reaction, and the trap cooled to the predetermined temperature is supplied. The reaction product is liquefied and collected by a collector. Thereby, highly purified TFPy can be obtained, without performing a special post-process. Furthermore, higher purity TFPy can be obtained by distilling the collected TFPy.

  In the production method, the reaction raw materials may be reacted in the reverse manner. That is, adding an alkali metal hydroxide and an aqueous solution to the reactor and reacting with 1233Z under a predetermined internal temperature and a predetermined pressure while stirring with the stirring blade is also one preferred embodiment of the present invention. One.

  In the case of “semi-continuous contact”, in the case of “continuous contact”, 1233Z, an alkali metal hydroxide and water may be added to the reactor.

  When distillation is performed, normal pressure may be used, but the boiling point of the target product TFPy is −47 ° C. and normal temperature (in particular, an atmospheric temperature that is not heated or cooled, and is usually 5 to 35 ° C.). , The same shall apply hereinafter). There are no particular restrictions on the material of the distillation tower, glass, stainless steel, tetrafluoroethylene resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, PFA resin, glass lined inside, etc. Can be used. A filler can also be packed in the distillation column.

  The reactor is not particularly limited as long as it can withstand the pressure when the reaction is performed under pressure. For example, general stainless steel, glass, fluororesin, or a reaction vessel made of a material lined with glass or fluororesin can be used.

  The condenser allows the TFPy vapor generated by the reaction to flow to the collector, but the 1233Z vapor (boiling point: 40 ° C.) that can be generated by the reaction is liquefied without flowing and returned to the reaction system. Used. Therefore, it is necessary to cool the aggregator at −47 to + 40 ° C., and it is preferable to cool to −47 to 0 ° C.

  Further, the aggregator is preferably a surface condenser in which the TFPy vapor and the refrigerant are in indirect contact with each other through a tube. The condenser is not particularly limited as long as it can withstand pressure when the reaction is performed under pressure. For example, the condenser is lined with general stainless steel, glass, fluororesin, or glass or fluororesin. A tube of material or the like can be used.

  The stirring blade is used to flow the contents. Stirring blades such as anchor blades, paddle blades, inclined paddle blades, twin star blades, and three swept blades can be used, and stirring blades generally used in organic synthesis can be used.

  The material of the extraction tube is not particularly limited as long as it can withstand the pressure when the reaction is performed under pressure. For example, general stainless steel, glass, fluororesin, or a tube of a material lined with glass or fluororesin may be used.

  There is no particular limitation on the material of the dropping device as long as it can withstand the pressure when the reaction is performed under pressure. For example, general stainless steel, glass, fluororesin, or a tube of a material lined with glass or fluororesin may be used.

  In the present invention, the condenser and the collector may be directly connected as long as the pressure can be adjusted separately.

  The collector is used to liquefy and collect the TFPy vapor flowing from the aggregator. The material is not particularly limited as long as it can withstand the cooling temperature described later. For example, general stainless steel, glass, fluororesin, or glass or fluororesin lining is used. In order to liquefy TFPy and collect it with a collector, the collector is cooled to −47 ° C. or lower.

  Although internal temperature should just be 0-100 degreeC, Preferably it is 40-80 degreeC, More preferably, it is 40-60 degreeC.

  The pressure can be operated at 0.05 to 2 MPaG, preferably 0.1 to 0.5 MPa. When the reaction pressure exceeds 2 MPaG, the reaction product TFPy and the base (in the present invention, alkali metal hydroxide) are promoted to contact, so that side reactions are likely to occur and the yield may be reduced. On the other hand, if the reaction pressure is lower than 0.05 MPaG, a sufficient reaction temperature cannot be obtained, and the reaction rate may decrease.

  Although the dropping time of the aqueous solution of the alkali metal hydroxide or 1233Z depends on the reaction scale, those skilled in the art appropriately adjust the dropping rate so that the dripping does not cause a rapid temperature increase of the reaction system.

  The cooling temperature of the collector is kept at −47 ° C. or lower in order to liquefy TFPy. For example, the condenser can be cooled using a cryogen such as ice water, methanol with dry ice, or acetone with dry ice. When the cooling temperature is higher than −47 ° C., TFPy is vaporized, so that it is difficult to collect and it may be difficult to continuously extract TFPy from the reaction system.

  The alkali metal hydroxide used in the present invention contributes to the reaction as a base in this reaction. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and rubidium hydroxide. Of these, sodium hydroxide and potassium hydroxide are preferred because they are inexpensive and easily available.

  Water used in the present invention plays a role as a solvent in this reaction. City water, pure water (water that has been desalted with an ion exchange resin, etc.), ultrapure water (water from which not only inorganic ions but organic substances, viable bacteria, fine particles, dissolved gas, etc. have been removed) and the like.

  The alkali metal hydroxide used in the present invention is preferably used as an aqueous solution because of its good reactivity and ease of workability. The concentration of the aqueous solution varies depending on the alkali metal, but for example, in the case of a potassium hydroxide aqueous solution, it is usually 5 to 60% by mass, preferably 10 to 55% by mass, and more preferably 15 to 48% by mass.

  The alkali metal hydroxide used in the present invention can be used alone or in combination of two or more.

  The alkali metal hydroxide used in the present invention requires a stoichiometric amount of 1 mole per mole of 1233Z. Usually, the range of 1 to 10 mol can be appropriately selected, but it is preferably 1 to 4 mol, and more preferably 1.0 to 2.5 mol. When less than 1 mol is used, the conversion rate of the reaction may decrease. Although more than 10 moles can be used, there is no particular advantage of using them in large amounts.

  1233Z used in the present invention may be obtained by any process. For example, 1233Z obtained by the following production methods (A) to (C) can be used.

  Hereinafter, the production methods (A) to (C) of 1233Z will be described.

[(A) Method for producing 1233Z including fluorination step, distillation step and isomerization step]

1233Z used in the present invention is manufactured by a manufacturing method including the following first to third steps (hereinafter, this manufacturing method may be referred to as “1233Z manufacturing method (A)”). Also good.

(1) First Step 240fa or 1,3,3,3-tetrachloropropene (hereinafter sometimes referred to as “1230”) is reacted with hydrogen fluoride to give (A) 1233E and (B ) A step of obtaining a first composition comprising 244fa, 235da, and at least one compound selected from 1-chloro-1,1,4,4,4-pentafluoro-2-butene (1335).

(2) Second Step From the first composition obtained in the first step, 3-chloro-1,1,1,3-tetrafluoropropane (244fa), 2-chloro-1,1,1,3, At least one selected from 3-pentafluoropropane (235da) and 1-chloro-1,1,4,4,4-pentafluoro-2-butene (hereinafter sometimes referred to as “1335”). Removing the compound consisting of 1 by distillation to obtain a second composition containing 1233E.

(3) Third step A step of isomerizing 1233E contained in the second composition obtained in the second step to obtain a third composition containing 1233Z.

  Hereinafter, the details of the first step, the second step, and the third step will be described.

(1) First Step The first step is a fluorination reaction step. Specifically, 240fa or 1230 is reacted with hydrogen fluoride to obtain a first composition containing 1233. Since 240fa is converted into 1230 when deHCl is intramolecularly, 240fa and 1230 can be regarded as equivalents.

  Depending on the reaction conditions, (A) 1233Z and 1233E are usually contained in the first composition at a predetermined ratio. Furthermore, as a by-product, (B) any one of 244fa, 235da, 1335 and the like, which are difficult to separate by distillation, have a boiling point close to 1233Z.

  For the first composition containing 1233, a known method can be used in which 240fa and hydrogen fluoride are reacted to perform rough distillation, washing with water, drying, or the like (see Japanese Patent Application Laid-Open No. 9-183740 and Japanese Patent No. 3031465). 240fa can be obtained by adding vinyl chloride to chloroform.

(2) Second step The second step is a distillation step. Specifically, from the first composition obtained in the first step, a compound consisting of at least one selected from 244fa, 235da, and 1335 is removed by distillation to obtain a second composition containing 1233E as a main component. It is a process to obtain.

  The first composition obtained by the fluorination reaction contains 1233Z (boiling point: 39 ° C.), which is the target compound, and impurities such as 244fa, 235da, and 1335, both of which have a boiling point of about 40 ° C. and difficult to be separated by distillation. May be included.

  1233E (boiling point: 19 ° C.) has a lower boiling point than the target compound 1233Z and can be easily separated by distillation from 244fa, 235da, and 1335. Therefore, according to the second step, 1233E that does not contain impurities that are difficult to distill can be used as a raw material in the isomerization reaction of the third step, so that it is possible to obtain 1233Z with higher purity.

  Of course, when a person skilled in the art allows these impurities to be mixed in the product, the distillation operation can be omitted, but usually 244fa, 235da, and 1243E are used as raw materials for the third step (isomerization reaction). It is preferable that impurities such as 1335 are not substantially contained. Here, “substantially free” specifically means that the content of each of these is less than 2%, preferably less than 1%, more preferably less than 0.5%, and even more preferably less than 0.1%. It is. Ultimately, the purity and distillation efficiency of 1233Z depend on their purity in the raw material 1233E.

  The method for removing these impurities is the most convenient and efficient method for purifying the first composition by distillation, but it can also be purified by other methods such as adsorption. A known method can be used for distillation. Any form such as filling or bubble bell tower may be used, and the filler is not particularly limited, such as helipak, Raschig ring, and poling. The distillation pressure is not particularly limited and can be performed under reduced pressure, normal pressure, or increased pressure, but the operation of atmospheric distillation or pressure distillation is easy.

  Although it is allowed to contain 1233Z in the raw material of the third step (isomerization reaction), theoretically it is converged to a thermodynamic equilibrium composition, so if 1233E containing 1233Z above the equilibrium composition is used. If 1233Z is desired, it is meaningless.

  In addition, low boiling components such as 1234E, 1234Z, a mixture of 1234E and 1234Z, and 245fa may be produced as a by-product in the fluorination reaction of 240fa, but these may be separated in advance by distillation or the like. You may mix in 1233E used as the raw material of a process (isomerization reaction). This is because it has been found that these can be easily separated from the target compound 1233Z by final distillation. Further, it has been found that, under the isomerization reaction conditions studied by the present inventors, these low-boiling components are not substantially converted into difficult-to-distillate substances in spite of high-temperature conditions under which organic substances decompose.

  As described above, the operation in the second step can be easily performed because 244fa, 235da, and 1335, which are difficult to be separated by distillation, can be removed only by removing a fraction having a higher boiling point than 1233E. In addition, since acid content and moisture may cause corrosion of the apparatus, if 1233E containing these is used, it is preferable to perform pretreatment such as washing with water and drying.

(3) Third Step The third step is an isomerization reaction step. Specifically, this is a step of isomerizing 1233E contained in the second composition obtained in the second step to obtain a third composition containing 1233Z as a main component.

  The isomerization step can be performed in a high temperature region under non-catalytic conditions.

  Usually, the isomerization reaction for converting 1233E to 1233Z is carried out using a supported catalyst carrying a metal oxide or a metal compound. However, when the reaction temperature is carried out in a high temperature region (for example, 450 ° C. or higher), the raw material may be caulked or tarred on the catalyst surface. In addition, since 1233 has a double bond in the molecule and has high reactivity, when the reaction temperature is higher than 450 ° C., it is not preferable as an impurity, and tar, oil components, trifluoropropynes, and the like are by-produced. May end up. Furthermore, when the reaction temperature is increased, running costs such as power consumption increase.

  Thus, in the catalytic reaction, if the reaction temperature is increased, the formation of 1233Z becomes advantageous. However, if the reaction temperature is increased, impurities such as coking and tarring on the catalyst surface and running costs are increased. From the viewpoint of productivity such as the above, it is difficult to produce 1233Z with high purity and efficiency on an industrial scale that meets equilibrium conditions advantageous for the production of 1233Z.

  In such a high temperature reaction, there is a concern about an unexpected pyrolysis reaction, but the selectivity of this reaction is very high, and impurities such as 244fa, 235da, and 1335 that are difficult to separate by distillation are substantially added to the product. Since it is not contained, 1233Z can be easily purified even if it is re-reacted using recycled 1233E. Of course, unreacted 1233E can be utilized as a foaming agent or the like, or fluorinated to be induced into useful substances such as 245fa and 1234.

  The isomerization reaction is performed by a gas phase reaction in which a second composition containing 1233E as a main component is introduced into the reaction system using a reactor.

  The material of the reactor is preferably a corrosion-resistant material such as carbon, ceramics, stainless steel, nickel, hastelloy, monel or inconel, and more preferably nickel, monel, hastelloy or inconel.

  The reaction mode is not particularly limited, either batch type or flow type, but a general gas phase flow type is preferable. It is also possible to accompany an inert gas such as nitrogen with the raw material. The reaction pressure is not particularly limited, either under pressure or under reduced pressure, but operation near normal pressure is easy. However, a pressure reaction of 1 MPa or more is not preferable because not only an expensive pressure-resistant device is required, but also polymerization of raw materials or products is concerned.

It is only necessary to heat the empty tube, but a filler such as a static mixer or Raschig ring may be added if desired. These materials are also preferably corrosion resistant materials as described above. If it is desired to use alumina or the like as a filler, it is preferable to calcinate at, for example, 1300 ° C. or higher to inactivate it in order to eliminate the catalytic activity. Otherwise, the raw material may caulk on the surface of the filler or tar. In addition, an unexpectedly difficult-to-distill material can be produced as a by-product. If the reaction is continued in this state, there is a risk that the coke deposits on the catalyst and clogs. The specific surface area of the filler is preferably 5 m ² / g or less. If it is greater than 5 m ² / g, it may exhibit catalytic activity, and tarring as described above may occur.

  The method for heating the apparatus (reactor) is not particularly limited, but a method of directly heating with an electric heater or a burner or a method of indirectly heating with a molten salt or sand is preferable.

  The temperature at which the isomerization reaction is carried out is 450 to 750 ° C, preferably 500 to 700 ° C, more preferably 550 to 650 ° C. By circulating a tube heated to a predetermined temperature, a part thereof is efficiently isomerized to 1233Z. The isomerization reaction from 1233E to 1233Z is endothermic, and the higher the temperature thermodynamically, the more advantageous. That is, when 1233Z, which is disadvantageous in thermodynamic equilibrium, is desired, there is a limitation on the equilibrium. Therefore, a yield of approximately 20% or more cannot be desired in the practical temperature range as described above. In that case, the reaction product is separated by distillation into the target compound 1233Z and the recovered raw material 1233E, and this 1233E can be recycled.

  Further, according to the Arrhenius equation, it is shown that the higher the reaction temperature is, the higher the reaction rate is. Therefore, naturally, the higher temperature reaches the equilibrium, but the faster the equilibrium is reached, the patent document (US Patent Application Publication No. 2010). In the case of using a catalyst which is described as effective in the specification of No. / 0152504), if the reaction is carried out at a high temperature of 400 ° C. or higher, the raw material and product are compounds having multiple bonds. It is often transformed into tar. In particular, when the reaction is carried out at a temperature of 400 ° C. or higher for a long time, the catalytic activity may be reduced or clogged depending on circumstances. When the non-catalyzed isomerization method found in the present invention is carried out, it has been found that the generation of tar and coke can be suppressed even at a reaction temperature of 450 ° C. or higher where equilibrium is advantageous. In other words, in the case of no catalyst, the isomerization hardly proceeds substantially below 400 ° C., but the isomerization can be efficiently performed in a temperature range of 450 ° C. to 750 ° C. However, when the reaction temperature is higher than 750 ° C., an unexpectedly difficult-to-distillation substance may be produced as a by-product, or impurities such as TFPy and 1336 may be produced as a by-product, resulting in an increase in oil and tar content. is there.

  The residence time of the isomerization reaction (no catalyst is present, but the same concept as the contact time) is usually 0.01 to 50 seconds, preferably 0.05 to 20 seconds. In general, when the residence time is shorter than 0.01 seconds, the conversion rate may be lowered. When the residence time is longer than 50 seconds, TFPy may be by-produced, coked, or a tar content may be generated. That is, the optimum residence time depends on the reaction temperature. For example, if the residence time is extremely short at 450 ° C., the reaction may not proceed substantially. If the residence time is extremely long at 750 ° C., an unexpectedly difficult-to-distillation substance may be produced as a by-product or in the presence of a catalyst. As in the above reaction, tar and oil may be by-produced, and the tube may be blocked by them.

  In the present specification, the residence time represents a value (seconds) obtained by dividing the volume (ml) of the reactor by the raw material supply rate (ml / second) in the gas phase flow system using the reactor.

  In the best mode (reaction temperature 600 ° C, residence time: 0.3 seconds), 24 hours continuous operation and 300 days a year, 1233 tons / year of 1233E can be processed in a reactor with a capacity of only 12 liters. In theory, 200 tons / year of refined 1233Z can be expected, which is a very efficient process compared to the best mode of the catalytic method (US Patent Application Publication No. 2010/0152504) at 150 ° C. to 350 ° C. is there.

  The 1233Z production method (A) may include the following fourth step or fifth step as appropriate in addition to the first to third steps described above.

(4) Fourth Step The fourth step is a step of increasing the purity of 1233Z by distilling the third composition mainly comprising 1233Z obtained in the third step.

  The third composition mainly composed of 1233Z that is isomerized by the isomerization reaction and flows out from the reactor can easily increase the purity of 1233Z using a known separation / purification method such as distillation.

  Specifically, the mixture of 1233E and 1233Z obtained by isomerization should be washed with water to remove the acid content, dried with zeolite, etc., and then easily separate 1233Z and 1233E with high purity by ordinary distillation operation. Can do. Of course, since the quality of 1233E is equivalent to the quality of the raw material 1233E, it can be subjected to the same isomerization reaction once more, or can be commercialized as a rigid urethane foam blowing agent as it is.

  The number of distillation columns in the distillation operation is not particularly limited, but a 10 to 50 distillation column is recommended. The purity of preferable high purity 1233Z is 98% or more, more preferably 99% or more. If the 4th process of 1233Z manufacturing method (A) is used, ultra high purity 1233Z of 99.9% or more can also be manufactured easily.

(5) Fifth Step The fifth step is a step of collecting 1233E separated in the fourth step and reusing it in any one of the first to third steps. The separated 1233E can be returned to the isomerization reaction step and the fluorination step again. Moreover, it can also be commercialized as a rigid urethane foam foaming agent as it is. According to this step, the recovered 1233E can be used effectively, and an improvement in productivity can be expected.

[(B) Production Method of 1233Z by Gas Phase Reaction]

1233Z used in the present invention is produced by a production method in which 1234 is reacted with hydrogen chloride in the gas phase in the presence of a catalyst (hereinafter, this production method may be referred to as “1233Z production method (B)”). It may be.

  This 1234 may be obtained by fluorinating 240fa and / or 1230.

  1234 which is a raw material compound of 1233Z production method (B) can be produced by any method, but 245fa which is industrially mass-produced is a known method (for example, JP 2008-19243 A). It is economical to be produced by deHFing in the reference). The product of 245fa catalytic de-HF reaction is preferably separated into 1234E, 1234Z and 245fa after distillation.

Here, it should be noted that the 1233Z production method (B) has the ability to convert 245fa into 1233 as well. Therefore, the general formula CF ₃ CH ₂ CHR ¹ R ² , such as 245fa (R ¹ and R ² are each independently a fluorine atom or a chlorine atom)
It can be converted to 1233 using 1234E or 1234Z containing a compound represented by

For example, this method is also effective when it is desired to convert 1234 used mixed refrigerants to 1233 for the blowing agent. The 1233Z production method (B) enables 1234E, 1234Z, and CF ₃ CH ₂ CHR ¹ R ² to be converted into useful 1233 at any ratio. The raw material of the present invention is preferably washed and dried. Of course, raw materials containing a small amount of HF can also be used, but attention must be paid to corrosion of the apparatus.

  Hydrogen chloride that can be used in the 1233Z production method (B) may be ultra-high purity hydrogen chloride, industrial hydrogen chloride, or by-product hydrogen chloride. In the case of by-product hydrogen chloride, 245fa or hydrogen chloride by-produced in the fluorination step of synthesizing the precursor of 245fa is preferable. Normally, by-product hydrogen chloride does not become a valuable resource unless HF and organic matter are separated to a high degree. For this reason, a high-performance distillation tower or other purification equipment is required, and is often discarded after being neutralized. Utilizing by-product hydrogen chloride in the fluorination reaction is preferable in terms of resource protection and waste reduction.

A C3 compound (a compound having 3 carbon atoms) having CF ₃ contained in hydrogen chloride by-produced in the precursor production process by 245fa or fluorination is preferable because there are many compounds that can be derived or separated into the target compound. Specifically, CF ₃ —CH═CHR ³ (R ³ is a chlorine atom or a fluorine atom), CF ₃ —CH ₂ CHR ¹ R ² (R ¹ and R ² are each independently a chlorine atom or a fluorine atom) ) Is a preferred compound that can be converted to 1233. Of course, hydrogen chloride produced as a by-product in other processes that are completely unrelated can be used, but it is necessary to confirm that the contained impurities can be separated from 1233 and that they do not become catalyst poisons.

  Usually, 245fa or by-product hydrogen chloride in the precursor synthesis step by fluorination often contains HF. In general, by-product hydrogen chloride containing even a small amount of HF, which is a corrosive toxic high-pressure gas, has no commercial value. However, it should be noted that the by-product hydrogen chloride containing HF is very effective for the 1233Z production method (B). This is because hydrogen chloride containing a small amount of HF has an effect of activating the catalyst. As will be described in detail later, the best mode catalyst in the present invention is treated with HF before use.

  The hydrogen chloride usable in the 1233Z production method (B) may be a crudely distilled product. By-product hydrogen chloride is usually recovered as a mixed gas of HCl and HF, but when used in this reaction, crude separated by crude distillation can be used. A preferable HF concentration is 0.001 to 10% by mass, and more preferably 0.1% to 5% by mass.

  Since high purity hydrogen chloride can be used, hydrogen chloride containing no HF is also possible. However, hydrogen chloride containing HF in the above range is preferable because it has an effect of maintaining the condition of the catalyst. However, if the content of HF is larger than this range, the ratio of the compound in which HF is added to 1233 or 1234 may increase. The ratio of hydrogen chloride to HF is preferably dry pressure distillation.

Next, the ratio of HCl (hydrogen chloride) / organic raw material in this reaction will be described. The “organic substance” described here is a raw material composition (a composition containing 1234E, 1234Z, CF ₃ CH ₂ CHR ¹ R ² as a main component). “HCI / organic ratio” is the respective molar ratio. The HCl / organic material ratio is preferably 0.1-30. More preferably, 0.5 to 20 is recommended. If the ratio is lower than 0.1, the conversion rate is insufficient, the coking of organic matter is promoted, and the catalyst may be lowered with time, which is not preferable. On the other hand, when the ratio is larger than 30, the load of hydrogen chloride recovery may increase or the production amount may decrease.

  Further, HF can be added as desired, but in that case, HCl / HF = 2 or more is preferable in terms of molar ratio. When HF is added excessively, the by-product of 245fa which is a warming substance may increase. Moreover, it is also possible to add inert gas, such as nitrogen and argon, as desired by those skilled in the art.

  Next, the catalyst concerning 1233Z manufacturing method (B) is demonstrated. The catalyst is preferably a halogenated metal. The halogenated metal refers to a state in which a metal atom is oxidized by a halogen, and generally has a metal-halogen bond (MX bond, M: metal, X: halogen atom). The metal mentioned here is not limited to zero-valent metal, but also includes metal oxides and metal salts. For example, the present invention includes an active species having a MX bond (for example, Al-F bond) on a part of its surface by fluorinating or chlorinating a metal salt or metal oxide such as aluminum phosphate, aluminum sulfate, or alumina. As a solid catalyst. The catalyst obtained by molding the aluminum fluoride powder is preferably fluorinated before use, but has an Al-F bond in advance, so that it can be used as it is. As a method for confirming the presence or absence of the MF bond, instrumental analysis by EZAFS, XAFS, XRF, XPS, IR, or XRD is preferable.

  As a simple method, the catalyst after completion of the reaction is calcined at 300 ° C. to remove the halogen physically adsorbed on the surface, and if a metal atom and a halogen atom are detected by any of the above analysis, the present invention is applied. It can be said that it is an effective catalyst. The calcining time required to remove the physically adsorbed halogen atom is preferably 12 to 120 hours. Further, when the calcination is performed under a nitrogen flow or under reduced pressure, the physically adsorbed halogen can be more efficiently removed. In particular, XAFS and XPS are preferable because the state of the metal-halogen bond can be analyzed in detail. Usually, the physically adsorbed halogen is often adsorbed as hydrogen halide.

  Preferred halogens are fluorine, chlorine, bromine and iodine, particularly fluorine and chlorine are preferred, and fluorine is particularly preferred. It is also effective to fluorinate part or most of the metal surface with hydrogen fluoride or the like. When a compound containing a halogen element is used as a raw material as in this reaction, a metal-halogen bond can be formed by bringing the raw material itself into contact with a metal. Therefore, by using the metal and the compound capable of forming the MX bond at the same time, it becomes a solid catalyst of the present invention having the MX bond as a result, and this reaction can be caused by the action of raw materials. (In this case, it is presumed that the MX bond is confirmed by analyzing the catalyst after the reaction). However, the method of generating active species having M—X bonds by distributing the raw material ozone depleting substance by omitting the step of positively fluorinating with hydrogen fluoride or the like is used in the metal halogenation step. The ozone depleting substance has the disadvantage of decomposing.

  As a preferable metal, the metal which belongs to 4-15 group of a periodic table is illustrated. Among these, aluminum atoms (atomic number 13) and transition metals having atomic numbers 22 to 78 are preferable. Specific examples include aluminum, titanium, chromium, manganese, nickel, copper, cobalt, zirconium, niobium, molybdenum, tin, antimony, and tantalum. These may be used alone, but it is also preferable to use a plurality of metals. Moreover, it is possible to add an element desired by those skilled in the art such as magnesium, sodium and potassium as a co-catalyst.

  In a catalyst having an M—X bond, a halogen atom (X) having a high electronegativity attracts M electrons, and therefore M is usually in a state where electrons are insufficient. A metal in such a state often exhibits Lewis acidity. In particular, a catalyst having a high electronegativity fluorine atom or chlorine atom as X, or a catalyst having a large number of MF bonds tends to exhibit stronger Lewis acidity. Therefore, a catalyst exhibiting Lewis acidity can also be said to be a suitable catalyst for this reaction. In particular, those in which X is F or Cl and there are many MF bonds can be said to be preferable catalysts in this reaction. Specifically, in the XPS measurement, those having an X / M (atomic ratio) of 2 or more are suitable.

  The size of the catalyst is preferably 1/30 to 1/3 of the inner diameter of the reaction tube used for the reaction, more preferably 1/20 to 1/5. If it is larger than these ranges, the raw material may slip through without contacting the catalyst, and if it is smaller than these ranges, the pressure loss may increase or may be blocked. Specifically, a catalyst having a size of about 0.5 mm to 20 mm, more preferably 2 mm to 10 mm is recommended.

  As a method for preparing a catalyst having such a size, there is a method in which a metal oxide or metal salt having an atomic number of 13 to 78 is molded into a spherical shape or a pellet shape. It is possible for those skilled in the art to press-mold metal oxides and metal salts using a compression molding machine, but pellets mainly composed of alumina (γ alumina, α alumina, etc.), titania and zirconia Balls (spheres) are commercially available. Also effective is a method of impregnating a solution containing the above-mentioned effective metal component using activated carbon (coconut shell charcoal, charcoal, peat, etc.) or a metal oxide thereof as a carrier (this catalyst is referred to as an impregnation catalyst). Further, it is desirable that the carrier is fluorinated with HF or the like in advance.

  The method for preparing the impregnation catalyst is not particularly limited, but the support in which the metal salt is supported is impregnated or sprayed on a solution in which a soluble compound such as nitrate, chloride or oxyhalide is dissolved, and then dried. By contacting with hydrogen fluoride, hydrogen chloride, chlorofluorohydrocarbon or the like under heating, it is obtained by halogen modification of a part or all of the supported metal or carrier. Further, fluorinated alumina, titania, stainless steel or the like (for example, fluorinated alumina) or activated carbon can also be used as a catalyst. Any method may be used for the fluorination method. For example, fluorinated alumina is heated to alumina that is commercially available for drying or as a catalyst carrier, and hydrogen fluoride is circulated in the gas phase, or near the room temperature. It can be prepared by spraying an aqueous hydrogen fluoride solution or immersing it in the aqueous solution and then drying.

  In the case of a compound that is liquid at around room temperature, such as antimony pentachloride, tin tetrachloride, or titanium tetrachloride, it can be impregnated directly into activated carbon, alumina, or the like.

  It is a preferable method that the catalyst prepared by any method is activated by contacting with a fluorinating agent such as hydrogen fluoride, fluorinated or fluorinated hydrocarbon in advance before use.

  Particularly preferred catalysts are alumina, titania, zirconia, niobia, chromium / activated carbon, nickel / activated carbon, iron / activated carbon, antimony / activated carbon, chromium / alumina, chromium / zirconia. Treating these catalysts with HF gas before the reaction is one of the preferred embodiments of the present invention, and the catalyst obtained by the operation is particularly preferred for use in the present reaction.

  Next, reaction conditions of the 1233Z production method (B) will be described. First, the reaction method of the 1233Z production method (B) is preferably a gas phase distribution method, and specifically, reaction methods such as a fixed bed circulation method, a fixed bed circulation method, and a fluidized bed circulation method are exemplified. The gas phase distribution method is simple. The reaction may be performed under reduced pressure or under pressure, but operation near normal pressure is easy.

Although the optimal reaction temperature of 1233Z manufacturing method (B) depends on the kind of catalyst, a state, and contact time, 200 to 500 degreeC is preferable. More preferably, it is 250 to 400 degreeC. When the temperature is lower than 200 ° C., the conversion rate is low. Moreover, when it is 400 degreeC or more, an undesirable side reaction increases or it causes coking.
The contact time depends on the raw material composition, but is usually preferably 0.1 seconds to 200 seconds, and more preferably 2 seconds to 150 seconds. When shorter than 0.1, a conversion rate may become low or a pressure loss may become large.

  If the catalytic activity is reduced by long-term operation, the coking substance on the catalyst surface can be removed by oxidation treatment using air or chlorine at 250 to 800 ° C. At this time, if treatment is performed using 100% air or chlorine, rapid heat generation may occur. Therefore, it is desirable to dilute with nitrogen or the like for safety. It is preferable to control the dilution rate of nitrogen while confirming the temperature of the heat spot. Further, it is recommended to perform a treatment with HF or HCl after the oxidation treatment.

  In the case of a gas phase distribution method, the product can be easily recovered by cooling. The cooling temperature is preferably from -80 ° C to + 5 ° C. When this temperature range is low, not only a special refrigerator is required but also solidification may occur in some cases. Moreover, when it is higher than this temperature, the collection efficiency may be lowered. The collected product is preferably washed with fluorine ions or chlorine ions with water or a basic aqueous solution. The cleaning method may be batch or continuous. When washing with an alkaline aqueous solution, neutralization heat may be generated. First, after removing most of the chlorine ions and fluorine ions with water, the alkaline aqueous solution is used to remove the alkali content. A method of washing with water is preferred. The sample after washing is preferably dried with a solid dehydrating agent such as zeolite.

  In general, organic substances are said to decompose at 200 ° C. to 300 ° C. Therefore, the high temperature reaction as in the present invention is a by-product of impurities that are difficult to purify by distillation due to decomposition of raw materials and products and unexpected reactions. Is concerned. From the viewpoint of safety and quality stability, especially high-purity products are required for working fluids, cleaning agents, solvents, and foaming agents, so the process cannot be established if by-product of difficult-to-separate substances is produced as a by-product in any high-yield reaction. . However, under the reaction conditions of the 1233Z production method (B), substantially difficult-to-distill substances are not recognized, and high purity can be easily achieved.

  The distillation equipment is not particularly limited, but preferably has 10 to 30 theoretical plates. If the number of stages is less than 10 stages, the distillation yield may be reduced. If the number of stages is more than 30 stages, there is no particular problem from the viewpoint of purification, but the equipment cost and running cost may increase. Since the boiling point of 1233E is 19 ° C., the refrigerant in the distillation column is preferably −50 ° C. to + 5 ° C., particularly preferably −20 ° C. to 0 ° C. When the refrigerant temperature is lower than −50 ° C., special refrigeration equipment is necessary, and the running cost becomes high. When the refrigerant temperature is higher than + 5 ° C., it is necessary to distill under a pressurized condition, and the loss increases.

  In the case of applications such as working fluids, cleaning agents, solvents, and foaming agents, not only the organic purity described above but also the halogen ion concentration and water management are required. Halogen ions such as fluorine ions and chlorine ions and moisture cause corrosion of the apparatus in the case of working fluids, corrosion of parts in the case of cleaning agents for metal parts, and poisoning of amine catalysts in the case of foaming agents. In other words, if the organic purity, halogen ion concentration, and moisture are preferable, it can be said that the quality can be used for working fluids, cleaning agents, solvents, foaming agents and the like. Usually, the organic purity is preferably 99% or more, more preferably 99.5% or more. The moisture is preferably 100 ppm or less, more preferably 30 ppm or less. The acid content is preferably 5 ppm or less, more preferably 0.5 ppm or less.

  The 1233Z production method (B) may include the following steps [1] to [4]. A known method can be applied to the process such as distillation.

  A process [1] for producing 1233 from 1230 and / or 240fa, comprising fluorinating 1230 and / or 240fa with hydrogen fluoride to obtain a first composition comprising 245fa and hydrogen chloride; Step [2] for separating 240fa and hydrogen chloride by distillation from one composition, and step for obtaining a second composition containing 1234 by dehydrofluorinating 245fa separated in step [2] [ 3], and the step [4] of obtaining 1233 by reacting the second composition with the hydrogen chloride separated in step [2].

[(C) Production method of 1233Z by radical isomerization]

1233Z used in the present invention is
A method for producing 1233Z comprising a radical isomerization step in which a raw material containing at least 1233E or 1233Z is reacted in the presence of a radical and the ratio of 1233E and 1233Z in the raw material is changed (hereinafter, this production method is referred to as “1233Z production method”). (C) ".
It may be manufactured by.

  “Radical isomerization” refers to the interconversion of 1233 trans isomer (1233E) or cis isomer (1233Z) in the presence of a catalytic amount of radicals in the reaction tube system (ie, 1233E to 1233Z, Isomerize 1233Z to 1233E). In the state where no radical exists in the low temperature region, the isomerization reaction 1233 substantially does not proceed. However, when a very small amount of the radical generator is added, the isomerization reaction proceeds at a surprising rate. Accordingly, in the 1233Z production method (C), since the radicals work efficiently as a catalyst, a solid catalyst is not particularly necessary.

  1233 used as the raw material of the present invention may be 1233E or 1233Z or a mixture thereof. 1233 manufactured by a known method can be used. For example, a mixture of 1233E and 1233Z obtained by reacting 240fa with hydrogen fluoride in a gas phase, and this mixture is subjected to a known purification treatment. Thus obtained composition may be used.

  The mixture of 1233E and 1233Z obtained by reacting the above 240fa with hydrogen fluoride usually may contain 1244Z and 244fa and 235da which are difficult to be separated by distillation, but in 1233Z production method (C), from 1233Z It is one of the advantages that it can be carried out without separating 244fa and 235da, and there is no problem even if a by-product derived from the production of the raw material used is included.

  Usually, 1233 obtained by a known production method is a mixture of 1233E and 1233Z, and the ratio of 1233E and 1233Z is governed by thermodynamic equilibrium. This equilibrium ratio depends on the temperature conditions, and also changes depending on the reaction conditions such as the type and shape of the reaction vessel and the presence of the catalyst.

  The isomerization reaction in the 1233Z production method (C) is to achieve the equilibrium ratio of 1233E to 1233Z by the radical reaction to the thermodynamic equilibrium point, and the isomer ratio of 1233Z to 1233E (1233Z / 1233E) is more than the equilibrium ratio. If so, at least a portion of 1233Z is converted to 1233E. On the other hand, if the isomer ratio of 1233Z to 1233E (1233Z / 1233E) is smaller than the equilibrium ratio, at least a portion of 1233E is converted to 1233Z. Since the ratio of 1233E / 1233Z is governed by thermodynamic equilibrium, the apparent conversion rate from 1233Z to 1233E becomes small when a raw material having a high content of 1233E is used. Similarly, when a raw material having a high content of 1233Z is used, the apparent conversion rate from 1233E to 1233Z becomes small.

  When 1233Z is desired as the target compound, that is, when 1233E is converted to 1233Z, the ratio of 1233E present in the raw material is at least 50% by mass, preferably 70% by mass, more preferably 90% by mass. Is preferred. Further, the isomer ratio of 1233Z / 1233E in the raw material is preferably 0 to 2, and the isomer ratio closer to 0 is more preferable.

  When 1233E is to be obtained as the target compound, that is, when converting from 1233Z to 1233E, the ratio of 1233Z present in the raw material is at least 30% by mass, preferably 50% by mass, more preferably 90% by mass. Is preferred. Further, the isomer ratio of 1233E / 1233Z in the raw material is preferably from 0 to 3, more preferably from 0 to 1, and the isomer ratio is preferably closer to 0.

  Since 1233E and 1233Z can be easily separated by distillation due to the difference in boiling points, when a mixture of 1233Z and 1233E is used as a raw material, it is preferable to perform distillation separation in advance. When 1233Z is the target compound, it is preferable to distill and separate a mixture of 1233Z and 1233E, using 1233Z as a product and 1233E as a raw material. On the other hand, when 1233E is the target compound, it is preferable to distill and separate a mixture of 1233Z and 1233E, using 1233E as a product and 1233E as a raw material.

  Further, the product obtained by the isomerization reaction of 1233Z production method (C) is collected, and 1233E or 1233Z which is the target compound is isolated by distillation or the like, and then unreacted 1233Z or 1233E is used again as a raw material. This is reasonable and preferable from the viewpoint of efficiently using the raw materials.

  In the 1233Z production method (C), if a radical can be generated in the reaction system, an isomerization reaction for interconverting the 1233 isomers (1233E which is a trans isomer and 1233Z which is a cis isomer) can proceed. . The method for generating radicals in the system is not particularly limited, and examples thereof include a method for generating radicals with light, heat, and a catalyst. In addition, when generating a radical by light, it is also possible to use a sensitizer etc. together. From the viewpoint of operability and simplicity, a method of adding an additive that easily generates radicals by applying external energy (hereinafter sometimes referred to as “radical generator” in the present specification for convenience). Is one of the preferred embodiments in the present invention.

  As a method for bringing a radical and a raw material containing 1233 into contact, for example, in the case of a gas phase reaction, a method in which light or heat is applied to the radical generator to activate the radical generator in advance and then introduced into the reaction tube, radical For example, a method of introducing a mixture of a generating agent and a raw material containing 1233 into a reaction tube and activating it with light or heat can be used. A method in which the mixture is simultaneously fed to the reaction tube is preferred. In addition, when supplying the raw material containing 1233, of course, it is also possible to entrain inert gas, such as nitrogen, with a raw material in the range which does not reduce productivity by adding excessively.

  Industrially, a method in which a mixture of a radical generator and a raw material containing 1233 is simultaneously supplied to a heated reaction tube, and thermal energy is generated by applying thermal energy to the mixture in the reaction tube is simple and preferable.

  Specifically, when 1233Z is desired as the target compound, trans-1-chloro-3,3,3-trifluoropropene, chlorine, oxygen, bromine, air, hydrogen peroxide, ozone, nitrogen oxides A method comprising heating a mixture containing at least one additive selected from the group consisting of carbon halides and isomerizing 1233E to 1233Z by a radical reaction is preferred. By radical reaction, at least part of 1233E can be converted to 1233Z, and the ratio of 1233Z to 1233E can be increased.

If you want to obtain 1233E as the target compound,
1233Z,
At least one additive selected from the group consisting of chlorine, oxygen, bromine, air, hydrogen peroxide, ozone, nitrogen oxide, and halogenated carbon;
A method in which 1233Z is isomerized to 1233E by a radical reaction by heating a mixture containing is preferable. By radical reaction, at least part of 1233Z can be converted to 1233E, and the ratio of 1233E to 1233Z can be increased.

  In the present invention, the radical means a chemical species such as an atom, molecule, or ion having an unpaired electron, a radical cation having a positive charge of the chemical species, a radical anion having a negative charge of the chemical species, and a charge of the chemical species. Includes neutral radicals, biradicals, carbenes and the like. Specific examples include fluorine radicals, chlorine radicals, bromine radicals, iodine radicals, oxygen radicals, hydrogen radicals, hydroxy radicals, nitroxide radicals, nitrogen radicals, alkyl radicals, difluorocarbenes, and carbon radicals.

  The radical generator in the 1233Z production method (C) is not particularly limited as long as it generates radicals by applying external energy such as light and heat. As a specific example of the radical generator, those that easily generate radicals in the reaction system are preferable. For example, halogen gas such as chlorine and bromine, air, oxygen, ozone, hydrogen peroxide, nitrogen oxide and the like Gas or halogenated carbon can be used. Halogenated carbons include alkanes such as methane, ethane, propane, butane, pentane and hexane, alkenes such as ethene, propene, butene, pentene and hexene, and alkynes such as ethyne, propyne, butyne, pentyne and hexyne. Mention may be made of halogenated carbons in which some or all of the hydrogen atoms in the class are substituted with fluorine, chlorine, bromine or iodine atoms. The halogenated carbon preferably contains at least one chlorine atom, bromine atom, or iodine atom. A compound having 4 or more fluorine atoms may hardly undergo radical cleavage, but in such a case, it is preferable to appropriately optimize the conditions for generating radicals such as temperature.

Specific examples of the carbon halide include CH ₃ Cl, CH ₃ Cl, CH ₂ Cl ₂ , CHCl ₃ , CCl ₄ , CH ₃ CH ₂ Cl, CH ₃ CCl ₃ , CH ₂ ClCH ₂ Cl, and CH ₂ = CCl _2. , CHCl = CCl ₂ , CCl ₂ = CCl ₂ , CHCl ₂ CHCl ₂ , CCl ₃ CH ₂ Cl, CH ₃ CH ₂ CH ₂ Cl, CH ₃ CHClCH ₃ , CH ₃ CHClCH ₂ Cl, CH ₃ Br, CH ₂ Br _{2 , CHBr 3, CBr 4, CH} 3 CH 2 Br, CH 3 CBr 3, CH 2 BrCH 2 Br, CH 2 = CBr 2, CHBr = CBr 2, CBr 2 = CBr 2, CHBr 2 CHBr 2, CBr 3 CH 2 _{Br, CH 3 CH 2 CH 2} Br, CH 3 CHBrCH 3, CH 3 CHBrCH 2 B _{, CH 3 I, CH 2 I} 2, CHI 3, CI 4, CH 3 CH 2 I, CH 3 CI 3, CH 2 ICH 2 I, CH 2 = CI 2, CHI = CI 2, CI 2 = CI 2, CHI ₂ CHI ₂ , CI ₃ CH ₂ BI, CH ₃ CH ₂ CH ₂ I, CH ₃ CHICH ₃ , CH ₃ CHICH ₂ I, CF ₂ HCl, CF ₃ I, CF ₂ I ₂ , CF ₃ Br, CF ₂ Br ₂ is exemplified.

  Among the above radical generators, oxygen, air, or chlorine is a preferred radical generator because it is inexpensive and easily available. Chlorine is suitable as a radical generator, but chlorine is very corrosive and has high solubility in 1233Z or 1233E. Therefore, after the isomerization reaction is completed, it must be washed away with a basic aqueous solution to which a reducing agent is added. There is. On the other hand, air or oxygen is a particularly preferred radical generator because it can be easily separated from the product.

  A preferred form of 1233Z production method (C) is to add a radical generator. Since the generation of radicals is known to be chained, it is preferable to add a small amount of radical generator. This is because the addition of an excessive radical generator not only wastes secondary materials but also places a burden on the separation process of the radical generator and 1233 after the reaction. Even in the case of air that is relatively easy to separate, as the amount of air added increases, the ability of the condensation process or distillation process decreases. Moreover, when chlorine is added excessively, a compound in which chlorine is added to the double bond is by-produced. In particular, since the compound having chlorine in 1233 is HCFC which is a global warming and ozone depleting substance, it is preferable that the amount of by-product of the chlorine adduct is small.

  As a result of conducting an experiment in which the addition ratio of the radical generator was changed, even if the addition amount was reduced to the lower limit of measurement of the chlorine flow meter in the experiment, there was substantially no effect on the conversion rate. It was found that the addition amount could be very small (see Example 3). However, the optimal amount of radical generator added depends on the type of radical generator and the structure of the reaction tube. For example, when comparing air, oxygen, and chlorine, the level of activity is in the order of chlorine> oxygen> air. Further, the collision between the radical generated from the radical generator and 1233 is very important. The probability of collision between 1233 and radicals varies depending on the diameter and length of the tube and the presence or absence of a filler such as a static mixer. Therefore, in the case of a reaction tube excellent in mixing, it is desirable to add a small amount of radical generator. The conversion can be achieved, but if not, the conversion can be improved by increasing the radical concentration by increasing the amount of radical generator added.

  Specifically, the amount of radical generator added depends on the type of radical generator and the shape of the reaction tube, but is usually 0.0001 mol% to 10 mol% with respect to 1233Z or 1233E as the raw material, 0.0001 mol% to 0.005 mol% is more preferable. In a reaction tube excellent in contact between radicals and 1233, since 1233 and radicals can sufficiently collide, the amount of radical generator added is preferably 0.0001 mol% to 0.005 mol%.

  As an example of a reaction tube excellent in contact between radicals and 1233, a reactor equipped with a static mixer, a Raschig ring, a pole ring, a wire mesh or the like that is inert to the reaction is exemplified. In the present invention, it is of course possible to place a packing in the reaction tube. However, a reaction tube having a large length / inner diameter ratio can efficiently bind radicals and 1233E even in an empty column having no packing as described above. It is particularly preferable because it not only enables contact but also excels in heat transfer. Specifically, the length / inner diameter ratio is 10 to 1000, preferably 20 to 500. When the ratio of length / inner diameter is smaller than 10, the contact between the radical and 1233 may not be sufficient, and when the ratio of length / inner diameter is larger than 1000, the apparatus cost increases or depending on the operating conditions. Pressure loss may increase. Usually, the reaction tube has an inner diameter of 8 mm to 150 mm and a length of 1 to 200 m, and an empty reaction tube having an inner diameter of 10 to 60 mm and a length of 2 to 50 m is a particularly preferable range. . The shape of the reaction tube is not particularly limited, and may be a straight tube or a coil shape, and may be folded using a joint or the like.

  As described above, in the 1233Z production method (C), radical generation proceeds in a chain. Therefore, when the reaction temperature at which the radical generator can generate radicals is reached, even if the radical initiator is recombined, it is easily cleaved again, so that this isomerization reaction is promoted even with a very small amount of catalyst. That is, one of the advantages of this isomerization reaction is that only a small amount of catalyst may be added.

  The material of the reactor is preferably carbon, ceramics, stainless steel, nickel, hastelloy, inconel, monel or the like. In addition, a quartz tube or the like can be used for a small facility. An unfilled reaction tube may be used, but a static mixer may be used if desired. In addition, fillers such as Raschig rings and pole rings can be added. These materials are also preferably corrosion resistant materials as described above. When the reaction apparatus is heated, the heating method is not particularly limited, but it may be heated directly with an electric heater or a burner, or indirectly with a molten salt or sand.

  In the 1233Z production method (C), a solid isomerization catalyst is not essential, but, of course, it can be used as desired by those skilled in the art. Specific examples include solid catalysts such as metals, metal oxides, metal halides, and activated carbon, and composites (for example, metal-supported activated carbon) can also be used. For example, when a solid catalyst is used in a region having a high reaction temperature of 350 ° C. or higher, 1233E or 1233Z may cause coking on the catalyst surface or produce oil. It is preferable to use a solid catalyst which has been deactivated by calcination.

  In the 1233Z production method (C), a solid isomerization catalyst may be used. However, in order not to reduce the efficiency of the radical reaction, the isomerization reaction is performed using an empty reactor that does not use a catalyst or packing. It is preferable to carry out. In the present specification, “empty tower” means that no object such as a catalyst or packing is present in the reactor or the internal space of the reaction tower. When an object such as a catalyst or a packing is present in the isomerization reaction region, the generated radical may disappear and the radical chain reaction may be stopped, resulting in a decrease in isomerization efficiency. For this reason, the 1233Z production method (C) is particularly preferably carried out in a vapor-phase circulation type empty column (see Example 3).

  In addition, when a solid isomerization catalyst is inserted, not the isomerization reaction but a radical generator and 1233 (1233E or 1233Z) may cause an unexpected reaction. In this case, since the reaction raw material 1233 is only converted into an undesirable by-product, the radical generator is consumed in the reaction with 1233, which may be undesirable.

  The reaction temperature is usually in the range of 150 to 800 ° C, preferably 150 to 450 ° C, more preferably 200 to 350 ° C. The preferable reaction temperature can be rephrased as a temperature at which radicals are efficiently generated from the radical generator. When the reaction temperature is lower than 150 ° C., radicals are not sufficiently generated, and the reaction rate may be very slow. On the other hand, when the temperature is higher than 800 ° C., the raw material or the purified organism may become an oily high-boiling product or may be caulked.

  On the high temperature side, when the target compound is 1233E, thermodynamic equilibrium is disadvantageous. When 1233E is used as the target compound, the reaction temperature is usually in the range of 150 to 800 ° C, preferably 150 to 450 ° C, more preferably 200 to 350 ° C. On the other hand, when 1233Z is used as the target compound, the temperature is preferably in the range of 150 to 800 ° C, more preferably 300 to 700 ° C, more preferably 350 to 600 ° C.

  The reaction may be a batch type or a distribution type, but a gas phase distribution system with high industrial productivity is preferred. The reaction pressure is not particularly limited, but operation near normal pressure is easy. However, a pressure reaction of 1 MPa or more is not preferable because not only an expensive pressure-resistant apparatus is required but also polymerization of raw materials or products is concerned.

  In general, in the case of a gas phase circulation system, productivity is often discussed by a value obtained by dividing the volume of a reaction system by a raw material supply rate. If the reaction system is filled with a catalyst, it is called the contact time. In the case of the 1233Z production method (C), a solid catalyst is not used, but it is also referred to as contact time for convenience.

  The contact time in the 1233Z production method (C) is not particularly limited as long as isomerization proceeds sufficiently, but is usually from 0.01 seconds to 50 seconds, preferably from 0.05 seconds to 20 seconds. In general, if the contact time is shorter than these, only the conversion rate greatly deviating from the thermodynamic equilibrium composition may be exhibited. On the contrary, when larger than these, even if the conversion rate close | similar to an equilibrium composition is shown, productivity may worsen or it may tartarize.

The mixture of 1233E and 1233Z obtained by isomerization removes radical generators and acid content by washing, and after drying with zeolite or the like, 1233E and 1233Z can be isolated by ordinary distillation operation. The obtained 1233E and 1233Z can also be used as a raw material for the reaction.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these embodiments.

  Unless otherwise noted, the composition of the organic substance was measured by gas chromatography using an FID detector, and the recorded “area%” was displayed as “GC%”.

<1233Z Production Method (A)>

[Example 1-1]
In the hood, a reaction tube (outer diameter 8 mm, inner diameter 6 mm, length 600 mm), in which nothing was filled, wrapped with two sheathed heaters each capable of temperature control independently, was placed vertically. A pressure gauge, nitrogen inlet, and organic substance inlet were installed at the top of the reaction tube, and a gas sampling port was installed at the outlet. The length of the upper heating zone (preheating part, 250 ° C. setting) is 200 mm, and the length of the lower heating zone (reaction part temperature is listed in Table 1) is 300 mm (reaction part volume: 8.48 ml). is there. At the outlet of the reaction tube, after passing through a gas washing bottle cooled with ice (content: 10 g of baking soda dissolved in 190 g of ion-exchanged water), a drying tower filled with synthetic zeolite (MS-3A), dry ice -A stainless steel (SUS) trap cooled with acetone (a rubber balloon with a pinhole at the outlet) was installed (see FIG. 1).

  While circulating nitrogen (300 ml / min), after heating the upper preheating part to 250 ° C. and the lower reaction part to 500 ° C., 1233E having a purity of 99.19% was supplied at a rate of 0.6 g / min. The nitrogen supply was stopped after 1 minute. Table 1 shows the results of analyzing the gas collected by the gas tight syringe from the gas sampling port after 4 hours. Further, as a result of visual observation, generation of oil was not recognized.

[Examples 1-2 to 1-13]
An experiment similar to Example 1-1 was performed except that the reaction temperature and the organic substance supply rate (residence time) were changed. The results are shown in Table 1. Further, as a result of visual observation, generation of oil was not recognized.

[Example 1-14]
The same experiment as in Example 1-13 was performed except that 100 ml / min of nitrogen was accompanied. The results are shown in Table 1. By nitrogen entrainment, by-product of low boiling point such as TFPy was suppressed.

[Comparative Examples 1-1 to 1-3]
An experiment similar to Example 1-1 was performed except that the reaction temperature and the organic substance supply rate (residence time) were changed. The results are shown in Table 1. In Comparative Examples 1-1 and 1-2, no oil was produced, but the conversion rate did not reach a practical level. In Comparative Example 1-3, a large amount of oil was generated (the gas sampling port was contaminated with oil and could not be analyzed by gas chromatography).

[Comparative Example 1-4]
After crushing the γ-alumina beads and filling 8.5 ml of particles of about 0.5 mm to 1.5 mm into the reaction tube, the same experiment as in Example 1-1 was performed under the conditions shown in Table 1. After the formation of oil was observed, the reaction tube was blocked and the experiment was stopped.

[Comparative Example 1-5]
The same experiment as Comparative Example 1-4 was performed except that AlF ₃ pellets were used. Similarly, after the production of oil was observed, the reaction tube was blocked and the experiment was stopped.

[Example 1-15]
In order to determine the mass balance, after sampling in Example 1-10, the gas washing bottle (contents: ion-exchanged water (200 ml)) and the SUS trap were exchanged and the reaction was continued under the same conditions. After feeding 124.59 g (after about 85 minutes), both of the liquid in the gas washing bottle and the SUS trap were put into a separatory funnel previously cooled in a refrigerator and separated. As a result, 124.33 g of organic matter was recovered (the organic matter recovery rate was 99.8%, the composition was TFPy: 0.04%, 1234E: 0.43%, 1336: 0.00%, 245fa: 0.09% 1234Z: 0.17%, 1233E: 82.81%, 1233Z: 15.82%, others: 0.64%). Further, when the upper aqueous phase was subjected to neutralization titration with sodium hydroxide and silver nitrate titration, the hydrochloric acid content in the organic matter was 0.002 wt%, and the hydrogen fluoride content was 0.05 wt%. From the above, it was shown that substantially no oil generation or coking occurred under these conditions.

[Example 1-16]
An experiment similar to Example 1-8 was conducted for 12 hours, except that a SUS gas washing bottle (3000 ml) containing 5% by mass of sodium bicarbonate water (500 ml) was used. The gas cleaning bottle and the liquid in the trap were combined and separated to obtain 2092.5 g of organic matter. To this, 102 g of 5% by mass of sodium bicarbonate water was added for washing and liquid separation to obtain 2047.7 g of organic matter. To this, 101 g of ion-exchanged water was added and washed and separated to obtain 2012. 1 g of organic matter (the pH of the aqueous phase at this time was 8). As a result of adding 105 g of ion-exchanged water to this organic phase and washing and separating in the same manner, 1979.1 g of an organic substance was obtained (the pH of the aqueous phase at this time was 7). To this organic matter, 50 g of synthetic zeolite (MS-3A) was added, stored in a refrigerator overnight, and then filtered to obtain 1910.1 g of a sample having a water content of 8 ppm. Table 2 shows the results of fractional distillation of this sample in a distillation column having 35 theoretical plates. The organic substance was analyzed by gas chromatography using a microsyringe cooled to −5 ° C. In fraction 8, high purity 1233Z of 99.94 GC% was obtained, and 244fa and 235da were not detected in this fraction.

[Example 1-17]
Table 1 shows the results of experiments similar to those in Example 1-8 as a recycled material (1233E: purity 99.61%) obtained by blending fractions 2 to 6 obtained by distillation in Example 1-16. The same result was obtained with recycled materials.

<1233Z Production Method (B)>

In Example 2, the number of display digits or less was rounded off. For example, 0.00GC% in the table indicates that it is less than 0.005 GC%.

[Preparation Example 2-1]
A stainless steel (SUS316) reaction tube having a length of 240 mm and an inner diameter of 3/4 inch was charged with 36 g of γ-alumina beads (manufactured by Sumitomo Chemical Co., Ltd., KHS-46). The jacket temperature was controlled at 50 ° C., and HF was circulated at 0.4 g / min via a vaporizer while nitrogen (50 cc / min) was circulated. Due to the heat of adsorption of HF and the heat of reaction on alumina, heat generation was observed particularly at the entrance, and the tropics moved gradually toward the exit. At this time, when the heat spot having the highest temperature exceeded 400 ° C., the HF supply rate was lowered to 0.1 g / min to suppress local heat generation. After the tropics reached the exit, the jacket set temperature was raised to 350 ° C. by 50 ° C., and the same operation was repeated.

  Thereafter, the jacket set temperature was set to 350 ° C., and the HF flow rate was slowly increased to 0.7 g / min. When the temperature of the heat spot at this time exceeded 400 ° C., the HF flow rate was similarly lowered to 0.1 g / min. From the point of time when the heat spot is virtually no longer observed under the conditions of jacket temperature 350 ° C. and HF flow rate 0.4 g / min, the treatment is continued for 2 hours under the same conditions. Was turned off, cooled, and an HF-treated alumina catalyst was obtained.

[Example 2-1] (Raw material: 1234E)
The electric furnace was heated while flowing nitrogen at 15 ml / min. When the temperature of the catalyst reached 350 ° C., hydrogen chloride (HCl) containing 2.3% by mass of HF was introduced through a vaporizer at 166 ml / min. Immediately after introducing 1234E (99.9 GC%, detailed raw material composition described in Table 3) filled in a 1000 ml cylinder through a vaporizer at 0.14 g / min (27.5 ml / min) with HCl flowing. The nitrogen flow was stopped. After confirming a steady state at a reaction temperature of 360 ° C., analysis was performed. The sampling method is as follows. A sample is taken in a 100 cc polyethylene bag containing water (10 g), shaken to absorb the acid content with water, then heated to 50 ° C. in an oven, and the gas phase is analyzed by a gas chromatograph of an FID detector. The results are shown in Table 3.

[Examples 2-2 to 2-4]
The experiment was performed under the conditions shown in Table 3 in the same procedure as in Example 2-1. The hydrogen chloride used was high-purity hydrogen chloride having a purity of 99.99 GC%.

  From Example 2-1 to 2-4, according to the method of this invention, when 1234E is used as a raw material, it turns out that 1233 is obtained with a high yield.

[Examples 2-5 to 2-9] (Raw material: 1234Z)
The experiment was performed under the conditions shown in Table 3 in the same procedure as in Example 2-1, with the raw material used being 1234Z. In Examples 2-5, 2-7, 2-8, and 2-9, 99.99GC% high-purity hydrogen chloride was used. In Example 2-6, hydrogen chloride containing HF was used as in Example 2-1.

  From Examples 2-5 to 2-9, according to the method of the present invention, even when 1234Z is used as a raw material, 1233 can be obtained in a high yield as in Examples 2-1 to 2-4. I understand.

[Example 2-10]
The reaction was continued for about 100 hours under the reaction conditions of Example 2-5. The product was collected with a stainless steel cylinder cooled with dry ice, washed with ice water, and then dried with zeolite to obtain 790 g of a crude product. This was distilled in a glass distillation column having 20 theoretical plates. A 99.9 GC% fraction was provided in Example 2-11 and a fraction based on 1233Z from 38 ° C. to 41 ° C. was provided in Example 2-12.

[Example 2-11] (Use: Cleaning agent)
A fraction of 1233E (310 g) having a purity of 99.9 GC% obtained by distillation in Example 2-10 was stored in a refrigerator at a temperature of 10 ° C. 100 g of this sample was put in an ultrasonic cleaning machine, and the glass lens with the fingerprint was cleaned for 100 seconds. After washing, the film was dried with a dryer for 60 seconds and visually observed. As a result, the fingerprint disappeared and no spots were observed.

[Example 2-12] (Use: Detergent)
The same experiment as in Example 2-11 was performed using a fraction (36 g, main component: 1233Z) at 38 ° C. to 41 ° C. in the distillation of Example 2-10. As a result, as in Example 2-11, the fingerprint disappeared and no stain was observed.

<1233Z Production Method (C)>

1233 isomerization reaction was carried out using the gas phase reactor shown in FIG. As shown in FIG. 1, the gas phase reactor is equipped with a reaction tube wound with two sheath heaters (upper preheating unit and lower reaction heating unit), each of which can be controlled independently. A pressure gauge, a carrier gas inlet, and a raw material inlet were provided at the top of the tube, and a gas sampling port was installed at the bottom of the reaction tube. Furthermore, a gas washing bottle cooled with ice, a drying tower, and a stainless steel trap cooled with a dry ice-acetone trap were installed in order after the outlet of the reaction tube. The gas washing bottle was filled with a solution of 10 g of baking soda dissolved in 190 g of ion exchange water. The drying tower was packed with synthetic zeolite (MS-3A). In addition, a rubber balloon with a pinhole was installed at the exit of the trap. The reaction tube was isomerized in an empty column (empty state) without using a packing such as a catalyst.

  As a procedure for the isomerization reaction, the upper and lower sheath heaters of the reaction tube are controlled to a predetermined temperature using a PID temperature controller while nitrogen is circulated from the carrier gas inlet, and then the raw material compound is supplied from the raw material inlet. Was introduced at a predetermined feed rate and at the same time the nitrogen flow was stopped. When the reaction showed a steady state, the product gas was collected at the gas sampling port and analyzed by a gas chromatograph. Table 4 shows the experimental conditions of Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-3 and the gas composition results obtained.

[Isomerization reaction from 1233E to 1233Z]
[Example 3-1]
While circulating nitrogen (300 ml / min), the upper preheating part was heated to 250 ° C. and the lower reaction heating part was heated to 450 ° C., and then, 1233E (1233Z: 1233Z: 0.09%) having a purity of 99.23% from the raw material inlet. Content) was 1.27 g / min, and chlorine (Cl ₂ ) as a radical generator was fed at a feeding rate of 4.3 ml / min, and after 1 minute, the nitrogen supply was stopped. After 4 hours, the gas collected from the gas sampling port with a gas tight syringe was analyzed. As a raw material supply method, a mixture of 1233E and chlorine (Cl ₂ ) serving as a radical generator was simultaneously supplied to the reaction tube. Further, as a result of visual observation, generation of oil was not recognized. In Example 3-1, quartz was used as the material for the reaction tube. The molar ratio of chlorine / 1233E is 0.020.

[Examples 3-2 and 3-3]
The same experiment as in Example 3-1 was performed except that the reaction temperature and the raw material supply rate were changed. Further, as a result of visual observation, generation of oil was not recognized. In Examples 3-2 and 3-3, the molar ratio of chlorine / 1233E is 0.020 as in Example 3-1. [Example 3-4]
The same experiment as in Example 3-3 was performed except that a Ni reaction tube having the same size was used instead of the quartz reaction tube. The results are shown in Table 4. Further, as a result of visual observation, generation of oil was not recognized. In particular, no significant difference in the difference in the material of the reaction tube was observed, suggesting that the presence of radicals was greater than the wall effect.

In Examples 3-1 to 3-4, even when chlorine was added as a radical generator, the by-product of CF ₃ -CHCl-CHCl ₂ in which chlorine was added to 1233E was only about 0.1%. There was no side reaction.

[Comparative Examples 3-1 to 3-3]
As Comparative Examples 3-1 to 3-3, the reaction was performed under the same experimental conditions as in Examples 3-1 to 3-3 except that chlorine was not added. As a result, when no chlorine was added, the isomerization reaction did not proceed.

[Isomerization reaction from 1233Z to 1233E]
An isomerization reaction was performed using a raw material containing 1233Z as a main component. The results of Examples 3-5 to 3-8 and Comparative Examples 3-4 to 3-6 are shown in Tables 5 to 7. The isomerization reaction from 1233Z to 1233E was performed in the same procedure as in Example 3-1, using the gas phase reactor shown in FIG.

[Example 3-5]
An isomerization reaction was carried out using 1233Z containing a predetermined amount of carbon tetrachloride (CCl ₄ ) as a radical generator.

[Comparative Example 3-4]
As a comparative example, an isomerization reaction was performed using 1233Z containing no carbon tetrachloride (CCl ₄ ) as a raw material.

As shown in Table 5, the composition after the isomerization reaction had a ratio of 1233E / 1233Z of 71.75 / 14.05 = 5.16 and only 0.3% carbon tetrachloride (CCl ₄ ) But the isomerization reaction is in progress. On the other hand, the composition of the composition after the isomerization reaction in Comparative Example 3-4 has a ratio of 1233E / 1233Z of 9.05 / 78.68 = 0.115, which is 1233Z compared to Example 3-5. It can be seen that the isomerization reaction does not proceed sufficiently.

[Example 3-6]
At a feed rate of 0.41 g / min of 1233Z having a purity of 99.67% as a raw material and at a feed rate of 2.4 ml of chlorine gas as a radical generator (the molar ratio of chlorine / 1233Z is 0.034, chlorine Was added to a reaction tube (manufactured by Hastelloy C276) heated to 200 ° C., and the same experiment as in Example 3-5 was performed.

[Comparative Example 3-5]
The same experiment as in Example 3-6 was performed except that chlorine gas was not added.

In Table 6, in Example 3-6, in the composition after the isomerization reaction, the 1233E / 1233Z ratio was 79.69 / 19.70 = 4.05, and when the radical generator was added, 1233Z was obtained in a high yield. Can be converted to 1233E, whereas in the system without the radical generator of Comparative Example 3-5, the 1233E / 1233Z ratio is 1.05 / 98.6 = 0.011, and the isomerization proceeds substantially. It wasn't.

[Examples 3-7 and 3-8]
An experiment similar to that in Example 3-5 was performed using air as a radical generator instead of chlorine gas. Since oxygen in the air is an active ingredient as a radical generator and the oxygen component in the composition of air is 20.9%, the molar ratio of oxygen / 1233Z in Examples 3-7 and 3-8 is substantially Therefore, they are 0.028 and 0.0028, respectively.

Table 7 shows that 1233Z can be converted to 1233E with a high yield by adding air as a radical generator. In Comparative Example 3-6, only nitrogen was added as a radical generator, but sufficient isomerization reaction did not proceed, suggesting that oxygen in the air is an effective component as a radical generator. It was.

<Manufacturing of TFPy>

The following Comparative Examples 4-1 and Examples 4-1 to 4-3 were performed using 1233Z produced in Examples 1 to 3.

[Comparative Example 4-1]
First, a pressure gauge, a double-pipe condenser and a stirring blade are attached to a 1 L capacity stainless steel reactor, and an extraction pipe provided with an extraction valve is attached to the double-pipe condenser. To make a TFPy manufacturing apparatus.

  Next, potassium hydroxide (89.60 g, 1.6 mol), water 507.70 g and 1233Z (104.40 g, 0.8 mol) were charged into the reactor, and after sealing, the mixture was stirred with the stirring blade. While heating at 60-70 ° C. for 4 hours. The final pressure at that time was 1.0 MPaG. After completion of the reaction, a −20 ° C. refrigerant was passed through the condenser, the extraction valve was opened, and the organic matter was liquefied and collected by the collector cooled with methanol + dry ice.

  The recovered organic matter was 43.44 g. The yield of TFPy was 58.3%. When the recovered liquid was analyzed by gas chromatography, the purity of TFPy was 98.9%.

[Example 4-1]
In the same TFPy production apparatus as in Comparative Example 4-1, the reactor was charged with potassium hydroxide (168.00 g, 3.0 mol), water 504.00 g and 1233Z (195.75 g, 1.5 mol). It is. After sealing, the mixture was heated at 50 ° C. for 2 hours while stirring with the stirring blade. A refrigerant at −20 ° C. was passed through the condenser from the start of the reaction, the extraction valve was adjusted so that the reaction pressure did not exceed 0.2 MPaG, and the organic matter was removed by the collector cooled with methanol + dry ice. Liquefied and collected.

  The recovered organic matter was 118.68 g. The yield of TFPy was 83.5%. When the recovered liquid was analyzed by gas chromatography, the purity of TFPy was 99.4%.

[Example 4-2]
In the same TFPy production apparatus as in Comparative Example 4-1, the reactor was equipped with a dropping pump. The reactor was charged with 1233Z (104.40 g, 0.8 mol), sealed, and heated to 50 ° C. while stirring with the stirring blade, and an aqueous potassium hydroxide solution [potassium hydroxide (89.60 g, 1 0.6 mol) and 507.70 g of water] were pumped in over 2 hours. A refrigerant at −20 ° C. was passed through the condenser from the start of the reaction, the extraction valve was adjusted so that the reaction pressure did not exceed 0.2 MPaG, and the organic matter was removed by the collector cooled with methanol + dry ice. Liquefied and collected.

  The recovered organic matter was 64.58 g. The yield of TFPy was 85.9%. When the recovered liquid was analyzed by gas chromatography, the purity of TFPy was 97.5%.

[Example 4-3]
Using the same apparatus as in Example 4-2, the reactor was charged with potassium hydroxide (89.60 g, 1.6 mol) and 507.70 g of water. After sealing, the reactor was stirred with the stirring blade while stirring. Heated to ° C. and 1233Z (104.40 g, 0.8 mol) was pumped in over 2 hours. A refrigerant at −20 ° C. was passed through the condenser from the start of the reaction, the extraction valve was adjusted so that the reaction pressure did not exceed 0.2 MPaG, and the organic matter was removed by the collector cooled with methanol + dry ice. Liquefied and collected.

The recovered organic matter was 54.43 g. The yield of TFPy was 72.4%. When the recovered liquid was analyzed by gas chromatography, the purity of TFPy was 98.5%.

  The 3,3,3-trifluoropropyne produced in the present invention can be used as functional materials such as refrigerants, working fluids, etching agents, aerosols, physiologically active substances, intermediates of functional materials, and monomers of polymer compounds. .

Claims (2)

(Z) -1-chloro-3,3,3-trifluoropropene is produced by a production method including the following first to third steps,
The (Z) -1-chloro-3,3,3-trifluoropropene is then brought into continuous contact with an alkali metal hydroxide in the presence of water or charged into the reactor. (Z) -1-Chloro-3,3,3-trifluoropropene was dropped into contact with an aqueous solution of an alkali metal hydroxide, and the produced 3,3,3-trifluoropropyne was continuously removed from the reaction system. 3. A method for producing 3,3,3-trifluoropropyne, which is characterized by being extracted.
First step:
1,1,1,3,3-pentachloropropane or 1,3,3,3-tetrachloropropene is reacted with hydrogen fluoride to give (A) (E) -1-chloro-3,3,3 -Trifluoropropene and (B) 3-chloro-1,1,1,3-tetrafluoropropane, 2-chloro-1,1,1,3,3-pentafluoropropane, and 1-chloro-1 , 1,4,4,4-pentafluoro-2-butene, a step of obtaining a first composition comprising at least one compound selected from the group consisting of:
Second step:
From the first composition obtained in the first step, 3-chloro-1,1,1,3-tetrafluoropropane, 2-chloro-1,1,1,3,3-pentafluoropropane, and 1 At least one compound selected from -chloro-1,1,4,4,4-pentafluoro-2-butene is removed by distillation to obtain (E) -1-chloro-3,3,3-trifluoro Obtaining a second composition comprising propene.
Third step:
(E) -1-chloro-3,3,3-trifluoropropene contained in the second composition obtained in the second step is isomerized at 450 to 700 ° C. in the absence of a catalyst, and (Z) Obtaining a third composition comprising -1-chloro-3,3,3-trifluoropropene; The method for producing the (Z) -1-chloro-3,3,3-trifluoropropene further includes the following fourth step, A method for producing lopropyne.
Fourth step:
The step of distilling the third composition to obtain (Z) -1-chloro-3,3,3-trifluoropropene having a purity of 98% or more.

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