JP7070419B2 - Method for producing 1-chloro-2,3,3-trifluoropropene - Google Patents

Description

The present invention relates to a method for producing 1-chloro-2,3,3-trifluoropropene.

Since hydrochlorofluorocarbon (HCFC) has an adverse effect on the ozone layer, its production is scheduled to be regulated. HCFCs include, for example, 3,3-dichloro-1,1,1,2,2-pentafluoropropane (HCFC-225ca) and 1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225ca). HCFC-225cc) and the like, but with the regulation of HCFC, it is desired to develop a compound that replaces the above HCFC.

An example of a compound that replaces HCFC is 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd, hereinafter simply referred to as "1233yd"). 1233yd is a novel compound with a low global warming potential (GWP) that is useful in detergents, solvents, refrigerants, foaming agents and aerosols. In 1233yd, there are 1233yd E-form and Z-form as geometric isomers, but depending on the application and compatibility with the components to be mixed, 1233yd Z-form or 1233yd E-form may be used alone, or 1233yd may be used. The Z-form and the E-form of 1233 yd may be used as a mixture.

As a method for producing 1233yd, 3-chloro-1,1,2,2-tetrafluoropropane (HCFC-244ca) is reacted with hydrogen fluoride in the gas phase under a nitrogen stream using chromium hydroxide as a catalyst. A method for producing 1,1,2,2,3-pentafluoropropane (HCFC-245ca) is disclosed (see, for example, Patent Document 1). In this method, 1233 yd is by-produced. Therefore, 1233 yd can be obtained by recovering the composition obtained by the above reaction and separating 1233 yd contained in the composition.

However, the 1233yd produced by the above method is a mixture of the E-form of 1233yd and the Z-form of 1233yd.
Separation of 1233yd E and Z bodies is not disclosed. Further, the above method does not adjust the composition of the E-form and the Z-form of 1233 yd.

Therefore, there is a demand for a method capable of selectively reacting any of the E-form and the Z-form of 1233 yd to produce 1233 yd having a predetermined composition industrially and efficiently.

International Publication No. 1994/14737

The present invention provides a production method capable of selectively reacting any of the E-form and the Z-form of 1233 yd to produce 1233 yd having a predetermined composition by an industrially advantageous and efficient method. The purpose.

The present invention provides a method for producing 1233 yd having the following configuration.
[1] Equilibrium ratio (molar ratio) of 1-chloro-2,3,3-trifluoropropene (E) and 1-chloro-2,3,3-trifluoropropene (Z) at a predetermined isomerization reaction temperature. The 1-chloro-2,3,3-trifluoropropene (E) in the raw material composition contained in a different molar ratio from the above is isomerized at the isomerization reaction temperature to 1-chloro-2,3. , 3-A method for producing 3-chloro-2,3,3-trifluoropropene (Z), which produces trifluoropropene (Z).
[2] In the raw material composition, the molar ratio (1-) of the 1-chloro-2,3,3-trifluoropropene (Z) to the 1-chloro-2,3,3-trifluoropropene (E). Chloro-2,3,3-trifluoropropene (Z) /1-chloro-2,3,3-trifluoropropene (E)) is smaller than the equilibrium ratio (molar ratio) at the isomerization reaction temperature, [ 1] The method for producing 1-chloro-2,3,3-trifluoropropene (Z) according to 1].
[3] The production of 1-chloro-2,3,3-trifluoropropene (Z) according to [1] or [2], wherein the isomerization reaction is carried out by contacting the raw material composition with a metal catalyst. Method.

[4] The 1-chloro-2,3,3-described in [3], wherein the metal catalyst is at least one substance selected from the group consisting of elemental metals, alloys, metal oxides and metal halides. A method for producing trifluoropropen (Z).
[5] The metals constituting the metal catalyst are Group 4 metal elements, Group 6 metal elements, Group 8 metal elements, Group 9 metal elements, Group 10 metal elements, Group 11 metal elements, and Group 12. The 1-chloro-2,3,3-trifluoropropene (Z) according to [3] or [4], which is at least one element selected from the group consisting of group metal elements and group 13 metal elements. Production method.
[6] The 1-chloro-2,3,3 according to any one of [3] to [5], wherein the metal catalyst is at least one compound selected from the group consisting of metal oxides and metal halides. -A method for producing trifluoropropene (Z).
[7] The 1-chloro-2,3,3-trifluoropropene (Z) according to any one of [4] to [6], wherein the metal oxide is at least one selected from alumina and chromia. Production method.
[8] The 1-chloro-2,3,3-trifluoropropene according to any one of [4] to [6], wherein the metal halide is a compound in which a part of the metal chloride is fluorinated. (Z) Manufacturing method.
[9] The method for producing 1-chloro-2,3,3-trifluoropropene (Z) according to any one of [1] to [8], wherein the isomerization reaction temperature is 0 ° C. or higher and 500 ° C. or lower. ..

[10] The method for producing 1-chloro-2,3,3-trifluoropropene (Z) according to any one of [1] to [9], wherein the isomerization reaction is carried out in a liquid phase.
[11] The method for producing 1-chloro-2,3,3-trifluoropropene (Z) according to any one of [1] to [9], wherein the isomerization reaction is carried out in the gas phase.
[12] The method for producing 1-chloro-2,3,3-trifluoropropene (Z) according to [11], wherein the isomerization reaction is carried out in the presence of an inert gas.
[13] The method for producing 1-chloro-2,3,3-trifluoropropene (Z) according to any one of [11] and [12], wherein the isomerization reaction is carried out at 0 ° C. or higher and 260 ° C. or lower. ..
[14] Equilibrium ratio (molar ratio) of 1-chloro-2,3,3-trifluoropropene (E) and 1-chloro-2,3,3-trifluoropropene (Z) at a predetermined isomerization reaction temperature. 1-Chloro-2,3,3-trifluoropropene (Z) in the raw material composition contained in a molar ratio different from that of) is isomerized at the isomerization reaction temperature to 1-chloro-2, A method for producing 1-chloro-2,3,3-trifluoropropene (E), which produces 3,3-trifluoropropene (E).
[15] In the raw material composition, the molar ratio (1-) of the 1-chloro-2,3,3-trifluoropropene (Z) to the 1-chloro-2,3,3-trifluoropropene (E). Chloro-2,3,3-trifluoropropene (Z) /1-chloro-2,3,3-trifluoropropene (E)) is larger than the equilibrium ratio (molar ratio) at the isomerization reaction temperature, [ 14]. The method for producing 1-chloro-2,3,3-trifluoropropene (E).

In the present specification, for halogenated hydrocarbons, when the abbreviation of the compound is described in parentheses after the compound name, the abbreviation is used in place of the compound name as necessary in the present specification. Further, for a compound having a double bond in the molecule and having an E-form and a Z-form, the E-form and the Z-form are indicated by (E) and (Z) at the end of the abbreviation of the compound, respectively. Those without the notation of (E) and (Z) at the end of the abbreviation of the compound name indicate E-form and / or Z-form.

According to the method for producing a Z-form of 1233 yd of the present invention, an E-form of 1233 yd can be selectively reacted to produce a Z-form of 1233 yd by an industrially advantageous and efficient method.
According to the method for producing a 1233 yd E-form of the present invention, a 1233 yd Z-form can be selectively reacted to produce a 1233 yd E-form by an industrially advantageous and efficient method.

6 is a graph showing the abundance ratio (mol%) of 1233 yd Z-form to the total of 1233 yd E-form and Z-form at each isomerization reaction temperature.

Hereinafter, embodiments of the present invention will be described in detail.
[Manufacturing method of 1233yd (Z) or 1233yd (E)]
As shown in the following formula [1], the method for producing 1233yd, which is one embodiment of the present invention, is 1-chloro-2,3,3-trifluoropropene (E) (HCFO-1233yd (E), hereinafter ". 1233yd (E) ”) and 1-chloro-2,3,3-trifluoropropene (Z) (HCFO-1233yd (Z), hereinafter also referred to as“ 1233yd (Z) ”) are isomerization reactions. This is a method for producing 1233yd (Z) by preparing a raw material composition containing a molar ratio different from the equilibrium ratio at temperature and isomerizing 1233yd (E) in the raw material composition. Further, in the method for producing 1233yd, which is another embodiment of the present invention, as shown in the following formula [2], 1233yd (Z) in the raw material composition is isomerized to obtain 1233yd (E). It is a manufacturing method.

The isomerization reaction between 1233yd (E) and 1233yd (Z) represented by the above formulas [1] and [2] is an equilibrium reaction. In the method for producing 1233yd of the present embodiment, the isomerization reaction is carried out under the conditions under which the isomerization reaction occurs (hereinafter, also referred to as "isomerization conditions"). The isomerization reaction represented by the above formula [1] or the formula [2] is also simply referred to as "isomerization reaction" below.

In the equilibrium state of the isomerization reaction, 1233yd (Z) and 1233yd (E) are present at a predetermined molar ratio (equilibrium ratio). As used herein, the equilibrium ratio means "the molar ratio of 1233 yd (Z) to 1233 yd (E) in the equilibrium state of the isomerization reaction", and in the equilibrium state [(1233 yd (Z) in 1233 yd). Number of moles) / (number of moles of 1233yd (E) in 1233yd)]. The equilibrium ratio varies depending on the reaction temperature (hereinafter, also referred to as isomerization reaction temperature), pressure, etc. at the time of isomerization reaction.

For example, the equilibrium ratio at atmospheric pressure and isomerization reaction temperature of 20 ° C. is about 97/3. The equilibrium ratio at atmospheric pressure and isomerization reaction temperature of 230 ° C. is about 91/9. Hereinafter, "1233yd (Z) / 1233yd (E)" represents the molar ratio of 1233yd (Z) to 1233yd (E).

Here, the abundance ratio (mol%) of 1233 yd (Z) to the total of 1233 yd (E) and 1233 yd (Z) at each isomerization reaction temperature is shown in FIG. From the graph of FIG. 1, it can be seen that as the isomerization reaction temperature increases, the abundance ratio of 1233yd (Z) decreases and the equilibrium ratio decreases.

In the method for producing 1233 yd (Z) of the present embodiment, 1233 yd (Z) can be produced by using a raw material composition in which 1233 yd (Z) / 1233 yd (E) is smaller than the equilibrium ratio at the isomerization reaction temperature. That is, by the isomerization reaction at the isomerization reaction temperature, the content ratio of 1233 yd (Z) in the reaction product is increased as compared with the content ratio in the raw material composition, and 1233 yd (Z) is produced. For example, according to the method for producing 1233yd (Z) of the present embodiment, by optimizing the conditions, a simple operation can be performed with respect to the total amount of 1233yd (Z) and 1233yd (E) in the reaction product. The content of 1233yd (Z) can also be 80 mol% or more.

On the other hand, in the method for producing 1233yd (E) of the present embodiment, 1233yd (E) is produced by using a raw material composition in which 1233yd (Z) / 1233yd (E) is larger than the equilibrium ratio at the isomerization reaction temperature. can. That is, by the isomerization reaction at the isomerization reaction temperature, the content ratio of 1233 yd (Z) in the reaction product is reduced from the content ratio in the raw material composition, and 1233 yd (E) is produced.

As described above, in the production method of the present embodiment, by adjusting 1233 yd (Z) / 1233 yd (E) in the raw material composition, the reaction from 1233 yd (E) to 1233 yd (Z) and 1233 yd (Z) From 1233yd (E), any reaction can be selectively carried out.

When the difference between 1233yd (Z) / 1233yd (E) in the raw material composition and the equilibrium ratio at the isomerization temperature is small, the difference between 1233yd (Z) and 1233yd (E) is larger than that when the difference is large. The apparent conversion rate between them is small. However, for example, as will be described later, in the case of producing 1233yd (Z), 1233yd (Z) obtained by the above isomerization reaction, distillation separation of 1233yd (Z) and 1233yd (E) obtained by the isomerization reaction, and 1233yd (distillation separation) obtained by the distillation separation ( By repeating the reisomerization of E), 1233yd (E) to 1233yd (Z) can be obtained by an industrially advantageous and efficient method. This also applies to the case of producing 1233yd (E).

[Raw material composition]
In the production method of the present embodiment, the raw material composition contains 1233 yd (E) and 1233 yd (Z) in a molar ratio different from the equilibrium ratio (molar ratio) at the isomerization reaction temperature. The raw material composition may contain impurities other than 1233yd (E) and 1233yd (Z) in addition to 1233yd (E) and 1233yd (Z). Impurities contained in the raw material composition include the raw materials for producing 1233 yd (E) and 1233 yd (Z), and are produced in addition to 1233 yd (E) and 1233 yd (Z) when producing 1233 yd (E) and 1233 yd (Z). By-products and the like. When the isomerization reaction is carried out using the raw material composition containing the above impurities, the by-products generated from the above impurities can be removed by known means such as distillation. As the impurity, it is preferable that the compound is inactive under the condition that 1233yd (E) or 1233yd (Z) undergoes an isomerization reaction.

1233yd (E) and 1233yd (Z) can be produced by known methods. For example, HCFC-244ca is reacted with hydrogen fluoride to obtain 1233yd as a by-product in producing HCFC-245ca.

The 1233 yd obtained by the above method may be used as it is as a raw material composition, or the 1233 yd may be separated into an E-form and a Z-form of 1233 yd by a known method such as distillation to prepare a desired mixing ratio. May be used as a raw material composition.

Further, in the composition obtained by the above method, in addition to 1233yd, the product HCFC-245ca, the production raw material HCFC-244ca, and 1-chloro-3,3-difluoro by-produced in the production process are included. Propin etc. are included. This composition may be used as it is as a raw material composition.

The manufacturing method of this embodiment can be either a batch method or a continuous distribution method. The manufacturing method of the present embodiment is preferably a continuous distribution method in terms of manufacturing efficiency.

[Isomerization conditions]
As described above, when producing 1233 yd (Z), for example, 1233 yd (Z) / 1233 yd (E) in the raw material composition is set to a condition smaller than the equilibrium ratio at a predetermined isomerization reaction temperature. On the other hand, when producing 1233yd (E), for example, the condition is that 1233yd (Z) / 1233yd (E) in the raw material composition is larger than the equilibrium ratio at a predetermined isomerization reaction temperature.

Further, in the production method of the present embodiment, by subjecting a raw material composition satisfying the above conditions to an isomerization reaction under predetermined isomerization conditions, a desired compound can be produced by the above isomerization reaction. Further, the isomerization reaction is promoted by a method of contacting the raw material composition with the metal catalyst in the reactor, a method of contacting the raw material composition with the radical generator in the reactor, a method of heating the raw material composition, or the like. be able to. According to these methods, the isomerization reaction can be rapidly advanced to reach an equilibrium state. Therefore, the above method is suitable as an industrial method in which 1233yd (E) is isomerized to produce 1233yd (Z), or 1233yd (Z) is isomerized to produce 1233yd (E).

In the production method of the present embodiment, the isomerization reaction may be carried out in a liquid phase or a gas phase. When the reaction is carried out in the liquid phase, there is an advantage that the reaction can be carried out in a reactor having a smaller size when the same amount of the target product is produced, as compared with the case where the reaction is carried out in the gas phase. On the other hand, when the reaction is carried out in the gas phase, the reaction time can be shortened as compared with the case where the reaction is carried out in the liquid phase, and the by-product 1,2,3-trichloro-3-fluoropropene (ClCHF) can be shortened. -There is an advantage that the production of CCl = CHCl can be suppressed, and there is an advantage that the amount of the target product produced per hour is increased.

[Reactor]
The reactor used in the production method of the present embodiment is not particularly limited as long as it can withstand the temperature and pressure in the reactor described later, and for example, a glass flask, an autoclave, or a cylindrical vertical reactor is used. Can be used. As the material of the reactor, glass, iron, nickel, iron or an alloy containing nickel as a main component is used. Further, the reactor may be provided with an electric heater or the like for heating the inside of the reactor.

<Isomerization using a metal catalyst>
In the production method of the present embodiment, the isomerization reaction is preferably carried out using a metal catalyst. By using a metal catalyst, the reaction rate can be improved and the production efficiency can be improved. The metal catalyst has a catalytic action on the isomerization reaction. Examples of the metal catalyst include metals (elemental substances or alloys), metal oxides, metal halides and the like. As the metal catalyst, one type may be used alone, or two or more types may be used in combination.

Among these, metal oxides or metal halides are preferable because the isomerization reaction proceeds efficiently.

Examples of the metal constituting the metal catalyst include a transition metal element, a group 12 metal element, a group 13 metal element, a group 14 metal element, and a group 15 metal element. Among them, Group 4 metal elements, Group 6 metal elements, Group 8 metal elements, Group 9 metal elements, Group 10 metal elements, Group 11 metal elements, Group 12 metal elements, Group 13 metal elements, Group 14 metal elements and Group 15 metal elements are preferable, Group 4 metal elements, Group 6 metal elements, Group 8 metal elements, Group 10 metal elements, Group 11 metal elements, Group 12 metal elements, Group 13 metal elements are preferred.

When the metal constituting the metal catalyst is a transition metal element, a group 12 metal element, a group 13 metal element, a group 14 metal element, or a group 15 metal element, specifically, titanium (Ti) or zirconium. (Zr), Hafnium (Hf) (Group 4 Metal Element), Niob (Nb), Tantal (Ta) (Group 5 Metal Element), Chromium (Cr), Tungsten (W) (Group 6 Metal Element), Renium (Re) (Group 7 metal element), iron (Fe), ruthenium (Ru) (Group 8 metal element), cobalt (Co), rhodium (Rh) (Group 9 metal element), nickel (Ni) , Palladium (Pd), Platinum (Pt) (Group 10 metal element), Copper (Cu) (Group 11 metal element), Zinc (Zn) (Group 12 element), Boron (B), Aluminum (Al) , Gallium (Ga), indium (In) (Group 13 metal element), tin (Sn) (Group 14 metal element), antimon (Sb) (Group 15 metal element) at least one selected from the group. It is more preferable that it is an element of.

The metal catalyst may be one of the above-mentioned metals or an alloy of two or more kinds of metals. The metal oxide may be one kind of oxide of the above-mentioned metal, or may be a composite oxide of two or more kinds of metals. The metal halide may be one kind of halide of the above-mentioned metal, or may be a composite halide of two or more kinds of metals.

Further, the metal catalyst may be supported on a carrier. Examples of the carrier include an alumina carrier, a zirconia carrier, a silica carrier, a silica alumina carrier, a carbon carrier typified by activated carbon, a barium sulfate carrier, a calcium carbonate carrier and the like. Examples of the activated carbon include activated carbon prepared from raw materials such as wood, charcoal, fruit gala, coconut gala, peat, lignite, and coal. When the carrier is a compound of the same type as the metal catalyst, it may have a function as a metal catalyst.

Further, the metal catalyst is preferably activated in advance from the viewpoint of improving reactivity. Examples of the activation treatment method include a method of contacting the metal catalyst with the activation treatment agent under heating or non-heating. As the activation treatment agent, for example, hydrogen fluoride, hydrogen chloride, fluorine-containing hydrocarbon and the like can be used. As the activation treatment agent, one type may be used alone, or two or more types may be used in combination. Above all, it is preferable to use a fluorine-containing hydrocarbon as the activation treatment agent. Examples of the fluorine-containing hydrocarbon used as the activation treatment agent include trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), chlorotrifluoromethane (CFC-13), and dichlorofluoromethane (HCFC-21). , Chlorodifluoromethane (HCFC-22), trifluoromethane (HFC-23), tetrafluoroethylene (FO-1114) and the like are suitable. Further, 1233yd (E) or 1233yd (Z) in the raw material composition can also be used as the activation treatment agent.

Further, the metal catalyst can be reactivated in addition to the activation treatment before the reaction. That is, in the isomerization reaction, when the activity of the metal catalyst decreases and the conversion rate between the E-form and the Z-form of 1233 yd decreases (when it takes a long time to reach the isomerization equilibrium). It is preferable to reactivate the metal catalyst. As a result, the activity of the metal catalyst can be regenerated and the metal catalyst can be reused.

Examples of the reactivation treatment method include a method in which the metal catalyst is brought into contact with the activation treatment agent under heating or non-heating, as in the activation treatment before use. As the treatment agent for the reactivation treatment (reactivation treatment agent), oxygen, hydrogen fluoride, hydrogen chloride, chlorine-containing / fluorine-containing hydrocarbon and the like can be used. Examples of the chlorine-containing / fluorine-containing hydrocarbon include compounds in which a part of hydrogen in the hydrocarbon is replaced with chlorine, compounds in which fluorine is substituted, and compounds in which chlorine and fluorine are substituted, and carbon tetrachloride, chloroform, and the like. Dichloromethane (HCC-30), chloromethane, vinyl chloride, CFC-11, CFC-12, CFC-13, HCFC-21, HCFC-22, HFC-23, FO-1114, 1233yd (E), 1233yd (Z) And so on. Further, in the reactivation treatment, an inert gas such as nitrogen, argon or helium can be used to dilute the reactivation treatment agent from the viewpoint of suppressing side reactions and improving the durability of the metal catalyst.

The metal catalyst may be activated before being housed in the reactor, but it is preferable to perform the activation treatment in the state of being housed in the reactor because the operation is simple and the work efficiency is good. Therefore, it is preferable to introduce the activation treatment agent into a reactor containing a metal catalyst to perform the activation treatment. The activation treatment agent may be introduced into the reactor at room temperature, but from the viewpoint of improving the reactivity, it is preferable to control the temperature by heating or the like when introducing the activator into the reactor.

Further, in order to increase the efficiency of the activation treatment, it is preferable to perform the activation treatment in a state where the inside of the reactor is heated. In that case, the temperature inside the reactor is preferably heated to 50 to 400 ° C.

(Isomerization in liquid phase)
When the method for producing 1233 yd of the present embodiment is carried out in a liquid phase, the raw material composition in a liquid state can be brought into contact with a metal catalyst in a reaction vessel.

When the method for producing 1233 yd of the present embodiment is carried out in a liquid phase, a metal halide is preferable as the metal catalyst. Among them, it is more preferable to use a halide containing at least one element selected from the group consisting of Al, Sb, Nb, Ta, W, Re, B, Sn, Ga, In, Zr, Hf and Ti.

Metal halides include metal chlorides such as GaCl ₂ , GaCl ₃ , ZrCl ₄ , BCl ₃ , AlCl ₃ , HfCl ₄ , InCl ₃ , and TiCl ₄ , or partially fluorinated metal chlorides. For example _, AlFCl ₂ , AlF ₂ Cl, TiCl ₂ F ₂ , TiCl F ₃ , ZrCl ₂ F _2, ZrCl ₂ F, ZrCl F ₂ and the like can be used. Further, as a metal catalyst, metal bromides such as GaBr ₃ , GaI ₃ , HfBr ₄ , InI ₃ , and TiBr ₄ , metal iodides or metal bromides thereof, and a part of these metal bromides and metal iodides are chlorinated by the above activation treatment or the like. Iodide can be used. Among them, compounds in which a part of the metal chloride is fluorinated, for example, AlFCl ₂ and AlF ₂ Cl, are preferable from the viewpoint that the isomerization reaction can proceed efficiently.

The amount of such a metal catalyst added is preferably 1 to 100% by mass as an external addition with respect to the total amount (100% by mass) of 1233yd (E) and 1233yd (Z) in the raw material composition. 5 to 50% by mass is more preferable, and 5 to 15% by mass is further preferable. Within the above range, the isomerization reaction can proceed efficiently.

When the production method of the present embodiment is carried out in a liquid phase, it is preferable to add a reaction solvent in order to control the heat of reaction. When the above metal catalyst is used, the reaction solvent is a compound that is inert to the metal catalyst and dissolves the starting material and the target substance, but does not dissolve the metal catalyst. In addition, it is a compound that can be easily separated from the target product by distillation or the like. As such a reaction solvent, for example, an aprotic organic solvent having a boiling point of 60 ° C. to 200 ° C., specifically carbon tetrachloride, chloroform or the like is preferable.

When the isomerization reaction is carried out in a liquid phase using a metal catalyst, the reaction conditions are preferably 0 to 150 ° C., more preferably 10 to 100 ° C., and 10 to 50 ° C. Is even more preferable. Within the above range, the isomerization reaction can proceed efficiently. The reaction time depends on the reaction temperature and the type of metal catalyst, but is usually preferably 0.5 to 200 hours, more preferably 1 to 100 hours, still more preferably 1 to 10 hours from the viewpoint of production efficiency.

(Isomerization in gas phase)
When the method for producing 1233 yd of the present embodiment is carried out in a gas phase using a metal catalyst, the isomerization reaction can be carried out by bringing the raw material composition into contact with the metal catalyst in the reactor. Specifically, for example, it can be carried out by accommodating a metal catalyst in a reactor, forming a reaction portion, and distributing a raw material composition through the reaction portion. In this case, the metal catalyst may be housed in either a fixed bed type or a fluidized bed type. When it is a fixed floor type, it may be either a horizontal fixed floor type or a vertical fixed floor type. When a mixed gas composed of multiple components is generated by the above isomerization reaction, it is easy to prevent the concentration distribution of each component from occurring depending on the location due to the difference in specific gravity. Therefore, the metal catalyst may be of the vertical fixed bed type. preferable. Hereinafter, regarding the method of carrying out the production method of 1233yd of the present embodiment in the gas phase, the production method of the present embodiment is carried out by a continuous flow method, and the raw material composition is brought into contact with a metal catalyst in the gas phase state to carry out an isomerization reaction. The reaction conditions will be described, but the present invention is not limited thereto.

When the production method of the present embodiment is carried out in the gas phase, it is preferable to use a simple substance of a metal or a metal oxide as the metal catalyst. Specific examples thereof include iron, cobalt, nickel, palladium, chromium oxide (chromia), aluminum oxide (alumina), zinc oxide, iron fluoride, aluminum fluoride, aluminum chloride, chromium fluoride and chromium chloride. Among these metal catalysts, alumina and chromia are preferable because they are easily available and the isomerization reaction proceeds efficiently.

When the method for producing 1233 yd of the present embodiment is carried out in the gas phase, a diluted gas is added to the reactor together with the raw material composition from the viewpoints of suppressing side reactions, ease of supplying the starting substance to the reactor, and adjusting the flow rate. It is preferable to supply to. Further, when the isomerization reaction is carried out in the presence of the above-mentioned metal catalyst, there is an advantage that the durability of the metal catalyst is improved by using the diluted gas.

Examples of the diluting gas include nitrogen, carbon dioxide, a rare gas (helium and the like), a gas of an organic compound which is inactive in the isomerization reaction of the present embodiment, and the like. Examples of the inert organic compound include saturated hydrocarbons such as methane, ethane, propane, butane, pentane, and hexane, trifluoromethane (HFC-23), difluoromethane (HFC-32), and pentafluoroethane (HFC-125). , Fluorocarbons such as tetrafluoroethane (HFC-134 or HFC-134a), trifluoroethane (HFC-143 or HFC-143a), difluoroethane (HFC-152 or HFC-152a), tetrafluoropropane (HFC-254eb, etc.) Hydrocarbons can be mentioned. The amount of the diluted gas is not particularly limited, but specifically, it is preferably 1 to 10000 mol%, more preferably 10 to 1000 mol% with respect to the raw material composition (100 mol%) supplied to the reactor. , More preferably 30-500 mol%, most preferably 50-150 mol%. One type of diluting gas may be used alone, or two or more types may be used in combination.

When the production method of the present embodiment is carried out in the gas phase, the raw material composition may be introduced into the reactor after preheating. The preheating temperature at this time is preferably 20 to 300 ° C., preferably 50 to 250 ° C. from the viewpoint of vaporizing 1233yd (E) and 1233yd (Z) in the raw material composition and improving the reactivity. Is more preferable.

When a diluting gas is used, it is preferable that the raw material composition and the diluting gas are preheated to the above-mentioned preferable temperature and then introduced into the reactor from the viewpoint of improving the reactivity. The raw material composition and the diluted gas may be preheated to the above temperatures and then mixed, and then supplied to the reactor. Alternatively, the raw material composition and the diluted gas may be mixed and then preheated and supplied to the reactor. good.

In the production method of the present embodiment, the reaction conditions when the isomerization reaction is carried out in the gas phase are 1.0 MPa for the reaction pressure, for example, when pressurization is required for the purpose of shortening the reaction time. It is possible to set the pressure condition from normal pressure to 1.0 MPa under the following pressurizing conditions and the internal pressure in the reactor. From the viewpoint of ease of industrial implementation, it is preferable to carry out the reaction under normal pressure or a slight pressure of 0.2 MPa or less. Normal pressure is atmospheric pressure.

The contact temperature (reaction temperature) between the raw material composition and the metal catalyst is preferably 0 to 500 ° C., more preferably 50 to 350 ° C., further preferably 100 to 260 ° C., and most preferably 150 to 250 ° C. as the temperature inside the reactor. preferable. When the reaction temperature is equal to or higher than the above lower limit, the isomerization reaction can proceed efficiently. On the other hand, when the reaction temperature is not more than the above upper limit value, the production of by-products due to the decomposition of 1233 yd (E) and 1233 yd (Z) can be suppressed. The contact time (reaction time) between the raw material composition and the metal catalyst in the reactor is preferably 0.1 to 1000 seconds, more preferably 1 to 100 seconds. The contact time corresponds to the residence time of the raw material composition in the reactor, and can be controlled by adjusting the supply amount (flow rate) of the raw material composition to the reactor.

<Isomerization by contact with radical generator>
In the production method of the present embodiment, the isomerization reaction can be carried out by contacting the raw material composition with a radical generator. Radical generators are those that are activated by heat or light to generate radicals. Examples of the method of contacting the raw material composition with a radical generator to carry out an isomerization reaction include a method of contacting the raw material composition with a radical generator activated by heat or light in a reactor. .. In this case, the isomerization reaction is preferably carried out in the gas phase.

The radical generator may be activated by either heat or light, or both may be used in combination. Industrially, activation by heat alone is preferable, and a mixture of a raw material composition and a radical generator is supplied to a heated reactor, heat energy is applied to the mixture in the reactor, and the radical generator is heated by heat. The method of activating is simple and preferable.

When the radical generator is activated by light, the radical generator may be irradiated with light. Specific examples of the light to be irradiated include ultraviolet rays including light having a wavelength of 200 to 400 nm and visible light. Examples of the light source used for such light irradiation include a high-pressure mercury lamp, a low-pressure mercury lamp, and a metal halide lamp.

As a method of irradiating light, for example, a light source equipped with a jacket made of a corrosion-resistant material, which transmits light of at least the wavelength required for the isomerization reaction and is inert to the components existing in the reaction system, is used as a reaction component. Examples thereof include a method of inserting it into a gas and irradiating the reaction component with light from the inside of the reactor. When the light source generates heat, the jacket is preferably a jacket having cooling means, depending on the reaction temperature.

Radicals are chemical species such as atoms, molecules, or ions that have unpaired electrons, and the chemical species include radical cations with a positive charge, radical anions with a negative charge, radicals with a neutral charge, biradicals, carbens, and the like. include. Specific examples thereof include fluorine radicals, chlorine radicals, bromine radicals, iodine radicals, oxygen radicals, hydrogen radicals, hydroxy radicals, nitroxy radicals, nitrogen radicals, alkyl radicals, difluorocarbene and carbon radicals.

The radical generator for generating radicals as described above is a compound other than 1233yd (E) and 1233yd (Z) that generates radicals by applying external energy such as heat or light. Specific examples of the radical generator include halogen gases such as chlorine and bromine, halogenated hydrocarbons and the like, air, oxygen, ozone, hydrogen peroxide and the like. The halogenated hydrocarbon includes a part or all of hydrogen atoms bonded to carbon atoms in alkenes such as methane, ethane, propane, butane, pentan, and hexane, and alkenes such as ethene, propene, butene, penten, and hexene. Is a halogenated hydrocarbon in which is substituted with a fluorine, chlorine, bromine or iodine atom, and the halogenated hydrocarbon contains at least one of fluorine, chlorine, bromine or iodine. One type of radical generator may be used alone, or two or more types may be used in combination.

Among the above-mentioned radical generators, oxygen, air and chlorine are preferable because they are inexpensive and easily available. Of these, chlorine is preferable because it easily generates radicals. Further, air or oxygen is suitable as the radical generator from the viewpoint of easy separation from the product.

The amount of the radical generator supplied to the reactor is preferably in a small amount. This is because the formation of radicals is linked. Further, the addition of an excessive radical generator not only wastes auxiliary materials, but also causes a load in the separation step between the target substance or starting substance after the reaction and the radical generator.

<Isomerization by heating>
The isomerization reaction in the method for producing 1233 yd of the present embodiment can be carried out by varying the temperature of the raw material composition, for example, by heating. When the isomerization reaction is carried out by heating, the isomerization reaction can be carried out by heating the raw material composition in the reactor. Specifically, for this heating, the raw material composition may be supplied into a reactor heated by a heating furnace such as an electric furnace. In this case, the isomerization reaction is preferably carried out in the gas phase.

When the isomerization reaction is carried out by heating, the reaction pressure is preferably normal pressure or a slight pressure of 0.2 MPa or less, as in the case of using a metal catalyst. The heating temperature (reaction temperature) is preferably 400 to 1000 ° C, more preferably 400 to 900 ° C. The residence time (reaction time) of the raw material composition in the reactor is preferably 0.001 to 1000 seconds, more preferably 0.01 to 100 seconds. By raising the reaction temperature within the above-mentioned preferable range or lengthening the reaction time, the conversion rate between the isomers is improved, and the isomers are contained at the equilibrium ratio at the reaction temperature or at a ratio close to the equilibrium ratio. Can be obtained.

(Reaction product)
In the production method of the present embodiment, the target product, 1233yd (E) or 1233yd (Z), can be obtained in the reaction product flowing out of the reactor. The reaction product may contain by-products produced from impurities and the like contained in the raw material composition, and by-products produced by decomposition of 1233 yd (E) or 1233 yd (Z). Specific examples of by-products are 1,2,3-trichloro-3-fluoropropene and the like. These by-products in the reaction product can be removed to the extent desired by known means such as distillation.

Further, in the above isomerization reaction, as described above, an equilibrium state of the isomerization reaction is formed under the isomerization conditions. Therefore, even if the reaction conditions (isomerization conditions) are adjusted to be suitable, the reaction product contains the isomerization reaction. Includes starting material in addition to the object. That is, the reaction product contains both 1233yd (E) and 1233yd (Z).

Since 1233yd (E) and 1233yd (Z) in the reaction product have different boiling points, they can be separated by a conventional distillation method. Therefore, the reaction product obtained above is subjected to acid washing, alkali washing, dehydration with an adsorbent such as synthetic zeolite, removal of by-products, and distillation as necessary to obtain high-purity 1233yd (E) and 1233yd (Z) can be obtained respectively. Specifically, the reaction product containing 1233 yd (E) and 1233 yd (Z) washed above is supplied to a distillation column and distilled, and 1233 yd (E) is used as a main component from the top of the column. Distillates can be obtained from the bottom of the tower, and cans containing 1233 yd (Z) can be obtained.

For example, when the target product is 1233 yd (Z), the 1233 yd (Z) / 1233 yd (E) contained in the distillate obtained by distillation is smaller than the equilibrium ratio. Therefore, by using this distillate as a raw material composition and subjecting it to an isomerization reaction in the same manner as described above, it is possible to convert 1233 yd (E) in the distillate into 1233 yd (Z).

On the other hand, when the target product is 1233 yd (E), the 1233 yd (Z) / 1233 yd (E) contained in the canned product obtained by distillation becomes larger than the equilibrium ratio. Therefore, by using the canned product as a raw material composition and subjecting it to an isomerization reaction in the same manner as described above, it is possible to convert 1233 yd (Z) in the distillate into 1233 yd (E).
By repeating the isomerization reaction and distillation in this way, the desired product can be efficiently produced.

As described above, according to the production method of the present embodiment, by subjecting the raw material composition to an isomerization reaction under predetermined isomerization conditions, 1233yd (E) is isomerized by an industrially advantageous and efficient method. , 1233yd (Z) can be produced, or 1233yd (Z) can be isomerized to produce 1233yd (E).

[Analysis conditions]
In the production of the following various compounds, a gas chromatograph (GC) was used for composition analysis of the obtained reaction composition. As the column, DB-1301 (length 60 m × inner diameter 250 μm × thickness 1 μm, manufactured by Agilent Technologies, Inc.) was used.

[Manufacturing of 1233yd (Z)]
(Example 1)
First, the metal catalyst was activated as shown below. That is, a Dimroth condenser in which a refrigerant cooled to -20 ° C was circulated was installed in a three-necked flask (internal volume 50 mL), and 100 g (0.75 mol) of aluminum trichloride (AlCl ₃ ) was added thereto. After charging and cooling to 0 ° C., 230 g (2.2 mol) of dichlorofluoromethane (CHFCl ₂ ) was slowly added dropwise with stirring.

The isomerization of dichlorofluoromethane proceeded with the generation of low boiling point gas. Then, as the isomerization progressed, the halogen exchange reaction between the metal catalyst aluminum trichloride (AlCl ₃ ) and the activation treatment agent dichlorofluoromethane proceeded, and fluorine-substituted aluminum halide was produced. .. After continuing the reaction for 1 hour, the volatile components were removed and the metal catalyst was dried. In this way, partially fluorinated aluminum chloride was obtained.

Next, 1 g of partially fluorinated aluminum chloride obtained in the above reaction was placed as a metal catalyst in a glass reactor (internal volume 50 mL) equipped with a Dimroth condenser cooled to 0 ° C., and carbon tetrachloride was added as a solvent. 10 g of carbon was added. Next, the temperature of the reactor is set to 20 ° C., which is a mixture of E-form and Z-form of 1233 yd, and the molar ratio of Z-form to E-form (1233 yd (Z) / 1233 yd (E)) is 0.01 /. 10 g (0.08 mol) of the raw material composition of 99.99 was slowly added, and the reaction was carried out for 1 hour with stirring. The composition (molar ratio) of the raw material composition used in Example 1 is shown in Table 1.

The liquid after the reaction was separated by filtration to remove the metal catalyst, and 20 g of the reaction product was recovered as a liquid phase. Then, the liquid phase of the obtained reaction product was analyzed using a gas chromatograph to determine the composition of the reaction product. The results are shown in Table 1 together with the reaction conditions.

(Example 2)
The isomerization reaction was carried out in the same procedure as in Example 1 except that the content ratio of the E-form and the Z-form of 1233 yd in the raw material composition was changed. Table 2 shows the composition, reaction conditions and results of the raw material composition.

(Examples 3 and 4)
First, the metal catalyst was activated as follows. That is, a pellet-shaped activated alumina (diameter 3 mm, height 3 mm, specific surface area 160 m ² / g, manufactured by JGC Catalysts and Chemicals Co., Ltd., product name N612N) is used in a reaction tube made of Inconel (registered trademark) 600 having an inner diameter of 2.54 cm and a length of 100 cm. It was filled in (reactor) and immersed in a salt bath. The salt bath was heated to 250 ° C., and a mixed gas of 2/1 (molar ratio) of nitrogen / HCFC-22 (CHClF ₂ ) was circulated in the reactor for 10 hours to activate the metal catalyst.

Next, the temperature of the salt bath (reaction temperature) was set to 230 ° C. in Example 3 and 280 ° C. in Example 4. Further, the supply of HCFC-22 was stopped, and a mixed gas of a raw material composition and nitrogen similar to that in Example 1 was supplied into the reactor with a contact time (reaction time) of 20 seconds. The raw material composition was circulated in the reactor under the conditions shown in Table 3 and subjected to an isomerization reaction. The composition of the reaction product was analyzed by analyzing the gas composition at the outlet of the reactor with a gas chromatograph. Table 3 shows the composition, reaction conditions and analysis results of the raw material composition.

(Example 5)
The isomerization reaction was carried out under the same conditions as in Example 3 except that the reaction temperature was changed to 400 ° C. without using a metal catalyst. Table 3 shows the composition, reaction conditions and analysis results of the raw material composition.

(Example 6)
The isomerization reaction was carried out in the same procedure as in Example 3 except that the content ratio of the E-form and the Z-form of 1233 yd in the raw material composition was changed. Table 4 shows the composition, reaction conditions and analysis results of the raw material composition.

[Manufacturing of 1233yd (E)]
(Example 7)
In a glass reactor (internal volume 50 mL) equipped with a Dimroth condenser cooled to 0 ° C., 1 g of partially fluorinated aluminum chloride obtained in the above reaction was placed as a metal catalyst, and 10 g of carbon tetrachloride was added as a solvent. added. Next, the temperature of the reactor was set to 20 ° C., and the mixture was a mixture of E-form and Z-form of 1233 yd, and the molar ratio of Z-form to E-form (1233 yd (Z) / 1233 yd (E)) was 99.99. 10 g (0.08 mol) of the raw material composition at /0.01 was slowly added, and the reaction was carried out for 1 hour with stirring. The composition of the raw material composition is shown in Table 5.

Next, the liquid after the reaction was filtered off to remove the metal catalyst, and 20 g of the reaction product was recovered as a liquid phase. The obtained liquid phase was then analyzed using a gas chromatograph to determine the composition of the reaction product. The analysis results are shown in Table 5 together with the reaction conditions.

(Example 8)
The isomerization reaction was carried out in the same procedure as in Example 7 except that the composition of the raw material composition was changed. Table 6 shows the composition, reaction conditions and analysis results of the raw material composition.

(Examples 9 and 10)
As in Example 3, the activated alumina obtained above was used as the metal catalyst. Further, in the same manner as in Example 3, the reaction temperature was set to 230 ° C. in Example 9 and 280 ° C. in Example 10, and a mixed gas of the raw material composition and nitrogen having the composition shown in Table 7 was supplied to the reactor. .. The raw material composition was circulated in the reactor under the conditions shown in Table 7 and subjected to an isomerization reaction. The composition of the reaction product was analyzed by analyzing the gas composition at the outlet of the reactor with a gas chromatograph. Table 7 shows the composition, reaction conditions and analysis results of the raw material composition.

(Example 11)
The isomerization reaction was carried out in the same procedure as in Example 9 except that the reaction temperature was changed to 400 ° C. without using a metal catalyst. Table 7 shows the composition, reaction conditions and analysis results of the raw material composition.

(Example 12)
The isomerization reaction was carried out in the same procedure as in Example 9 except that the composition of the raw material composition was changed. Table 8 shows the composition, reaction conditions and analysis results of the raw material composition.

From Tables 1 to 8, it can be seen that by subjecting the raw material composition to an isomerization reaction under predetermined isomerization conditions, the isomerization reaction can be carried out to produce 1233 yd (Z) or 1233 yd (E).

Claims (3)

1-Chloro-2,3,3-trifluoropropene (E) and 1-chloro-2,3,3-trifluoropropene (Z) differ from the equilibrium ratio (molar ratio) at a given isomerization reaction temperature. The 1-chloro-2,3,3-trifluoropropene (E) in the raw material composition contained in a molar ratio is isomerized by contacting it with a metal catalyst at the isomerization reaction temperature in the gas phase. 1-Chloro-2,3,3-trifluoropropene (Z) is a method for producing.
The metal catalyst is at least one compound selected from the group consisting of metal oxides and metal halides.
The metal oxide is at least one selected from alumina and chromia.
The metal halide is a compound in which a part of the metal chloride is fluorinated .
A method for producing 1-chloro-2,3,3-trifluoropropene (Z), wherein the isomerization reaction temperature is 100 ° C to 260 ° C. In the raw material composition, the molar ratio (1-chloro-2) of the 1-chloro-2,3,3-trifluoropropene (Z) to the 1-chloro-2,3,3-trifluoropropene (E). , 3,3-Trifluoropropene (Z) /1-chloro-2,3,3-trifluoropropene (E)) is smaller than the equilibrium ratio (molar ratio) at the isomerization reaction temperature, according to claim 1. The method for producing 1-chloro-2,3,3-trifluoropropene (Z) according to the above method. The method for producing 1-chloro-2,3,3-trifluoropropene (Z) according to claim 1 or 2, wherein the isomerization reaction is carried out in the presence of an inert gas.

Images