Method for producing unsaturated chlorofluorocarbons and compositions

Abstract

Provided are a method for geometric isomerization of a specific geometric isomer (isomer 1) represented by formula (1) to produce a specific corresponding geometric isomer (isomer 2) represented by formula (1), the method including a step for bringing the specific geometric isomer (isomer 1) represented by formula (1) into contact with a compound (A), which is at least one of dichlorotrifluoropropane and hydrogen chloride, in the gas phase, and a composition.

Description

[Technical Field]

[0001] The present disclosure relates to a method and composition for producing unsaturated chlorofluorocarbons, and relates to a method and composition for geometrically isomerizing 1-chloro-3,3,3-trifluoropropene or 1-chloro-2,3,3-trifluoropropene geometric isomer (isomer 1) to produce the corresponding geometric isomer (isomer 2). [Background technology]

[0002] Unsaturated chlorofluorocarbons typified by 1-chloro-3,3,3-trifluoropropene and 1-chloro-2,3,3-trifluoropropene have low ozone depletion potential (ODP) and global warming potential (GWP), and are therefore expected to be one of the compounds that can be used in cleaning agents, foaming agents, refrigerants, etc. For example, Patent Document 1 discloses a method for isomerizing cis isomers of 1-chloro-3,3,3-trifluoropropene to trans isomers, and a method for isomerizing trans isomers of 1-chloro-3,3,3-trifluoropropene to cis isomers. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent No. 6156374 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of an embodiment of the present disclosure is to provide a method and composition for efficiently producing unsaturated chlorofluorocarbons. [Means for solving the problem]

[0005] Means for solving the above problems include the following embodiments.

[0006] <1> A method for producing a corresponding geometric isomer (isomer 2) represented by the following formula (1) by geometric isomerization of a geometric isomer (isomer 1) represented by the following formula (1), The method includes a step of contacting a geometric isomer (isomer 1) represented by the following formula (1) with a compound (A) which is at least one of dichlorotrifluoropropane and hydrogen chloride in a gas phase, A method in which the geometric isomer (isomer 1) represented by the formula (1) is a cis isomer, the produced geometric isomer (isomer 2) is a trans isomer, and the compound (A) is hydrogen chloride; or the geometric isomer (isomer 1) represented by the formula (1) is a trans isomer, the produced geometric isomer (isomer 2) is a cis isomer, and the compound (A) is 1,1-dichloro-3,3,3-trifluoropropane. CF 3-n H n -CX=CClH (1) (n is 0 and X is a hydrogen atom.) <2> The geometric isomer (isomer 1) represented by formula (1) is a cis isomer, the produced geometric isomer (isomer 2) is a trans isomer, and the compound (A) is hydrogen chloride. <1> The method described below. <3> The geometric isomer (isomer 1) represented by formula (1) is a trans isomer, the produced geometric isomer (isomer 2) is a cis isomer, and the compound (A) is 1,1-dichloro-3,3,3-trifluoropropane. <1> The method described below. <4> The contacting is carried out in the presence of at least one of a catalyst and a filler. <1> ~ <3> 10. The method according to any one of claims 1 to 9. <5> The contacting is carried out in the presence of activated carbon. <1> ~ <4> 10. The method according to any one of claims 1 to 9. <6> The contacting is carried out at a temperature greater than 150°C and less than 500°C. <1> ~ <5> 10. The method according to any one of claims 1 to 9. <7> A raw material composition for producing a corresponding geometric isomer (isomer 2) represented by the following formula (1) by geometric isomerization of a geometric isomer (isomer 1) represented by the following formula (1): The compound (A) contains a geometric isomer (isomer 1) represented by the following formula (1) and at least one of dichlorotrifluoropropane and hydrogen chloride, A composition in which the geometric isomer (Isomer 1) represented by the formula (1) is a cis isomer, the produced geometric isomer (Isomer 2) is a trans isomer, and the compound (A) is hydrogen chloride; or the geometric isomer (Isomer 1) represented by the formula (1) is a trans isomer, the produced geometric isomer (Isomer 2) is a cis isomer, and the compound (A) is 1,1-dichloro-3,3,3-trifluoropropane. CF 3-n H n -CX=CClH (1) (n is 0 and X is a hydrogen atom.) The present invention relates to the above <1> ~ <7> However, other matters (for example, the following [1] to

[14] ) are also described below. [1] A method for producing a corresponding geometric isomer (isomer 2) represented by the following formula (1) by geometric isomerization of a geometric isomer (isomer 1) represented by the following formula (1), A method comprising the step of contacting a geometric isomer (Isomer 1) represented by the following formula (1) in a gas phase with a compound (A) which is at least one of dichlorotrifluoropropane and hydrogen chloride: CF 3-n H n -CX=CClH (1) (n is 0 or 1, X is a fluorine atom or a hydrogen atom, When n is 0, X is a hydrogen atom and the dichlorotrifluoropropane is 1,1-dichloro-3,3,3-trifluoropropane; When n is 1, X is a fluorine atom, and the dichlorotrifluoropropane is at least one of 1,1-dichloro-2,3,3-trifluoropropane and 1,2-dichloro-2,3,3-trifluoropropane. [2] The method according to [1], wherein the geometric isomer (isomer 1) represented by formula (1) is a cis isomer, and the produced geometric isomer (isomer 2) is a trans isomer. [3] The method according to [2], wherein the geometric isomer (isomer 1) represented by formula (1) is Z-1-chloro-3,3,3-trifluoropropene, and the produced geometric isomer (isomer 2) is E-1-chloro-3,3,3-trifluoropropene. [4] The method according to [2], wherein the geometric isomer (isomer 1) represented by formula (1) is Z-1-chloro-2,3,3-trifluoropropene, and the geometric isomer (isomer 2) produced is E-1-chloro-2,3,3-trifluoropropene. [5] The method according to any one of [2] to [4], wherein the compound (A) is hydrogen chloride. [6] The method according to [1], wherein the geometric isomer (isomer 1) represented by formula (1) is a trans isomer, and the produced geometric isomer (isomer 2) is a cis isomer. [7] The method according to [6], wherein the geometric isomer (isomer 1) represented by formula (1) is E-1-chloro-3,3,3-trifluoropropene, and the produced geometric isomer (isomer 2) is Z-1-chloro-3,3,3-trifluoropropene. [8] The method according to [6], wherein the geometric isomer (isomer 1) represented by formula (1) is E-1-chloro-2,3,3-trifluoropropene, and the produced geometric isomer (isomer 2) is Z-1-chloro-2,3,3-trifluoropropene. [9] The method according to any one of [6] to [8], wherein the compound (A) is dichlorotrifluoropropane.

[10] The method according to any one of [1] to [9], wherein the contacting is carried out in the presence of at least one of a catalyst and a filler.

[11] The method according to any one of [1] to

[10] , wherein the contact is carried out in the presence of activated carbon.

[12] The method according to any one of [1] to

[11] , wherein the contacting is carried out at a temperature higher than 150°C and lower than 500°C.

[13] A raw material composition for producing a corresponding geometric isomer (isomer 2) represented by the following formula (1) by geometric isomerization of a geometric isomer (isomer 1) represented by the following formula (1): A composition comprising a geometric isomer (isomer 1) represented by the following formula (1) and a compound (A) which is at least one of dichlorotrifluoropropane and hydrogen chloride: CF 3-n H n -CX=CClH (1) (n is 0 or 1, X is a fluorine atom or a hydrogen atom, When n is 0, X is a hydrogen atom and the dichlorotrifluoropropane is 1,1-dichloro-3,3,3-trifluoropropane; When n is 1, X is a fluorine atom, and the dichlorotrifluoropropane is at least one of 1,1-dichloro-2,3,3-trifluoropropane and 1,2-dichloro-2,3,3-trifluoropropane.

[14] A composition comprising a geometric isomer represented by the following formula (1) and a compound (A) which is at least one of dichlorotrifluoropropane and hydrogen chloride: CF 3-n H n -CX=CClH (1) (n is 0 or 1, X is a fluorine atom or a hydrogen atom, When n is 0, X is a hydrogen atom and the dichlorotrifluoropropane is 1,1-dichloro-3,3,3-trifluoropropane; When n is 1, X is a fluorine atom, and the dichlorotrifluoropropane is at least one of 1,1-dichloro-2,3,3-trifluoropropane and 1,2-dichloro-2,3,3-trifluoropropane. [Effects of the Invention]

[0007] According to one embodiment of the present disclosure, a method and composition for efficiently producing unsaturated chlorofluorocarbons can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0008] Hereinafter, embodiments of the present disclosure will be described. However, the present disclosure can be implemented in various forms without departing from the spirit thereof, and should not be construed as being limited to the description of the embodiments exemplified below. Furthermore, even if there are other effects different from those brought about by the aspects of the following embodiments, those that are clear from the description in this specification or that can be easily predicted by a person skilled in the art are naturally considered to be brought about by the present disclosure.

[0009] Furthermore, in this specification, for halogenated hydrocarbons, the abbreviation of the compound is written in parentheses after the compound name, and if necessary, this abbreviation is used instead of the compound name. Furthermore, for compounds that have a double bond in the molecule and exist as trans isomers (E isomer) and cis isomers (Z isomer), the E isomer and the Z isomer are indicated by adding (E) and (Z) to the end of the compound abbreviation, respectively. Note that when the abbreviation of a compound name does not have an (E) or (Z) at the end, it indicates the E isomer and / or the Z isomer.

[0010] In this specification, when Isomer 1 is a Z-form, the corresponding Isomer 2 is an E-form. Also, when Isomer 1 is an E-form, the corresponding Isomer 2 is a Z-form. The cis form of Isomer 1 is represented by the following structure:

[0011] [ka]

[0012] The trans form of Isomer 1 is represented by the following structure:

[0013] [ka]

[0014] Isomer 1 is Z-1-chloro-3,3,3-trifluoropropene (cis isomer), E-1-chloro-3,3,3-trifluoropropene (trans isomer), Z-1-chloro-2,3,3-trifluoropropene (cis isomer), or E-1-chloro-2,3,3-trifluoropropene (trans isomer). When Isomer 1 is Z-1-chloro-3,3,3-trifluoropropene, the corresponding Isomer 2 is E-1-chloro-3,3,3-trifluoropropene.

[0015] When Isomer 1 is E-1-chloro-3,3,3-trifluoropropene, the corresponding Isomer 2 is Z-1-chloro-3,3,3-trifluoropropene.

[0016] When Isomer 1 is Z-1-chloro-2,3,3-trifluoropropene, the corresponding Isomer 2 is E-1-chloro-2,3,3-trifluoropropene.

[0017] When Isomer 1 is E-1-chloro-2,3,3-trifluoropropene, the corresponding Isomer 2 is Z-1-chloro-2,3,3-trifluoropropene.

[0018] [Manufacturing method overview] Hereinafter, a method for producing 1-chloro-3,3,3-trifluoropropene (hereinafter also referred to as "1233zd") and 1-chloro-2,3,3-trifluoropropene (hereinafter also referred to as "1233yd") according to this embodiment (hereinafter also referred to as "this production method") will be described.

[0019] The present production method is a method for producing a corresponding geometric isomer (isomer 2) represented by the following formula (1) by geometric isomerization of a geometric isomer (isomer 1) represented by the following formula (1): The method includes a step of contacting a geometric isomer (isomer 1) represented by the following formula (1) in a gas phase with a compound (A) which is at least one of dichlorotrifluoropropane and hydrogen chloride as a promoter. CF 3-n H n -CX=CClH (1) (n is 0 or 1, X is a fluorine atom or a hydrogen atom, When n is 0, X is a hydrogen atom and the dichlorotrifluoropropane is 1,1-dichloro-3,3,3-trifluoropropane; When n is 1, X is a fluorine atom, and the dichlorotrifluoropropane is at least one of 1,1-dichloro-2,3,3-trifluoropropane and 1,2-dichloro-2,3,3-trifluoropropane.

[0020] In this production method, the compound (A) is at least one of dichlorotrifluoropropane and hydrogen chloride, and functions as an accelerator for the isomerization reaction. When Isomer 1 is a cis-isomer, the compound (A) is preferably, but not limited to, hydrogen chloride. For example, in the isomerization reaction of Z-1-chloro-3,3,3-trifluoropropene, hydrogen chloride is preferred as a promoter, but dichlorotrifluoropropane also functions as a promoter to promote the isomerization reaction. When Isomer 1 is a trans isomer, the compound (A) is preferably, but not limited to, dichlorotrifluoropropane. For example, in the isomerization reaction of E-1-chloro-3,3,3-trifluoropropene, dichlorotrifluoropropane is preferred as a promoter, but hydrogen chloride also functions as a promoter to promote the isomerization reaction.

[0021] In the isomerization step, the total amount of compound (A) relative to 1 mole of the geometric isomer represented by formula (1) (isomer 1) is preferably 0.001 mole or more and 1 mole or less, more preferably 0.005 mole or more and 0.5 mole or less, and even more preferably 0.01 mole or more and 0.2 mole or less, but is not limited thereto.

[0022] The isomerization step is carried out in a gas phase. The isomerization can be carried out in a batch or flow manner, but the gas phase flow method is preferred because it has high industrial productivity.

[0023] The isomerization step may be carried out in the presence of at least one of a catalyst and a packing material. Specifically, a reaction tube is packed with at least one of a catalyst and a packing material, and the gaseous geometric isomer represented by formula (1) (isomer 1) is brought into contact with compound (A). The isomerization step is preferably carried out in the presence of a packing material, but is not limited thereto.

[0024] The isomerization reaction of this embodiment is carried out in the presence of compound (A). This allows efficient geometric isomerization of the geometric isomer (isomer 1) represented by formula (1) above to the corresponding geometric isomer (isomer 2). That is, compound (A) functions as a promoter for the geometric isomerization of 1233zd or 1233yd.

[0025] When 1233zd is isomerized to obtain the corresponding geometric isomer, the dichlorotrifluoropropane is 1,1-dichloro-3,3,3-trifluoropropane (hereinafter also referred to as "243fa"). In the isomerization process, 243fa itself can also be converted to 1233zd, which contributes to improving the production efficiency of 1233zd.

[0026] When 1233yd is isomerized to obtain the corresponding geometric isomer, the dichlorotrifluoropropane is at least one of 1,1-dichloro-2,3,3-trifluoropropane (hereinafter also referred to as "243eb") and 1,2-dichloro-2,3,3-trifluoropropane (hereinafter also referred to as "243ba"). In the isomerization step, 243eb and 243ba themselves can be converted to 1233yd, which contributes to improving the production efficiency of 1233yd.

[0027] 1233zd(Z) and 1233zd(E) can be separated by precision distillation due to the difference in boiling points. Therefore, when 1233zd(E) is isomerized to obtain 1233zd(Z), it is rational and preferable from the viewpoint of efficient use of raw materials to collect the product containing 1233zd(Z) obtained by isomerization, isolate 1233zd(Z) and 1233zd(E) by distillation, and then reuse the recovered 1233zd(E) as raw material for isomerization.

[0028] Similarly, when 1233zd(Z) is isomerized to obtain 1233zd(E), it is rational and preferable from the viewpoint of efficient use of raw materials to collect the product containing 1233zd(E) obtained by isomerization, isolate 1233zd(E) and 1233zd(Z) by distillation or the like, and then reuse the recovered 1233zd(Z) as raw material for isomerization.

[0029] When 1233zd(Z) is used as a raw material and is isomerized to 1233zd(E), it is acceptable for the raw material 1233zd(Z) to contain the target product 1233zd(E), but in order to efficiently proceed with isomerization, it is preferable to use a raw material with a 1233zd(E) / 1233zd(Z) mass ratio of 1233zd(E) / 1233zd(Z) = 1 / 99 or less, more preferably 0.1 / 99.9 or less, and even more preferably 0.01 / 99.99 or less.

[0030] When 1233zd(E) is used as a raw material and is isomerized to 1233zd(Z), the target product 1233zd(Z) may be mixed in the raw material 1233zd(E), but in order to efficiently proceed with isomerization, it is preferable to use a raw material with a mass ratio of 1233zd(E) / 1233zd(Z) of 1233zd(E) / 1233zd(Z) = 10 / 1 or more, more preferably 50 / 1 or more, and even more preferably 100 / 1 or more.

[0031] 1233yd(Z) and 1233yd(E) can be separated by precision distillation due to the difference in boiling points. Therefore, when 1233yd(E) is isomerized to obtain 1233yd(Z), it is rational and preferable from the viewpoint of efficient use of raw materials to collect the product containing 1233yd(Z) obtained by isomerization, isolate 1233yd(Z) and 1233yd(E) by distillation, and then use the recovered 1233yd(E) again as raw material for isomerization.

[0032] Similarly, when 1233yd(Z) is isomerized to obtain 1233yd(E), it is rational and preferable from the viewpoint of efficient use of the raw material to collect the product containing 1233yd(E) obtained by isomerization, isolate 1233yd(E) and 1233yd(Z) by distillation or the like, and then reuse the recovered 1233yd(Z) as a raw material for isomerization.

[0033] In the isomerization step of the compound represented by the formula (1), the compound (A) may be supplied to the reaction tube as a raw material together with the compound represented by the formula (1), or may be supplied to the reaction tube separately from the raw material containing the compound represented by the formula (1).

[0034] Examples of catalysts that can be used in the isomerization step include metal catalysts, which are not particularly limited, but preferably contain at least one metal selected from the group consisting of aluminum, chromium, titanium, manganese, iron, nickel, cobalt, copper, magnesium, zirconium, molybdenum, zinc, tin, lanthanum, and antimony.

[0035] The metal catalyst may be a supported catalyst supported on a carrier such as activated carbon. Supported metals include, but are not limited to, aluminum, chromium, titanium, manganese, iron, nickel, cobalt, copper, magnesium, zirconium, molybdenum, zinc, tin, lanthanum, and antimony. These metals are supported as fluorides, chlorides, fluorochlorides, oxyfluorides, oxychlorides, and oxyfluorochlorides, and two or more metal compounds may be supported together. As the carrier, not only activated carbon but also metals such as alumina, chromia, zirconia, titania, etc. can be used. From the viewpoint of reaction efficiency, it is preferable to use activated carbon as the carrier.

[0036] Examples of packing materials that can be used in the isomerization step include, but are not limited to, activated carbon, stainless steel Raschig rings, stainless steel nets, quartz Raschig rings, and glass Raschig rings. From the viewpoint of reaction efficiency, activated carbon is preferably used.

[0037] Examples of activated carbon include plant-based activated carbon made from charcoal, coconut shell charcoal, palm kernel charcoal, and ash; coal-based activated carbon made from peat, lignite, brown coal, bituminous coal, and anthracite; petroleum-based activated carbon made from petroleum residue and petroleum carbon; and synthetic resin-based activated carbon made from polyvinylidene chloride (PCC). The activated carbon used in this embodiment can be selected from these commercially available activated carbons. For example, coconut shell charcoal for gas purification and catalyst carriers (Granular Shirasagi GX, SX, CX, and XRC manufactured by Osaka Gas Chemicals; PCB manufactured by Toyo Calgon; and Yasi Coal, Kuraray Coal GG, and GC manufactured by Taihei Chemical Industry Co., Ltd.) is preferably used. In this embodiment, when activated carbon is used as a filler, it is preferable to use activated carbon that does not support a metal. Activated carbon that does not support a metal is advantageous from the standpoints of cost and waste disposal. In this embodiment, activated carbon that does not support a metal refers to activated carbon in which the metal content in the activated carbon catalyst is 0% by mass or more and 5% by mass or less, preferably 0% by mass or more and 1% by mass or less, and more preferably 0% by mass or more and 0.1% by mass or less.

[0038] The activated carbon used may be in granular form, or may be in the form of spheres, fibers, powder, or honeycomb, as long as it is suitable for the reactor. The specific surface area and pore volume of the activated carbon are sufficient within the ranges specified for commercially available products, but the specific surface area should not exceed 400 m. 2 / g or more is desirable, and 800m 2 / g or more 3000m 2 / g or less. 3 / g or more, and 0.2 cm 3 / g or more 1.0cm 3 It is more preferable that the saturation coefficient is 1 / g or less.

[0039] The reaction temperature of the isomerization reaction is not particularly limited as long as it is equal to or higher than the boiling point of Isomer 1, but is preferably higher than 150°C and lower than 500°C. If the reaction temperature of the isomerization reaction is higher than 150°C, the target product can be obtained in good yield, and if it is lower than 500°C, impurities are less likely to be produced as by-products, and the target product can be obtained with high purity. The reaction temperature of the isomerization reaction is preferably 180°C or higher and 380°C or lower, particularly preferably 220°C or higher and 330°C or lower, and even more preferably higher than 250°C and 330°C or lower. The method for heating the reaction tube is not particularly limited, but examples include direct heating with an electric heater or burner, and indirect heating using molten salt or sand.

[0040] The reaction time of the isomerization reaction is defined by the "contact time" explained below. That is, the volume of the reaction tube (the total volume of a catalyst or packing material if used in the reaction tube) is A, and the volume of the raw material gas introduced into the reaction tube per second is B. B is calculated from the number of moles of raw material and diluent gas introduced per second, as well as the pressure and temperature, assuming that the raw material gas is an ideal gas. In this case, the value obtained by dividing A by B (= A / B) is the contact time.

[0041] Since the contact time depends on the temperature (reaction temperature), shape, and catalyst of the reaction tube, it is desirable to optimize it by appropriately adjusting the feed rate of the raw materials for each set temperature, shape of the reaction tube, and type of catalyst. From the viewpoint of recovery and reuse of unreacted raw materials, it is preferable to adopt a contact time that gives a raw material conversion rate of 5% or more, and more preferably, the contact time is optimized to give a conversion rate of 10% or more.

[0042] The contact time is not particularly limited, but is usually from 10 seconds to 180 seconds, preferably from 30 seconds to 120 seconds. In a preferred embodiment, when the reaction temperature is in the range of more than 150° C. and less than 500° C., the contact time may be, but is not limited to, 10 seconds or more and 180 seconds or less.

[0043] The reaction pressure is not particularly limited, but is preferably near atmospheric pressure. Pressure reactions above 1 MPa are not preferred because they require expensive pressure-resistant equipment and may cause polymerization of the raw materials or products. The reaction can also be carried out using an inert gas such as nitrogen or argon as a diluent.

[0044] A reactor that can be used for isomerization preferably includes a reaction tube, units for introducing and discharging various gases, and the like. These are formed from materials highly resistant to hydrogen chloride. Examples of such materials include, but are not limited to, quartz, carbon, ceramics, stainless steel such as austenitic stainless steel, high-nickel alloys such as Monel (registered trademark), Hastelloy (registered trademark), and Inconel (registered trademark), and copper-clad steel. The shape of the reaction tube is not particularly limited. The reaction tube may be empty or may contain packing inert to the reaction, such as a static mixer, Raschig rings, Pall rings, or wire mesh.

[0045] [Composition Overview] The present disclosure also relates to the following compositions: A raw material composition for producing a corresponding geometric isomer (isomer 2) represented by the following formula (1) by geometric isomerization of a geometric isomer (isomer 1) represented by the following formula (1): A composition comprising a geometric isomer (isomer 1) represented by the following formula (1) and a compound (A) which is at least one of dichlorotrifluoropropane and hydrogen chloride: CF 3-n H n -CX=CClH (1) (n is 0 or 1, X is a fluorine atom or a hydrogen atom, When n is 0, X is a hydrogen atom and the dichlorotrifluoropropane is 1,1-dichloro-3,3,3-trifluoropropane; When n is 1, X is a fluorine atom, and the dichlorotrifluoropropane is at least one of 1,1-dichloro-2,3,3-trifluoropropane and 1,2-dichloro-2,3,3-trifluoropropane.

[0046] The present disclosure also relates to the following compositions: A composition comprising a geometric isomer represented by the following formula (1) and a compound (A) which is at least one of dichlorotrifluoropropane and hydrogen chloride: CF 3-n H n -CX=CClH (1) (n is 0 or 1, X is a fluorine atom or a hydrogen atom, When n is 0, X is a hydrogen atom and the dichlorotrifluoropropane is 1,1-dichloro-3,3,3-trifluoropropane; When n is 1, X is a fluorine atom, and the dichlorotrifluoropropane is at least one of 1,1-dichloro-2,3,3-trifluoropropane and 1,2-dichloro-2,3,3-trifluoropropane. The components in the above composition are as described above. [Example]

[0047] The production of unsaturated chlorofluorocarbons according to the present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited to these examples. Here, the "GC%" in the composition analysis values ​​of the raw materials and reaction products represents the "GC area%" of the composition obtained by measuring the raw materials and reaction products by gas chromatography (detector: FID). Note that the displayed value is rounded to the nearest digit. For example, 0.0GC% indicates less than 0.05GC%.

[0048] Geometric isomerization of 1.1233zd(E) [Example 1] A gas phase reactor having a reaction tube filled with 100 cc of activated carbon (Shirasagi G2X, manufactured by Osaka Gas Chemicals Co., Ltd.) was equipped with a metal electric heater and an external heating device (a mantle heater, manufactured by Tokyo Kiki Co., Ltd.), and heated while flowing nitrogen gas through the reactor at a flow rate of approximately 50 mL / min.

[0049] Next, while nitrogen gas was flowing at a flow rate of 50 mL / min, a mixture containing 1233zd(E) (85.8 GC%), 1233zd(Z) (0.0 GC%), 243fa (13.6 GC%), and 0.6 GC% of other components as starting materials was fed into the reaction tube through a vaporizer at a flow rate of 0.6 g / min. The introduction of nitrogen gas was stopped when the flow rate of the raw materials stabilized, during which time the temperature inside the reaction tube was 250 °C. After confirming that the reaction was stable, the gas flowing out of the reactor was bubbled through water to remove acidic gases, and the product was analyzed by gas chromatography. The reaction temperature, contact time, and gas chromatography analysis results are shown in Table 1. 1233zdE / Z indicates the production ratio of 1233zd(E) to 1233zd(Z) (i.e., the amount of 1233zd(E) produced (GC%) divided by the amount of 1233zd(Z) produced (GC%)). The composition of the above raw materials is also shown in Table 1.

[0050] [Examples 2 to 5] Except for changing the reaction temperature and contact time, the isomerization reaction was carried out in the same manner as in Example 1. The reaction temperatures and contact times in Examples 2 to 5, and the gas chromatographic analysis results of the products of the isomerization reaction are shown in Table 1.

[0051] [Table 1]

[0052] A mixture of 1233zd(E):243fa in a molar ratio of 6.9:1 (i.e., 0.145 moles of 243fa per mole of 1233zd(E)) was used as the raw material in Examples 1 to 5. Analysis of this raw material by gas chromatography revealed that 1233zd(E) was 85.8 GC%, 1233zd(Z) (0.0 GC%), 243fa was 13.6 GC%, and other components were 0.6 GC%.

[0053] To confirm the conversion of 243fa to 1233zd(E) or 1233zd(Z), a vapor phase dehydrochlorination reaction of 243fa was carried out.

[0054] [Reference example 1] While nitrogen gas was flowing at a flow rate of 50 mL / min, a mixture of 243fa (95.2 GC%) and 1233zd(Z) (0.0 GC%) was vaporized through a vaporizer at a flow rate of 1.5 g / min as the starting material for the isomerization reaction and fed into the reaction tube. When the flow rate of the raw materials stabilized, the introduction of nitrogen gas was stopped, during which time the temperature inside the reaction tube was 250 °C. After confirming that the reaction had stabilized, the gas flowing out of the reactor was blown into water to remove acidic gases, and the product was analyzed by gas chromatography. The reaction temperature, contact time, and gas chromatography analysis results are shown in Table 2. The composition of the above raw materials is also shown in Table 2.

[0055] [Reference examples 2~4] Except for changing the reaction temperature and contact time, the isomerization reaction was carried out in the same manner as in Reference Example 1. The reaction temperatures and contact times in Reference Examples 2 to 4, and the gas chromatographic analysis results of the products of the isomerization reaction are shown in Table 2.

[0056] [Table 2]

[0057] As is clear from Table 2, 243fa was converted to 1233zd, and the product composition was such that 1233zd(E) was the main product and 1233zd(Z) was the main by-product. It was also found that increasing the reaction temperature improved the conversion of 243fa, but the production ratio of 1233zd(E) to 1233zd(Z) did not change. Regardless of the reaction temperature or contact time, the production ratio of 1233zd(E) to 1233zd(Z) was approximately 7 (1233zdE / Z = approximately 7).

[0058] To confirm the reaction-accelerating effect of 243fa, Example 3 in Table 1 was used to calculate the theoretical amounts of 1233zd(Z) and 1233zd(E) when all of the added 243fa was converted to 1233zd(Z) or 1233zd(E). Table 3 shows these amounts.

[0059] [Table 3]

[0060] As is clear from Table 3, in Example 3, more 1233zd(Z) than the theoretical amount of 1233zd(Z) produced from 243fa was produced, and it is believed that the effect of 243fa acting as an accelerator of the isomerization reaction contributes more than the effect of converting 243fa to 1233zd(Z).

[0061] [Comparative Example 1] A gas phase reactor having a reaction tube filled with 100 cc of activated carbon (Shirasagi G2X, manufactured by Osaka Gas Chemicals Co., Ltd.) was equipped with a metal electric heater and an external heating device (a mantle heater, manufactured by Tokyo Kiki Co., Ltd.), and heated while flowing nitrogen gas through the reactor at a flow rate of approximately 50 mL / min.

[0062] Next, while nitrogen gas was flowing at a rate of 50 ml / min, a mixture containing the starting materials 1233zd(E) (>99.9 GC%) and 1233zd(Z) (0.0 GC%) was fed into the reaction tube at a rate of 0.6 g / min through a vaporizer. When the flow rate of the raw materials stabilized, the introduction of nitrogen gas was stopped, during which time the temperature inside the reaction tube was 300°C. After confirming that the reaction had stabilized, the gas flowing out of the reactor was blown into water to remove acidic gases, and the product was analyzed by gas chromatography. The reaction temperature, contact time, and gas chromatography analysis results are shown in Table 4. The composition of the above raw materials is also shown in Table 4.

[0063] Comparative Example 2 Except for changing the contact time, the isomerization reaction was carried out in the same manner as in Comparative Example 1. The reaction temperature and contact time in Comparative Example 2, and the results of gas chromatography analysis of the product of the isomerization reaction are shown in Table 4.

[0064] [Table 4]

[0065] As is clear from a comparison of Tables 1 and 4, the conversion of 1233zd(E) to 1233zd(Z) is significantly improved by isomerizing 1233zd(E) in the presence of 243fa. In particular, the conversion is significantly improved when the reaction temperature is set to 300°C.

[0066] 2.1233zd(Z) geometric isomerization [Example 6] The same procedure as in Example 1 was carried out, except that a mixture of 1233zd(E) (0.0 GC%) and 1233zd(Z) (>99.9 GC%) was used as the starting material for the isomerization reaction, and hydrogen chloride (HCl) as compound (A) was supplied to the reaction tube at a supply rate of 5 mL / min. The amount of HCl in the starting material was 0.05 mol per mol of 1233zd(Z). The results of gas chromatography analysis are shown in Table 5.

[0067] [Examples 7 to 10] Except for changing the reaction temperature and the amount of HCl added, the isomerization reaction was carried out in the same manner as in Example 6. Table 5 shows the reaction temperature and contact time, the amount of HCl added, and the gas chromatography analysis results of the products of the isomerization reaction in Examples 7 to 10.

[0068] [Table 5]

[0069] Comparative Example 3 A gas phase reactor having a reaction tube filled with 100 cc of activated carbon (Shirasagi G2X, manufactured by Osaka Gas Chemicals Co., Ltd.) was equipped with a metal electric heater and an external heating device (a mantle heater, manufactured by Tokyo Kiki Co., Ltd.), and heated while flowing nitrogen gas through the reactor at a flow rate of approximately 50 mL / min.

[0070] Next, while feeding nitrogen at 50 mL / min, a mixture containing the starting materials 1233zd(E) (0.0 GC%) and 1223zd(Z) (>99.9 GC%) was fed into the reaction tube through a vaporizer at a flow rate of 0.6 g / min. When the flow rate of the raw materials stabilized, the introduction of nitrogen gas was stopped, during which the temperature inside the reaction tube was 250 °C. After confirming that the reaction was stable, the gas flowing out of the reactor was blown into water to remove acidic gases, and the product was analyzed by gas chromatography. The gas chromatography analysis results are shown in Table 6.

[0071] [Comparative Examples 4 to 5] Except for changing the reaction temperature, the isomerization reaction was carried out in the same manner as in Comparative Example 3. Table 6 shows the reaction temperatures and contact times in Comparative Examples 4 and 5, as well as the gas chromatographic analysis results of the products of the isomerization reaction.

[0072] [Table 6]

[0073] As is clear from Tables 5 and 6, the conversion of 1233zd(Z) to 1233zd(E) is significantly improved by isomerizing 1233zd(Z) in the presence of HCl. It is also clear that the promoting effect of increasing the amount of HCl added is greater. These results suggest that isomerization proceeds via 243fa due to the addition and elimination of HCl. Furthermore, it is speculated that the promotion of isomerization of 1233zd(E) by 243fa is due to the contribution of hydrogen chloride generated by the decomposition of these promoters to the reaction.

[0074] Furthermore, as is clear from Tables 4 and 6, the conversion of 1233zd(Z) to 1233zd(E) can be carried out in the same manner as the conversion of 1233zd(E) to 1233zd(Z). From this, it can be inferred that the conversion rate of 1233zd(Z) to 1233zd(E) can be significantly improved by isomerizing 1233zd(Z) in the presence of 243fa.

[0075] Geometric isomerization of 3.1233yd The isomerization reaction was carried out in the same manner as in Examples 1 to 5, except that starting materials containing at least one of 1233yd(E) and 1233yd(Z) and at least one of 243eb and 243ba were used. The isomerization reaction from 1233yd(E) to 1233yd(Z), or from 1233yd(Z) to 1233yd(E), was carried out in the same manner as in Examples 6 to 10, except that a liquid containing at least one of 1233yd(E) and 1233yd(Z) was used instead of a mixture of 1233zd(E) (0.0 GC%) and 1233zd(Z) (>99.9 GC%). These products were analyzed by gas chromatography.

[0076] In the isomerization reaction from 1233yd(E) to 1233yd(Z) or from 1233yd(Z) to 1233yd(E), the inclusion of at least one of compound (A), 243eb, 243ba, and HCl, in the raw material can significantly improve the isomerization reaction from 1233yd(E) to 1233yd(Z) or the conversion rate from 1233yd(Z) to 1233yd(E). When 243eb or 243ba is used, decomposition of these compounds produces 1233yd and hydrogen chloride, and it is presumed that this hydrogen chloride contributes to the reaction. [Industrial Applicability]

[0077] According to one embodiment of the present disclosure, a method and composition for efficiently producing unsaturated chlorofluorocarbons can be provided.

[0078] Although the present disclosure has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the disclosure. This application is based on a Japanese patent application (Patent Application No. 2020-212438) filed on December 22, 2020, the contents of which are incorporated herein by reference.

Claims

1. A method for producing a corresponding geometric isomer (isomer 2) represented by the following formula (1) by geometric isomerization of a geometric isomer (isomer 1) represented by the following formula (1): The method includes a step of contacting a geometric isomer (isomer 1) represented by the following formula (1) with a compound (A) which is at least one of dichlorotrifluoropropane and hydrogen chloride in a gas phase, A method in which the geometric isomer (isomer 1) represented by the formula (1) is a cis isomer, the produced geometric isomer (isomer 2) is a trans isomer, and the compound (A) is hydrogen chloride; or the geometric isomer (isomer 1) represented by the formula (1) is a trans isomer, the produced geometric isomer (isomer 2) is a cis isomer, and the compound (A) is 1,1-dichloro-3,3,3-trifluoropropane. CF ３－ｎ H ｎ -CX=CClH (1) (n is 0 and X is a hydrogen atom.)

2. The method according to claim 1, wherein the geometric isomer (isomer 1) represented by formula (1) is a cis isomer, the produced geometric isomer (isomer 2) is a trans isomer, and the compound (A) is hydrogen chloride.

3. The method according to claim 1, wherein the geometric isomer (isomer 1) represented by formula (1) is a trans isomer, the produced geometric isomer (isomer 2) is a cis isomer, and the compound (A) is 1,1-dichloro-3,3,3-trifluoropropane.

4. The method of any one of claims 1 to 3, wherein the contacting is carried out in the presence of at least one of a catalyst and a filler.

5. The method of any one of claims 1 to 4, wherein the contacting is carried out in the presence of activated carbon.

6. The method of any one of claims 1 to 5, wherein the contacting is carried out at greater than 150°C and less than 500°C.

7. A raw material composition for producing a corresponding geometric isomer (isomer 2) represented by the following formula (1) by geometric isomerization of a geometric isomer (isomer 1) represented by the following formula (1): The compound (A) contains a geometric isomer (isomer 1) represented by the following formula (1), and at least one of dichlorotrifluoropropane and hydrogen chloride, A composition in which the geometric isomer (isomer 1) represented by the formula (1) is a cis isomer, the produced geometric isomer (isomer 2) is a trans isomer, and the compound (A) is hydrogen chloride; or the geometric isomer (isomer 1) represented by the formula (1) is a trans isomer, the produced geometric isomer (isomer 2) is a cis isomer, and the compound (A) is 1,1-dichloro-3,3,3-trifluoropropane. CF ３－ｎ H ｎ -CX=CClH (1) (n is 0 and X is a hydrogen atom.)

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