CN112204003A - Method for producing 1-chloro-2, 3,3,4,4,5, 5-heptafluoro-1-pentene - Google Patents
Method for producing 1-chloro-2, 3,3,4,4,5, 5-heptafluoro-1-pentene Download PDFInfo
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Abstract
Provided is a process for producing 1-chloro-2, 3,3,4,4,5, 5-heptafluoro-1-pentene, which can efficiently remove 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water, can increase the recovery rate of 1-chloro-2, 3,3,4,4,5, 5-heptafluoro-1-pentene, and can increase the purity of 1-chloro-2, 3,3,4,4,5, 5-heptafluoro-1-pentene. A process for producing 1-chloro-2, 3,3,4,4,5, 5-heptafluoro-1-pentene, which comprises distilling a composition for distillation containing 1-chloro-2, 3,3,4,4,5, 5-heptafluoro-1-pentene, water and 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne to remove 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water.
Description
Technical Field
The present invention relates to a process for producing 1-chloro-2, 3,3,4,4,5, 5-heptafluoro-1-pentene.
Background
Hydrochlorofluorocarbons (HCFCs) have a negative impact on the ozone layer and therefore their production is planned to be limited. The HCFC may, for example, be 3, 3-dichloro-1, 1,1,2, 2-pentafluoropropane (CF)3-CF2-CHCl2HCFC-225 ca. ) 1, 3-dichloro-1, 1,2,2, 3-pentafluoropropane (CClF)2-CF2-CHFCl, HCFC-225 cb. ) And the like. With the limitation of HCFCs, it is desired to develop compounds that substitute for HCFCs.
Examples of the compound that substitutes for HCFC include 1-chloro-2, 3,3,4,4,5, 5-heptafluoro-1-pentene (CHCl ═ CF-CF)2-CF2-CF2H, HCFO-1437 dycc. Hereinafter referred to as "1437 dycc". ). 1437dycc has a small greenhouse effect potential (GWP), and is expected to be a compound suitable for use in applications such as cleaning agents, solvents, refrigerants, foaming agents, and aerosols.
Non-patent document 1 discloses the following method: 2,2,3,3,4,4,5, 5-octafluoro-1-pentanol (hereinafter referred to as "OFPO") and triphenylphosphine dichloride are reacted to obtain 5-chloro-1, 1,2,2,3,3,4, 4-octafluoropentane (HCFC-448occc, hereinafter referred to as "448 occc"), and 448occc is reacted with sodium methoxide to perform a dehydrofluorination reaction to obtain 1437 dycc.
Documents of the prior art
Non-patent document
Non-patent document 1: journal of organic chemistry (Zhurnal organic heskoi Khimii), (Russia), 1988, Vol.24, No. 8, page 1626-
Disclosure of Invention
Technical problem to be solved by the invention
However, it is known that the reaction product produced by the above method contains 1437dycc and 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne produced by further dehydrofluorination at 1437 dycc. The 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne has a problem of lowering thermal and chemical stability of 1437 dycc. In order not to cause such unfavorable problems, it is preferable to reduce the amount of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne coexisting with 1437dycc as much as possible.
In addition, in the 1437dycc production process, water may be mixed into the reaction product to include water. When water (moisture) coexists with 1437dycc, it may cause deterioration in reliability and performance when used as a cleaning agent, a solvent, a refrigerant, a foaming agent or an aerosol, causing various problems. In order not to cause such an adverse problem, it is preferable to reduce the amount of water coexisting with 1437dycc as much as possible.
Generally, the boiling point difference is used to remove by-products and impurities from the reaction product by distillation. However, since 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne has a boiling point lower than 1437dycc and water has a boiling point higher than 1437dycc, a two-stage distillation step of separating a low boiling point component and a high boiling point component is required when separating them by a general distillation column. Thus, more efficient methods of manufacturing 1437dycc are sought.
The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for producing 1437dycc, which is capable of efficiently removing 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water from a composition containing 1437dycc, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water, and which has a high recovery rate of 1437dycc and an improved purity of 1437 dycc.
Technical scheme for solving technical problem
The present invention provides a 1437dycc manufacturing method with the following structure.
[1] A process for producing 1437dycc, characterized by distilling a composition for distillation containing 1437dycc, water and 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne to remove 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water.
[2] The production process according to [1], wherein the 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water are removed by forming an azeotropic composition or an azeotrope-like composition.
[3] The production method according to [1] or [2], wherein the content of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne in the distillation composition is 0.001 to 15% by mass based on the total amount of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water.
[4] The production method according to any one of [1] to [3], wherein a content ratio of 1437dycc to the total amount of the distillation composition is 50% by mass or more.
[5] The production method according to [4], wherein a content ratio of 1437dycc to the total amount of the composition for retort is 90% by mass or more.
[6] The production method according to any one of [1] to [5], wherein the composition for distillation is obtained by adding water to a mixture containing 1437dycc and 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne, and then distilling the mixture.
[7] The production process according to any one of [1] to [6], wherein the composition for distillation is prepared from the reaction composition obtained by dehydrofluorinating 1-chloro-2, 2,3,3,4,5, 5-octafluoropentane.
[8] The production process according to any one of the above [1] to [7], wherein the distillation is carried out in a distillation column under distillation conditions of a column top temperature of 10 to 95 ℃ and a column internal pressure of 50 to 760 mmHg.
In the present specification, when an abbreviation of a compound is described in parentheses after the compound name for a halogenated hydrocarbon, the abbreviation is used instead of the compound name as necessary. In addition, compounds having a double bond in the molecule and having an E-form and a Z-form are represented by the symbols (E) and (Z) after the abbreviation of the compounds having the E-form and the Z-form, respectively. In addition, a substance not labeled with (E) or (Z) at the end of the abbreviation of the compound name means any of E-form, Z-form, and a mixture of E-form and Z-form.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the 1437dycc production method of the present invention, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water can be efficiently removed from a composition containing 1437dycc, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water. Therefore, the recovery rate of 1437dycc can be improved, and the purity of 1437dycc can be improved.
Drawings
FIG. 1 is a view showing an example of a distillation apparatus used in the production method of the embodiment.
Detailed Description
Embodiments of the present invention will be described below.
The 1437dycc production method of the present embodiment distills a composition for distillation containing 1437dycc, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne, and water, and removes the 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and the water from the composition for distillation. In the method of producing 1437dycc according to this embodiment, 1437dycc can be purified and a composition having an improved 1437dycc purity can be produced by removing 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water from the composition for distillation. Here, the 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water in the composition for distillation may be partially or completely removed.
In the present invention, it is preferable to remove 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water from the distillation composition by forming an azeotropic composition or an azeotrope-like composition upon distillation of the distillation composition.
(azeotropic composition and azeotrope-like composition)
Generally, an azeotropic composition is a mixture of 2 or more compounds, and the composition of a gas phase generated by vaporization of a liquid phase is the same as the composition of the liquid phase, or the composition of a liquid phase generated by liquefaction of a gas phase is the same as the composition of the gas phase. Since the composition of the azeotropic composition does not change by evaporation or condensation, it is suitable for distillation or reflux. In addition, the composition of the azeotropic composition will vary with pressure conditions.
Azeotrope-like compositions exhibit similar characteristics to azeotropic compositions. That is, the azeotrope-like composition is such that the composition of the gas phase produced by vaporization of the liquid phase is substantially the same as the composition of the liquid phase, or the composition of the liquid phase produced by liquefaction of the gas phase is substantially the same as the composition of the gas phase. Since the composition of the azeotrope-like composition hardly changes by evaporation or condensation, the azeotrope-like composition can be applied to distillation or reflux as in the case of the azeotropic composition.
The present inventors have found that 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne forms an azeotropic composition or an azeotrope-like composition with water. It has further been found that azeotropic or azeotrope-like compositions of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne with water are formed preferentially over azeotropic or azeotrope-like compositions of 1437dycc with water.
And an azeotropic or azeotrope-like composition of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne with water has a boiling point lower than 1437 dycc. That is, the boiling point of an azeotropic composition or azeotrope-like composition of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water is about 65 to 85 ℃ relative to the boiling point of about 89 ℃ of 1437 dycc. In addition, the boiling point is the boiling point at atmospheric pressure. The atmospheric pressure was 101.325 kPa.
Accordingly, by forming 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne into an azeotropic composition or an azeotrope-like composition with water, 1437dycc, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water can be separated from 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and the water in a composition for distillation comprising 1437dycc, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water. Thus, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water can be efficiently removed from the composition for distillation, and the recovery rate of 1437dycc and the purity of 1437dycc can be improved.
In an azeotropic composition of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water, the relative volatility of water represented by the following formula (1) with respect to 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne is 1.00, and in an azeotrope-like composition of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water, the relative volatility represented by the following formula (1) is a value within a range of 1.00 ± 0.20 under atmospheric pressure. If the relative volatility of the azeotrope-like composition is within the ranges described, nearly the same effect as that of the azeotropic composition can be obtained.
Relative volatility (mole% water in vapor phase/mole% 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne in vapor phase)/(mole% water in liquid phase/mole% 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne in liquid phase) … (1)
The composition range in which the desired relative volatility can be obtained can be determined as follows. First, the composition of a mixture of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water was gradually changed, and the compositions of the liquid phase and the gas phase were measured by a karl fischer moisture meter or a gas chromatograph. The relative volatility was determined by the above formula (1) using the compositions of the liquid phase and the gas phase. From this, the correlation between the composition and the relative volatility was obtained. From this correlation, a composition that achieves a desired relative volatility can be obtained.
In the azeotropic composition and azeotrope-like composition of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water, the ratio of the amount of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne to the total amount of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water is preferably 0.001 to 15% by mass. When the above ratio is within the above range, the relative volatility is likely to be within the range of 1.00. + -. 0.20, and the boiling point is likely to be about 65 to 85 ℃. From the viewpoint of lowering the boiling point by bringing the relative volatility close to 1.00, the above proportion is more preferably 0.01 to 10% by mass, still more preferably 0.05 to 5% by mass, and particularly preferably 1.5 to 3% by mass.
(composition for distillation)
The composition for distillation comprises 1437dycc, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water. The composition for distillation is not particularly limited as long as it contains 1437dycc, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water. Further, the composition for distillation may contain components other than 1437dycc, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne, and water. The distillation composition may be liquid or gaseous.
1437dycc has Z formula and E formula as geometrical isomers according to the position of the substituent on the double bond. The 1437dycc of the distillation composition used in this embodiment may be either one of a Z-form body (1437dycc (Z)) and an E-form body (1437dycc (E)), or a mixture of 1437dycc (Z) and 1437dycc (E). The mixture of 1437dycc (z) and 1437dycc (e) is preferably a mixture of 1437dycc (z) of 50% or more, more preferably a mixture of 90% or more, and still more preferably a mixture of 95% or more.
A composition for distillation can be prepared using a reaction composition containing 1437dycc produced when 1437dycc is obtained by the method described later or the like, and at least 1 kind selected from 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water. That is, when 1437dycc, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water are contained as a reaction product generated when 1437dycc is obtained, the reaction product can be used as it is as a composition for distillation. The reaction product may be washed with water or alkali, and the composition from which acidic substances such as hydrogen fluoride and hydrogen chloride contained in the reaction product have been removed may be used as a composition for distillation. In the present invention, the term "preparing" of the composition includes the case where the above-mentioned reaction composition or the like is used as it is.
1437 dcc can be obtained, for example, by dehydrofluorinating 448occc in the presence of a base. The dehydrofluorination reaction can be carried out by either a liquid-phase reaction or a gas-phase reaction in the presence of a base. The dehydrofluorination reaction by a liquid phase reaction means that 448occc in a liquid state was subjected to the dehydrofluorination reaction. The dehydrofluorination reaction by a gas phase reaction means that 448occc in a gas state was subjected to a dehydrofluorination reaction. From the viewpoint of reaction efficiency, the dehydrofluorination reaction of 448occc is preferably carried out by a liquid-phase reaction.
The base may be any base that can effect the dehydrofluorination reaction, and examples thereof include metal hydroxides, metal oxides, metal carbonates, and metal alkoxides. The alkali can be used alone in 1 kind, also can be more than 2 kinds of combination use.
Examples of the metal hydroxide include alkali metal hydroxides and alkaline earth metal hydroxides. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide and potassium hydroxide. Examples of the alkaline earth metal hydroxide include magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide.
Examples of the metal oxide include alkali metal oxides and alkaline earth metal oxides. Sodium oxide is given as an alkali metal oxide. As the alkaline earth metal oxide, calcium oxide is exemplified.
The metal carbonate may, for example, be an alkali metal carbonate or an alkaline earth metal carbonate. The alkali metal carbonate may, for example, be a carbonate of lithium, sodium or potassium. The alkaline earth metal carbonate may, for example, be a carbonate of beryllium, magnesium, calcium, strontium or barium.
The metal alkoxide may, for example, be an alkali metal alkoxide. Examples of the alkali metal alkoxide include sodium methoxide, sodium ethoxide, potassium methoxide, and potassium ethoxide.
The base is preferably a metal hydroxide, more preferably potassium hydroxide or sodium hydroxide, from the viewpoint of easy handling and high reactivity. In particular, when the dehydrofluorination reaction is carried out by a liquid phase reaction, the use of the above metal hydroxide is advantageous because it has a high solubility in water.
In the case of performing the dehydrofluorination reaction by a liquid-phase reaction, it is preferable to perform the reaction in the presence of a phase transfer catalyst in order to increase the reaction rate.
Specific examples of the phase transfer catalyst include quaternary ammonium salts, quaternary phosphonium salts, quaternary arsonium salts, sulfonium salts and crown ethers, with quaternary ammonium salts, quaternary phosphonium salts, quaternary arsonium salts and sulfonium salts being preferred, and quaternary ammonium salts being more preferred.
Specific examples of the quaternary ammonium salt include tetra-n-butylammonium chloride (TBAC), tetra-n-butylammonium bromide (TBAB), and methyltri-n-octylammonium chloride (TOMAC).
Specific examples of the quaternary phosphonium salt include quaternary phosphonium salts in which tetraethylphosphonium ion, tetra-n-butylphosphonium ion, ethyltri-n-octylphosphonium ion, hexadecyltriethylphosphonium ion, hexadecyltri-n-butylphosphonium ion, n-butyltriphenylphosphonium ion, n-pentyltriphenylphosphonium ion, methyltriphenylphosphonium, benzyltriphenylphosphonium, or tetraphenylphosphonium ion is combined with a chloride ion, fluoride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, phosphate ion, perchlorate ion, hydrogen sulfate ion, hydroxide ion, acetate ion, benzoate ion, benzenesulfonate ion, or p-toluenesulfonate ion as a counter ion thereof.
Specific examples of the quaternary arsonium salt include trityl arsonium fluoride, tetraphenyl arsonium fluoride, trityl arsonium chloride, tetraphenyl arsonium chloride, and tetraphenyl arsonium bromide.
Specific examples of the sulfonium salt include di-n-butylsulfonium methyliodide, tri-n-butylsulfonium tetrafluoroborate, dihexylsulfonium methyliodide, dicyclohexylsulfonium methyliodide, dodecylsulfonium methylethylchloride, and tris (diethylamino) trimethylsulfonium orthosilicate.
Specific examples of the crown ether include 18-crown-6, dibenzo-18-crown-6 and dicyclohexyl-18-crown-6.
Among the above-mentioned phase transfer catalysts, TBAC, TBAB and TOMAC are preferable from the viewpoints of easiness of industrial availability, cost, easiness of handling and reactivity.
In addition, in the case of conducting the dehydrofluorination reaction of 448occc by a gas phase reaction, it may be conducted in the presence of activated carbon or a metal catalyst.
The specific surface area of the activated carbon used for the gas phase reaction is preferably 10 to 3000m from the viewpoint of increasing the reaction conversion rate and suppressing by-products2A concentration of 20 to 2500m2A more preferable range is 50 to 2000m2(ii) in terms of/g. The specific surface area of the activated carbon was measured by a method based on the BET method.
Specific examples of the activated carbon include activated carbon prepared from charcoal, coal, coconut shell, and the like. More specifically, the carbon particles include formed carbon particles having a length of about 2 to 5mm, pulverized carbon particles having a particle size of about 4 to 50 mesh, granular carbon particles, and powdered carbon particles.
It is preferable to sufficiently dry the activated carbon before use in the reaction. From the viewpoint of improving reactivity and selectivity, the amount of water in the activated carbon is preferably 10 mass% or less, more preferably 5 mass% or less, and still more preferably 1 mass% or less, with the total amount of the activated carbon and water being 100 mass%.
Specific examples of the metal catalyst include iron (0), cobalt (0), nickel (0), palladium (0), chromium oxide (chromia), aluminum oxide (alumina), zinc oxide, tin oxide, magnesium oxide, lanthanum oxide, nickel oxide, fluorinated aluminum oxide, fluorinated chromium oxide, fluorinated magnesium oxide, lanthanum oxide, alkali metal halide, alkaline earth metal halide, and chromium hydroxide.
In the above-described 448occc dehydrofluorination reaction, in the case of conducting the dehydrofluorination reaction by a gas phase reaction, it is preferable to use activated carbon or an alkaline earth metal fluoride, more preferably activated carbon or BaF, from the viewpoint of improving the reactivity and selectivity2、SrF2、CaF2。
Typically, in addition to 1437dycc, the reaction product obtained from the dehydrofluorination reaction of 448occc also contains 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne produced by further dehydrofluorination of 1437 dycc. In addition, water mixed in the dehydrofluorination reaction of 448occc may be contained in the reaction product. That is, a reaction composition containing 1437dycc and at least 1 selected from 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water can be obtained by the above-mentioned dehydrofluorination reaction of 448 occc. The reaction composition obtained by the above method may be used as it is as a composition for distillation, or a product prepared by adding at least 1 selected from the group consisting of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water depending on the content of water and 1-chloro-3, 3,4,4, 4,5, 5-hexafluoro-1-pentyne contained in the reaction composition may be used as a composition for distillation.
As the reaction composition, a reaction composition containing 1437dycc and 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and containing no water (the 1 st reaction composition); and a reaction composition containing 1437dycc, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne, and water (reaction composition No. 2).
A composition for distillation can be obtained by adding water to the reaction composition No. 1, i.e., the reaction composition containing 1437dycc and 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and containing no water.
In the case of the reaction composition of the 2 nd reaction composition containing 1437dycc, water and 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne, the reaction composition can be used as a composition for distillation in this state as it is. In addition, water may be added to the reaction composition of the 2 nd reaction in correspondence with the content of water and 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne.
The content of 1437dycc in the composition for distillation used in the present embodiment is preferably 50 mass% or more, more preferably 80 mass% or more, and still more preferably 90 mass% or more, based on the total amount of the composition for distillation. If the content of 1437dycc is not less than the lower limit, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water can be efficiently removed, and the recovery rate of 1437dycc in the bottom sediment can be improved.
The content of each of water and 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne in the composition for distillation is not necessarily limited. By including water and 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne in the distillation composition, an azeotropic or azeotrope-like composition may be formed from the water and 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne.
In addition, it is preferable that all of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water in the composition for distillation form an azeotropic composition or an azeotrope-like composition to efficiently remove them from the composition for distillation. From this viewpoint, the ratio of the content of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne to the total of the content of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and the content of water in the composition for distillation is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, even more preferably 0.05 to 5% by mass, and particularly preferably 1.5 to 3% by mass.
The proportion of water in the distillation composition can be adjusted by adding water. For example, when the proportion of water is small, the proportion of water can be increased by adding water.
The composition for distillation may contain components other than 1437dycc, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne, and water. The components other than 1437dycc, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water include by-products produced in the step of obtaining 1437dycc from the starting material and 448occc by dehydrofluorination in order to produce 1437dycc, in addition to 1437dycc and 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne. Specific examples of components that may be contained in the distillation composition other than 1437dycc, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water include 448occc, 3,3,4,4,5, 5-hexafluoro-1-pentyne, 1,1,1,2,2, 3,3,4,4, 5-nonafluoropentane, 2,3,3,4,4,5, 5-heptafluoro-1-pentene, 1,2,3,3,4,4,5, 5-octafluoro-1-pentene, and alcohols such as OFPO and methanol.
From the viewpoint of improving the recovery rate of 1437dycc, the content of components other than 1437dycc, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water is preferably 30% by mass or less, more preferably 10% by mass or less, based on the total amount of the distillation composition. In particular, since alcohols such as OFPO and methanol may inhibit the formation of an azeotropic composition between 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water, when these compounds are contained, it is preferably 5% by mass or less, more preferably 1% by mass or less, based on the total amount of the distillation composition.
(distillation)
The 1437dycc production method of this embodiment distills a composition for distillation containing 1437dycc, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne, and water. By allowing 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water to coexist in the composition for distillation, an azeotropic composition or an azeotrope-like composition of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water can be formed.
As described above, 1437dycc has a boiling point higher than that of an azeotropic composition or azeotrope-like composition of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water, and therefore, by distilling the distillation composition, at least a part of the azeotropic composition or azeotrope-like composition of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water can be removed from the distillation composition. As a result, a composition having a reduced content of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water, i.e., a composition having an improved purity of 1437dycc, can be obtained.
The distillation apparatus may be any apparatus capable of removing at least a part of an azeotropic composition or an azeotrope-like composition of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water from the composition for distillation, and a known distillation apparatus may be used.
FIG. 1 is a view showing an example of a distillation apparatus.
The distillation apparatus 10 includes, for example, a distillation column 11, and a pipe 12 for supplying a composition for distillation, a pipe 13 for taking out a distillate from the top of the distillation column 11, and a pipe 14 for taking out a bottom sediment from the bottom of the distillation column 11 are connected to the distillation column 11. The distillation apparatus 10 may be either a batch type or a continuous type. The distillation column 11 may be either a hollow type or a multistage type.
In such a distillation apparatus 10, for example, a distillate containing an azeotropic composition or azeotrope-like composition of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water can be obtained from the top of the column. In addition, a bottoms containing 1437dycc may be obtained from the bottom of the column.
In addition, in the case where the azeotropic composition or azeotrope-like composition containing more than the composition range of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water in the distillation composition contains an excess of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne or water, for example, a bottom product obtained from the bottom of a column may contain the excess of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne or water.
In the case of the multi-stage distillation column 10, the composition for distillation is usually supplied to the middle stage of the multi-stage distillation column 10. In this case, the distillate of the azeotropic composition or azeotrope-like composition comprising 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water can be obtained from a stage above the stage to which the distillation composition is supplied. Further, the bottom sediment containing 1437dycc can be obtained from a lower stage than the stage where the distillation composition is supplied.
The pressure during distillation is preferably 50 to 760mmHg absolute pressure, more preferably 100 to 500mmHg, and still more preferably 200 to 400 mmHg. Under such a pressure, the column top temperature of the distillation column is preferably 10 to 95 ℃. By setting the pressure during distillation and the temperature at the top of the distillation column within the above ranges, at least a part of the azeotropic composition or azeotrope-like composition of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water can be efficiently removed from the composition for distillation.
For example, when the pressure during distillation is 300mmHg absolute, the column top temperature of the distillation column is preferably 40 ℃ or higher, more preferably 43 ℃ or higher, and still more preferably 45 ℃ or higher, from the viewpoint of increasing the recovery amount of a distillate of an azeotropic composition or azeotrope-like composition comprising 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water and increasing the recovery rate of 1437dycc in the bottom sediment. Further, from the viewpoint of making the proportion of 1437dycc contained in the distillate smaller, it is preferably 60 ℃ or lower, more preferably 57 ℃ or lower, and still more preferably 55 ℃ or lower.
Distillation can be carried out again using the bottoms containing 1437dycc as the distillation composition. In the case where the bottom sediment contains 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water, the distillation is carried out to separate the 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and the water, whereby a bottom sediment having a purity of 1437dycc further improved can be obtained.
Further, by using the bottom sediment containing 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne as a composition for distillation and performing distillation again, a bottom sediment having an increased proportion of 1437dycc can be obtained.
In the 1437dycc production method of the present embodiment, the recovery rate of the bottom sediment can be adjusted to 85% or more, for example, by distillation. The recovery of the bottom sediment is preferably 90% or more, more preferably 95% or more. Here, the recovery rate [% ] of the bottom sediment can be obtained from the supply amount of the distillation composition and the recovery amount of the bottom sediment by the following equation.
The recovery rate [% ] of the bottom sediment is (recovery amount of the bottom sediment)/(supply amount of the distillation composition) × 100
In the 1437dycc production method according to the present embodiment, the recovery rate of 1437dycc in the bottom sediment can be set to 90% or more, for example, by distillation. The recovery rate of 1437dycc in the bottom sediment is preferably 93% or more, more preferably 95% or more.
Here, the recovery rate [% ] of the bottom sediment can be determined from the amount of 1437dycc in the distillation composition and the amount of 1437dycc in the bottom sediment by the following formula.
Recovery rate of 1437dycc in the bottom sediment [% ] (amount of 1437dycc in the bottom sediment)/(amount of 1437dycc in the composition for distillation) × 100
Further, by such distillation, for example, the ratio of the content of 1437dycc to the total content of 1437dycc, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water in the bottom sediment (1437dycc purity) can be set to 85 mass% or more. The above proportion is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, and most preferably 99% by mass.
The content of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne in the bottom sediment is preferably 1000ppm or less, more preferably 100ppm or less, relative to the content of 1437 dycc.
The water content in the bottom sediment can be reduced by contacting the bottom sediment obtained by distillation with a solid adsorbent such as activated carbon or zeolite. The water content in the bottom sediment after contact with the solid adsorbent is preferably 1000ppm or less, more preferably 100ppm or less, based on the total content of 1437 dycc.
Examples
The present invention will be described in detail below with reference to examples. In addition, the present invention is not limited to these examples.
(example 1)
448occc and tetra-n-butylammonium bromide (TBAB) were charged into a reactor, and 34 mass% potassium hydroxide (KOH) aqueous solution was added dropwise thereto to conduct a dehydrofluorination reaction at 448occc at 30 ℃. After 8 hours of reaction, the organic layer was recovered to obtain a composition for distillation.
As the distillation column, a multistage distillation column having a theoretical plate number of 50 blocks was prepared. The composition for distillation was supplied from the top of the distillation column to the 20 th block at a feed rate of 1.0 kg/h. As shown in Table 1, 1437dycc (Z) was supplied at 0.98 kg/hr, water was supplied at 0.0080 kg/hr, 1437dycc (E) was supplied at 0.010 kg/hr, and 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne (hereinafter referred to as "pentyne" in tables 1 to 4) was supplied at 0.0010 kg/hr. Thereafter, continuous distillation was carried out with the operating pressure set to 300mmHg and the column top temperature set to 50.0. + -. 0.5 ℃.
In distillation, a distillate is extracted from the top of the column, and a bottom sediment is extracted from the bottom of the column. Further, the distillate and the bottom sediment were collected by a Karl Fischer moisture meter to determine the amount of water collected and by a gas chromatograph to determine the amounts of 1437dycc (Z), 1437dycc (E) and 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne. Further, the recovery rate (recovery amount/supply amount) is determined from the supply amount and the recovery amount.
Table 1 shows the supply amount of the composition for distillation, and shows the recovery amount and recovery rate of the distillate and the bottom sediment, respectively. Further, Table 2 shows the composition (1437dycc (Z), 1437dycc (E) or the content ratio of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne) of the composition for distillation, the distillate and the bottom sediment.
The composition of the distillation composition can be determined from the amounts of the respective components supplied. The compositions of the distillate and the bottom sediment can be determined from the amounts of the respective components recovered.
[ Table 1]
[ Table 2]
As is clear from tables 1 and 2, by using a distillation composition containing 1437dycc, water and 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne, the recovery rate of the bottom sediment can be made 98 mass% or more, and the proportion of 1437dycc content in the bottom sediment can be made 99 mass% or more.
(example 2)
As shown in table 3, distillation and measurement were performed in the same manner as in example 1 while changing the supply amount of each component in the composition for distillation. The recovery amounts and recoveries of the distillate and the bottoms, respectively, are shown in table 3. Further, table 4 shows the compositions of the composition for distillation, the distillate and the bottom sediment, respectively.
[ Table 3]
[ Table 4]
As is clear from tables 3 and 4, by using a distillation composition containing 1437dycc, water and 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne, the recovery rate of the bottom sediment can be made 91 mass% or more, and the proportion of 1437dycc content in the bottom sediment can be made 98 mass% or more.
Possibility of industrial utilization
According to the present invention, 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water can be efficiently removed, the recovery rate of 1437dycc is increased, and the purity of 1437dycc is increased. Therefore, the present invention can be effectively utilized in a wide range of fields using 1437dycc of a cleaning agent, a solvent, a refrigerant, and the like.
In addition, the entire contents of the specification, claims, drawings and abstract of japanese patent application No. 2018-103779 filed 2018, 05, 30 are cited herein as disclosure of the specification of the present invention.
Description of the symbols
10 … … distillation apparatus, 11 … … distillation column, 12, 13, 14 … … piping.
Claims (8)
1. A process for producing 1-chloro-2, 3,3,4,4,5, 5-heptafluoro-1-pentene, which comprises distilling a composition for distillation containing 1-chloro-2, 3,3,4,4,5, 5-heptafluoro-1-pentene, water and 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne to remove 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water.
2. The process according to claim 1, wherein the 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water are removed by forming an azeotropic composition or an azeotrope-like composition.
3. The production method according to claim 1 or 2, wherein the content of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne in the distillation composition is 0.001 to 15% by mass based on the total amount of 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne and water.
4. The production method according to any one of claims 1 to 3, wherein the content of 1-chloro-2, 3,3,4,4,5, 5-heptafluoro-1-pentene relative to the total amount of the distillation composition is 50% by mass or more.
5. The production method according to claim 4, wherein the content of 1-chloro-2, 3,3,4,4,5, 5-heptafluoro-1-pentene relative to the total amount of the composition for distillation is 90% by mass or more.
6. The production process according to any one of claims 1 to 5, wherein the composition for distillation is obtained by adding water to a mixture containing 1-chloro-2, 3,3,4,4,5, 5-heptafluoro-1-pentene and 1-chloro-3, 3,4,4,5, 5-hexafluoro-1-pentyne, and then distilling the mixture.
7. The production process according to any one of claims 1 to 6, wherein the composition for distillation is prepared from the reaction composition obtained by dehydrofluorinating 1-chloro-2, 2,3,3,4,4,5, 5-octafluoropentane.
8. The production process according to any one of claims 1 to 7, wherein the distillation is carried out in a distillation column under distillation conditions of a column top temperature of 10 to 95 ℃ and a column internal pressure of 50 to 760 mmHg.
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| JP2018-103779 | 2018-05-30 | ||
| JP2018103779 | 2018-05-30 | ||
| PCT/JP2019/021400 WO2019230842A1 (en) | 2018-05-30 | 2019-05-29 | Method for producing 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene |
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