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WO2024252818A1 - Procédé de séparation de fluorure de vinylidène et d'acétylène - Google Patents

Procédé de séparation de fluorure de vinylidène et d'acétylène Download PDF

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Publication number
WO2024252818A1
WO2024252818A1 PCT/JP2024/016134 JP2024016134W WO2024252818A1 WO 2024252818 A1 WO2024252818 A1 WO 2024252818A1 JP 2024016134 W JP2024016134 W JP 2024016134W WO 2024252818 A1 WO2024252818 A1 WO 2024252818A1
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WO
WIPO (PCT)
Prior art keywords
acetylene
vdf
mixture
extraction
extraction solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/016134
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English (en)
Japanese (ja)
Inventor
覚人 三竹
英史 塩田
哲央 大塚
達也 鎌塚
明日香 山川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of WO2024252818A1 publication Critical patent/WO2024252818A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/22—Aliphatic unsaturated hydrocarbons containing carbon-to-carbon triple bonds
    • C07C11/24—Acetylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
    • C07C17/386—Separation; Purification; Stabilisation; Use of additives by distillation with auxiliary compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
    • C07C7/08—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by extractive distillation

Definitions

  • This disclosure relates to a method for separating vinylidene fluoride and acetylene.
  • Vinylidene fluoride is useful as a monomer for fluororesins.
  • Patent Document 1 describes a method for separating vinylidene fluoride (VdF) and trifluoroethane, which includes a step of adding a first extraction solvent, which is at least one selected from the group consisting of alcohols, ketones, esters, amides, ethers, sulfoxides, and nitriles having 1 to 3 carbon atoms, to a first mixture containing VdF and trifluoroethane to obtain a second mixture, and an extractive distillation step of distilling the second mixture to obtain a distillate mainly composed of VdF and a bottoms product mainly composed of the first extraction solvent and containing trifluoroethane.
  • a first extraction solvent which is at least one selected from the group consisting of alcohols, ketones, esters, amides, ethers, sulfoxides, and nitriles having 1 to 3 carbon atoms
  • Patent Document 1 is a method for separating VdF and trifluoroethane, and is not necessarily applicable to separating VdF and acetylene.
  • One aspect of the present disclosure aims to provide a method for efficiently separating VdF and acetylene from a mixture of VdF and acetylene.
  • a method for separating vinylidene fluoride and acetylene comprising: ⁇ 2> The method for separating vinylidene fluoride and acetylene according to ⁇ 1>, wherein in the mixture for extraction, the ratio of the molar amount of the extraction solvent to the molar amount of acetylene is 0.1 to 1000.
  • ⁇ 3> The method for separating vinylidene fluoride and acetylene according to ⁇ 1> or ⁇ 2>, further comprising a step of distilling the bottoms to recover an extraction solvent.
  • ⁇ 4> The method for separating vinylidene fluoride and acetylene according to ⁇ 3>, wherein the recovered extraction solvent is reused in the step of obtaining a mixture for extraction.
  • ⁇ 5> The method for separating vinylidene fluoride and acetylene according to any one of ⁇ 1> to ⁇ 4>, wherein the first mixture further contains ethylene.
  • ⁇ 6> The method for separating vinylidene fluoride and acetylene according to any one of ⁇ 1> to ⁇ 5>, wherein the extraction solvent is chloroform.
  • a method for efficiently separating VdF and acetylene from a mixture of VdF and acetylene is provided.
  • a numerical range indicated using “to” means a range that includes the numerical values before and after “to” as the minimum and maximum values, respectively.
  • the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in the present disclosure.
  • the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.
  • combinations of two or more preferred aspects are more preferred aspects.
  • the amount of each component means the total amount of the multiple substances, unless otherwise specified.
  • distillate refers to material that is distilled from the top of a distillation column
  • bottoms refers to material that is distilled from the bottom of a distillation column.
  • main component means that the molar amount of components other than the component in question is relatively small.
  • the amount of the "main component” is preferably 50 mol % or more of the total, more preferably 60 mol % or more, even more preferably 70 mol % or more, and most preferably 80 mol % or more.
  • the boiling point of a compound is a value at normal pressure, which is 1.013 ⁇ 10 5 Pa.
  • the method for separating VdF and acetylene disclosed herein includes the steps of: mixing a first mixture containing VdF and acetylene with an extracting solvent that is at least one compound selected from the group consisting of methanol, acetone, chloroform, and 1-chloro-2,3,3-trifluoro-1-propene to obtain an extraction mixture; and distilling the extraction mixture to obtain a distillate whose main component is vinylidene fluoride and a bottoms product whose main component is the extracting solvent and further contains acetylene.
  • an extracting solvent that is at least one compound selected from the group consisting of methanol, acetone, chloroform, and 1-chloro-2,3,3-trifluoro-1-propene
  • the method for separating VdF and acetylene disclosed herein allows for efficient separation of VdF and acetylene.
  • VdF is useful as a monomer for fluororesin, but for example, when a polymerization reaction is carried out using a composition containing VdF and acetylene as an impurity, the acetylene reacts with the polymerization initiator, making it difficult for the desired polymerization reaction to proceed. This can easily result in the rate of the polymerization reaction slowing down or stopping, making it difficult to obtain the desired polymer. For this reason, it is desirable to separate VdF and acetylene to obtain high-purity VdF. However, VdF has a boiling point of -83°C, and acetylene has a boiling point of -84°C. Because VdF and acetylene have similar boiling points, it is difficult to separate and purify VdF and acetylene by normal distillation.
  • Patent Document 1 describes a method for separating VdF from trifluoroethane, but an extraction solvent suitable for the method for separating VdF from trifluoroethane is not necessarily a suitable extraction solvent for the method for separating VdF from acetylene.
  • VdF and acetylene can be efficiently separated by using an extraction solvent containing at least one selected from the group consisting of methanol, acetone, chloroform, and 1-chloro-2,3,3-trifluoro-1-propene.
  • the method for separating VdF and acetylene disclosed herein includes a step of mixing a mixture containing VdF and acetylene with a compound having a boiling point of ⁇ 60 to 0° C. to obtain a mixture for extraction (hereinafter also referred to as the “mixing step”).
  • the first mixture containing VdF and acetylene may contain other components other than VdF and acetylene, but from the viewpoint of efficiently obtaining high-purity VdF, it is preferable that the content of other components is small.
  • examples of other components include fluoroolefins other than VdF and ethylene.
  • the first mixture contains ethylene, which may be mixed in during the production process of VdF.
  • the total content of VdF and acetylene relative to the total amount of the first mixture is, for example, 50 mol% or more, may be 80 mol% or more, may be 90 mol% or more, may be 99 mol% or more, or may be 100 mol%.
  • the molar ratio of VdF to acetylene is not particularly limited. From the viewpoint of production efficiency, the ratio of the molar amount of acetylene to the molar amount of VdF (i.e., the molar ratio) is preferably 0.01 to 1, more preferably 0.01 to 0.5, and even more preferably 0.01 to 0.1.
  • the first mixture may be, for example, a reaction product containing VdF obtained by reacting various raw materials for the purpose of producing VdF.
  • the extraction solvent is at least one compound selected from the group consisting of methanol, acetone, chloroform, and 1-chloro-2,3,3-trifluoro-1-propene.
  • Chloroform is the preferred extraction solvent because it has excellent separation properties between VdF and acetylene. Furthermore, when chloroform is used as the extraction solvent, it also has excellent separation properties between VdF and ethylene.
  • the boiling point of ethylene is -103.7°C, which is lower than the boiling point of VdF. Therefore, when normal distillation is performed, ethylene is accompanied by VdF, making separation difficult, but by using chloroform, which has a high affinity for ethylene, VdF and ethylene can be separated.
  • the ratio of the molar amount of the extraction solvent to the molar amount of acetylene is 0.1 to 1000.
  • extractive distillation tower when a first mixture containing VdF and acetylene is supplied to the extractive distillation tower, and an extractive solvent is also supplied to the extractive distillation tower, "extractive solvent/acetylene” represents the molar ratio of the amount of extractive solvent supplied to the extractive distillation tower to the amount of acetylene supplied to the extractive distillation tower.
  • the mixing step from the viewpoint of separating VdF and acetylene with high efficiency, it is preferable to select the type of extraction solvent and adjust the amount of extraction solvent added so that the relative volatility Rv of the extraction mixture is greater than 1.1.
  • the relative volatility Rv is preferably 1.2 or more, and more preferably 1.3 or more.
  • Rv of VdF to acetylene is expressed by the following formula.
  • Rv (molar fraction of VdF in the gas phase / mole fraction of VdF in the liquid phase) / (molar fraction of acetylene in the gas phase / mole fraction of acetylene in the liquid phase)
  • the method of mixing the first mixture containing VdF and acetylene with the extraction solvent is not particularly limited.
  • the extraction solvent may be added to the first mixture containing VdF and acetylene, or the first mixture containing VdF and acetylene may be added to the extraction solvent.
  • an extraction solvent to the extractive distillation tower to which the first mixture containing VdF and acetylene has been supplied, prepare the extraction mixture in the extractive distillation tower, and perform distillation immediately after the preparation is completed.
  • the extraction mixture may contain other components other than VdF, acetylene, and the extraction solvent.
  • Other components other than VdF, acetylene, and the extraction solvent that may be contained in the extraction mixture include other components that may be contained in the first mixture containing VdF and acetylene.
  • the method for separating VdF and acetylene disclosed herein includes a step of distilling the extraction mixture to obtain a distillate whose main component is VdF and a bottoms product whose main component is the extraction solvent and further contains acetylene (hereinafter also referred to as the "extractive distillation step").
  • the extractive distillation process can be carried out using a commonly used distillation apparatus, for example, a distillation tower such as a plate tower, a packed tower, etc.
  • a distillation tower such as a plate tower, a packed tower, etc.
  • Various conditions of the extractive distillation process for example, the operating temperature, operating pressure, reflux ratio, total number of stages in the distillation tower, position of the charging stage, position of the extraction solvent supply stage, etc., are not particularly limited and can be appropriately selected to achieve the desired separation.
  • the number of stages of the distillation tower can be, for example, 1 to 100, and from the viewpoint of obtaining VdF with high purity, 30 or more is preferable, and 50 or more is more preferable. Since both VdF and acetylene have low boiling points, it is preferable to carry out the extractive distillation under pressure, for example, a pressure of 0 to 5 MPaG (gauge pressure).
  • the temperatures at the top and bottom of the distillation tower are determined according to the operating pressure and the composition of the distillate and bottom products.
  • the temperature at the top of the tower be -60 to 100°C and the temperature at the bottom of the tower be -10 to 300°C.
  • Extractive distillation can be performed in either a batch or continuous manner, or in a semi-continuous manner in which the distillate and bottom products are intermittently withdrawn or intermittently charged, but it is preferable to continuously supply the extraction solvent to the distillation apparatus.
  • the above-mentioned extraction solvent has an affinity for acetylene. Therefore, by extractively distilling an extraction mixture containing VdF, acetylene, and the extraction solvent, a distillate containing VdF as the main component is obtained from the top side of the extractive distillation tower.
  • the composition of this distillate is not limited as long as it contains VdF as the main component, but the molar fraction of VdF in the distillate is preferably 90 mol% or more, and more preferably 99 mol% or more.
  • the molar fraction of acetylene in the distillate is preferably 1/10 or less, and more preferably 1/100 or less, of the molar fraction of acetylene in the extraction mixture.
  • the molar fraction of acetylene in the distillate is preferably 10 mol% or less, more preferably 1 mol% or less, and even more preferably 0.1 mol% or less.
  • a bottom product containing the extraction solvent as the main component and further containing acetylene is obtained from the bottom side of the extractive distillation tower.
  • the composition of this bottom product is not limited as long as it contains the extraction solvent as the main component, but the molar fraction of the extraction solvent in the bottom product is preferably 30 mol % or more, and more preferably 50 mol % or more.
  • the molar fraction of acetylene in the bottom product is preferably higher than the molar fraction of acetylene in the extraction mixture.
  • the molar fraction of acetylene in the bottom product is more preferably 1.1 or more of the molar fraction of acetylene in the extraction mixture, and even more preferably 2 or more.
  • the method for separating VdF and acetylene according to the present disclosure preferably further includes a step of distilling the bottoms to recover the extraction solvent (hereinafter also referred to as the "distillation step").
  • the distillation process can be carried out using a distillation apparatus similar to that used in the extractive distillation process.
  • the various conditions of the distillation process such as the operating temperature, operating pressure, reflux ratio, total number of stages in the distillation column, and the position of the feed stage, are not particularly limited and can be appropriately selected to achieve the desired separation.
  • the distillation process separates the extraction solvent from the VdF and acetylene, allowing the extraction solvent to be recovered.
  • a bottom product containing the extraction solvent is obtained from the bottom side of the distillation tower. It is preferable to reuse the recovered extraction solvent in the above-mentioned extraction distillation process.
  • the difference in boiling points between acetylene and the extraction solvent is large, so that the separation between acetylene and the extraction solvent is excellent. Therefore, a high-purity extraction solvent can be recovered, making it suitable for reuse.
  • Examples 1 to 4 are examples, and Examples 5 to 9 are comparative examples.
  • AS-300 Product name "AS-300”, manufactured by AGC Co., Ltd. A mixture of 1-chloro-2,3,3-trifluoro-1-propene (E) and 1-chloro-2,3,3-trifluoro-1-propene (Z).
  • AC-2000 Product name "ASAHIKLIN AC-2000", manufactured by AGC Co., Ltd. 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane.
  • AE-3000 Product name "ASAHIKLIN AE-3000", manufactured by AGC Co., Ltd. 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de séparation de VdF et d'acétylène, le procédé comprenant : une étape consistant à obtenir un mélange d'extraction par mélange d'un premier mélange contenant du VdF et de l'acétylène avec un solvant d'extraction qui est au moins un composé choisi dans le groupe constitué par le méthanol, l'acétone, le chloroforme et le 1-chloro-2,3,3-trifluoro-1-propène ; et une étape de distillation du mélange d'extraction consistant à obtenir un distillat dont le composant principal est le VdF, et un article conditionné dont le composant principal est le solvant d'extraction et contenant en outre de l'acétylène.
PCT/JP2024/016134 2023-06-08 2024-04-24 Procédé de séparation de fluorure de vinylidène et d'acétylène Pending WO2024252818A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023-095061 2023-06-08
JP2023095061 2023-06-08

Publications (1)

Publication Number Publication Date
WO2024252818A1 true WO2024252818A1 (fr) 2024-12-12

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4842620B1 (fr) * 1968-01-12 1973-12-13
WO2013137408A1 (fr) * 2012-03-14 2013-09-19 旭硝子株式会社 Procédé de production de 2,3,3,3-tétrafluoropropène
WO2013137409A1 (fr) * 2012-03-14 2013-09-19 旭硝子株式会社 Procédé de production de 2,3,3,3-tétrafluoropropène et de 1,1-difluoroéthylène
WO2015072305A1 (fr) * 2013-11-14 2015-05-21 旭硝子株式会社 Procédé de séparation de fluorure de vinylidène et de trifluorométhane et procédé de production de fluorure de vinylidène
WO2017029868A1 (fr) * 2015-08-17 2017-02-23 ダイキン工業株式会社 Procédé de séparation de composé de carbone insaturé halogéné
JP2019501862A (ja) * 2016-01-14 2019-01-24 エスアールエフ リミテッド 含フッ素オレフィンの製造方法
CN110818529A (zh) * 2019-10-11 2020-02-21 江苏梅兰化工有限公司 一种制备高纯偏氟乙烯的新工艺

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4842620B1 (fr) * 1968-01-12 1973-12-13
WO2013137408A1 (fr) * 2012-03-14 2013-09-19 旭硝子株式会社 Procédé de production de 2,3,3,3-tétrafluoropropène
WO2013137409A1 (fr) * 2012-03-14 2013-09-19 旭硝子株式会社 Procédé de production de 2,3,3,3-tétrafluoropropène et de 1,1-difluoroéthylène
WO2015072305A1 (fr) * 2013-11-14 2015-05-21 旭硝子株式会社 Procédé de séparation de fluorure de vinylidène et de trifluorométhane et procédé de production de fluorure de vinylidène
WO2017029868A1 (fr) * 2015-08-17 2017-02-23 ダイキン工業株式会社 Procédé de séparation de composé de carbone insaturé halogéné
JP2019501862A (ja) * 2016-01-14 2019-01-24 エスアールエフ リミテッド 含フッ素オレフィンの製造方法
CN110818529A (zh) * 2019-10-11 2020-02-21 江苏梅兰化工有限公司 一种制备高纯偏氟乙烯的新工艺

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