JP4905349B2 - Method for recovering fluorine-containing alcohol - Google Patents
Method for recovering fluorine-containing alcohol Download PDFInfo
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- JP4905349B2 JP4905349B2 JP2007505929A JP2007505929A JP4905349B2 JP 4905349 B2 JP4905349 B2 JP 4905349B2 JP 2007505929 A JP2007505929 A JP 2007505929A JP 2007505929 A JP2007505929 A JP 2007505929A JP 4905349 B2 JP4905349 B2 JP 4905349B2
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- 238000000034 method Methods 0.000 title claims description 26
- 229910052731 fluorine Inorganic materials 0.000 title claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 13
- 239000011737 fluorine Substances 0.000 title claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 150000001298 alcohols Chemical class 0.000 claims description 40
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 19
- 238000004821 distillation Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 10
- NBUKAOOFKZFCGD-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)F NBUKAOOFKZFCGD-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 150000001340 alkali metals Chemical group 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 13
- 235000002639 sodium chloride Nutrition 0.000 description 12
- 239000007788 liquid Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 229910001410 inorganic ion Inorganic materials 0.000 description 8
- 238000011084 recovery Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- XZNOAVNRSFURIR-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-ol Chemical compound FC(F)(F)C(O)(C(F)(F)F)C(F)(F)F XZNOAVNRSFURIR-UHFFFAOYSA-N 0.000 description 1
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- PSQZJKGXDGNDFP-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)(F)F PSQZJKGXDGNDFP-UHFFFAOYSA-N 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/86—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、含フッ素アルコールと水とを含有する混合液から、含フッ素アルコールを回収する技術に関する。 The present invention relates to a technique for recovering a fluorinated alcohol from a mixed liquid containing a fluorinated alcohol and water.
含フッ素アルコールは、ＣＤ−ＲやＤＶＤ−Ｒ等の情報記録媒体を製造する際、記録層となる色素の溶媒として利用されており、大容量記録メディアの製造には欠かせないものである。
上記記録媒体の製造工程においては、水を含んだ含フッ素アルコールの廃液が大量に発生する。この廃液から含フッ素アルコールを回収し、再利用できれば、環境負荷の低減および製造コストの削減が図られるため、低コストで含フッ素アルコールと水との混合液から水を除去する技術が望まれている。The fluorine-containing alcohol is used as a solvent for a dye serving as a recording layer when an information recording medium such as a CD-R or DVD-R is manufactured, and is indispensable for manufacturing a large-capacity recording medium.
In the manufacturing process of the recording medium, a large amount of waste liquid of fluorine-containing alcohol containing water is generated. If the fluorinated alcohol can be recovered from this waste liquid and reused, the environmental burden and manufacturing costs can be reduced. Therefore, a technique for removing water from a mixed liquid of fluorinated alcohol and water at low cost is desired. Yes.
しかし、含フッ素アルコールと水との混合液は共沸組成を有する場合があるため、蒸留で水を除去することは非常に困難である。例えば、含フッ素アルコールの一種である２，２，３，３−テトラフルオロプロパノール（以下、ＴＦＰＯという。）と水との混合液の共沸組成はＴＦＰＯ ７３質量％、水 ２７質量％である。 However, since a mixed solution of a fluorinated alcohol and water may have an azeotropic composition, it is very difficult to remove water by distillation. For example, the azeotropic composition of a mixture of 2,2,3,3-tetrafluoropropanol (hereinafter referred to as TFPO), which is a kind of fluorine-containing alcohol, and water is 73% by mass of TFPO and 27% by mass of water.
特許文献１には、ＴＦＰＯと水との混合液からＴＦＰＯを回収するにあたり、パーベーパレーション法によって水を分離する方法が開示されているが、より簡便で効率的な方法が望まれていた。 Patent Document 1 discloses a method of separating water by a pervaporation method when recovering TFPO from a mixture of TFPO and water, but a simpler and more efficient method has been desired.
本発明は、ＣＤ−ＲやＤＶＤ−Ｒの製造工程などで発生する、含フッ素アルコールと水とを含有する混合液から水を分離し、含フッ素アルコールを簡便に回収する方法の提供を目的とする。 It is an object of the present invention to provide a method for easily recovering a fluorinated alcohol by separating water from a mixed solution containing a fluorinated alcohol and water, which is generated in a production process of CD-R or DVD-R. To do.
本発明は、含フッ素アルコールおよび水を含有する混合液を２層分離させる工程を有する含フッ素アルコールの回収方法である。
本発明においては、含フッ素アルコールおよび水を含有する混合液に無機塩を添加することにより、含フッ素アルコールの水に対する溶解性が低下することから層分離が起こると考えられる。この現象は、フッ素原子が疎水性であること、フッ素原子の効果によって水酸基が解離しやすくなっていること、含フッ素アルコールが大きな比重を有する化合物であることに関係していると考えられる。
含フッ素アルコールの比重は水よりも大きいため、主として含フッ素アルコールを含有する層が下に形成され、主として水を含有する層が上に形成される。
本発明は、下記を特徴とする要旨を有する。
(１) 含フッ素アルコールおよび水を含有する混合液に無機塩を添加し、２層分離させる工程を有することを特徴とする含フッ素アルコールの回収方法。
(２) 含フッ素アルコールが、下式１（ただし、Ｒｆはフッ素原子または炭素数１〜４のフルオロアルキル基、Ｒ１、Ｒ２はそれぞれ独立に水素原子または炭素数１〜３のアルキル基、ｎは１〜４の整数である。）で表される化合物である上記(１)に記載の回収方法。
Ｈ−（ＣＲｆＦＣＦ２）ｎ−ＣＲ１Ｒ２−ＯＨ・・・式１
(３) 含フッ素アルコールが２，２，３，３−テトラフルオロプロパノールである上記(１)に記載の回収方法。
(４) 無機塩を、上記混合液中の水に対して、生成する無機イオン（無機塩は１００％解離したものと見なす）の合計がモル比換算で０．１０以上となる量添加する上記(１)〜(３)のいずれかに記載の回収方法。
(５) 無機塩として塩化ナトリウムを用いる上記(１)〜(４)のいずれかに記載の回収方法。
(６) 上記２層分離させる工程で得られた下層中の含フッ素アルコールの含有割合が８０質量％以上である上記(１)〜(５)のいずれかに記載の回収方法。
(７) 上記２層分離させる工程で得られた下層を、さらに蒸留する蒸留工程を有する上記(１)〜(６)のいずれかに記載の回収方法。
(８) 上記蒸留工程により、水分濃度が１０００ｐｐｍ以下である含フッ素アルコールを得る上記(７)に記載の回収方法。The present invention is a method for recovering a fluorinated alcohol, which comprises a step of separating a liquid mixture containing a fluorinated alcohol and water into two layers.
In the present invention, it is considered that layer separation occurs because the solubility of the fluorinated alcohol in water is reduced by adding an inorganic salt to the mixed solution containing the fluorinated alcohol and water. This phenomenon is considered to be related to the fact that the fluorine atom is hydrophobic, the hydroxyl group is easily dissociated by the effect of the fluorine atom, and the fluorine-containing alcohol is a compound having a large specific gravity.
Since the specific gravity of the fluorinated alcohol is greater than that of water, a layer mainly containing the fluorinated alcohol is formed below, and a layer mainly containing water is formed on the top.
The present invention has a gist characterized by the following.
(1) A method for recovering a fluorine-containing alcohol, comprising a step of adding an inorganic salt to a mixed solution containing a fluorine-containing alcohol and water and separating the mixture into two layers.
(2) The fluorinated alcohol is represented by the following formula 1 (wherein R f is a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms, R 1 and R 2 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) , N is an integer of 1 to 4.) The recovery method according to (1) above, which is a compound represented by:
H- (CR f FCF 2) n -CR 1 R 2 -OH ··· Formula 1
(3) The recovery method according to the above (1), wherein the fluorinated alcohol is 2,2,3,3-tetrafluoropropanol.
(4) The inorganic salt is added in an amount such that the total amount of inorganic ions generated (the inorganic salt is considered to be 100% dissociated) with respect to the water in the mixed solution is 0.10 or more in terms of molar ratio. The recovery method according to any one of (1) to (3).
(5) The recovery method according to any one of (1) to (4), wherein sodium chloride is used as the inorganic salt.
(6) The recovery method according to any one of (1) to (5), wherein the content ratio of the fluorinated alcohol in the lower layer obtained in the step of separating the two layers is 80% by mass or more.
(7) The recovery method according to any one of (1) to (6), further including a distillation step of further distilling the lower layer obtained in the step of separating the two layers.
(8) The recovery method according to (7), wherein a fluorinated alcohol having a water concentration of 1000 ppm or less is obtained by the distillation step.
本発明では２層分離させる工程において、主として水を含有する上層と、主として含フッ素アルコールを含有する下層とに短時間で層分離させることができる。この層分離によれば、下層中の含フッ素アルコールの含有割合を８０質量％以上、特には８５質量％以上、さらには９０質量％以上の高濃度にできる。よって、この下層をさらに蒸留等によって精製すれば、簡便で効率的に高純度の含フッ素アルコールを得ることができる。 In the present invention, in the step of separating the two layers, the upper layer mainly containing water and the lower layer mainly containing a fluorine-containing alcohol can be separated in a short time. According to this layer separation, the content of the fluorinated alcohol in the lower layer can be set to a high concentration of 80% by mass or more, particularly 85% by mass or more, and further 90% by mass or more. Therefore, if this lower layer is further purified by distillation or the like, a highly pure fluorine-containing alcohol can be obtained simply and efficiently.
本発明における好ましい含フッ素アルコールとしては、パーフルオロ−ｔ−ブタノール、２，２，３，３，３−ペンタフルオロプロパノール、１，１，１，３，３，３−ヘキサフルオロ−２−プロパノール、２，２，２−トリフルオロエタノールなどの炭素数２〜７のフルオロアルコール類、フルオロフェノール類、および下式１で表される化合物が挙げられる。
Ｈ−（ＣＲｆＦＣＦ２）ｎ−ＣＲ１Ｒ２−ＯＨ ・・・式１
ただし、Ｒｆはフッ素原子または炭素数１〜４のフルオロアルキル基、Ｒ１、Ｒ２はそれぞれ独立に水素原子または炭素数１〜３のアルキル基、ｎは１〜４の整数である。Preferred fluorinated alcohols in the present invention include perfluoro-t-butanol, 2,2,3,3,3-pentafluoropropanol, 1,1,1,3,3,3-hexafluoro-2-propanol, Examples thereof include C2-C7 fluoroalcohols such as 2,2,2-trifluoroethanol, fluorophenols, and compounds represented by the following formula 1.
H- (CR f FCF 2) n -CR 1 R 2 -OH ··· Formula 1
However, R f is a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms, R 1, R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, n represents an integer of 1 to 4.
式１で表される化合物の好ましい具体例としては、Ｈ（ＣＦ２）２ＣＨ２ＯＨ（２，２，３，３−テトラフルオロプロパノール、ＴＦＰＯ）、Ｈ（ＣＦ２）４ＣＨ２ＯＨ、ＨＣＦ２ＣＦ２ＣＨ（ＣＨ３）ＯＨ、ＨＣＦ２ＣＦ２Ｃ（ＣＨ３）２ＯＨ、ＨＣ（ＣＦ３）ＦＣＦ２ＣＨ２ＯＨ、ＨＣ（ＣＦ３）ＦＣＦ２ＣＨ（ＣＨ３）ＯＨ、ＨＣ（ＣＦ３）ＦＣＦ２Ｃ（ＣＨ３）２ＯＨなどが挙げられる。Preferable specific examples of the compound represented by Formula 1 include H (CF 2 ) 2 CH 2 OH (2,2,3,3-tetrafluoropropanol, TFPO), H (CF 2 ) 4 CH 2 OH, HCF 2 CF 2 CH (CH 3 ) OH, HCF 2 CF 2 C (CH 3 ) 2 OH, HC (CF 3 ) FCF 2 CH 2 OH, HC (CF 3 ) FCF 2 CH (CH 3 ) OH, HC (CF 3 ) FCF 2 C (CH 3 ) 2 OH and the like.
本発明において処理される、含フッ素アルコールおよび水を含有する混合液中の水の含有割合は５０質量％以下であるのが好ましく、特には２５質量％以下であるのが好ましい。上記水の含有割合が大きすぎる場合は、無機塩をより多く添加することが必要となる他、２層分離後の蒸留工程において、より時間がかかる傾向があるため、あらかじめ単蒸留する等して水をある程度除去しておくのが好ましい。 The content of water in the mixed solution containing the fluorinated alcohol and water treated in the present invention is preferably 50% by mass or less, and particularly preferably 25% by mass or less. If the water content is too large, it is necessary to add more inorganic salt, and in the distillation step after separation of the two layers, it tends to take more time. It is preferable to remove some water.
本発明において使用する無機塩としてはアルカリ金属塩が好ましく、なかでも解離しやすいという観点から塩酸塩や硫酸塩等の強酸塩が好ましい。
無機塩としては、具体的には、塩化ナトリウム、硫酸ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、フッ化ナトリウム、硫酸カリウム等が挙げられる。なかでも、含フッ素アルコールと水との混合液に溶解しやすく、安価であることから塩化ナトリウムまたは硫酸ナトリウムが好ましく、特には塩化ナトリウムが好ましい。As the inorganic salt used in the present invention, alkali metal salts are preferable, and strong acid salts such as hydrochlorides and sulfates are particularly preferable from the viewpoint of easy dissociation.
Specific examples of the inorganic salt include sodium chloride, sodium sulfate, sodium carbonate, sodium hydrogen carbonate, sodium fluoride, potassium sulfate and the like. Among these, sodium chloride or sodium sulfate is preferable because it is easily dissolved in a mixed solution of fluorine-containing alcohol and water and is inexpensive, and sodium chloride is particularly preferable.
本発明においては、無機塩を、含フッ素アルコールおよび水を含有する混合液中の水に対して、生成する無機イオン（無機塩は１００％解離したものと見なす）の合計がモル比換算で０．１０以上となる量添加するのが好ましく、特には０．１３以上となる量の無機塩を添加するのが好ましい。上記モル比が０．１０未満である場合は、下層における水の含有割合が大きくなるとともに層分離しにくくなる。なお、上記無機イオンとは、無機塩が解離して生成する陽イオンと陰イオンの両方をさす。 In the present invention, the total amount of inorganic ions (the inorganic salt is considered to be 100% dissociated) is 0 in terms of molar ratio with respect to the water in the mixed solution containing the fluorinated alcohol and water. It is preferable to add an amount of 10 or more, and it is particularly preferable to add an amount of inorganic salt of 0.13 or more. When the molar ratio is less than 0.10, the content of water in the lower layer increases and the layers are difficult to separate. In addition, the said inorganic ion refers to both the cation and anion which a mineral salt dissociates and produces | generates.
無機イオンのモル数の計算方法を以下に例示すると、ＮａＣｌ １ｍｏｌを添加した場合は、Ｎａ＋ １ｍｏｌと Ｃｌ− １ｍｏｌに解離することから、無機イオンとしては合計２ｍｏｌとなる。また、Ｎａ２ＳＯ４ １ｍｏｌを添加した場合は、Ｎａ＋ ２ｍｏｌとＳＯ４ ２− １ｍｏｌに解離することから、無機イオンとしては合計３ｍｏｌとなる。
なお、通常、無機塩を過剰に添加しても特にメリットはないので、無機塩の添加量は、２層分離が起こり、下層における含フッ素アルコールの含有割合が一定以上となる最低限の量とするのが好ましい。To illustrate how to calculate the number of moles of inorganic ions in the following, the case of adding NaCl 1 mol, Na + 1 mol and Cl - from dissociating to 1 mol, the total 2mol as inorganic ions. In addition, when 1 mol of Na 2 SO 4 is added, it dissociates into Na + 2 mol and SO 4 2-1 mol, so that the total amount of inorganic ions is 3 mol.
Usually, there is no particular merit even if the inorganic salt is added in excess, so the amount of the inorganic salt added is the minimum amount at which the two-layer separation occurs and the content ratio of the fluorinated alcohol in the lower layer becomes a certain level or more. It is preferable to do this.
含フッ素アルコールおよび水を含有する混合液への無機塩の添加は、常圧、常温で行えばよく、通常、温度制御等をする必要はない。添加した無機塩が上記混合液と均一に混ざるよう撹拌翼等で混合する。
２層分離させるためには、これを静置すればよいが、遠心分離器等を用いて分離させてもかまわない。静置して２層分離させる場合、静置時間は、各層の厚さや界面の面積にもよるが、３〜１２時間程度とすればよい。The addition of the inorganic salt to the mixed solution containing the fluorinated alcohol and water may be performed at normal pressure and normal temperature, and it is usually unnecessary to control the temperature. It mixes with a stirring blade etc. so that the added inorganic salt may mix with the said liquid mixture uniformly.
In order to separate the two layers, this may be left still, but may be separated using a centrifuge or the like. When the two layers are allowed to stand, the standing time may be about 3 to 12 hours, although it depends on the thickness of each layer and the area of the interface.
本発明における２層分離工程で得られる下層中の含フッ素アルコールの含有割合は８０質量％以上が好ましく、特には８５質量％以上、さらには９０質量％以上であるのが好ましい。上記含フッ素アルコールの含有割合が大きいほど、次工程で蒸留を実施する場合の負荷が小さくなるので好ましい。 The content ratio of the fluorinated alcohol in the lower layer obtained in the two-layer separation step in the present invention is preferably 80% by mass or more, particularly 85% by mass or more, and more preferably 90% by mass or more. The larger the content ratio of the fluorinated alcohol, the more preferable because the load in carrying out distillation in the next step is reduced.
本発明における２層分離工程で得られる上層には、通常、５〜１０質量％程度の含フッ素アルコールが含まれるが、この上層中の含フッ素アルコールについては、得られた上層を、次のバッチの２層分離工程において用いる無機塩の一部として繰り返し利用することにより有効に回収できる。 The upper layer obtained by the two-layer separation step in the present invention usually contains about 5 to 10% by mass of fluorinated alcohol. For the fluorinated alcohol in this upper layer, the obtained upper layer is used in the next batch. It can be effectively recovered by repeatedly using it as a part of the inorganic salt used in the two-layer separation step.
本発明においては、上記２層分離させる工程で得られた下層をさらに蒸留する蒸留工程を有することが好ましい。これにより、下層中の水をさらに除去し、水分濃度の低い含フッ素アルコールを得ることができる。
蒸留条件は特に限定されず、通常の多段蒸留で水を除去できる。本発明における２層分離工程で得られる下層は水の含有割合が小さいため、この蒸留工程に要する時間は短時間ですむ。In this invention, it is preferable to have the distillation process which further distills the lower layer obtained at the process of carrying out the said 2 layer separation. Thereby, the water in the lower layer can be further removed, and a fluorinated alcohol having a low moisture concentration can be obtained.
Distillation conditions are not particularly limited, and water can be removed by ordinary multistage distillation. Since the lower layer obtained in the two-layer separation step in the present invention has a small water content, the time required for this distillation step is short.
蒸留工程においては、上記下層を蒸留すること等により、水分濃度が１０００ｐｐｍ以下の含フッ素アルコールを得ることが好ましい。これは、含フッ素アルコールを情報記憶媒体に用いる色素の溶媒として用いる場合、水分濃度は低い方が好ましいためである。水分濃度は特には５００ｐｐｍ以下、さらには２００ｐｐｍ以下とするのが好ましい。上記水分濃度とするため、本発明においては、蒸留工程の後に、さらに、ゼオライト等で含フッ素アルコール中の水分を除去する工程を設けてもよい。 In the distillation step, it is preferable to obtain a fluorinated alcohol having a water concentration of 1000 ppm or less by, for example, distilling the lower layer. This is because when the fluorinated alcohol is used as a solvent for the dye used in the information storage medium, it is preferable that the moisture concentration is low. The water concentration is particularly preferably 500 ppm or less, and more preferably 200 ppm or less. In order to obtain the water concentration, in the present invention, a step of removing water in the fluorinated alcohol with zeolite or the like may be further provided after the distillation step.
以下、本発明を、実施例（例１、例２）を参照して説明する。 Hereinafter, the present invention will be described with reference to Examples (Examples 1 and 2).
［例１］
２，２，３，３−テトラフルオロプロパノール（ＴＦＰＯ） ５０ｇ、脱イオン水 １５ｇを分液ロートに入れて振とうさせたところ、両者は完全に混ざり合い、均一な混合液となった。これに塩化ナトリウム ３．５ｇを添加し、振とうさせた後、３時間静置したところ混合液は２層分離した。なお、上記塩化ナトリウムの添加量を、混合液中の水に対する無機イオンのモル比に換算すると０．１４である。分離した上層と下層を分取したところ、上層 １３．９ｇ、下層 ５４．２ｇが得られた。上層および下層におけるＴＦＰＯの濃度をＮＭＲにて定量したところ、上層のＴＦＰＯ濃度は５．８質量％、下層のＴＦＰＯ濃度は８９．３質量％であった。ＮＭＲの測定条件を以下に示す。[Example 1]
When 50 g of 2,2,3,3-tetrafluoropropanol (TFPO) and 15 g of deionized water were placed in a separatory funnel and shaken, they were completely mixed and became a uniform mixture. To this was added 3.5 g of sodium chloride, and after shaking, the mixture was allowed to stand for 3 hours. The mixture was separated into two layers. In addition, it is 0.14 when the addition amount of the said sodium chloride is converted into the molar ratio of the inorganic ion with respect to the water in a liquid mixture. When the separated upper layer and lower layer were separated, 13.9 g of the upper layer and 54.2 g of the lower layer were obtained. When the concentration of TFPO in the upper layer and the lower layer was quantified by NMR, the TFPO concentration in the upper layer was 5.8% by mass, and the TFPO concentration in the lower layer was 89.3% by mass. NMR measurement conditions are shown below.
＜ＮＭＲ測定条件＞
測定装置：日本電子社製 ＥＣＰ−４００、
測定核：１Ｈ、
測定法：シングルパルス法、
測定溶媒：なし（試料のみを試験管に採取）、
測定温度：室温、
試料管外径：５ｍｍ。<NMR measurement conditions>
Measuring device: ECP-400 manufactured by JEOL Ltd.
Measuring nucleus: 1 H,
Measurement method: Single pulse method,
Measurement solvent: None (only sample is collected in a test tube),
Measurement temperature: room temperature,
Sample tube outer diameter: 5 mm.
［例２］
２，２，３，３−テトラフルオロプロパノール（ＴＦＰＯ）の量を３５ｇとしたこと、および、塩化ナトリウムの添加量を９ｇとしたこと以外は例１と同様にして、ＴＦＰＯと脱イオン水の混合、分離を行った。なお、上記塩化ナトリウムの添加量を、混合液中の水に対する無機イオンのモル比に換算すると０．１６である。静置後、混合液は２層分離し、上層１６．１ｇ、下層３７．３ｇが得られ、上層のＴＦＰＯ濃度は５．５質量％、下層のＴＦＰＯ濃度は９０．０質量％であった。[Example 2]
Mixing TFPO and deionized water in the same manner as in Example 1 except that the amount of 2,2,3,3-tetrafluoropropanol (TFPO) was 35 g and the amount of sodium chloride was 9 g. Separated. In addition, when the addition amount of the said sodium chloride is converted into the molar ratio of the inorganic ion with respect to the water in a liquid mixture, it is 0.16. After standing, the mixed solution was separated into two layers to obtain 16.1 g of the upper layer and 37.3 g of the lower layer, the TFPO concentration of the upper layer was 5.5% by mass, and the TFPO concentration of the lower layer was 90.0% by mass.
本発明の含フッ素アルコールの回収方法は、ＣＤ−ＲやＤＶＤ−Ｒの製造工程で発生する廃液から含フッ素アルコールを回収し、再利用するプロセスとして有用である。
なお、２００５年２月２８日に出願された日本特許出願２００５−５３５９６号の明細書、特許請求の範囲、図面および要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。The method for recovering fluorine-containing alcohol of the present invention is useful as a process for recovering and reusing fluorine-containing alcohol from waste liquid generated in the production process of CD-R and DVD-R.
The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2005-53596 filed on February 28, 2005 are cited herein as disclosure of the specification of the present invention. Incorporated.
Claims (6)
Ｈ−（ＣＲｆＦＣＦ２）ｎ−ＣＲ１Ｒ２−ＯＨ・・・式１ Formula 1 (wherein R f is a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms, R 1 and R 2 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n is an integer of 1 to 4) An inorganic salt that forms an inorganic salt that is an alkali metal hydrochloride or sulfate with respect to the water in the mixed solution in the mixed solution that contains the fluorine-containing alcohol and water that is the compound represented by A method for recovering a fluorinated alcohol, comprising a step of adding an amount such that the sum of ions (inorganic salt is considered to be 100% dissociated) is 0.10 or more in terms of molar ratio and separating the two layers.
H- (CR f FCF 2) n -CR 1 R 2 -OH ··· Formula 1
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| PCT/JP2006/303640 WO2006093101A1 (en) | 2005-02-28 | 2006-02-27 | Method for recovery of fluorinated alcohol |
| JP2007505929A JP4905349B2 (en) | 2005-02-28 | 2006-02-27 | Method for recovering fluorine-containing alcohol |
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| CN102976897A (en) * | 2012-12-18 | 2013-03-20 | 山东科技大学 | Method for purifying tetrafluoro propanol |
| JP2015193589A (en) * | 2014-03-26 | 2015-11-05 | セントラル硝子株式会社 | METHOD FOR PRODUCING 1,1,1,3,3,3-HEXAFLUORO-tert-BUTANOL |
| US10811610B2 (en) * | 2017-01-27 | 2020-10-20 | Sumitomo Chemical Company, Limited | Composition and light emitting device obtained by using the composition |
| CN113979838B (en) * | 2021-08-04 | 2023-09-29 | 浙江巨圣氟化学有限公司 | Method for refining tetrafluoropropanol |
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| JPS6296437A (en) * | 1985-10-22 | 1987-05-02 | Showa Denko Kk | Purification of allyl alcohol |
| JP2001187756A (en) * | 1999-04-07 | 2001-07-10 | Daikin Ind Ltd | Method for recovering fluorine-based alcohol |
| JP2001233810A (en) * | 2000-02-25 | 2001-08-28 | Daikin Ind Ltd | Process for producing 2,2,3,4,4,4-hexafluoro-1-butanol and its use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6296437A (en) * | 1985-10-22 | 1987-05-02 | Showa Denko Kk | Purification of allyl alcohol |
| JP2001187756A (en) * | 1999-04-07 | 2001-07-10 | Daikin Ind Ltd | Method for recovering fluorine-based alcohol |
| JP2001233810A (en) * | 2000-02-25 | 2001-08-28 | Daikin Ind Ltd | Process for producing 2,2,3,4,4,4-hexafluoro-1-butanol and its use |
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| JPWO2006093101A1 (en) | 2008-08-07 |
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| CN101128410A (en) | 2008-02-20 |
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