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CN101119950B - Recovery method of fluorine-containing alcohol - Google Patents

Recovery method of fluorine-containing alcohol Download PDF

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Publication number
CN101119950B
CN101119950B CN2006800047567A CN200680004756A CN101119950B CN 101119950 B CN101119950 B CN 101119950B CN 2006800047567 A CN2006800047567 A CN 2006800047567A CN 200680004756 A CN200680004756 A CN 200680004756A CN 101119950 B CN101119950 B CN 101119950B
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China
Prior art keywords
fluorine
containing alcohol
acid
water
recovering
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Expired - Fee Related
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CN2006800047567A
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CN101119950A (en
Inventor
相田茂
小川章夫
引間聡
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AGC Inc
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Asahi Glass Co Ltd
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    • 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)

Abstract

Disclosed is a method for easily recovering a high concentration fluorine-containing alcohol from a liquid mixture containing water and a fluorine-containing alcohol which is produced during production of CD-R or DVD-R. Specifically disclosed is a method for recovering a fluorine-containing alcohol which comprises a step for separating a liquid mixture containing water and a fluorine-containing alcohol such as 2,2,3,3-tetrafluoropropanol into two layers by adding an acid such as a sulfuric acid into the liquid mixture. More preferably, this method may further contain a distillation step for distilling the lower layer obtained in the two-layer separation step.

Description

The recovery method of fluorine-containing alcohol
Technical field
The present invention relates to reclaim the technology of fluorine-containing alcohol from the mixed solution that contains fluorine-containing alcohol and water.
Background technology
Fluorine-containing alcohol is used as the solvent of the dyestuff that forms recording layer when information recording carriers such as manufacturing CD-R and DVD-R, be indispensable in the manufacturing of huge storage capacity recording medium.
In the manufacturing process of aforementioned recording medium, produce the waste liquid of aqueous fluorine-containing alcohol in a large number.If can reclaim fluorine-containing alcohol and utilize again from this waste liquid, can realize the minimizing of carrying capacity of environment and the reduction of manufacturing cost, therefore expectation removes the technology of anhydrating with low cost from the mixed solution of fluorine-containing alcohol and water.
But, because may having azeotropic, the mixed solution of fluorine-containing alcohol and water forms, be very difficult therefore with dephlegmate.For example, a kind of 2,2,3 as fluorine-containing alcohol, the azeotropic of the mixed solution of 3-C3-Fluoroalcohol (hereinafter referred to as TFPO) and water consists of 73 quality %TFPO, 27 quality % water.
Though disclosed in the patent documentation 1 when the mixed solution of TFPO and water reclaims TFPO by the method for pervaporation with water sepn, expect easier, high-efficiency method.
Patent documentation 1: the Japanese Patent spy opens 2001-187756 communique (claim 5)
The announcement of invention
The object of the present invention is to provide from the mixed solution that contains fluorine-containing alcohol and water water sepn, reclaim the method for fluorine-containing alcohol easily.
The invention provides the recovery method of fluorine-containing alcohol, it is characterized in that, have when recovery contains fluorine-containing alcohol in the mixed solution of fluorine-containing alcohol and water, in above-mentioned mixed solution, add acid and make it be separated into 2 layers operation.
Among the present invention, think that (proton breaks away from from the hydroxyl) balance of dissociating of the hydroxyl of fluorine-containing alcohol is significantly to the non-side shifting of dissociating by adding acid, layering so take place in the decreased solubility of water.It is relevant that this phenomenon is considered to also with fluorine atom, and to be hydrophobicity, hydroxyl dissociate easily because of the effect of fluorine atom becomes, fluorine-containing alcohol is compound with big proportion etc.
Because the proportion of fluorine-containing alcohol is bigger than water, the layer that therefore mainly contains fluorine-containing alcohol is formed at the bottom, and the layer that mainly contains water is formed at top.
By the present invention, make in its operation that is separated into 2 layers, can be layered as the upper strata of mainly containing water and the lower floor of mainly containing fluorine-containing alcohol.By this layering, can make containing of fluorine-containing alcohol in the lower floor proportional is above, the above high densitys of 90 quality % particularly of 80 quality %.Therefore, carry out purifying if this lower floor waited by distillation again, then not can with the water azeotropic, can obtain highly purified fluorine-containing alcohol easily.
The best mode that carries out an invention
As the fluorine-containing alcohol among the present invention, can exemplify the alcohols that perfluor trimethyl carbinol etc. has perfluoroalkyl, 2,2,3,3,3-five fluorine propyl alcohol, 1,1,1,3,3, fluoro alcohols such as 3-hexafluoro-2-propyl alcohol, 2,2,2 tfifluoroethyl alcohol, fluoro phenols and the compound of representing with following formula 1.
H-(CR fFCF 2) n-CR 1R 2-OH ... formula 1
Wherein, R fBe the Polyfluoroalkyl of fluorine atom or carbon number 1～4, R 1, R 2Independent respectively is the alkyl of hydrogen atom or carbon number 1～3, and n is 1～4 integer.
Compound as formula 1 expression specifically can exemplify H (CF 2) 2CH 2OH (TFPO), H (CF 2) 4CH 2OH, HCF 2CF 2CH (CH 3) OH, HCF 2CF 2C (CH 3) 2OH, HC (CF 3) FCF 2CH 2OH, HC (CF 3) FCF 2CH (CH 3) OH, HC (CF 3) FCF 2C (CH 3) 2OH.
Water among the present invention in the handled mixed solution that contains fluorine-containing alcohol and water to contain proportional better be below 50 quality %, good especially is below 25 quality %.Not only need to add more acid containing under the proportional excessive situation of above-mentioned water, and in the distillation process after 2 layers of separation, need more times probably, better is to carry out simple distillation etc. in advance therefore, removes water to a certain degree earlier.
As the acid of using among the present invention, better be mineral acid, be more preferably strong acid such as sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, wherein preferably sulfuric acid, nitric acid, hydrochloric acid.In addition, make its operation that is separated into 2 layers after, implement under the situation of the redistilled distillation process of lower floor that will obtain the angle of perishable water distilling apparatus never, the good especially sulfuric acid that is to use.
Among the present invention, the addition of acid better is to make proton (H +) reach the amount of (supposing that sour 100% dissociates) more than 0.10 with respect to the water in the mixed solution that contains fluorine-containing alcohol and water with the mol ratio conversion, good especially is more than 0.15, is more preferably more than 0.20.Above-mentioned mol ratio is less than 0.1 o'clock, not only the water in the lower floor to contain proportional change big, and be difficult to layering.
In addition, common excessive interpolation acid does not have special benefit yet, the addition of acid better be adopt to take place in 2 layers of separation, the lower floor fluorine-containing alcohol contain proportional MIN amount more than certain value.
Acid gets final product to being added under normal pressure, the normal temperature of the mixed solution that contains fluorine-containing alcohol and water, does not need temperature control etc. usually.Mix by agitating wing etc., make the acid and the above-mentioned mixed solution mixing of interpolation.
Get final product in order to make it be separated into 2 layers, it to be left standstill, also can use separating centrifuge etc. to separate.Leave standstill and make under its situation that is separated into 2 layers, time of repose gets final product about 3～12 hours also according to the area at the thickness of each layer and interface and different.
Fluorine-containing alcohol in the lower floor that obtains in 2 layers of separation circuit of the present invention to contain proportional better be more than 80 quality %, good especially is more than the 90 quality %, is more preferably more than the 92 quality %.Containing of above-mentioned fluorine-containing alcohol is proportional big more, and the load when then implementing distillation in the subsequent handling is more little, so be the bigger the better.
Usually contain the fluorine-containing alcohol about 10～30 quality % in the upper strata that obtains in 2 layers of separation circuit of the present invention, but for the fluorine-containing alcohol in this upper strata, can reuse by the part of the acid used in 2 layers of separation circuit of upper strata that will obtain, can reclaim effectively as next batch.
Among the present invention, better be to have the lower floor that to obtain in above-mentioned 2 layers of separation circuit to carry out the distillatory distillation process again.Thus, can further remove the water in the sub-cloud, obtain the little fluorine-containing alcohol of moisture concentration.
Distillation condition is not particularly limited, and can remove by common multistage distillation and anhydrate.The water of the lower floor that obtains in 2 layers of separation circuit of the present invention contains proportional little, so the required time of this distillation process shortens.
In the distillation process, better be by above-mentioned lower floor being distilled etc., obtaining the fluorine-containing alcohol of moisture concentration below 1000ppm.This is because when fluorine-containing alcohol was used as the solvent of the dyestuff that uses in the information recording carrier, moisture concentration was low more good more.Moisture concentration is good especially to be below 500ppm, is more preferably below 200ppm.In order to make it reach above-mentioned moisture concentration, among the present invention, the operation that siccative such as using zeolite is removed the moisture in the fluorine-containing alcohol can be set preferably behind distillation process again.
Embodiment
Below, the present invention will be described with reference to embodiment (example 1～3).
[example 1]
Add 50g TFPO, 15g deionized water and vibration in separating funnel after, both mix fully, form the mixed solution of homogeneous.Slowly splash into the vitriol oil of 11.5g 96 quality % therein, left standstill after the vibration 3 hours, mixed solution is separated into 2 layers.In addition, the addition of the above-mentioned vitriol oil is converted into the proton (H with respect to the water in the mixed solution +) mol ratio be 0.27.Divide and to get the upper and lower of having separated, obtain 24.6g upper strata, 49.8g lower floor.TFPO concentration in the upper and lower is undertaken quantitatively by NMR, and the TFPO concentration on upper strata is 24.5 quality % as a result, and the TFPO concentration of lower floor is 93.7 quality %.The condition determination of NMR is as follows.
＜NMR condition determination 〉
Determinator: NEC corporate system ECP400,
Measure nuclear: 1H,
Assay method: the monopulse method,
Measure solvent: do not have (only with sampling to developmental tube),
Measure temperature: room temperature,
Developmental tube external diameter: 5mm.
[example 2]
Except the amount of splashing into of the vitriol oil of 96 quality % is 9g, similarly operate with example 1, carry out TFPO and deionized water mixing, separate.In addition, the addition of the above-mentioned vitriol oil is converted into the proton (H with respect to the water in the mixed solution +) mol ratio be 0.21.After leaving standstill, mixed solution is separated into 2 layers, obtains 23.0g upper strata, 50.7g lower floor, and the TFPO concentration on upper strata is 18.3 quality %, and the TFPO concentration of lower floor is 93.4 quality %.
[example 3]
Except the amount of splashing into of the vitriol oil of 96 quality % is 4.5g, similarly operate with example 1, carry out TFPO and deionized water mixing, separate.In addition, the addition of the above-mentioned vitriol oil is converted into the proton (H with respect to the water in the mixed solution +) mol ratio be 0.11.After leaving standstill, mixed solution is separated into 2 layers, obtains 15.7g upper strata, 53.7g lower floor, and the TFPO concentration on upper strata is 15.5 quality %, and the TFPO concentration of lower floor is 90.0 quality %.
The possibility of utilizing on the industry
The recovery method of fluorine-containing alcohol of the present invention can reclaim as the waste liquid that produces the technology of fluorine-containing alcohol and recycling from the manufacturing process of CD-R and DVD-R.
In addition, quote the announcement of all the elements of Japanese patent application 2005-37888 number specification sheets, claims, accompanying drawing and the summary of filing an application on February 15th, 2005 here as specification sheets of the present invention.

Claims (9)

1.含氟醇的回收方法，其特征在于，具有在回收含有含氟醇和水的混合液中的含氟醇时，在上述混合液中添加酸而使其分离成2层的工序，1. The recovery method of fluorine-containing alcohol is characterized in that, when recovering the fluorine-containing alcohol in the mixed solution containing fluorine-containing alcohol and water, adding acid to the above-mentioned mixed solution to separate it into two steps, 其中，假设酸100％解离，酸的添加量为使质子H+相对于上述混合液中的水以摩尔比换算达到0.10以上的量。Here, assuming that the acid is 100% dissociated, the acid is added in an amount such that the proton H + becomes 0.10 or more in terms of molar ratio with respect to water in the above mixed solution. 2.如权利要求1所述的含氟醇的回收方法，其特征在于，含氟醇为以下式1：2. the recovery method of fluorine-containing alcohol as claimed in claim 1, is characterized in that, fluorine-containing alcohol is following formula 1: H-(CRfFCF2)n-CR1R2-OH  式1H-(CR f FCF 2 ) n -CR 1 R 2 -OH Formula 1 表示的化合物；其中，Rf为氟原子或碳数1～4的多氟烷基，R1、R2分别独立为氢原子或碳数1～3的烷基，n为1～4的整数。The compound represented by: wherein, R f is a fluorine atom or a polyfluoroalkyl group with 1 to 4 carbons, R 1 and R 2 are independently a hydrogen atom or an alkyl group with 1 to 3 carbons, and n is an integer of 1 to 4 . 3.如权利要求1所述的含氟醇的回收方法，其特征在于，含氟醇为2，2，3，3-四氟丙醇。3. the recovery method of fluorine-containing alcohol as claimed in claim 1, is characterized in that, fluorine-containing alcohol is 2,2,3,3-tetrafluoropropanol. 4.如权利要求1所述的含氟醇的回收方法，其特征在于，酸为硫酸。4. the recovery method of fluorine-containing alcohol as claimed in claim 1, is characterized in that, acid is sulfuric acid. 5.如权利要求1所述的含氟醇的回收方法，其特征在于，上述使其分离成2层的工序中得到的下层中的含氟醇的含有比例在80质量％以上。5. The method for recovering fluorine-containing alcohol according to claim 1, wherein the content of the fluorine-containing alcohol in the lower layer obtained in the step of separating into two layers is 80% by mass or more. 6.如权利要求1所述的含氟醇的回收方法，其特征在于，还具有将上述使其分离成2层的工序中得到的下层进行蒸馏的蒸馏工序。6. The method for recovering fluorine-containing alcohol according to claim 1, further comprising a distillation step of distilling the lower layer obtained in the step of separating into two layers. 7.如权利要求6所述的含氟醇的回收方法，其特征在于，通过上述蒸馏工序，得到水分浓度在1000ppm以下的含氟醇。7. The method for recovering fluorine-containing alcohols according to claim 6, wherein the fluorine-containing alcohols having a water concentration of 1000 ppm or less are obtained through the distillation step. 8.如权利要求6或7所述的含氟醇的回收方法，其特征在于，在上述蒸馏工序后，具有使其与干燥剂接触而除去含氟醇中的水分的工序。8. The method for recovering fluorine-containing alcohol according to claim 6 or 7, further comprising a step of removing moisture from the fluorine-containing alcohol by contacting it with a desiccant after the distillation step. 9.如权利要求8所述的含氟醇的回收方法，其特征在于，上述干燥剂为沸石。9. The method for recovering fluorine-containing alcohols according to claim 8, wherein the desiccant is zeolite.
CN2006800047567A 2005-02-15 2006-02-09 Recovery method of fluorine-containing alcohol Expired - Fee Related CN101119950B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP037888/2005 2005-02-15
JP2005037888 2005-02-15
PCT/JP2006/302260 WO2006087964A1 (en) 2005-02-15 2006-02-09 Method for recovering fluorine-containing alcohol

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CN102718630B (en) * 2012-06-11 2014-07-02 中昊晨光化工研究院 Tetrafluoropropanol rectification purifying method
CN111892502A (en) * 2020-09-11 2020-11-06 安徽灵达高新材料有限公司 Efficient separation method of mixture of acrylic ester and methanol
CN113979838B (en) * 2021-08-04 2023-09-29 浙江巨圣氟化学有限公司 Method for refining tetrafluoropropanol

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5233098A (en) * 1990-05-30 1993-08-03 Central Glass Company, Limited Method for removing and recovering fluorinated alcohol from waste gas
CN1270948A (en) * 1999-04-20 2000-10-25 大金工业株式会社 Recovery method for fluorine series solvent

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0685856B2 (en) * 1990-06-20 1994-11-02 セントラル硝子株式会社 Recovery method of fluorinated alcohol
JP2001187755A (en) * 1999-04-20 2001-07-10 Daikin Ind Ltd Recovery method for fluorinated solvent

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5233098A (en) * 1990-05-30 1993-08-03 Central Glass Company, Limited Method for removing and recovering fluorinated alcohol from waste gas
CN1270948A (en) * 1999-04-20 2000-10-25 大金工业株式会社 Recovery method for fluorine series solvent

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JPWO2006087964A1 (en) 2008-07-03
CN101119950A (en) 2008-02-06
TW200639144A (en) 2006-11-16

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