CN101128410A - Method for recovery of fluorinated alcohol - Google Patents
Method for recovery of fluorinated alcohol Download PDFInfo
- Publication number
- CN101128410A CN101128410A CNA2006800061920A CN200680006192A CN101128410A CN 101128410 A CN101128410 A CN 101128410A CN A2006800061920 A CNA2006800061920 A CN A2006800061920A CN 200680006192 A CN200680006192 A CN 200680006192A CN 101128410 A CN101128410 A CN 101128410A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- containing alcohol
- recovery method
- water
- inorganic salt
- 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.)
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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
Abstract
A method for recovering a fluorinated alcohol comprising the step of adding an inorganic salt to a mixed solution comprising the fluorinated alcohol and water to cause two-phase separation. This method can recover a fluorinated alcohol by separating water from a mixed solution of the fluorinated alcohol and water which is produced during a CD-R or DVD-R production process.
Description
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 in the mixed solution that contains fluorine-containing alcohol and water that from the manufacturing process of CD-R and DVD-R etc., produces water sepn, reclaim the method for fluorine-containing alcohol easily.
The present invention has to make the mixed solution that contains fluorine-containing alcohol and water be separated into the recovery method of fluorine-containing alcohol of 2 layers operation.
Among the present invention, think that fluorine-containing alcohol is for the decreased solubility of water, so layering takes place by add inorganic salt in containing the mixed solution of fluorine-containing alcohol and 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.
The present invention comprises the main idea with following characteristics.
(1) recovery method of fluorine-containing alcohol is characterized in that, has in containing the mixed solution of fluorine-containing alcohol and water the inorganic salt of interpolation and makes it be separated into 2 layers operation.
As the recovery method of above-mentioned (1) described fluorine-containing alcohol, it is characterized in that (2) fluorine-containing alcohol is with following formula 1
H-(CR
fFCF
2)
n-CR
1R
2-OH ... formula 1
(wherein, R
fBe the fluoro-alkyl of fluorine atom or carbon number 1～4, R
1, R
2Respectively independent be the alkyl of hydrogen atom or carbon number 1～3, and n is 1～4 integer) compound represented.
As the recovery method of above-mentioned (1) described fluorine-containing alcohol, it is characterized in that (3) fluorine-containing alcohol is 2,2,3, the 3-C3-Fluoroalcohol.
(4) as the recovery method of each described fluorine-containing alcohol in above-mentioned (1)～(3), it is characterized in that the addition of inorganic salt converts in the amount more than 0.10 with mol ratio with respect to the water in the above-mentioned mixed solution for the summation of the mineral ion (supposing that inorganic salt 100% dissociate) of generation.
(5) as the recovery method of each described fluorine-containing alcohol in above-mentioned (1)～(4), it is characterized in that, use sodium-chlor as inorganic salt.
(6) as the recovery method of each described fluorine-containing alcohol in above-mentioned (1)～(5), it is characterized in that, above-mentionedly make containing of fluorine-containing alcohol in the lower floor that obtains in its operation that is separated into 2 layers proportional more than 80 quality %.
(7) as the recovery method of each described fluorine-containing alcohol in above-mentioned (1)～(6), it is characterized in that having the above-mentioned lower floor that obtains in its operation that is separated into 2 layers that makes is carried out the distillatory distillation process again.
(8) as the recovery method of above-mentioned (7) described fluorine-containing alcohol, it is characterized in that,, obtain the fluorine-containing alcohol of moisture concentration below 1000ppm by above-mentioned distillation process.
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 at short notice.By this layering, can make containing of fluorine-containing alcohol in the lower floor proportional is 80 quality % high densitys above, that particularly 85 quality % are above or even 90 quality % are above.Therefore, if this lower floor is carried out purifying by distillation etc. again, then can obtain highly purified fluorine-containing alcohol simply, efficiently.
The best mode that carries out an invention
As preferred fluorine-containing alcohol among the present invention, can exemplify the perfluor trimethyl carbinol, 2,2,3,3,3-five fluorine propyl alcohol, 1,1,1,3,3, the fluoro alcohols of carbon numbers 2～7 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 fluoro-alkyl 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 with following formula 1 expression specifically can exemplify H (CF
2)
2CH
2OH (2,2,3, the 3-C3-Fluoroalcohol, 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 inorganic salt 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 inorganic salt that use among the present invention, better be an alkali metal salt, calm easy dissociated angle, wherein strong acid salts such as preferably salt hydrochlorate and vitriol.
As inorganic salt, specifically can exemplify sodium-chlor, sodium sulfate, yellow soda ash, sodium bicarbonate, Sodium Fluoride, vitriolate of tartar etc.Wherein, because easily be dissolved in the mixed solution and the low price of fluorine-containing alcohol and water, better be sodium-chlor and sodium sulfate, good especially is sodium-chlor.
Among the present invention, better to be the summation that makes mineral ion (supposing that inorganic salt 100% dissociate) with respect to the water in the mixed solution that contains fluorine-containing alcohol and water convert with mol ratio the addition of inorganic salt reaches amount more than 0.10, and good especially is more than 0.13.Above-mentioned mol ratio is less than 0.10 o'clock, not only the water in the lower floor to contain proportional change big, and be difficult to layering.In addition, above-mentioned mineral ion is meant that inorganic salt dissociate and these two kinds of the positively charged ion that generates and negatively charged ion.
The method of calculation of the mole number of mineral ion are as follows: add under the situation of 1mol NaCl, be dissociated into 1molNa
+With 1mol Cl
-So mineral ion adds up to 2mol.In addition, add 1mol Na
2SO
4Situation under, be dissociated into 2mol Na
+With 1mol SO
4 2-So mineral ion adds up to 3mol.
In addition, common excessive interpolation inorganic salt do not have special benefit yet, the addition of inorganic salt 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.
Inorganic salt get final product to being added under normal pressure, the normal temperature of the mixed solution that contains fluorine-containing alcohol and water, do not need temperature control etc. usually.Mix by agitating wing etc., make the inorganic salt 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 85 quality %, is more preferably more than the 90 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 5～10 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 inorganic salt that use in 2 layers of separation circuit of upper strata that will obtain, it is reclaimed 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 of using zeolite etc. to remove the moisture in the fluorine-containing alcohol can be set behind distillation process again.
Embodiment
Below, the present invention will be described with reference to embodiment (example 1, example 2).
[example 1]
Add 50g 2,2,3 in separating funnel, after 3-C3-Fluoroalcohol (TFPO), 15g deionized water and the vibration, both mix fully, form the mixed solution of homogeneous.Add 3.5g sodium-chlor therein, left standstill after the vibration 3 hours, mixed solution is separated into 2 layers.In addition, to be converted into the mol ratio with respect to the mineral ion of the water in the mixed solution be 0.14 to the addition of above-mentioned sodium-chlor.Divide and to get the upper and lower of having separated, obtain 13.9g upper strata, 54.2g lower floor.TFPO concentration in the upper and lower is undertaken quantitatively by NMR, and the TFPO concentration on upper strata is 5.8 quality % as a result, and the TFPO concentration of lower floor is 89.3 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 2,2,3, the amount of 3-C3-Fluoroalcohol (TFPO) is that the addition of 35g, sodium-chlor is beyond the 9g, similarly operates with example 1, carry out TFPO and deionized water mixing, separate.In addition, to be converted into the mol ratio with respect to the mineral ion of the water in the mixed solution be 0.16 to the addition of above-mentioned sodium-chlor.After leaving standstill, mixed solution is separated into 2 layers, obtains 16.1g upper strata, 37.3g lower floor, and the TFPO concentration on upper strata is 5.5 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 be as producing from the manufacturing process of CD-R and DVD-R Waste liquid reclaims the technology of fluorine-containing alcohol and recycling.
In addition, quote the announcement of all the elements of Japanese patent application 2005-53596 number specification sheets, claims, accompanying drawing and the summary of filing an application on February 28th, 2005 here as specification sheets of the present invention.
Claims (8)
1. the recovery method of fluorine-containing alcohol is characterized in that, has in containing the mixed solution of fluorine-containing alcohol and water the inorganic salt of interpolation and makes it be separated into 2 layers operation.
2. the recovery method of fluorine-containing alcohol as claimed in claim 1 is characterized in that, fluorine-containing alcohol is with following formula 1
H-(CR
fFCF
2)
n-CR
1R
2-OH ... formula 1
The compound of expression; Wherein, R
fBe the fluoro-alkyl 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.
3. the recovery method of fluorine-containing alcohol as claimed in claim 1 is characterized in that, fluorine-containing alcohol is 2,2,3, the 3-C3-Fluoroalcohol.
4. as the recovery method of each described fluorine-containing alcohol in the claim 1～3, it is characterized in that, suppose that inorganic salt 100% dissociate, the addition of inorganic salt is the summation of the mineral ion of generation to be converted with mol ratio with respect to the water in the above-mentioned mixed solution reach amount more than 0.10.
5. as the recovery method of each described fluorine-containing alcohol in the claim 1～4, it is characterized in that,, use sodium-chlor as inorganic salt.
6. as the recovery method of each described fluorine-containing alcohol in the claim 1～5, it is characterized in that, above-mentionedly make containing of fluorine-containing alcohol in the lower floor that obtains in its operation that is separated into 2 layers proportional more than 80 quality %.
7. as the recovery method of each described fluorine-containing alcohol in the claim 1～6, it is characterized in that having the above-mentioned lower floor that obtains in its operation that is separated into 2 layers that makes is carried out the distillatory distillation process again.
8. the recovery method of fluorine-containing alcohol as claimed in claim 7 is characterized in that, by above-mentioned distillation process, obtains the fluorine-containing alcohol of moisture concentration below 1000ppm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005053596 | 2005-02-28 | ||
| JP053596/2005 | 2005-02-28 | ||
| PCT/JP2006/303640 WO2006093101A1 (en) | 2005-02-28 | 2006-02-27 | Method for recovery of fluorinated alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101128410A true CN101128410A (en) | 2008-02-20 |
| CN101128410B CN101128410B (en) | 2011-04-06 |
Family
ID=36941130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800061920A Expired - Fee Related CN101128410B (en) | 2005-02-28 | 2006-02-27 | Method for recovery of fluorinated alcohol |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4905349B2 (en) |
| CN (1) | CN101128410B (en) |
| TW (1) | TW200702327A (en) |
| WO (1) | WO2006093101A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924235A (en) * | 2012-11-26 | 2013-02-13 | 山东科技大学 | Purification method for octafluoropentyl alcohol |
| CN102976897A (en) * | 2012-12-18 | 2013-03-20 | 山东科技大学 | Method for purifying tetrafluoro propanol |
| CN110235266A (en) * | 2017-01-27 | 2019-09-13 | 住友化学株式会社 | Composition and the light-emitting component obtained using the composition |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113979838B (en) * | 2021-08-04 | 2023-09-29 | 浙江巨圣氟化学有限公司 | Method for refining tetrafluoropropanol |
Family Cites Families (3)
| 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 |
| JP4810715B2 (en) * | 2000-02-25 | 2011-11-09 | ダイキン工業株式会社 | Process for producing 2,2,3,4,4,4-hexafluoro-1-butanol and use thereof |
-
2006
- 2006-02-27 JP JP2007505929A patent/JP4905349B2/en not_active Expired - Fee Related
- 2006-02-27 WO PCT/JP2006/303640 patent/WO2006093101A1/en active Application Filing
- 2006-02-27 CN CN2006800061920A patent/CN101128410B/en not_active Expired - Fee Related
- 2006-03-01 TW TW095106819A patent/TW200702327A/en not_active IP Right Cessation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924235A (en) * | 2012-11-26 | 2013-02-13 | 山东科技大学 | Purification method for octafluoropentyl alcohol |
| CN102924235B (en) * | 2012-11-26 | 2016-04-20 | 山东科技大学 | A kind of method of purification of octafluoropentanol |
| CN102976897A (en) * | 2012-12-18 | 2013-03-20 | 山东科技大学 | Method for purifying tetrafluoro propanol |
| CN110235266A (en) * | 2017-01-27 | 2019-09-13 | 住友化学株式会社 | Composition and the light-emitting component obtained using the composition |
| CN110235266B (en) * | 2017-01-27 | 2021-04-02 | 住友化学株式会社 | Composition and light-emitting element obtained using same |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI346100B (en) | 2011-08-01 |
| WO2006093101A1 (en) | 2006-09-08 |
| CN101128410B (en) | 2011-04-06 |
| TW200702327A (en) | 2007-01-16 |
| JP4905349B2 (en) | 2012-03-28 |
| JPWO2006093101A1 (en) | 2008-08-07 |
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Granted publication date: 20110406 Termination date: 20140227 |