CN103073458A - Method for recovering trifluoromethanesulfonic acid in wastewater - Google Patents
Method for recovering trifluoromethanesulfonic acid in wastewater Download PDFInfo
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- CN103073458A CN103073458A CN2013100088249A CN201310008824A CN103073458A CN 103073458 A CN103073458 A CN 103073458A CN 2013100088249 A CN2013100088249 A CN 2013100088249A CN 201310008824 A CN201310008824 A CN 201310008824A CN 103073458 A CN103073458 A CN 103073458A
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- trifluoromethanesulfonic acid
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Abstract
The invention discloses a method for recovering trifluoromethanesulfonic acid in wastewater, which comprises the following steps: adding inorganic alkali into trifluoromethanesulfonic acid-containing wastewater and reacting; then evaporating to dryness, adding ethanol and reflowing, filtrating, cooling, standing and separating out trifluoromethanesulfonic acid inorganic salt, filtrating, drying; then adding concentrated sulphuric acid into the trifluoromethanesulfonic acid inorganic salt and dissolving; and finally reducing pressure and recovering trifluoromethanesulfonic acid, wherein the trifluoromethanesulfonic acid in the wastewater exists in the form of free state or organic alkali salt. The trifluoromethanesulfonic acid recovered by the method has high purity and high productivity, and the recovery method is simple and convenient, and is suitable for large-scale industrial application; and the method provided by the invention is safe, and provides a beneficial solution method for reducing cost and environment pollution as much as possible.
Description
Technical field
The present invention relates to a kind of method that reclaims trifluoromethanesulfonic acid in the waste water, be specifically related to a kind of method that from contain trifluoromethanesulfonic acid waste water, reclaims trifluoromethanesulfonic acid.
Background technology
Trifluoromethanesulfonic acid is the strong organic acid of knowing at present, have strongly-acid and reductibility, generally as organic synthesis reagent, also can be used as isomerization and alkylating catalyzer, to such an extent as to be widely used in the industries such as medicine, chemical industry, such as nucleosides, microbiotic, steroid, protein, join carbohydrate, VITAMIN is synthetic, silicon rubber modification etc.Especially find at this three aspects: wider, the firstth, in organic synthesis, for the protection of functional group, be highly effective methyl-monosilane base reagent; The secondth, in organic synthesis, participate in multiple organic compound carbon carbon and become key to increase the reaction of carbochain; The 3rd is to make catalyzer in some reaction.
Trifluoromethanesulfonic acid is as a kind of reagent newly developed, and its price is higher, all does the waste water discharging after at present trifluoromethanesulfonic acid reaction is finished, and does not utilize if do not add to reclaim, and can cause product cost higher, and fluorine wherein also can welding.US Patent No. 5603812 is with trifluoromethanesulfonic acid monohydrate and the together molecular distillation of trifluoromethanesulfonic acid front three amine salt, can only obtain a small amount of trifluoromethanesulfonic acid, also further do not tell the trifluoromethanesulfonic acid recovery method in the trifluoromethanesulfonic acid front three amine salt, European patent EP 0671213A1 provides the concrete grammar that reclaims trifluoromethanesulfonic acid from organic alkali salt of the trifluoromethanesulfonic acids such as trifluoromethanesulfonic acid front three amine salt as follows:
CF
3SO
3HN(CH
3)
3 + H
2SO
4 → CF
3SO
3H + [ N(CH
3)
3]
2 H
2SO
4，
But find that in the production of mass-producing the method is very large with the material viscosity such as sulfuric acid front three amine salt that the vitriol oil takes off the organic bases generation, has a strong impact on the recovery of trifluoromethanesulfonic acid.
Trifluoromethanesulfonic acid participates in organic synthesis or as after the reactions such as catalyzer, all do the waste water discharging, and often contain a large amount of inorganic salts and some high boiling point organic compound classes in these waste water, the not clear organism class of the inorganic salt of some Halogens and some particularly, the method for studying a kind of safe, highly purified recovery trifluoromethanesulfonic acid are the current problems that solve of needing.
Summary of the invention
The object of the present invention is to provide a kind of method that reclaims trifluoromethanesulfonic acid in the waste water.
The technical solution used in the present invention is:
A kind of method that reclaims trifluoromethanesulfonic acid in the waste water may further comprise the steps:
1) add the mineral alkali reaction in the waste water that contains trifluoromethanesulfonic acid, then evaporating water gets solid matter, and the trifluoromethanesulfonic acid in the described waste water exists with the form of free state or organic alkali salt;
2) add alcohol reflux in solid matter, filter, cooling is left standstill and is separated out the trifluoromethanesulfonic acid inorganic salt, filters, and drying gets the trifluoromethanesulfonic acid inorganic salt;
3) in the trifluoromethanesulfonic acid inorganic salt, add concentrated sulfuric acid dissolution, then the reclaim under reduced pressure trifluoromethanesulfonic acid.
Preferably, step 2) be cooled to 0～5 ℃.
Preferably, step 2) return time is 1～2h.
Preferably, the mineral alkali of step 1) adding and the trifluoromethanesulfonic acid equimolar amount in the waste water.
Preferably, mineral alkali is inorganic strong alkali.
Preferably, mineral alkali is at least a in potassium hydroxide, the sodium hydroxide.
Preferably, step 1) adopts evaporated under reduced pressure moisture.
Preferably, step 2) consumption of ethanol is 5～10 times of solid matter weight.Preferably, described ethanol is dehydrated alcohol.
Preferably, step 3) trifluoromethanesulfonic acid inorganic salt and vitriol oil equimolar amount.
Owing to often containing a large amount of inorganic salts and some other high boiling point organic impurity in the waste water that contains trifluoromethanesulfonic acid, Halogen inorganic salt particularly, if directly in the solid matter of step 1) gained, add the vitriol oil in the inventive method, can produce hydrogen halide and other not clear organic impuritys, can produce explosion hazard, and have a strong impact on the quality of the trifluoromethanesulfonic acid of recovery, and the invention provides a kind of safe recovery method, then avoided the danger of blast by adding alcohol reflux.
The invention has the beneficial effects as follows:
The trifluoromethanesulfonic acid purity that the inventive method reclaims is high, productive rate is high, and recovery method is simple and convenient, is applicable to use in the large-scale industry; The inventive method safety has been avoided the danger that not clear organism explodes because of reaction generation under strong acid in the waste water; The present invention has removed the Halogen inorganic salt, has avoided the Halogen inorganic salt to produce hydrogen halide under strong acid, so that affect trifluoromethanesulfonic acid purity; The present invention provides a kind of useful solution for reducing as much as possible cost and environmental contamination reduction.
Embodiment
A kind of method that reclaims trifluoromethanesulfonic acid in the waste water may further comprise the steps:
1) if the trifluoromethanesulfonic acid in the waste water is free state, then neutralize with mineral alkali, form trifluoromethanesulfonic acid inorganic salt Ran Hou Bamboo and fall moisture content, add alcohol reflux, filtered while hot is removed inorganic salts, then the trifluoromethanesulfonic acid inorganic salt are separated out in cooling, allow high boiling point organic compound stay in the ethanol, after trifluoromethanesulfonic acid inorganic salt drying, add again vitriol oil underpressure distillation and reclaim trifluoromethanesulfonic acid;
2) if being form with organic alkali salt, the trifluoromethanesulfonic acid in the waste water exists, also displace organic bases with mineral alkali, form trifluoromethanesulfonic acid inorganic salt Ran Hou Bamboo and fall moisture content and organic bases, add alcohol reflux, filtered while hot is removed inorganic salts, and then the trifluoromethanesulfonic acid inorganic salt are separated out in cooling, allow high boiling point organic compound stay in the ethanol, reclaim trifluoromethanesulfonic acid with adding again vitriol oil underpressure distillation after the trifluoromethanesulfonic acid inorganic salt drying.
Preferably, step 2) be cooled to 0～5 ℃.
Preferably, step 2) return time is 1～2h.
Preferably, the mineral alkali of step 1) adding and the trifluoromethanesulfonic acid equimolar amount in the waste water.
Preferably, mineral alkali is inorganic strong alkali.
Preferably, mineral alkali is at least a in potassium hydroxide, the sodium hydroxide.
Preferably, step 1) adopts evaporated under reduced pressure moisture.
Preferably, step 2) consumption of ethanol is 5～10 times of solid matter weight.Preferably, described ethanol is dehydrated alcohol.
Preferably, step 3) trifluoromethanesulfonic acid inorganic salt and vitriol oil equimolar amount.
The present invention is further illustrated below in conjunction with specific embodiment, but be not limited to this.
Embodiment 1
A kind of method that reclaims trifluoromethanesulfonic acid in the waste water may further comprise the steps:
1) gets 1000 g and contain the waste water of trifluoromethanesulfonic acid front three amine salt in there-necked flask, contain trifluoromethanesulfonic acid front three amine salt 20.9 g(0.1mol in the waste water), add 4 g sodium hydroxide (0.1 mol), stirring reaction 10 minutes, then be that 80 ℃, vacuum pressure are evaporate to dryness moisture content under 250 handkerchiefs in temperature, obtain 35 g solid matters;
2) add 175 g dehydrated alcohol backflow 2h in 35 g solid matters, filter out insolubles, then be cooled to 5 ℃, leave standstill 3 h, filter, drying obtains 15.1 g trifluoromethanesulfonic acid sodium;
3) in 15.1 g trifluoromethanesulfonic acid sodium, add 8.6g(0.088 mol) vitriol oil, after the dissolving, be warmed up to 100 ℃, vacuum pressure 500 handkerchiefs reclaim, and obtain anhydrous trifluoromethanesulfonic acid 10.5g, content 98%.
Embodiment 2
A kind of method that reclaims trifluoromethanesulfonic acid in the waste water may further comprise the steps:
1) gets 1000 g and contain trifluoromethanesulfonic acid waste water in there-necked flask, contain trifluoromethanesulfonic acid 15g(0.1 mol in the waste water), add 5.6g potassium hydroxide (0.1 mol), stirring reaction 10 minutes, then be that 80 ℃, vacuum pressure are evaporate to dryness moisture content under 250 handkerchiefs in temperature, obtain the 40g solid matter;
2) add 400g dehydrated alcohol backflow 1h in the 40g solid matter, filtered while hot is fallen insolubles, then is cooled to 0 ℃, leaves standstill 3h, filters, and drying obtains 13.2g trifluoromethanesulfonic acid potassium;
3) in 13.2g trifluoromethanesulfonic acid potassium, add 6.88g(0.07 mol) vitriol oil, after the dissolving, be warmed up to 100 ℃, vacuum pressure 500 handkerchiefs reclaim, and obtain anhydrous trifluoromethanesulfonic acid 9.3g, content 98.3%.
Embodiment 3
A kind of method that reclaims trifluoromethanesulfonic acid in the waste water may further comprise the steps:
1) gets 1000 g and contain the waste water of trifluoromethanesulfonic acid front three amine salt in there-necked flask, contain trifluoromethanesulfonic acid front three amine salt 20.9 g(0.1mol in the waste water), add 5.6g potassium hydroxide (0.1 mol), stirring reaction 10 minutes, then be that 80 ℃, vacuum pressure are evaporate to dryness moisture content under 250 handkerchiefs in temperature, obtain the 42g solid matter;
2) add the dehydrated alcohol backflow 1.5h of 7 times of weight in the 42g solid matter, filter out insolubles, then be cooled to 4 ℃, leave standstill 3 h, filter, drying obtains 13g trifluoromethanesulfonic acid potassium;
In 13g trifluoromethanesulfonic acid potassium, add 6.78g(0.069mol) vitriol oil, after the dissolving, be warmed up to 100 ℃, vacuum pressure 500 handkerchiefs reclaim, and obtain anhydrous trifluoromethanesulfonic acid 9g, content 98%.
Claims (10)
1. method that reclaims trifluoromethanesulfonic acid in the waste water may further comprise the steps:
1) add the mineral alkali reaction in the waste water that contains trifluoromethanesulfonic acid, then evaporating water gets solid matter, and the trifluoromethanesulfonic acid in the described waste water exists with the form of free state or organic alkali salt;
2) add alcohol reflux in solid matter, filter, cooling is left standstill and is separated out the trifluoromethanesulfonic acid inorganic salt, filters, and drying gets the trifluoromethanesulfonic acid inorganic salt;
3) in the trifluoromethanesulfonic acid inorganic salt, add concentrated sulfuric acid dissolution, then the reclaim under reduced pressure trifluoromethanesulfonic acid.
2. method according to claim 1 is characterized in that: step 2) be cooled to 0～5 ℃.
3. method according to claim 1 is characterized in that: step 2) return time is 1～2h.
4. method according to claim 1 is characterized in that: the mineral alkali that step 1) adds and the trifluoromethanesulfonic acid equimolar amount in the waste water.
5. according to claim 1 or 4 described methods, it is characterized in that: mineral alkali is inorganic strong alkali.
6. method according to claim 5 is characterized in that: mineral alkali is at least a in potassium hydroxide, the sodium hydroxide.
7. method according to claim 1 is characterized in that: step 1) employing evaporated under reduced pressure moisture.
8. method according to claim 1 is characterized in that: step 2) consumption of ethanol is 5～10 times of solid matter weight.
9. method according to claim 8, it is characterized in that: described ethanol is dehydrated alcohol.
10. method according to claim 1 is characterized in that: step 3) trifluoromethanesulfonic acid inorganic salt and vitriol oil equimolar amount.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725283A (en) * | 2015-04-14 | 2015-06-24 | 江西国化实业有限公司 | Trifluoromethanesulfonic acid preparation method |
| CN105218409A (en) * | 2015-10-21 | 2016-01-06 | 安徽工业大学 | A kind of method reclaiming trifluoromethanesulfonic acid from trifluoromethanesulfonic acid amine salt waste water |
| CN105237441A (en) * | 2015-11-02 | 2016-01-13 | 中国石油天然气股份有限公司 | Device and method for recovering methane sulfonic acid |
| CN111116431A (en) * | 2019-12-31 | 2020-05-08 | 中船重工（邯郸）派瑞特种气体有限公司 | Device and method for recovering trifluoromethanesulfonic acid from trifluoromethanesulfonic acid-containing wastewater |
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| EP0614699A1 (en) * | 1993-03-12 | 1994-09-14 | Haldor Topsoe A/S | Process for the recovery of spent fluorinated sulphonic acid catalyst in an alkylation process |
| EP0671213A1 (en) * | 1994-03-10 | 1995-09-13 | Haldor Topsoe A/S | Process for the recovery of alkylation catalyst |
| US5472921A (en) * | 1993-04-20 | 1995-12-05 | Haldor Topsoe A/S | Process for the recovery of spent fluorinated sulphonic acid catalyst in an alkylation process |
| CN1128248A (en) * | 1994-06-13 | 1996-08-07 | 赫多特普索化工设备公司 | Process for the recovery of a strong acid from an aqueous solution |
| CN1280037A (en) * | 1999-06-30 | 2001-01-17 | 赫多特普索化工设备公司 | Method for recovering strong acid from aqueous solution |
| CN101747240A (en) * | 2008-12-11 | 2010-06-23 | 张家港市国泰华荣化工新材料有限公司 | Method for preparing trifluoromethyl sulfonic acid CF3SO3H by electrochemical fluorination gas-phase product of methanesulfonyl fluoride CH3SO2F |
-
2013
- 2013-01-10 CN CN201310008824.9A patent/CN103073458B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0614699A1 (en) * | 1993-03-12 | 1994-09-14 | Haldor Topsoe A/S | Process for the recovery of spent fluorinated sulphonic acid catalyst in an alkylation process |
| US5472921A (en) * | 1993-04-20 | 1995-12-05 | Haldor Topsoe A/S | Process for the recovery of spent fluorinated sulphonic acid catalyst in an alkylation process |
| EP0671213A1 (en) * | 1994-03-10 | 1995-09-13 | Haldor Topsoe A/S | Process for the recovery of alkylation catalyst |
| CN1128248A (en) * | 1994-06-13 | 1996-08-07 | 赫多特普索化工设备公司 | Process for the recovery of a strong acid from an aqueous solution |
| CN1280037A (en) * | 1999-06-30 | 2001-01-17 | 赫多特普索化工设备公司 | Method for recovering strong acid from aqueous solution |
| CN101747240A (en) * | 2008-12-11 | 2010-06-23 | 张家港市国泰华荣化工新材料有限公司 | Method for preparing trifluoromethyl sulfonic acid CF3SO3H by electrochemical fluorination gas-phase product of methanesulfonyl fluoride CH3SO2F |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725283A (en) * | 2015-04-14 | 2015-06-24 | 江西国化实业有限公司 | Trifluoromethanesulfonic acid preparation method |
| CN105218409A (en) * | 2015-10-21 | 2016-01-06 | 安徽工业大学 | A kind of method reclaiming trifluoromethanesulfonic acid from trifluoromethanesulfonic acid amine salt waste water |
| CN105237441A (en) * | 2015-11-02 | 2016-01-13 | 中国石油天然气股份有限公司 | Device and method for recovering methane sulfonic acid |
| CN111116431A (en) * | 2019-12-31 | 2020-05-08 | 中船重工（邯郸）派瑞特种气体有限公司 | Device and method for recovering trifluoromethanesulfonic acid from trifluoromethanesulfonic acid-containing wastewater |
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Denomination of invention: Method for recovering trifluoromethanesulfonic acid in wastewater Effective date of registration: 20200107 Granted publication date: 20141119 Pledgee: Bank of China, Limited by Share Ltd, Guangzhou, Panyu branch Pledgor: Guangzhou Wisdom Bio-Technology Co., Ltd. Registration number: Y2020440000002 |
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Address after: 510555 No.78 Fenghuang SANHENG Road, Zhongxin Guangzhou Knowledge City, Huangpu District, Guangzhou, Guangdong Province Patentee after: GUANGZHOU WISDOM BIO-TECHNOLOGY Co.,Ltd. Address before: Flowers bow Tang Ju Wei Hui tiger head East Town Huadu District, Guangdong city of Guangzhou province 510890 Patentee before: GUANGZHOU WISDOM BIO-TECHNOLOGY Co.,Ltd. |
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Date of cancellation: 20210310 Granted publication date: 20141119 Pledgee: Bank of China Limited by Share Ltd. Guangzhou Panyu branch Pledgor: GUANGZHOU WISDOM BIO-TECHNOLOGY Co.,Ltd. Registration number: Y2020440000002 |