CN103073458B - Method for recovering trifluoromethanesulfonic acid in wastewater - Google Patents
Method for recovering trifluoromethanesulfonic acid in wastewater Download PDFInfo
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- CN103073458B CN103073458B CN201310008824.9A CN201310008824A CN103073458B CN 103073458 B CN103073458 B CN 103073458B CN 201310008824 A CN201310008824 A CN 201310008824A CN 103073458 B CN103073458 B CN 103073458B
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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 waste water, be specifically related to a kind of from the method containing reclaiming trifluoromethanesulfonic acid trifluoromethanesulfonic acid waste water.
Background technology
Trifluoromethanesulfonic acid is the strong organic acid of knowing at present, there is 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 industry such as medicine, chemical industry, 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 one reagent newly developed, and its price is higher, and trifluoromethanesulfonic acid is all made discharge of wastewater after having reacted at present, if do not add recycling, can cause product cost higher, and fluorine wherein also can welding.US Patent No. 5603812 is by the molecular distillation together with trifluoromethanesulfonic acid front three amine salt of trifluoromethanesulfonic acid monohydrate, can only obtain a small amount of trifluoromethanesulfonic acid, also further do not tell the trifluoromethanesulfonic acid recovery method in trifluoromethanesulfonic acid front three amine salt, European patent EP 0671213A1 provides that from organic alkali salt of the trifluoromethanesulfonic acids such as trifluoromethanesulfonic acid front three amine salt, to reclaim the concrete grammar of trifluoromethanesulfonic acid as follows:
CF
3SO
3HN(CH
3)
3 + H
2SO
4 → CF
3SO
3H + [ N(CH
3)
3]
2 H
2SO
4，
But it is very large in the production of mass-producing, to find that the method vitriol oil takes off the material viscosity such as the sulfuric acid front three amine salt of organic bases generation, has a strong impact on the recovery of trifluoromethanesulfonic acid.
Trifluoromethanesulfonic acid participates in organic synthesis or as after the reaction such as catalyzer, all make discharge of wastewater, and in these waste water, often contain a large amount of inorganic salts and some high boiling point organic compound classes, the particularly inorganic salt of some Halogens and some not clear organism classes, a kind of study safe, highly purified recovery trifluoromethanesulfonic acid method is the current problem that needs solution.
Summary of the invention
The object of the present invention is to provide a kind of method that reclaims trifluoromethanesulfonic acid in waste water.
The technical solution used in the present invention is:
A method that reclaims trifluoromethanesulfonic acid in waste water, comprises the following steps:
1) add mineral alkali reaction to containing in the waste water of trifluoromethanesulfonic acid, then evaporating water, obtains solid matter, and the trifluoromethanesulfonic acid in described waste water exists with the form of free state or organic alkali salt;
2) in solid matter, add alcohol reflux, filter, cooling, leave standstill and separate out trifluoromethanesulfonic acid inorganic salt, filter, dry, obtain trifluoromethanesulfonic acid inorganic salt;
3) in trifluoromethanesulfonic acid inorganic salt, add concentrated sulfuric acid dissolution, then reclaim under reduced pressure trifluoromethanesulfonic acid.
Preferably, step 2) be cooled to 0～5 DEG C.
Preferably, step 2) return time is 1～2h.
Preferably, the trifluoromethanesulfonic acid equimolar amount in step 1) adds mineral alkali and waste water.
Preferably, mineral alkali is inorganic strong alkali.
Preferably, mineral alkali is at least one in potassium hydroxide, 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 containing in the waste water of trifluoromethanesulfonic acid, particularly Halogen inorganic salt, if directly add the vitriol oil in the solid matter of step 1) gained 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, avoided the danger of blast by adding alcohol reflux.
The invention has the beneficial effects as follows:
The inventive method reclaim trifluoromethanesulfonic acid purity high, productive rate is high, recovery method is simple and convenient, is applicable to apply in large-scale industry; The inventive method safety, has avoided not clear organism in waste water to produce the danger of exploding because reacting under strong acid; The present invention has removed Halogen inorganic salt, has avoided 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 costs as much as possible and reducing environmental pollution.
Embodiment
A method that reclaims trifluoromethanesulfonic acid in waste water, comprises the following steps:
1) if the trifluoromethanesulfonic acid in waste water is free state, 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 cooling trifluoromethanesulfonic acid inorganic salt of separating out, allow high boiling point organic compound stay in ethanol, after trifluoromethanesulfonic acid inorganic salt are dried, then add vitriol oil underpressure distillation recovery trifluoromethanesulfonic acid;
2) if the trifluoromethanesulfonic acid in waste water is to exist with the form of organic alkali salt, 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, then the cooling trifluoromethanesulfonic acid inorganic salt of separating out, allow high boiling point organic compound stay in ethanol, after trifluoromethanesulfonic acid inorganic salt are dried, add again vitriol oil underpressure distillation and reclaim trifluoromethanesulfonic acid.
Preferably, step 2) be cooled to 0～5 DEG C.
Preferably, step 2) return time is 1～2h.
Preferably, the trifluoromethanesulfonic acid equimolar amount in step 1) adds mineral alkali and waste water.
Preferably, mineral alkali is inorganic strong alkali.
Preferably, mineral alkali is at least one in potassium hydroxide, 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.
Below in conjunction with specific embodiment, the present invention is further illustrated, but be not limited to this.
embodiment 1
A method that reclaims trifluoromethanesulfonic acid in waste water, comprises the following steps:
1) get 1000 g containing the waste water of trifluoromethanesulfonic acid front three amine salt in there-necked flask, in waste water, contain trifluoromethanesulfonic acid front three amine salt 20.9 g(0.1mol), add 4 g sodium hydroxide (0.1 mol), stirring reaction 10 minutes, then be that 80 DEG C, vacuum pressure are evaporate to dryness moisture content under 250 handkerchiefs in temperature, obtain 35 g solid matters;
2) in 35 g solid matters, add 175 g dehydrated alcohol backflow 2h, filter out insolubles, be then cooled to 5 DEG C, leave standstill 3 h, filter, dry, obtain 15.1 g trifluoromethanesulfonic acid sodium;
3) in 15.1 g trifluoromethanesulfonic acid sodium, add 8.6g(0.088 mol) vitriol oil, after dissolving, be warmed up to 100 DEG C, vacuum pressure 500 handkerchiefs reclaim, and obtain anhydrous trifluoromethanesulfonic acid 10.5g, content 98%.
embodiment 2
A method that reclaims trifluoromethanesulfonic acid in waste water, comprises the following steps:
1) get 1000 g and contain trifluoromethanesulfonic acid waste water in there-necked flask, in waste water, contain trifluoromethanesulfonic acid 15g(0.1 mol), add 5.6g potassium hydroxide (0.1 mol), stirring reaction 10 minutes, then be that 80 DEG C, vacuum pressure are evaporate to dryness moisture content under 250 handkerchiefs in temperature, obtain 40g solid matter;
2) in 40g solid matter, add 400g dehydrated alcohol backflow 1h, filtered while hot is fallen insolubles, is then cooled to 0 DEG C, leaves standstill 3h, filters, dry, obtains 13.2g trifluoromethanesulfonic acid potassium;
3) in 13.2g trifluoromethanesulfonic acid potassium, add 6.88g(0.07 mol) vitriol oil, after dissolving, be warmed up to 100 DEG C, vacuum pressure 500 handkerchiefs reclaim, and obtain anhydrous trifluoromethanesulfonic acid 9.3g, content 98.3%.
embodiment 3
A method that reclaims trifluoromethanesulfonic acid in waste water, comprises the following steps:
1) get 1000 g containing the waste water of trifluoromethanesulfonic acid front three amine salt in there-necked flask, in waste water, contain trifluoromethanesulfonic acid front three amine salt 20.9 g(0.1mol), add 5.6g potassium hydroxide (0.1 mol), stirring reaction 10 minutes, then be that 80 DEG C, vacuum pressure are evaporate to dryness moisture content under 250 handkerchiefs in temperature, obtain 42g solid matter;
2) to the dehydrated alcohol backflow 1.5h that adds 7 times of weight in 42g solid matter, filter out insolubles, be then cooled to 4 DEG C, leave standstill 3 h, filter, dry, obtain 13g trifluoromethanesulfonic acid potassium;
In 13g trifluoromethanesulfonic acid potassium, add 6.78g(0.069mol) vitriol oil, after dissolving, be warmed up to 100 DEG C, vacuum pressure 500 handkerchiefs reclaim, and obtain anhydrous trifluoromethanesulfonic acid 9g, content 98%.
Claims (7)
1. a method that reclaims trifluoromethanesulfonic acid in waste water, comprises the following steps:
1) add mineral alkali reaction to containing in the waste water of trifluoromethanesulfonic acid, then evaporating water, obtains solid matter, and the trifluoromethanesulfonic acid in described waste water exists with the form of free state or organic alkali salt;
2) in solid matter, add alcohol reflux, filter, cooling, leave standstill and separate out trifluoromethanesulfonic acid inorganic salt, filter, dry, obtain trifluoromethanesulfonic acid inorganic salt;
3) in trifluoromethanesulfonic acid inorganic salt, add concentrated sulfuric acid dissolution, then reclaim under reduced pressure trifluoromethanesulfonic acid;
Wherein, the trifluoromethanesulfonic acid equimolar amount in step 1) adds mineral alkali and waste water; Mineral alkali is at least one in potassium hydroxide, sodium hydroxide.
2. method according to claim 1, is characterized in that: step 2) be cooled to 0～5 DEG C.
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: step 1) adopts evaporated under reduced pressure moisture.
5. method according to claim 1, is characterized in that: step 2) consumption of ethanol is 5～10 times of solid matter weight.
6. method according to claim 5, is characterized in that: described ethanol is dehydrated alcohol.
7. method according to claim 1, is characterized in that: step 3) trifluoromethanesulfonic acid inorganic salt and vitriol oil equimolar amount.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725283B (en) * | 2015-04-14 | 2016-09-28 | 江西国化实业有限公司 | A kind of preparation method of trifluoromethanesulfonic acid |
| 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 |
| CN105237441B (en) * | 2015-11-02 | 2017-06-13 | 中国石油天然气股份有限公司 | A kind of apparatus and method for reclaiming Loprazolam |
| CN111116431B (en) * | 2019-12-31 | 2022-08-05 | 中船(邯郸)派瑞特种气体股份有限公司 | Device and method for recovering trifluoromethanesulfonic acid from trifluoromethanesulfonic acid-containing wastewater |
Citations (6)
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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 |
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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 |
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