CN103073458A - Method for recovering trifluoromethanesulfonic acid in wastewater - Google Patents

Method for recovering trifluoromethanesulfonic acid in wastewater Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
trifluoromethanesulfonic acid
waste water
inorganic salt
add
alkali
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.)
Granted
Application number
CN2013100088249A
Other languages
Chinese (zh)
Other versions
CN103073458B (en
Inventor
吴世林
张贵东
邸维龙
史志君
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GUANGZHOU WISDOM BIO-TECHNOLOGY Co Ltd
Original Assignee
GUANGZHOU WISDOM BIO-TECHNOLOGY Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by GUANGZHOU WISDOM BIO-TECHNOLOGY Co Ltd filed Critical GUANGZHOU WISDOM BIO-TECHNOLOGY Co Ltd
Priority to CN201310008824.9A priority Critical patent/CN103073458B/en
Publication of CN103073458A publication Critical patent/CN103073458A/en
Application granted granted Critical
Publication of CN103073458B publication Critical patent/CN103073458B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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

A kind of method that reclaims trifluoromethanesulfonic acid in the waste water
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.
CN201310008824.9A 2013-01-10 2013-01-10 Method for recovering trifluoromethanesulfonic acid in wastewater Active CN103073458B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310008824.9A CN103073458B (en) 2013-01-10 2013-01-10 Method for recovering trifluoromethanesulfonic acid in wastewater

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310008824.9A CN103073458B (en) 2013-01-10 2013-01-10 Method for recovering trifluoromethanesulfonic acid in wastewater

Publications (2)

Publication Number Publication Date
CN103073458A true CN103073458A (en) 2013-05-01
CN103073458B CN103073458B (en) 2014-11-19

Family

ID=48150180

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310008824.9A Active CN103073458B (en) 2013-01-10 2013-01-10 Method for recovering trifluoromethanesulfonic acid in wastewater

Country Status (1)

Country Link
CN (1) CN103073458B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
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

Citations (6)

* Cited by examiner, † Cited by third party
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
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

Patent Citations (6)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
CN103073458B (en) 2014-11-19

Similar Documents

Publication Publication Date Title
CN103073458B (en) Method for recovering trifluoromethanesulfonic acid in wastewater
CN108658785B (en) The separation method of difficult separation system containing triethylamine
CN104892666B (en) A kind of preparation method of high-purity phosphoric acid tributyl
CN103333052B (en) Between a kind of separation industries to mixture cresol to prepare the method for pure p-cresol and pure meta-cresol
CN102107889A (en) Method for treating ammonium chloride in sodium bicarbonate mother solution at normal temperature
CN102826956B (en) Method for separating methyl propionate-methanol-water system by integration of salt-effect extraction and rectification
CN103641780B (en) A kind of method of purifying isoquinoline from coal tar crude product
CN103467378A (en) Process method for producing caprolactam by using recovered waste chinlon silks and leftovers and application of phosphoric acid serving as catalyst in process method
CN103896307A (en) Method for refining coke oven gas desulfurization waste liquid salt extraction product ammonium sulfate again
CN204400883U (en) Pentamethylene diamine purification system
CN101270063A (en) Method for preparing high purity solid cyanoacetic acid
CN104725285A (en) Method for removing sulfate from sodium isopropyl benzenesulfonate
CN102992288B (en) Method for preparing high pure phosphoric acid from calcium hydrogen phosphate
CN103803622A (en) Method using aluminum chloride hexahydrate dehydration to prepare anhydrous aluminum chloride
CN104447529A (en) Method for extracting and purifying 3,6-matrigon
CN103450008A (en) Method for recovering mandelic acid from waste water
CN103694137A (en) Production method of 2-fluorine-4-nitrobenzonitrile
CN103183610B (en) A kind of method from low-purity methyl acetate high-purity methyl acetate
CN102757367A (en) Splitting process of racemic ethyl benzene sulfonic acid
CN106966901A (en) A kind of preparation method of 6- hydroxyls -8- Lipase Catalyzed Resolution of Racemic Ethyl
CN106187987B (en) A kind of environmentally friendly method of purification of acrylic -1,3- sultones
CN103540749A (en) Method for recovering rhodium from rhodium octoate organic waste liquor
CN115924880B (en) Method for preparing sodium hexafluorophosphate by aqueous phase method and application thereof
CN102659670A (en) Method for preparing light stabilizer 4-p-toluenesulfonamide-2,2,6,6-tetramentylniperidine
CN102603605B (en) Preparation method of (S)-4-hydroxy-2-oxo-1-pyrrolidineacetamide

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
PE01 Entry into force of the registration of the contract for pledge of patent right
PE01 Entry into force of the registration of the contract for pledge of patent right

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

CP02 Change in the address of a patent holder
CP02 Change in the address of a patent holder

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.

PC01 Cancellation of the registration of the contract for pledge of patent right
PC01 Cancellation of the registration of the contract for pledge of patent right

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