CN101948378A - Process for removing fluorine from trifluoroacetic acid - Google Patents
Process for removing fluorine from trifluoroacetic acid Download PDFInfo
- Publication number
- CN101948378A CN101948378A CN2010102757662A CN201010275766A CN101948378A CN 101948378 A CN101948378 A CN 101948378A CN 2010102757662 A CN2010102757662 A CN 2010102757662A CN 201010275766 A CN201010275766 A CN 201010275766A CN 101948378 A CN101948378 A CN 101948378A
- Authority
- CN
- China
- Prior art keywords
- trifluoroacetic acid
- fluorine
- activated alumina
- add
- still
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a process for removing fluorine from trifluoroacetic acid. The process comprises the following steps of: adding fluorine-containing trifluoroacetic acid and excessive active aluminum oxide into a reaction kettle, wherein complex reaction is performed on fluorine-containing impurities in the trifluoroacetic acid and the active aluminum oxide; and AlF2+ complex ions produced by the complex reaction are adsorbed on the surface of the active aluminum oxide; continuously distilling the trifluoroacetic acid, from which the fluorine is removed, out of the reaction kettle, condensing and collecting the trifluoroacetic acid; continuously adding both the fluorine-containing trifluoroacetic acid and the active aluminum oxide into the reaction kettle at the same time to keep liquid level in the reaction kettle constant; and pumping out the active aluminum oxide, to which the AlF2+ complex ions are adsorbed, from the bottom of the reaction kettle, removing the active aluminum oxide by filtration of a filter, and circulating filtrate into the reaction kettle. The process of the invention has the advantages of short process flow, easy operation, high fluorine removal efficiency, cheap and readily available fluorine removing agent and low fluorine removal cost.
Description
Technical field
The present invention relates to a kind of defluorinating process, relate in particular to a kind of trifluoroacetic acid defluorinating process.
Technical background
Trifluoroacetic acid is the main raw material that many fluorine-containing fine chemical products are introduced trifluoromethyl group, and in addition, it is also huge at field application potentials such as material, solvent, catalyzer.
The trifluoroacetyl chloride that is made by trifluorobichloroethane or trifluoro monochlorethane and trifluorobichloroethane mixture photochemical oxidation contains a certain amount of fluorion in the trifluoroacetic acid that hydrolysis obtains, the trifluoroacetic acid product of this fluoride ion sell or through middle dealer resell disperse to sell the user after, just might cause potential safety hazard and accidents such as equipment corrosion, leakage because of the user's using method that has is incorrect, the user who has utilizes back discharging fluoride waste not up to standard, cause surrounding enviroment fluoride pollution etc., thereby cause the safety and environmental protection problem.
Therefore, fluorine-containing trifluoroacetic acid defluorination problem just seems particularly urgent, content of fluoride ion≤100ppm in trifluoroacetic acid when general requirement is dispatched from the factory, fluorion in the trifluoroacetic acid exists with the hydrofluoric acid form, the method of rectifying commonly used is removed, and promptly collects front-end volatiles and remove when the rectification and purification trifluoroacetic acid, and the shortcoming that this method exists is the content of fluoride ion≤100ppm that will guarantee in the trifluoroacetic acid, the front-end volatiles of collecting will certainly be taken a lot of trifluoroacetic acids out of, cause the trifluoroacetic acid waste.
Summary of the invention
The purpose of this invention is to provide a kind of trifluoroacetic acid defluorinating process.
For achieving the above object, the technical solution used in the present invention is:
This trifluoroacetic acid defluorinating process is: add fluorine-containing trifluoroacetic acid and excessive activated alumina in reactor, wherein, fluorine-containing impurity and activated alumina in the trifluoroacetic acid carry out complex reaction, the AlF that described complex reaction generates
2+Complexing ion is adsorbed on remaining activated alumina surface; Remove that trifluoroacetic acid continuous still battery behind the fluorine goes out reactor and condensation is collected, in reactor, add fluorine-containing trifluoroacetic acid and activated alumina continuously simultaneously so that in the reactor liquid level keep constant, adsorbed AlF
2+The activated alumina of complexing ion is extracted out after strainer removes by filter at the bottom of by the still of reactor, and filtrate cycle is got back in the reactor.
Further, to add fashionable mass percent concentration to reactor be 80～99% to fluorine-containing trifluoroacetic acid of the present invention.
Further, the present invention by mass, described activated alumina add-on is 0.30%～1.20% of a fluorine-containing trifluoroacetic acid add-on.
Further, the present invention by mass, described activated alumina add-on is 0.60%～0.90% of a fluorine-containing trifluoroacetic acid add-on.
Further, the present invention is 80 ℃～105 ℃ to the temperature that described trifluoroacetic acid carries out continuous still battery.
Further, the residence time of trifluoroacetic acid of the present invention in reactor is 1hr～3hr.
The invention has the beneficial effects as follows: technical process of the present invention is short, easy handling, and the fluorine removing rate height, defluorinating agent is cheap and easy to get, and the defluorination cost is low; Can remove the most fluorions in the fluorine-containing trifluoroacetic acid, make the content of fluoride ion≤100ppm in the trifluoroacetic acid.And trifluoroacetic acid is the main raw material that many fluorine-containing fine chemical products are introduced trifluoromethyl group, and in addition, it is also huge at field application potentials such as material, solvent, catalyzer, so the present invention has broad application prospects.
Embodiment
In theory, six grades of complex reactions can take place in activated alumina and fluorion under nearly neutrallty condition, and the complexing ion reaction equation is as follows:
Al
3++F
-→AlF
2++AlF
2 ++AlF
3+AlF
4 -+AlF
5 2-+AlF
6 3-
The complexing ion stability constant is followed successively by: log β
1=6.13, log β
2=11.15, log β
3=15.00, log β
4=17.75, log β
5=19.37, log β
6=19.84.
Defluorinating process of the present invention is to carry out in trifluoroacetic acid, and pH value of solution is very low, and activated alumina is as defluorinating agent add-on contained content of fluoride ion, i.e. Al in the trifluoroacetic acid in the trifluoroacetic acid
3+Amount is much larger than F
-Amount is at low pH and Al
3+Can think under the excessive condition that the one-level complex reaction mainly takes place the aluminium fluorine is that defluorination mechanism reaction equation of the present invention is:
Al
3++F
-→AlF
2+
The present invention adopts activated alumina to make defluorinating agent, has high specific surface area, so that the AlF that the absorption as much as possible of unit mass defluorinating agent generates
2+Aluminium fluorine complexing ion.
Be reflected in the still formula stirred reactor and carry out, add a certain amount of activated alumina and fluorine-containing trifluoroacetic acid in the still continuously, adding speed goes out the decision of reactor speed by the trifluoroacetic acid continuous still battery, to keep level stability in the reactor.The temperature that the trifluoroacetic acid continuous still battery goes out is controlled at 80 ℃～105 ℃, promptly near the boiling point of different concns trifluoroacetic acid solution, activated alumina defluorinating agent add-on has obvious promoter action to fluorine removing rate, but too high defluorinating agent add-on can cause and stir the load increasing in the reactor, and the defluorination cost rises.The residence time of fluorine-containing trifluoroacetic acid in reactor also is an important factor in order of fluorine removing rate, and it is very big that the speed of reaction between the aluminium fluorine is influenced by the pH value, is 4.3 o'clock at pH, and reaction rate constant is 5.25 * 10
-2s
-1, when pH reduced to 3.44, reaction rate constant dropped to 8.45 * 10 rapidly
-4s
-1, therefore reaction must guarantee certain residence time under low pH condition, the speed that goes out reactor by the continuous still battery of control trifluoroacetic acid is regulated the residence time, so that the aluminium fluorion fully reacts.
Trifluoroacetic acid behind the defluorination is gone out by continuous still battery in the reactor and collects through condenser condenses.Adsorbed AlF
2+The activated alumina of aluminium fluorine complexing ion is extracted out at the bottom of to a certain degree afterwards by still in the still inner accumulated, removes by filter through filter, and filtrate cycle is got back in the still.
The present invention will be described in further detail in conjunction with following embodiment.
In following examples, the content of fluoride ion before and after the defluorination in the trifluoroacetic acid is measured by PF-1 type fluoride ion selective electrode.
Embodiment 1
In the 500L enamel still, add activated alumina 1.2kg, the adding mass percent concentration is 99% fluorine-containing trifluoroacetic acid solution 400kg, fluoride ion 990ppm wherein, start stirring, activated alumina is dispersed in the trifluoroacetic acid solution, fluorion in the fluorine-containing trifluoroacetic acid and activated alumina carry out complex reaction, the AlF that complexing generates
2+Aluminium fluorine complexing ion is adsorbed on remaining activated alumina surface; After complex reaction reaches 2 hours, the trifluoroacetic acid solution of heating in the enamel still, the control heating power goes out trifluoroacetic acid solution with the 200kg/hr continuous still battery about 80 ℃, and condensation is collected, and obtains trifluoroacetic acid solution behind the defluorination; In still, add fluorine-containing trifluoroacetic acid solution with 200kg/hr continuously simultaneously, constant with liquid level in the maintenance still, therefore the residence time of fluorine-containing trifluoroacetic acid solution in still is approximately 2hr, in still, add activated alumina with 0.6kg/hr, therefore by mass, the activated alumina add-on is 0.30% of a fluorine-containing trifluoroacetic acid add-on.When the still internal adsorption AlF
2+The activated alumina of aluminium fluorine complexing ion is accumulated to a certain amount of back and extracts out through filter at the bottom of the still and remove by filter, and filtrate cycle is got back in the enamel still.Trifluoroacetic acid solution behind the defluorination of condensation collection is analyzed, and wherein content of fluoride ion is 90ppm after measured, and fluorine removing rate is 90.91%.
Embodiment 2
In the 500L enamel still, add activated alumina 2.4kg, the adding mass percent concentration is 99% fluorine-containing trifluoroacetic acid solution 400kg, fluoride ion 990ppm wherein, start stirring, activated alumina is dispersed in the trifluoroacetic acid solution, fluorion in the fluorine-containing trifluoroacetic acid and activated alumina carry out complex reaction, the AlF that complexing generates
2+Aluminium fluorine complexing ion is adsorbed on remaining activated alumina surface; After complex reaction reaches 2 hours, the trifluoroacetic acid solution of heating in the enamel still, the control heating power goes out trifluoroacetic acid solution with the 200kg/hr continuous still battery about 80 ℃, and condensation is collected, and obtains trifluoroacetic acid solution behind the defluorination; In still, add fluorine-containing trifluoroacetic acid solution with 200kg/hr continuously simultaneously, constant with liquid level in the maintenance still, therefore the residence time of fluorine-containing trifluoroacetic acid solution in still is approximately 2hr, in still, add activated alumina with 1.2kg/hr, therefore by mass, the activated alumina add-on is 0.60% of a fluorine-containing trifluoroacetic acid add-on.When the still internal adsorption AlF
2+The activated alumina of aluminium fluorine complexing ion is accumulated to a certain amount of back and extracts out through filter at the bottom of the still and remove by filter, and filtrate cycle is got back in the enamel still.Trifluoroacetic acid solution behind the defluorination of condensation collection is analyzed, and wherein content of fluoride ion is 75ppm after measured, and fluorine removing rate is 92.42%.
Embodiment 3
In the 500L enamel still, add activated alumina 3.6kg, the adding mass percent concentration is 99% fluorine-containing trifluoroacetic acid solution 400kg, fluoride ion 990ppm wherein, start stirring, activated alumina is dispersed in the trifluoroacetic acid solution, fluorion in the fluorine-containing trifluoroacetic acid and activated alumina carry out complex reaction, the AlF that complexing generates
2+Aluminium fluorine complexing ion is adsorbed on remaining activated alumina surface; After complex reaction reaches 2 hours, the trifluoroacetic acid solution of heating in the enamel still, the control heating power goes out trifluoroacetic acid solution with the 200kg/hr continuous still battery about 80 ℃, and condensation is collected, and obtains trifluoroacetic acid solution behind the defluorination; In still, add fluorine-containing trifluoroacetic acid solution with 200kg/hr continuously simultaneously, constant with liquid level in the maintenance still, therefore the residence time of fluorine-containing trifluoroacetic acid solution in still is approximately 2hr, in still, add activated alumina with 1.8kg/hr, therefore by mass, the activated alumina add-on is 0.90% of a fluorine-containing trifluoroacetic acid add-on.。When the still internal adsorption AlF
2+The activated alumina of aluminium fluorine complexing ion is accumulated to a certain amount of back and extracts out through filter at the bottom of the still and remove by filter, and filtrate cycle is got back in the enamel still.Trifluoroacetic acid solution behind the defluorination of condensation collection is analyzed, and wherein content of fluoride ion is 65ppm after measured, and fluorine removing rate is 93.43%.
Embodiment 4
In the 500L enamel still, add activated alumina 4.8kg, the adding mass percent concentration is 99% fluorine-containing trifluoroacetic acid solution 400kg, fluoride ion 990ppm wherein, start stirring, activated alumina is dispersed in the trifluoroacetic acid solution, fluorion in the fluorine-containing trifluoroacetic acid and activated alumina carry out complex reaction, the AlF that complexing generates
2+Aluminium fluorine complexing ion is adsorbed on remaining activated alumina surface; After complex reaction reaches 2 hours, the trifluoroacetic acid solution of heating in the enamel still, the control heating power goes out trifluoroacetic acid solution with the 200kg/hr continuous still battery about 80 ℃, and condensation is collected, and obtains trifluoroacetic acid solution behind the defluorination; In still, add fluorine-containing trifluoroacetic acid solution with 200kg/hr continuously simultaneously, constant with liquid level in the maintenance still, therefore the residence time of fluorine-containing trifluoroacetic acid solution in still is approximately 2hr, in still, add activated alumina with 2.4kg/hr, therefore by mass, the activated alumina add-on is 1.20% of a fluorine-containing trifluoroacetic acid add-on.When the still internal adsorption AlF
2+The activated alumina of aluminium fluorine complexing ion is accumulated to a certain amount of back and extracts out through filter at the bottom of the still and remove by filter, and filtrate cycle is got back in the enamel still.Trifluoroacetic acid solution behind the defluorination of condensation collection is analyzed, and wherein content of fluoride ion is 62ppm after measured, and fluorine removing rate is 93.74%.
Embodiment 5
In the 500L enamel still, add activated alumina 3.0kg, the adding mass percent concentration is 90% fluorine-containing trifluoroacetic acid solution 400kg, fluoride ion 900ppm wherein, start stirring, activated alumina is dispersed in the trifluoroacetic acid solution, fluorion in the fluorine-containing trifluoroacetic acid and activated alumina carry out complex reaction, the AlF that complexing generates
2+Aluminium fluorine complexing ion is adsorbed on remaining activated alumina surface; After complex reaction reaches 2 hours, the trifluoroacetic acid solution of heating in the enamel still, the control heating power goes out trifluoroacetic acid solution with the 200kg/hr continuous still battery about 95 ℃, and condensation is collected, and obtains trifluoroacetic acid solution behind the defluorination; In still, add fluorine-containing trifluoroacetic acid solution with 200kg/hr continuously simultaneously, constant with liquid level in the maintenance still, therefore the residence time of fluorine-containing trifluoroacetic acid solution in still is approximately 2hr, in still, add activated alumina with 1.5kg/hr, therefore by mass, the activated alumina add-on is 0.75% of a fluorine-containing trifluoroacetic acid add-on.When the still internal adsorption AlF
2+The activated alumina of aluminium fluorine complexing ion is accumulated to a certain amount of back and extracts out through filter at the bottom of the still and remove by filter, and filtrate cycle is got back in the enamel still.Trifluoroacetic acid solution behind the defluorination of condensation collection is analyzed, and wherein content of fluoride ion is 68ppm after measured, and fluorine removing rate is 92.44%.
Embodiment 6
In the 500L enamel still, add activated alumina 3.0kg, the adding mass percent concentration is 90% fluorine-containing trifluoroacetic acid solution 400kg, fluoride ion 900ppm wherein, start stirring, activated alumina is dispersed in the trifluoroacetic acid solution, fluorion in the fluorine-containing trifluoroacetic acid and activated alumina carry out complex reaction, the AlF that complexing generates
2+Aluminium fluorine complexing ion is adsorbed on remaining activated alumina surface; After complex reaction reaches 3 hours, the trifluoroacetic acid solution of heating in the enamel still, the control heating power goes out trifluoroacetic acid solution with the 133kg/hr continuous still battery about 95 ℃, and condensation is collected, and obtains trifluoroacetic acid solution behind the defluorination; In still, add fluorine-containing trifluoroacetic acid solution with 133kg/hr continuously simultaneously, constant with liquid level in the maintenance still, therefore the residence time of fluorine-containing trifluoroacetic acid solution in still is approximately 3hr, in still, add activated alumina with 1.0kg/hr, therefore by mass, the activated alumina add-on is 0.75% of a fluorine-containing trifluoroacetic acid add-on.When the still internal adsorption AlF
2+The activated alumina of aluminium fluorine complexing ion is accumulated to a certain amount of back and extracts out through filter at the bottom of the still and remove by filter, and filtrate cycle is got back in the enamel still.Trifluoroacetic acid solution behind the defluorination of condensation collection is analyzed, and wherein content of fluoride ion is 62ppm after measured, and fluorine removing rate is 93.11%.
Embodiment 7
In the 500L enamel still, add activated alumina 3.0kg, the adding mass percent concentration is 80% fluorine-containing trifluoroacetic acid solution 400kg, fluoride ion 800ppm wherein, start stirring, activated alumina is dispersed in the trifluoroacetic acid solution, fluorion in the fluorine-containing trifluoroacetic acid and activated alumina carry out complex reaction, the AlF that complexing generates
2+Aluminium fluorine complexing ion is adsorbed on remaining activated alumina surface; After complex reaction reaches 2 hours, the trifluoroacetic acid solution of heating in the enamel still, the control heating power goes out trifluoroacetic acid solution with the 200kg/hr continuous still battery about 105 ℃, and condensation is collected, and obtains trifluoroacetic acid solution behind the defluorination; In still, add fluorine-containing trifluoroacetic acid solution with 200kg/hr continuously simultaneously, constant with liquid level in the maintenance still, therefore the residence time of fluorine-containing trifluoroacetic acid solution in still is approximately 2hr, in still, add activated alumina with 1.5kg/hr, therefore by mass, the activated alumina add-on is 0.75% of a fluorine-containing trifluoroacetic acid add-on.When the still internal adsorption AlF
2+The activated alumina of aluminium fluorine complexing ion is accumulated to a certain amount of back and extracts out through filter at the bottom of the still and remove by filter, and filtrate cycle is got back in the enamel still.Trifluoroacetic acid solution behind the defluorination of condensation collection is analyzed, and wherein content of fluoride ion is 66ppm after measured, and fluorine removing rate is 91.75%.
Embodiment 8
In the 500L enamel still, add activated alumina 3.0kg, the adding mass percent concentration is 80% fluorine-containing trifluoroacetic acid solution 400kg, fluoride ion 800ppm wherein, start stirring, activated alumina is dispersed in the trifluoroacetic acid solution, fluorion in the fluorine-containing trifluoroacetic acid and activated alumina carry out complex reaction, the AlF that complexing generates
2+Aluminium fluorine complexing ion is adsorbed on remaining activated alumina surface; After complex reaction reaches 1 hour, the trifluoroacetic acid solution of heating in the enamel still, the control heating power goes out trifluoroacetic acid solution with the 400kg/hr continuous still battery about 105 ℃, and condensation is collected, and obtains trifluoroacetic acid solution behind the defluorination; In still, add fluorine-containing trifluoroacetic acid solution with 400kg/hr continuously simultaneously, constant with liquid level in the maintenance still, therefore the residence time of fluorine-containing trifluoroacetic acid solution in still is approximately 1hr, in still, add activated alumina with 3.0kg/hr, therefore by mass, the activated alumina add-on is 0.75% of a fluorine-containing trifluoroacetic acid add-on.When the still internal adsorption AlF
2+The activated alumina of aluminium fluorine complexing ion is accumulated to a certain amount of back and extracts out through filter at the bottom of the still and remove by filter, and filtrate cycle is got back in the enamel still.Trifluoroacetic acid solution is analyzed behind the defluorination that condensation is collected, and wherein content of fluoride ion is 71ppm after measured, and fluorine removing rate is 91.13%.
Claims (6)
1. trifluoroacetic acid defluorinating process is characterized in that: add fluorine-containing trifluoroacetic acid and excessive activated alumina in reactor, wherein, fluorine-containing impurity and activated alumina in the trifluoroacetic acid carry out complex reaction, the AlF of described complex reaction generation
2+Complexing ion is adsorbed on remaining activated alumina surface; Remove that trifluoroacetic acid continuous still battery behind the fluorine goes out reactor and condensation is collected, in reactor, add fluorine-containing trifluoroacetic acid and activated alumina continuously simultaneously so that in the reactor liquid level keep constant, adsorbed AlF
2+The activated alumina of complexing ion is extracted out after strainer removes by filter at the bottom of by the still of reactor, and filtrate cycle is got back in the reactor.
2. a kind of trifluoroacetic acid defluorinating process according to claim 1 is characterized in that: it is 80～99% that described fluorine-containing trifluoroacetic acid adds fashionable mass percent concentration to reactor.
3. a kind of trifluoroacetic acid defluorinating process according to claim 1 is characterized in that: by mass, described activated alumina add-on is 0.30%～1.20% of a fluorine-containing trifluoroacetic acid add-on.
4. a kind of trifluoroacetic acid defluorinating process according to claim 3 is characterized in that: by mass, described activated alumina add-on is 0.60%～0.90% of a fluorine-containing trifluoroacetic acid add-on.
5. a kind of trifluoroacetic acid defluorinating process according to claim 1 is characterized in that: the temperature of described trifluoroacetic acid being carried out continuous still battery is 80 ℃～105 ℃.
6. a kind of trifluoroacetic acid defluorinating process according to claim 1 is characterized in that: the residence time of described trifluoroacetic acid in reactor is 1hr～3hr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102757662A CN101948378A (en) | 2010-09-07 | 2010-09-07 | Process for removing fluorine from trifluoroacetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102757662A CN101948378A (en) | 2010-09-07 | 2010-09-07 | Process for removing fluorine from trifluoroacetic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101948378A true CN101948378A (en) | 2011-01-19 |
Family
ID=43452025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102757662A Pending CN101948378A (en) | 2010-09-07 | 2010-09-07 | Process for removing fluorine from trifluoroacetic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101948378A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951130A (en) * | 2014-03-14 | 2014-07-30 | 浙江大学 | Treatment method of fluoride-containing wastewater |
| CN107778165A (en) * | 2016-08-30 | 2018-03-09 | 天津市科密欧化学试剂有限公司 | A kind of purification process of chromatographically pure trifluoroacetic acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0163975A1 (en) * | 1984-05-15 | 1985-12-11 | Asahi Glass Company Ltd. | Process for producing trifluoroacetic acid and trifluoroacetyl chloride |
| CN1363510A (en) * | 2002-01-07 | 2002-08-14 | 浙江衢化氟化学有限公司 | Process for defluorinating anhydrous hydrogen chloride |
| CN1421404A (en) * | 2001-11-27 | 2003-06-04 | 中国科学院生态环境研究中心 | Drinking water defluorinating process and equipment |
| CN1954906A (en) * | 2005-10-28 | 2007-05-02 | 中国科学院生态环境研究中心 | Compound metal oxide de-fluorine sorbent |
-
2010
- 2010-09-07 CN CN2010102757662A patent/CN101948378A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0163975A1 (en) * | 1984-05-15 | 1985-12-11 | Asahi Glass Company Ltd. | Process for producing trifluoroacetic acid and trifluoroacetyl chloride |
| CN1421404A (en) * | 2001-11-27 | 2003-06-04 | 中国科学院生态环境研究中心 | Drinking water defluorinating process and equipment |
| CN1363510A (en) * | 2002-01-07 | 2002-08-14 | 浙江衢化氟化学有限公司 | Process for defluorinating anhydrous hydrogen chloride |
| CN1954906A (en) * | 2005-10-28 | 2007-05-02 | 中国科学院生态环境研究中心 | Compound metal oxide de-fluorine sorbent |
Non-Patent Citations (2)
| Title |
|---|
| 尤来方 等: "三氟醋酸的应用和制备", 《有机氟工业》, no. 1, 15 February 1996 (1996-02-15), pages 6 - 9 * |
| 张在利 等: "三氟乙酸的制备及应用", 《化工新型材料》, vol. 32, no. 9, 25 September 2004 (2004-09-25), pages 44 - 46 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951130A (en) * | 2014-03-14 | 2014-07-30 | 浙江大学 | Treatment method of fluoride-containing wastewater |
| CN103951130B (en) * | 2014-03-14 | 2016-01-27 | 浙江大学 | A kind for the treatment of process of fluoride waste |
| CN107778165A (en) * | 2016-08-30 | 2018-03-09 | 天津市科密欧化学试剂有限公司 | A kind of purification process of chromatographically pure trifluoroacetic acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20160308261A1 (en) | Zero lead pollution process for recycling used lead acid batteries | |
| CN1017165B (en) | Process for production or recovery of acids from metalliferous solutims of such acid | |
| JP5392576B2 (en) | Method for recovering silicon, titanium and fluorine | |
| CN105439356A (en) | Method and device for synchronously recycling sulfuric acid and fluorine and chlorine from polluted acid | |
| CN104760998B (en) | A kind of tungsten recovery method of tungstenic solution based on discarded SCR denitration | |
| CN104383801B (en) | Method and system for treating electronic scrap smoke | |
| CN106277043B (en) | The method that separating metal oxide is extracted from catalyst for denitrating flue gas | |
| CN1904097A (en) | Technology of preparing fluorine less niobium oxide by oxalic acid system extraction method | |
| CN101948378A (en) | Process for removing fluorine from trifluoroacetic acid | |
| CN111170320B (en) | Device and method for recycling waste acid solution for polycrystalline silicon texturing | |
| CA1214382A (en) | Method for regenerating pickling acids | |
| CN109626632A (en) | A kind of method of leaded waste acid recycling | |
| CN115207506A (en) | Method for recovering electrolyte of waste lithium ion battery | |
| CN103614560A (en) | Method of recycling scandium in titanium white waste acid | |
| CN110494420B (en) | Method for purifying caprolactam from a solution of crude caprolactam without organic solvent extraction | |
| CN102828036A (en) | Method of preparing potassium metavanadate solution from vanadium slag | |
| CN117699744A (en) | Simple and safe preparation method of analytically pure sulfuric acid | |
| CN110453097B (en) | Method for distilling and extracting germanium from fluorine-containing germanium concentrate | |
| CN108118152A (en) | A kind of method of fluorine ion in efficient removal manganese sulfate solution | |
| CN112830875A (en) | Method and system for recycling acid wastewater and rectification residual liquid in trichloro-acetic chloride production process | |
| CN109536202A (en) | A kind of preprocess method of cold-rolling oil Preparation of Biodiesel from Waste Oils raw material | |
| CN115010091A (en) | Impurity removal method for hydrogen fluoride, purification method for hydrogen fluoride and purification device for hydrogen fluoride | |
| CN115745274A (en) | Method for treating waste acid and wastewater from lead smelting | |
| CN108975402A (en) | A method of preparing bulky grain high purity vanadic anhydride | |
| CN106148709B (en) | Nickel recovery and treatment method in chemical nickel plating waste solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110119 |