CN106145161A - A kind of method being produced high-purity sodium fluoride by fluoro organic liquid waste - Google Patents
A kind of method being produced high-purity sodium fluoride by fluoro organic liquid waste Download PDFInfo
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- CN106145161A CN106145161A CN201510201650.7A CN201510201650A CN106145161A CN 106145161 A CN106145161 A CN 106145161A CN 201510201650 A CN201510201650 A CN 201510201650A CN 106145161 A CN106145161 A CN 106145161A
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- fluorine
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Abstract
The invention belongs to technical field of organic chemistry, the invention provides a kind of by fluorine-containing organic liquid waste produce high-purity sodium fluoride method: with Ishikawa reagent produce fluorine-containing organic liquid waste as raw material, in the presence of a catalyst with alkali reaction, obtain high-purity sodium fluoride by-product denitrifier additive with the high yield of 90%.The features such as the present invention has easy and simple to handle, and production cost is low, and product purity is high, and reaction condition is gentle, are suitable for industrialized production.
Description
Technical field
The invention belongs to technical field of organic chemistry, be a kind of method being produced high-purity sodium fluoride by organic fluoride waste liquid.
Background technology
Ishikawa reagent is N, N-diethyl-1,1,1,2,3,3-hexafluoro propylamine and N, N-diethyl-(E)-five fluorine third
Enamine mixture (Nippon Kagaku Kaishi, 1985,11,2161-8), is the industrial fluoro reagent commonly used,
The consumption of domestic 1 year, more than 2000 tons, produces substantial amounts of organic fluorine waste liquid, at common microorganism after fluoro
Reason method is difficult to effectively process.High-purity sodium fluoride is widely used additive in industry, the most universal production
Method is to prepare fluohydric acid gas with fluorite and sodium sulfate reaction, prepares after absorbing by liquid caustic soda, and the method uses the fluorine of severe toxicity
Change hydrogen, high to equipment requirements and have high potential risk.The use Ishikawa reagent fluoro of our exploitation
The organic fluorine waste liquid of rear generation is the method for the high-purity sodium fluoride of raw material production, the most effectively solves Organic fluoride and gives up
The process difficult problem of liquid and produce the process of high-purity sodium fluoride and evaded the fluohydric acid gas of hypertoxic danger.The method has
Residue organic mixture after machine fluorine waste liquid defluorinate is also used as the additive of denitrifier, it is achieved thereby that organic
The whole of fluorine waste liquid effectively utilize.
Summary of the invention
The method that present invention aim at being synthesized high-purity sodium fluoride by fluorine-containing organic liquid waste, in the presence of a catalyst, fluorine
Fluorine-containing organic liquid waste and alkali reaction prepare high-purity sodium fluoride, simple to operate, low cost.
Concrete preparation condition is:
(1) reaction uses water, C1-C10Alcohols, C1-C10Amide-type, C1-C10Ethers or C1-C10Alkyl carboxylic
Acids single solvent or the mixed solvent of these solvents；
(2) alkali that reaction uses is alkali metal hydroxide, alkoxyl or aralkoxy metal base；
(3) response time is 1～1000 hour；
(4) reaction temperature is-100～500 DEG C；
(5) reaction uses all kinds of magnesium salts, silicate, transition-metal oxide, chloride or the height of these materials
Molecule loaded article is catalyst；
(6) fluorine-containing organic liquid waste with the weight ratio of alkali is: 1: 0.1～1000；
(7) fluorine-containing organic liquid waste with the w/v of solvent is: 1: 0.1～1000；
(8) fluorine-containing organic liquid waste is 1: 0.0000001～100 with the weight ratio of catalyst.
Wherein, reaction dissolvent is water, methanol, ethanol, ether, methyl tertiary butyl ether(MTBE), Isosorbide-5-Nitrae-dioxane, N, N-
Dimethylformamide or glacial acetic acid, or be single solvent, or be mixed solvent.
Wherein, reaction use alkali be sodium hydroxide, potassium hydroxide, calcium hydroxide, Feldalat NM, potassium tert-butoxide,
Feldalat KM, Sodium ethylate or potassium ethoxide.
Wherein, the response time is 1～36 hour, and reaction temperature is-50～150 DEG C.
Wherein, fluorine-containing organic liquid waste is 1: 0.1～20 with the weight ratio of alkali.
Wherein, fluorine-containing organic liquid waste is 1: 3～15 with the w/v of solvent.
Wherein, the catalyst used by reaction is the macromolecule loading thing of magnesium salt, silicate or these materials.
Wherein, fluorine-containing organic liquid waste is 1: 0.0001～10 with the weight ratio of catalyst.
A kind of method being produced high-purity sodium fluoride by fluorine-containing organic liquid waste of the present invention is in the presence of a catalyst, contains
Fluorine organic liquid waste and alkali reaction obtain high-purity sodium fluoride, and yield can reach 85%～90%.The method has operation
Simplicity, the features such as production cost is low, and product purity is high, and reaction condition is gentle, it is suitable for industrialized production.
The preferably reaction condition of the present invention is:
Fluorine-containing organic liquid waste reacts with sodium hydroxide in the presence of magnesium salt catalyst and obtains high-purity sodium fluoride.
Reaction uses methyl tertiary butyl ether(MTBE) to be solvent.
Reaction temperature controls at 0～140 DEG C.
Response time controlled at 5～24 hours.
Reaction uses magnesium salt to be catalyst.
Fluorine-containing organic liquid waste and sodium hydroxide weight ratio are 1: 0.6～1.
Fluorine-containing organic liquid waste is 1: 0.00001～0.0001 with catalyst weight ratio.
Fluorine-containing organic liquid waste is 1: 3～5 with the w/v of solvent.
Detailed description of the invention
Specifically describe this patent below by embodiment further, but be not limited to these embodiments.
Example 1: the preparation of high-purity sodium fluoride.
By fluorine-containing organic liquid waste 1kg, sodium hydroxide 600g, magnesium salt 0.1g insert in reaction bulb, stir at 120 DEG C
Mix reaction 12 hours, be cooled to room temperature, add MTBE (methyl tertiary butyl ether(MTBE)), centrifugation, obtain 652g high
Pure sodium fluoride, filtrate Distillation recovery MTBE applies mechanically, and residue is by-product denitrifier additive 610g.
Example 2: the preparation of high-purity sodium fluoride.
By fluorine-containing organic liquid waste 1kg, sodium hydroxide 700g, magnesium salt 0.1g insert in reaction bulb, stir at 130 DEG C
Mix reaction 12 hours, be cooled to room temperature, add MTBE (methyl tertiary butyl ether(MTBE)), centrifugation, obtain 560g high
Pure sodium fluoride, filtrate Distillation recovery MTBE applies mechanically, and residue is by-product denitrifier additive 590g.
Example 3: the preparation of high-purity sodium fluoride
By fluorine-containing organic liquid waste 1kg, sodium hydroxide 600g, magnesium salt 0.01g insert in reaction bulb, at 140 DEG C
Stirring reaction 12 hours, is cooled to room temperature, adds MTBE (methyl tertiary butyl ether(MTBE)), centrifugation, obtains 300g
High-purity sodium fluoride, filtrate Distillation recovery MTBE applies mechanically, and residue is by-product denitrifier additive 635g.
Claims (9)
1. the method that a fluorine-containing organic liquid waste produces high-purity sodium fluoride, it is characterised in that in the presence of a catalyst,
Fluorine-containing organic liquid waste and alkali reaction prepare high-purity sodium fluoride.
Reaction uses water, C1-C10Alcohols, C1-C10Amide-type, C1-C10Ethers or C1-C10Alkyl carboxylic acid class
Single solvent or the mixed solvent of these solvents；
(1) alkali that reaction uses is alkali metal hydroxide, alkoxyl or aralkoxy metal base；
(2) catalysts is all kinds of magnesium salt, silicate, transition-metal oxide, chloride or these materials
Macromolecule loading thing
(3) response time is 1-1000 hour；
(4) reaction temperature is-100-500 DEG C；
(5) fluorine-containing waste liquid with the weight ratio of alkali is: 1: 0.1-1000；
(6) fluorine-containing waste liquid with the w/v of solvent is: 1: 0.1-1000；
(7) fluorine-containing waste liquid is 1: 0.0000001-100 with the weight ratio of catalyst.
2. the method that the fluorine-containing organic liquid waste as described in right 1 produces high-purity sodium fluoride, it is characterised in that react molten
Agent be water, methanol, ethanol, ether, methyl tertiary butyl ether(MTBE), Isosorbide-5-Nitrae-dioxane, DMF or
Glacial acetic acid, or be single solvent, or be mixed solvent.
3. the method that the fluorine-containing organic liquid waste as described in right 1 produces high-purity sodium fluoride, it is characterised in that reaction makes
Alkali be sodium hydroxide, potassium hydroxide, calcium hydroxide, Feldalat NM, Feldalat KM, potassium tert-butoxide, Sodium ethylate
Or potassium ethoxide.
4. the method that the fluorine-containing organic liquid waste as described in right 1 produces high-purity sodium fluoride, it is characterised in that solve reaction
Time is 1-36 hour, and reaction temperature is-50-150 DEG C.
5. the method that the fluorine-containing organic liquid waste as described in right 1 produces high-purity sodium fluoride, it is characterised in that fluorine-containing have
Machine waste liquid is 1: 0.1-20 with the weight ratio of alkali.
6. the method that the fluorine-containing organic liquid waste as described in right 1 produces high-purity sodium fluoride, it is characterised in that fluorine-containing have
Machine waste liquid is 1: 3-15 with the w/v of solvent.
7. the method that the fluorine-containing organic liquid waste as described in right 1 produces high-purity sodium fluoride, it is characterised in that reaction institute
The macromolecule loading thing that catalyst is magnesium salt, silicate or these materials.
8. the method that the fluorine-containing organic liquid waste as described in right 1 produces high-purity sodium fluoride, it is characterised in that in reaction
Fluorine-containing organic liquid waste is 1: 0.0001-10 with the mol ratio of catalyst.
9. the method that the fluorine-containing organic liquid waste as described in right 1 produces high-purity sodium fluoride, it is characterised in that fluorine-containing have
Machine waste liquid derives from the waste liquid that Ishikawa reagent fluoro-reaction produces.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510201650.7A CN106145161A (en) | 2015-04-27 | 2015-04-27 | A kind of method being produced high-purity sodium fluoride by fluoro organic liquid waste |
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| CN201510201650.7A CN106145161A (en) | 2015-04-27 | 2015-04-27 | A kind of method being produced high-purity sodium fluoride by fluoro organic liquid waste |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793198A (en) * | 2018-08-20 | 2018-11-13 | 福建永晶科技股份有限公司 | A kind of preparation method and its preparation system of potassium hydrogen fluoride |
| CN114956123A (en) * | 2021-02-26 | 2022-08-30 | 江苏扬农化工股份有限公司 | Clean production method for recycling sodium fluoride from residual liquid of chlorotrifluoro chrysanthemic acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3660019A (en) * | 1969-02-01 | 1972-05-02 | Universal Oil Prod Co | Process for purifying industrial waste gases containing fluorine values |
| US4213951A (en) * | 1978-10-23 | 1980-07-22 | Occidental Research Corporation | Recovery of hydrofluoric acid from fluosilicic acid with high pH hydrolysis |
| CN101376507A (en) * | 2007-08-30 | 2009-03-04 | 多氟多化工股份有限公司 | Method for producing sodium fluoride |
| CN102020292A (en) * | 2010-10-25 | 2011-04-20 | 宁波诺尔丽化学科技有限公司 | Method for preparing sodium fluoride from organic fluoridation waste material |
-
2015
- 2015-04-27 CN CN201510201650.7A patent/CN106145161A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3660019A (en) * | 1969-02-01 | 1972-05-02 | Universal Oil Prod Co | Process for purifying industrial waste gases containing fluorine values |
| US4213951A (en) * | 1978-10-23 | 1980-07-22 | Occidental Research Corporation | Recovery of hydrofluoric acid from fluosilicic acid with high pH hydrolysis |
| CN101376507A (en) * | 2007-08-30 | 2009-03-04 | 多氟多化工股份有限公司 | Method for producing sodium fluoride |
| CN102020292A (en) * | 2010-10-25 | 2011-04-20 | 宁波诺尔丽化学科技有限公司 | Method for preparing sodium fluoride from organic fluoridation waste material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793198A (en) * | 2018-08-20 | 2018-11-13 | 福建永晶科技股份有限公司 | A kind of preparation method and its preparation system of potassium hydrogen fluoride |
| CN114956123A (en) * | 2021-02-26 | 2022-08-30 | 江苏扬农化工股份有限公司 | Clean production method for recycling sodium fluoride from residual liquid of chlorotrifluoro chrysanthemic acid |
| CN114956123B (en) * | 2021-02-26 | 2024-05-07 | 江苏扬农化工股份有限公司 | Clean production method for recovering sodium fluoride from residual trifluoro-permethric acid |
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