CN108114507A - A kind of method for extracting fluorine ion in the solution - Google Patents
A kind of method for extracting fluorine ion in the solution Download PDFInfo
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- CN108114507A CN108114507A CN201810041245.7A CN201810041245A CN108114507A CN 108114507 A CN108114507 A CN 108114507A CN 201810041245 A CN201810041245 A CN 201810041245A CN 108114507 A CN108114507 A CN 108114507A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D11/04—Solvent extraction of solutions which are liquid
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Abstract
The invention discloses a kind of methods for extracting fluorine ion in the solution, include the following steps：1）Solution to be extracted is pre-processed, obtains A product；2）Phosphoric acid ester organic solvent and siliceous organic solvent are mixed, obtain B product；3）B product are added in A product and carry out extraction reaction.The present invention is not only good with separation and Extraction effect, and selectivity is good, the characteristics of more cleaning and is cheap, also has the characteristics that extraction efficiency is high, easy to operate.
Description
Technical field
The present invention relates to a kind of method for extracting fluorine ion, particularly a kind of method for extracting fluorine ion in the solution.
Background technology
Fluorine is a kind of halogen family chemical element, its chemical symbol is F, its atomic number is 9, molecular formula F2.Due to original
Son is small and forced down 9 mutually exclusive electronics, so it is that activity is most strong in elemental nonmetal element, be strong oxidizer,
Fluorization agent, there is extremely strong corrosivity, and corrosivity and toxicity are most strong in severe toxicity or halogen family.But its compound stabilization and use
Extensively, such as corrosion resistant " kings of plastics " polytetrafluoroethylene (PTFE).Fluorine is indispensable trace element in human body, but due to fluorine and its
The all toxic and stronger corrosivity of some compounds, once so excess intake will carry out grievous injury to human body health care belt.Fluorine
And its compound can inhibit the catalysis of enzyme, moreover it is possible to decline serum calcium, inhibit clotting mechanism.Excessive sucking fluorination
Hydrogen or sodium fluoride for oral administration, can cause acute poisoning, cause to cough, generate heat, cough, feeling of chest tightness, blood pressure decline etc., make heart
It is suppressed with breathing, even results in death.Fluorine content is more than 1 mg/L in drinking water, and resident can be made to suffer from the disease of " den tal fluorosis "
Shape, concentration reach 4-6mg/L, and children will all suffer from " den tal fluorosis ", and higher Funing tablet can also cause serious rickets.Fluorine
And its soluble compound etc. also has high risks to plant.For case above, China provides fluorine content limit value in surface water
For 10 mg/L.So just seem especially urgent and important to the purified treatment of fluorine ion in fluorine-containing solution.
The precipitation method, concentration method, vaporizing extract process, crystallisation, solvent extraction fluorine removal are mainly used to fluorine-containing solution at present, and it is preceding
Four kinds of methods are China master methods to be applied.Solvent extraction is more foreign study and application, and China is at present to it
Research and application are less.China is mostly to precipitate fluorine using silica or sodium carbonate etc. to fluorine-containing solution treatment, and separation carries
Take effect poor.China studies deep removal, purified treatment of fluorine in fluorine-containing solution etc. opposite with external advanced country at present
Than still there is sizable gap.In order to efficiently extract the fluorine in fluorine-containing solution, it is necessary to seek cost-efficiently separation skill
Art.Solvent-extracted highly selective, simplicity, spatter property, cheapness etc. are the sharpest edges of its separation and Extraction.
The raw material of the fluorine-containing solution of solvent extraction is generally fluoride waste or leaching of ores liquid etc., and wherein fluorine content generally exists
100mg/L-2000mg/L.Due to, also containing zwitterions ingredients such as chlorine, rare earth, magnesium, aluminium, iron, being added in fluorine-containing solution
Precipitating reagent because selectivity it is low can be subject to very big interference, so as to purification and defluorination it is very unfavorable.Due to extractant it is highly selective,
High unicity, so solvent extraction is particularly suitable for extracting the fluorine ion in fluorine-containing solution.
Tsinghua University of China professor Wang Junmin carries fluorine to solvent method and has done correlative study, she makees by comparing amine and phenols
For the effect of extractant, finally point out that amine extracted effect is best.But it is extracted through level-one, extraction yield also only has 30% or so, through three
Grade extraction has just reached 80% or so.In summary, amine and phenols cannot efficiently extract fluorine ion as extractant, so
Multitple extraction is needed in extraction, operating process is added, improves production cost.Therefore, answered for fluorine-containing component in solution
Miscellaneous, the features such as acid-base property is different, it is necessary to the technique for exploring the high efficiency extraction fluorine in fluorine-containing solution system.
The content of the invention
It is an object of the present invention to provide a kind of methods for extracting fluorine ion in the solution.The present invention not only has separation
Extraction effect is good, and selectivity is good, the characteristics of more cleaning and is cheap, also has the characteristics that extraction efficiency is high, easy to operate.
Technical scheme：A kind of method for extracting fluorine ion in the solution, includes the following steps：
1）Solution to be extracted is pre-processed, obtains A product；
2）Phosphoric acid ester organic solvent and siliceous organic solvent are mixed, obtain B product；
3）B product are added in A product and carry out extraction reaction.
The foregoing method for extracting fluorine ion in the solution, the step 1）In, solution pretreatment to be extracted is will be fluorine-containing
The solution of ion carries out clarifying treatment, takes the clear liquid after clarification as extraction solution.
The foregoing method for extracting fluorine ion in the solution, the step 2）In, phosphoric acid ester organic solvent is phosphoric acid one
One or more in ester, di-phosphate ester or phosphotriester；Siliceous organic solvent is one in esters of silicon acis or polysiloxane
Kind is a variety of.
The foregoing method for extracting fluorine ion in the solution, the step 2）In, the body of phosphoric acid ester organic solvent in B product
Fraction is 10%-80%, and surplus is siliceous organic solvent.
The foregoing method for extracting fluorine ion in the solution, the volume fraction of phosphoric acid ester organic solvent is in the B product
40%-60%, surplus are siliceous organic solvent.
The foregoing method for extracting fluorine ion in the solution, the step 3）In, B product add in A product after need to standing 5-15min
In carry out extraction reaction.
The foregoing method for extracting fluorine ion in the solution, the B product, which need to stand to add in A product after 8-12min, to be extracted
Negating should.
The foregoing method for extracting fluorine ion in the solution, the step 3）In, the volume ratio of B product and A product is 1:1-20,
Extraction time is 10-60min.
The volume ratio of the foregoing method for extracting fluorine ion in the solution, the B product and A product is 1:10, extraction time is
30-40min。
The foregoing method for extracting fluorine ion in the solution, the temperature of the extraction reaction is 40-100 DEG C.
Beneficial effects of the present invention：
1st, the present invention selects after phosphoric acid ester and siliceous organic solvent mixed processing and extracts fluorine ion as extractant, it is in fluorine
Content is relatively low, in the case that fluoride solution acidity is higher, still has very high extraction yield, and is not required to adjust pH value, separation
Extraction effect is good, and selectivity is good, cleans and greatly reduces production cost.
2nd, during present invention extraction, in the case that other extraction conditions are constant, oil-water ratio is reduced to 1:When 20, still have higher
Extraction yield, and then reduce the usage amount of organic phase, cleannes are further improved, reduce cost.
3rd, the phosphoric acid ester and siliceous organic solvent that the present invention selects are as extractant and common extractant amine, phenols etc.
Compare, extraction efficiency greatly improves, and phosphoric acid ester and siliceous organic solvent cost are lower.
4th, the present invention need not add diluent, further using phosphoric acid ester and siliceous organic solvent as extractant
The usage amount of oil phase is reduced, therefore further saves cost and becomes more economical efficient.
5th, phosphoric acid ester used in the present invention and siliceous organic solvent extraction system have higher extraction yield, extraction effect
Fruit is good, quick, good selective.Integrated artistic is simple, and fluoride ion recovery is high, and consumption of raw materials is few.It realizes to fluorine
Effectively recycling, the purified treatment to be directed to fluorine-containing solution field provide a clear and definite, novel, efficient approach.
Specific embodiment
With reference to embodiment, the present invention is further illustrated, but is not intended as the foundation limited the present invention.
The embodiment of the present invention
Embodiment 1
The mixture of sulfuric phosphoric acid leachate of phosphorus ore is extracted, phosphorus ore leachate fluorinion concentration is 0.364g/L.Mono-organic phosphate in oil phase
Volume fraction is 30%, and polysiloxane volume fraction is 70%, and extractant is used as after 5min is stood after oil phase mixing.It will extraction
It according to volume ratio is 1 to take agent and phosphorus ore leachate:5 mixing, quickly stirring extracts 60min at 50 DEG C, according to GB/T 1872-
1995 Fluoride ion selective electrode methods measure extraction efficiency and reach 94.6%.
Embodiment 2
Fluoride waste is extracted, fluorinion concentration is 0.384g/L in the fluoride waste.Mono-organic phosphate volume fraction is in oil phase
50%, polysiloxane volume fraction is 50%, and extractant is used as after 6min is stood after oil phase mixing.By extractant and phosphorus ore
Leachate is 1 according to volume ratio:5 mixing, quickly stirring extracts 40min at 40 DEG C, according to GB/T 1872-1995 fluorine ions
Selection electrode method measures extraction efficiency and reaches 97.8%.
Embodiment 3
The mixture of sulfuric phosphoric acid leachate of phosphorus ore is extracted, phosphorus ore leachate fluorinion concentration is 0.364g/L.Mono-organic phosphate in oil phase
Volume fraction is 60%, and polysiloxane volume fraction is 40%, and extractant is used as after 7min is stood after oil phase mixing.It will extraction
It according to volume ratio is 1 to take agent and phosphorus ore leachate:5 mixing, quickly stirring extracts 60min at 60 DEG C, according to GB/T 1872-
1995 Fluoride ion selective electrode methods measure extraction efficiency and reach 98.0%.
Embodiment 4
Fluoride waste is extracted, fluorinion concentration is 0.384g/L in the fluoride waste.Di-phosphate ester volume fraction is in oil phase
70%, polysiloxane volume fraction is 30%, and extractant is used as after 8min is stood after oil phase mixing.By extractant and phosphorus ore
Leachate is 1 according to volume ratio:5 mixing, quickly stirring extracts 40min at 70 DEG C, according to GB/T 1872-1995 fluorine ions
Selection electrode method measures extraction efficiency and reaches 98.2%.
Embodiment 5
The mixture of sulfuric phosphoric acid leachate of phosphorus ore is extracted, phosphorus ore leachate fluorinion concentration is 0.364g/L.Di-phosphate ester in oil phase
Volume fraction is 80%, and esters of silicon acis volume fraction is 20%, and extractant is used as after 9min is stood after oil phase mixing.By extractant with
Phosphorus ore leachate is 1 according to volume ratio:5 mixing, quickly stirring extracts 60min at 80 DEG C, according to GB/T 1872-1995 fluorine
Ion selective electrode method measures extraction efficiency and reaches 97.9%.
Embodiment 6
The mixture of sulfuric phosphoric acid leachate of phosphorus ore is extracted, phosphorus ore leachate fluorinion concentration is 0.364g/L.Di-phosphate ester in oil phase
Volume fraction is 90%, and esters of silicon acis volume fraction is 10%, and extractant is used as after 10min is stood after oil phase mixing.By extractant
With phosphorus ore leachate according to volume ratio be 1:5 mixing, quickly stirring extracts 60min at 90 DEG C, according to GB/T 1872-1995
Fluoride ion selective electrode method measures extraction efficiency and reaches 97.6%.
Embodiment 7
The mixture of sulfuric phosphoric acid leachate of phosphorus ore is extracted, phosphorus ore leachate fluorinion concentration is 0.364g/L.Phosphotriester in oil phase
Volume fraction is 70%, and esters of silicon acis volume fraction is 30%, and extractant is used as after 11min is stood after oil phase mixing.By extractant
With phosphorus ore leachate according to volume ratio be 1:6 mixing, quickly stirring extracts 60min at 100 DEG C, according to GB/T1872-1995
Fluoride ion selective electrode method measures extraction efficiency and reaches 93.5%.
Embodiment 8
The mixture of sulfuric phosphoric acid leachate of phosphorus ore is extracted, phosphorus ore leachate fluorinion concentration is 0.364g/L.Phosphotriester in oil phase
Volume fraction is 70%, and esters of silicon acis volume fraction is 30%, and extractant is used as after 12min is stood after oil phase mixing.By extractant
With phosphorus ore leachate according to volume ratio be 1:7 mixing, quickly stirring extracts 60min at 55 DEG C, according to GB/T 1872-1995
Fluoride ion selective electrode method measures extraction efficiency and reaches 93.2%.
Embodiment 9
The mixture of sulfuric phosphoric acid leachate of phosphorus ore is extracted, phosphorus ore leachate fluorinion concentration is 0.364g/L.Phosphotriester in oil phase
Volume fraction is 70%, and esters of silicon acis volume fraction is 30%, and extractant is used as after 13min is stood after oil phase mixing.By extractant
With phosphorus ore leachate according to volume ratio be 1:10 mixing, quickly stirring extracts 60min at 65 DEG C, according to GB/T 1872-1995
Fluoride ion selective electrode method measures extraction efficiency and reaches 91.6%.
Embodiment 10
The mixture of sulfuric phosphoric acid leachate of phosphorus ore is extracted, phosphorus ore leachate fluorinion concentration is 0.364g/L.Phosphotriester in oil phase
Volume fraction is 70%, and esters of silicon acis volume fraction is 30%, and extractant is used as after 15min is stood after oil phase mixing.By extractant
With phosphorus ore leachate according to volume ratio be 1:20 mixing, quickly stirring extracts 60min at 85 DEG C, according to GB/T 1872-1995
Fluoride ion selective electrode method measures extraction efficiency and reaches 85.3%.
The fluorine ion of the low concentration of association is extracted from phosphorus ore leachate using the present invention, can substantially reduce and be produced into
This, reduces the waste of resource, has great application prospect.
Claims (10)
- A kind of 1. method for extracting fluorine ion in the solution, which is characterized in that include the following steps：1）Solution to be extracted is pre-processed, obtains A product；2）Phosphoric acid ester organic solvent and siliceous organic solvent are mixed, obtain B product；3）B product are added in A product and carry out extraction reaction.
- 2. the method according to claim 1 for extracting fluorine ion in the solution, it is characterised in that：The step 1）In, it treats Extraction solution pretreatment is that the solution of fluoride ion is carried out clarifying treatment, takes the clear liquid after clarification as extraction solution.
- 3. the method according to claim 1 for extracting fluorine ion in the solution, it is characterised in that：The step 2）In, phosphorus Esters of gallic acid organic solvent is the one or more in mono-organic phosphate, di-phosphate ester or phosphotriester；Siliceous organic solvent is silicic acid One or more in ester or polysiloxane.
- 4. the method according to claim 1 for extracting fluorine ion in the solution, it is characterised in that：The step 2）In, B product The volume fraction of middle phosphoric acid ester organic solvent is 10%-80%, and surplus is siliceous organic solvent.
- 5. the method according to claim 4 for extracting fluorine ion in the solution, it is characterised in that：Phosphate in the B product The volume fraction of class organic solvent is 40%-60%, and surplus is siliceous organic solvent.
- 6. the method according to claim 1 for extracting fluorine ion in the solution, it is characterised in that：The step 3）In, B product It need to stand to add in A product after 5-15min and carry out extraction reaction.
- 7. the method according to claim 6 for extracting fluorine ion in the solution, it is characterised in that：The B product need to stand 8- It is added in after 12min in A product and carries out extraction reaction.
- 8. the method according to claim 1 for extracting fluorine ion in the solution, it is characterised in that：The step 3）In, B product Volume ratio with A product is 1:1-20, extraction time 10-60min.
- 9. the method according to claim 8 for extracting fluorine ion in the solution, it is characterised in that：The body of the B product and A product Product is than being 1:10, extraction time 30-40min.
- 10. the method according to claim 1 for extracting fluorine ion in the solution, it is characterised in that：The extraction reaction Temperature is 40-100 DEG C.
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| CN201810041245.7A CN108114507B (en) | 2018-01-16 | 2018-01-16 | Method for extracting fluorine ions in solution |
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| CN201810041245.7A CN108114507B (en) | 2018-01-16 | 2018-01-16 | Method for extracting fluorine ions in solution |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3972982A (en) * | 1975-03-03 | 1976-08-03 | Monsanto Company | Process for removing fluorine compounds from phosphoric acid |
| JPS5319993A (en) * | 1976-08-10 | 1978-02-23 | Mitsui Toatsu Chem Inc | Production of phosphoric acid of low fluorine content |
| CN101164890A (en) * | 2007-10-16 | 2008-04-23 | 中国科学院长春应用化学研究所 | Method for separating cerium, reclaiming fluorin and preparing cerous fluoride ultra-micro powder for mixed extraction system |
| CN102021336A (en) * | 2010-12-12 | 2011-04-20 | 昆明理工大学 | Method for separating zinc, fluorine and chlorine from fluorine- and chlorine-containing zinc sulfate solution |
-
2018
- 2018-01-16 CN CN201810041245.7A patent/CN108114507B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3972982A (en) * | 1975-03-03 | 1976-08-03 | Monsanto Company | Process for removing fluorine compounds from phosphoric acid |
| JPS5319993A (en) * | 1976-08-10 | 1978-02-23 | Mitsui Toatsu Chem Inc | Production of phosphoric acid of low fluorine content |
| CN101164890A (en) * | 2007-10-16 | 2008-04-23 | 中国科学院长春应用化学研究所 | Method for separating cerium, reclaiming fluorin and preparing cerous fluoride ultra-micro powder for mixed extraction system |
| CN102021336A (en) * | 2010-12-12 | 2011-04-20 | 昆明理工大学 | Method for separating zinc, fluorine and chlorine from fluorine- and chlorine-containing zinc sulfate solution |
Non-Patent Citations (1)
| Title |
|---|
| 李春丽: "磷酸三丁酯和二异丙醚溶剂萃取体系脱除湿法磷酸中氟的研究", 《化学世界》 * |
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