CN108118152A - A kind of method of fluorine ion in efficient removal manganese sulfate solution - Google Patents
A kind of method of fluorine ion in efficient removal manganese sulfate solution Download PDFInfo
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- CN108118152A CN108118152A CN201711443180.0A CN201711443180A CN108118152A CN 108118152 A CN108118152 A CN 108118152A CN 201711443180 A CN201711443180 A CN 201711443180A CN 108118152 A CN108118152 A CN 108118152A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention provides a kind of methods of fluorine ion in efficient removal manganese sulfate solution, this method is to add in a certain amount of pending manganese sulfate solution in consersion unit, measure the content of fluorine ion in the solution, under the conditions of temperature is 30 50 DEG C, pH value is 26, add in the solid cerium hydroxide of certain content of fluoride ion ratio, with 150 350 revs/min of rotating speed it is small to material stirring 8 12 when after stop stirring, stand 12 18 it is small when, material is transferred in filter plant and is filtered operation, filtrate is the qualified manganese sulfate solution after fluorine removal, and filter cake presses solid-liquid mass ratio 1:When 16 ratio addition reverse osmosis water agitator treating 0.5 is small, the fluorine-containing cerium hydroxide being obtained by filtration enters step for regeneration.The method of the present invention, can be by a large amount of remaining fluoride ion removings in manganese sulfate solution system, and content of fluoride can be down to below 100ppm in solution after processing, and defluorinating agent cerium hydroxide can be recycled after regeneration, greatly save production cost.
Description
Technical field
The present invention relates to a kind of removals of fluorine ion impurity in a kind of minimizing technology of impurity more particularly to metal salt solution
Method, the method for specifically relating to fluorine ion in a kind of efficient removal manganese sulfate solution.
Background technology
Manganese sulfate solution is subject to extensive as most common manganese salt solution in battery industry and electrolytic manganese metal industry
Using.At present, the manganese sulfate in China mainly by manganese ore by after sulfuric acid to leach again through cleaning.It is given birth in common manganese sulfate
In production. art, in order to remove the metal ions such as calcium, magnesium, usually using in manganous fluoride, zinc fluoride, sodium fluoride, potassium fluoride, ammonium fluoride
One or more remove calcium and magnesium ion as auxiliary agent, as China Patent Publication No. for CN101875507A,
Technical solution disclosed in CN101508467A, CN104229898A, though these schemes can preferably remove calcium and magnesium ion,
There are problems that fluoride largely remains.Since in electrolytic manganese production process, the fluorine ion of primary raw material manganese sulfate solution contains
It will influence product quality when amount is more than 90ppm or even the damage of electrolytic manganese production equipment can be caused, and with manganese oxide ore, carbon
Sour manganese ore etc. containing manganese ore be raw material production manganese sulfate solution, using the above program clean after its content of fluoride ion still above
140ppm。
In existing industrial production, it is common removal manganese sulfate solution in fluorine ion method be by add in milk of lime into
Row is that calcium hydroxide is made to form insoluble calcirm-fluoride with fluorine ion, and passes through the silica in solution and adsorbed；The party
The shortcomings that method is that the pH values of solution part can be more than 7 during milk of lime is added in, this is easy for that manganese sulfate is caused to damage
It loses, and the insoluble calcirm-fluoride formed when pH is less than 6 counter can dissolve, and cause the fluorine ion removed again in the form of ion
It exists in solution, therefore it is difficult that the fluorine ion in manganese sulfate solution is down to below 100ppm to use this method.
The Chinese patent application of Application No. 201210084081.9 discloses a kind of electrolytic manganese metal production manganese sulfate
Fluoride ion removing method in solution, this method are as defluorinating agent, to being remained in manganese sulfate solution using calcium carbonate and diatomite
Fluorine ion be removed, the drawback is that：（1）Calcium ion can be introduced manganese sulfate solution using calcium carbonate in acid condition
In, cause solution calcium ion residual quantity higher；（2）Operation temperature is higher, and manganese sulfate solution is mostly acid solution, in acyclic acidic
Great amount of carbon dioxide can be generated using calcium carbonate under border, there are some potential safety problemss.
The Chinese patent application of Application No. 201510260553.5 discloses fluorine ion in a kind of high-purity sulphuric acid manganese solution
Minimizing technology, this method be using mixed light rare earth sulfate or single rare earth sulfate as defluorinating agent, to sulfuric acid
Remaining fluorine ion is removed in manganese solution, the drawback is that：（1）Sulfuric acid rare earth salt has certain dissolving in water solution system
Degree though its hydrolysis can be inhibited by introducing sulfuric acid rare earth salt in acid system, but still can cause one or more rare earth ions to remain
In manganese sulfate solution, influence the use of manganese sulfate solution or even cause the damage of production equipment；（2）Rare earth is as economic valency
The higher and non-renewable mineral resources of value, recycling have great importance, and program rare earth usage amount it is larger and
Used rare earth sulfate is not recycled, effectively, fully, environmentally friendlyly can not recycle defluorinating agent, cost is higher；
（3）The program contains high concentration fluorine ion in processing（＞ 1000ppm）Manganese sulfate solution when, it is necessary to add in more sulfuric acid rare earth
Salt, this will cause rare earth ion largely to be remained in manganese sulfate solution, and remaining rare earth ion is particularly the rare earth of+III valencys
Ion, to remove it needs addition oxalates or heightening pH value to precipitate rare earth ion, this process can generate manganese oxalate
Precipitation triggers hydrolysis to generate manganous hydroxide precipitation, causes the loss of manganese sulfate material, thus the technology is more difficult in reality
It is used in border.
At present for the remaining manganese sulfate solution system of the high concentration fluorine ion occurred in actual production, fluoride processing
Technique is also immature, this just seriously limits the application of manganese sulfate solution industrially.
The content of the invention
To solve the problems, such as present on, the object of the present invention is to provide fluorine ions in a kind of efficiently removal manganese sulfate solution
Method, this method is simple for process and defluorinating agent can be recycled, at low cost.
In order to achieve the above object, the efficient method for removing fluorine ion in manganese sulfate solution of the present invention, includes as follows successively：
（1）A certain amount of pending manganese sulfate solution is added in consersion unit, the content of fluorine ion in the solution is measured, in temperature
Spend be 2-6 for 30-50 DEG C, pH value under the conditions of, add in solid cerium hydroxide, the addition of solid cerium hydroxide is with fluorine ion:
The amount of solid cerium hydroxide=0.005-0.027 adds in；
（2）Open consersion unit agitating device, with 150-350 revs/min of rotating speed it is small to material stirring 8-12 when after stop
Stirring when standing 12-18 is small, material is transferred in filter plant and is filtered operation, and filtrate is the qualified manganese sulfate after fluorine removal
Solution, filter cake press solid-liquid mass ratio 1:The ratio of 1-6 add in reverse osmosis water agitator treating 0.5 it is small when, the fluorine-containing hydrogen that is obtained by filtration
Cerium oxide enters step for regeneration.
The precipitation that manganese sulfate crystallizes under low temperature in order to prevent, in the above method, step（1）The manganese sulfate solution used is with Mn
Meter concentration is 100-120g/L.
The step for regeneration of above-mentioned fluorine-containing cerium hydroxide is：By solid-liquid mass ratio 1:It is 1-7mol/L's that 10-18, which adds in concentration,
Sodium hydroxide solution, with 150-300 revs/min of rotating speed stirring 6-12 it is small when after stand 8-12 it is small when, filtered after the completion of standing,
With solid-liquid mass ratio 1:The ratio of 10-15 to filter cake add in reverse osmosis water stirring washing, stirring 0.5-1.5 it is small when after filter, if
Filtrate pH value >=7.5 repeat above-mentioned water washing operations to filtrate pH ＜ 7.5, filter cake are transferred in drying equipment, at 80-90 DEG C
Constant pressure and dry or vacuum drying obtain solid cerium hydroxide.
In order to reduce the introducing of impurity, in the above method, step（1）Consersion unit for glass, polypropylene, polychlorostyrene second
Reaction kettle, retort or the reactive tank that one or more in alkene, polytetrafluoroethylene (PTFE), stainless steel are process.
In the above method, step（2）Filter plant be filter, filter press or leaf filter.
The method of fluorine ion, compared with existing defluorination method, has such as in the efficient removal manganese sulfate solution of the present invention
The advantages of lower：
（1）Using solid cerium hydroxide as defluorinating agent, not only ion exchange can occur with fluorine ion using solid cerium hydroxide,
And solid cerium hydroxide has fluorine ion certain physisorption, and it is larger so as to handle fluoride residual quantity
Manganese sulfate solution system；
（2）Using cerium hydroxide as defluorinating agent, since the cerium hydroxide for exchanging and being adsorbed with fluorine ion is easy to and fluorine ion point
From can be used with regeneration cycle, substantially reduce production cost；
（3）Using cerium hydroxide as defluorinating agent, the foreign ion introduced in manganese sulfate solution is few, and it is higher can to obtain purity
Manganese sulfate solution；
（4）It is simple for process, operating condition is mild, molten particularly suitable for electrolytic manganese metal commercial sulphuric acid manganese without high temperature and pressure
The fluorine removal processing of liquid.
Specific embodiment
Technical scheme is further described with reference to specific embodiment, but these embodiments are not used
To limit the scope of the invention, on the premise of theory of the present invention is not departed from, the small change to reaction process process conditions,
It is within the scope of protection of the invention.
Embodiment 1
1st, manganese sulfate solution defluorinating process：By 603.8 grams of pH=3.9, contents（In terms of Mn）113g/L content of fluoride 4700ppm
Manganese sulfate solution be put into glass reaction kettle, add in 187.5 grams of cerium hydroxide (i.e. by n=0.0151 gram fluorine ion/gram hydrogen-oxygen
Change the ratio input cerium hydroxide of cerium）, at a temperature of 30-50 DEG C, when small with 200 revs/min of rotating speed stirring 8, stand 12
Filter material after hour, filtrate is the manganese sulfate solution of fluorine removal qualification, the production available for manganese sulfate product.
Above-mentioned filtrate is detected through HPIC, and fluorine ion residual quantity drops to 52ppm from 4700ppm, and fluoride ion removing rate is
98.9%, it is detected through ICP-AES, the residual quantity of cerium is 10ppm.
2nd, the regeneration of cerium hydroxide defluorinating agent：The above-mentioned filter cake being obtained by filtration is collected and with solid-liquid mass ratio 1:1 ratio
Example add in reverse osmosis water, when small with 200 revs/min of rotating speed agitator treating 0.5 after filter, filter cake press solid-liquid mass ratio 1:15
Ratio adds in the sodium hydroxide solution of 3mol/L, with 200 revs/min of rotating speed stirring 4 it is small when after stand 15 it is small when, mistake after standing
Filter detects content of fluoride ion in filtrate, then with solid-liquid mass ratio 1:10 ratio adds in reverse osmosis water agitator treating to material, stirs
Mix 2 it is small when after filter, if liquid pH value be not less than 7.5, repeat above-mentioned water washing operations to pH below 7.5, after material filtering will
Cerium hydroxide is transferred in drying equipment, is recycled and is used after being dried in vacuo at 80 DEG C.
Above-mentioned filtrate measures through HPIC, content of fluoride ion 7200ppm namely after this method regenerates, and exchanges and absorption
The cerium hydroxide fluorine ion eluting rate of fluorine ion is 96.8%.
Embodiment 2
1st, manganese sulfate solution defluorinating process：By 1373.8 grams of pH=4.5, contents（In terms of Mn）110g/L, content of fluoride
The manganese sulfate solution of 3200ppm is put into glass reaction kettle, add in 230.2 grams of cerium hydroxide (i.e. by n=0.0239 gram fluorine ion/
The ratio input cerium hydroxide of gram cerium hydroxide）, at a temperature of 30-50 DEG C, when small with 200 revs/min of rotating speed stirring 8,
Stand 12 it is small when after filter material, filtrate be fluorine removal qualification manganese sulfate solution, the production available for manganese sulfate product.
Above-mentioned filtrate is detected through HPIC, and fluorine ion residual quantity drops to 87ppm from 3200ppm, and fluoride ion removing rate is
97.3%, it is detected through ICP-AES, the residual quantity of cerium is 5ppm.
2nd, the regeneration of cerium hydroxide defluorinating agent：The above-mentioned filter cake being obtained by filtration is collected and with solid-liquid mass ratio 1:1 ratio
Example add in reverse osmosis water, when small with 200 revs/min of rotating speed agitator treating 0.5 after filter, filter cake press solid-liquid mass ratio 1:14
Ratio adds in the sodium hydroxide solution of 3mol/L, with 200 revs/min of rotating speed stirring 4 it is small when after stand 15 it is small when, mistake after standing
Filter detects content of fluoride ion in filtrate, then with solid-liquid mass ratio 1:10 ratio adds in reverse osmosis water agitator treating to material, stirs
Mix 2 it is small when after filter, if liquid pH value be not less than 7.5, repeat above-mentioned water washing operations to pH below 7.5, after material filtering will
Cerium hydroxide is transferred in drying equipment, is recycled and is used after being dried in vacuo at 80 DEG C.
Above-mentioned filtrate measures through HPIC, content of fluoride ion 7100ppm namely after this method regenerates, and exchanges and absorption
The cerium hydroxide fluorine ion eluting rate of fluorine ion is 95.9%.
Embodiment 3
1st, manganese sulfate solution defluorinating process：By 140.6 grams of pH=4.2, contents（In terms of Mn）111g/L, content of fluoride 4700ppm
Manganese sulfate solution be put into glass reaction kettle, add in 40.25 grams of cerium hydroxide (i.e. by n=0.0164 gram fluorine ion/gram hydrogen-oxygen
Change the ratio input cerium hydroxide of cerium）, at a temperature of 30-50 DEG C, when small with 200 revs/min of rotating speed stirring 8, stand 12
Filter material after hour, filtrate is the manganese sulfate solution of fluorine removal qualification, the production available for manganese sulfate product.
Above-mentioned filtrate is detected through HPIC, and fluorine ion residual quantity drops to 63ppm from 4700ppm, and fluoride ion removing rate is
98.7%, it is detected through ICP-AES, the residual quantity of cerium is 7ppm.
2nd, the regeneration of cerium hydroxide defluorinating agent：The above-mentioned filter cake being obtained by filtration is collected and with solid-liquid mass ratio 1:1 ratio
Example add in reverse osmosis water, when small with 200 revs/min of rotating speed agitator treating 0.5 after filter, filter cake press solid-liquid mass ratio 1:15
Ratio adds in the sodium hydroxide solution of 3mol/L, with 200 revs/min of rotating speed stirring 4 it is small when after stand 15 it is small when, mistake after standing
Filter detects content of fluoride ion in filtrate, then with solid-liquid mass ratio 1:10 ratio adds in reverse osmosis water agitator treating to material, stirs
Mix 2 it is small when after filter, if liquid pH value be not less than 7.5, repeat above-mentioned water washing operations to pH below 7.5, after material filtering will
Cerium hydroxide is transferred in drying equipment, is recycled and is used after being dried in vacuo at 80 DEG C.
Above-mentioned filtrate measures through HPIC, content of fluoride ion 7000ppm namely after this method regenerates, and exchanges and absorption
The cerium hydroxide fluorine ion eluting rate of fluorine ion is 96.2%.
Fluorine removal processing is carried out to manganese sulfate solution using the method for the present invention it can be seen from the above-mentioned data detected, no
Only fluorine removing rate is high, and defluorinating agent cerium hydroxide regeneration rate is also high.The defluorination method of the present invention is to manganese sulfate product
Purifying and subsequent electrolytic manganese, the production of battery material have great importance.
Claims (5)
1. the method for fluorine ion, includes as follows successively in a kind of efficient removal manganese sulfate solution：
（1）A certain amount of pending manganese sulfate solution is added in consersion unit, the content of fluorine ion in the solution is measured, in temperature
Spend be 2-6 for 30-50 DEG C, pH value under the conditions of, add in solid cerium hydroxide, the addition of solid cerium hydroxide is with fluorine ion:Gu
The amount of body cerium hydroxide=0.005-0.027 adds in；
（2）Open consersion unit agitating device, with 150-350 revs/min of rotating speed it is small to material stirring 8-12 when after stop
Stirring when standing 12-18 is small, material is transferred in filter plant and is filtered operation, and filtrate is the qualified manganese sulfate after fluorine removal
Solution, filter cake press solid-liquid mass ratio 1:The ratio of 1-6 add in reverse osmosis water agitator treating 0.5 it is small when, the fluorine-containing hydrogen that is obtained by filtration
Cerium oxide enters step for regeneration.
2. the method for fluorine ion in efficient removal manganese sulfate solution according to claim 1, it is characterised in that：The method
In, step（1）The manganese sulfate solution used counts concentration as 100-120g/L using Mn.
3. the method for fluorine ion in efficient removal manganese sulfate solution according to claim 1 or 2, it is characterised in that：It is described
The step for regeneration of fluorine-containing cerium hydroxide is：By solid-liquid mass ratio 1:10-18 adds in the sodium hydroxide solution that concentration is 1-7mol/L,
When standing 8-12 is small after when small with 150-300 revs/min of rotating speed stirring 6-12, filtered after the completion of standing, with solid-liquid mass ratio
1:The ratio of 10-15 to filter cake add in reverse osmosis water stirring washing, stirring 0.5-1.5 it is small when after filter, if filtrate pH value >=
7.5, repeat above-mentioned water washing operations to filtrate pH ＜ 7.5, filter cake be transferred in drying equipment, at 80-90 DEG C constant pressure and dry or
Vacuum drying, obtains solid cerium hydroxide.
4. the method for fluorine ion in efficient removal manganese sulfate solution according to claim 3, it is characterised in that：The method
In, step（1）Consersion unit be glass, polypropylene, polyvinyl chloride, polytetrafluoroethylene (PTFE), the one or more in stainless steel add
Reaction kettle, retort or the reactive tank that work forms.
5. the method for fluorine ion in efficient removal manganese sulfate solution according to claim 3, it is characterised in that：The method
In, step（2）Filter plant be filter, filter press or leaf filter.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112267023A (en) * | 2020-09-25 | 2021-01-26 | 衢州华友钴新材料有限公司 | Two-stage defluorination method for fluorine-containing material |
| CN115124084A (en) * | 2022-08-09 | 2022-09-30 | 贵州金瑞新材料有限责任公司 | Calcium removal method of manganese sulfate solution |
| CN115159604A (en) * | 2022-07-23 | 2022-10-11 | 贵州金瑞新材料有限责任公司 | Evaporative crystallization method of manganese sulfate |
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| CN85105637A (en) * | 1985-02-21 | 1986-09-17 | 旭化成工业株式会社 | The adsorption treatment method of dissolving fluorine |
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| CN85105637A (en) * | 1985-02-21 | 1986-09-17 | 旭化成工业株式会社 | The adsorption treatment method of dissolving fluorine |
Non-Patent Citations (1)
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| 焦中志等: "稀土铈基无机吸附剂对氟的吸附性能", 《环境化学》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112267023A (en) * | 2020-09-25 | 2021-01-26 | 衢州华友钴新材料有限公司 | Two-stage defluorination method for fluorine-containing material |
| CN112267023B (en) * | 2020-09-25 | 2022-07-08 | 衢州华友钴新材料有限公司 | Two-stage defluorination method for fluorine-containing material |
| CN115159604A (en) * | 2022-07-23 | 2022-10-11 | 贵州金瑞新材料有限责任公司 | Evaporative crystallization method of manganese sulfate |
| CN115124084A (en) * | 2022-08-09 | 2022-09-30 | 贵州金瑞新材料有限责任公司 | Calcium removal method of manganese sulfate solution |
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Application publication date: 20180605 |