CN107619952A - A kind of method that lithium is leached from flyash - Google Patents
A kind of method that lithium is leached from flyash Download PDFInfo
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- CN107619952A CN107619952A CN201710835276.5A CN201710835276A CN107619952A CN 107619952 A CN107619952 A CN 107619952A CN 201710835276 A CN201710835276 A CN 201710835276A CN 107619952 A CN107619952 A CN 107619952A
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- lithium
- carbonate
- agglutinant
- potassium carbonate
- flyash
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a kind of method that lithium is leached from flyash.Lithium is leached using agglutinant calcining and activating microwave field acidleach process integration.Potassium carbonate, potassium chloride, the single agglutinant of sodium acetate or potassium carbonate and sodium carbonate, potassium carbonate and cesium carbonate mixed sintering agent are uniformly blended and 10min 2.5h calcined in Muffle furnace in flyash, sodium carbonate mass fraction is 1% 40% in potassium carbonate and sodium carbonate mixed sintering agent, and potassium carbonate and cesium carbonate mass fraction in cesium carbonate mixed sintering agent are 50% 99%.Clinker after calcining adds hydrochloric acid or sulfuric acid and heats leaching lithium by microwave, and microwave heating further increases the leaching rate of lithium and highly shortened extraction time.Workable, the time-consuming short and leaching rate of present invention process is high, and equipment requirement is low, easy to spread.- microwave hot acid-leaching process integration leaching lithium is efficiently activated by agglutinant of the present invention, the high efficiente callback of flyash lithium resource can be realized.
Description
Technical field
The invention belongs to technical field of energy material, the method that lithium metal is leached more particularly to from flyash.
Background technology
Lithium is described as " energy metal of 21 century ", has in the field such as metallurgy, medicine, lubricating grease, glass ceramics, chemical industry
Using.With the swift and violent hair of the industry such as new-energy automobile, communication and consumer electronics product in recent years, electric car and power network energy storage
Exhibition, the demand of lithium even more increase year by year, trigger the rapid rise of price of the raw material such as lithium carbonate, lithium hydroxide.
The lithium in the whole world about 70% is present in salt lake, and 30% comes from ore.Although China salt lake lithium ore resources rich reserves,
But it is larger to develop difficulty；Although it is the more ripe method of earliest adopted technology that lithium ore, which carries lithium, but pass through upper a century
Exploitation, be on the verge of exhaustion, this also cause China at present still from the more lithium product of external import.
China's flyash discharge capacity is huge, and the utilization of flyash is primarily used to the spike of cement, concrete, builds the road,
Value is relatively low, considers the increasingly strict of its recycling recycling and environmental protection, valuable element is extracted from flyash
As the focus of many scholar's research.In flyash extract aluminium technique it is more ripe, can by the direct acid-hatching of young eggs, pre-desiliconizing-
Soda lime sintering process, limestone sintering process and other sintering process, the recovery rate of some processes can reach more than 90%.But from powder
The technology for extracting lithium in coal ash only has a small amount of relevant report, and process route is immature, and extraction efficiency is low, lithium extractive technique according to
So it is in the exploratory stage.Patent CN104477948 discloses " a kind of method that lithium carbonate is extracted from flyash ", hot fine coal
Grey warm water is put into reactor and obtains the logical CO of coal ash pulp2Directly lithium bicarbonate mixed solution, crystallization treatment are obtained after carbonating
Carbonic acid crystalline lithium is obtained, this method reaction rate is slow, and recovery rate is low and adds the cost of carbon dioxide.Patent
CN102923742 discloses a kind of addition sodium carbonate or sodium carbonate with calcium carbonate mixture with applying alkali after flyash blending roasting
The method that liquid leaches and extracts lithium, patent CN102923743 disclose addition sodium sulphate and potassium sulfate mixture with it is flyash mixed
Being put into autoclave after mixed roasting adds sulfuric acid leaching to extract lithium, and time-consuming for both approaches, roasting postprocessing working procedures are cumbersome and powder
Lithium is carried after coal ash desiliconization, it is impossible to makes full use of lithium.Patent CN105692659 discloses carries out alkali by adding alkali lye with flyash
Lithium is leached in molten reaction, and then Adsorption Concentration precipitation produces lithium carbonate product, and alkali soluble reaction rate is slow, and time-consuming for lithium leaching process.
Application of the microwave technology in organic synthesis field shows that microwave heating response speed accelerates number than conventional method
Ten or even thousands of times, and the material that conventional method is difficult to generate can be synthesized.So far, microwave technique application is in flyash
The leaching and extraction of middle lithium yet there are no relevant report.
The content of the invention
The defects of in order to overcome prior art, the invention provides a kind of agglutinant calcining and activating-microwave field acidleach joint
The method that technique leaches lithium metal from flyash, this method lithium leaching effect is good, take short, technical process simply, equipment is wanted
Ask low, prospects for commercial application wide.
To achieve these goals, the present invention adopts the following technical scheme that：
By potassium carbonate, potassium chloride, the single sintering activator of sodium acetate and potassium carbonate and sodium carbonate, potassium carbonate and cesium carbonate
Mixed sintering activator be applied to flyash in lithium leaching, United microwave heating technique realize lithium efficient Rapid Leaching and
Recovery.
Present invention research is found：By the mixing of potassium carbonate, potassium chloride, sodium acetate and potassium carbonate and sodium carbonate or cesium carbonate
Thing is added into as agglutinant calcines the leaching effect for being greatly improved lithium after flyash, agglutinant used passes through pyroreaction
It is easy to break the associative key of lithium and sial in flyash, promotes more lithiums to be discharged from alumino-silicate, microwave leaching ratio
The autoclave of existing report, alkali soluble reaction, water-bath acidleach further increase the leaching of lithium and highly shortened leaching
Time.Agglutinant calcining and activating-leaching of the microwave acid dipping process integration to lithium in flyash has extraordinary effect.
The invention provides a kind of method that lithium is leached in flyash, including：
Powder is mixed using two kinds of mixed sintering agent of single agglutinant and potassium carbonate and sodium carbonate, potassium carbonate and cesium carbonate
Coal ash is calcined, and the clinker after calcining leaches lithium by microwave hot acid-leaching, and present method solves existing flyash lithium leaching process
The problems such as middle reaction rate is slow, time-consuming, treatment process is cumbersome, operating procedure is simple and greatlys save time, equipment requirement
It is low, it is easy to spread.Lithium is leached by effective agglutinant calcining and activating-microwave hot acid-leaching process integration, flyash can be realized
The high efficiente callback of middle lithium resource.
Wherein, with potassium carbonate, potassium chloride, sodium acetate separately as agglutinant or potassium carbonate and sodium carbonate, potassium carbonate and carbon
Sour two kinds of mixing of caesium are used as agglutinant.
Preferably, sodium carbonate mass fraction is 1%-40% in the potassium carbonate and sodium carbonate mixed sintering agent, potassium carbonate
It is 50%-99% with cesium carbonate mass fraction in cesium carbonate mixed sintering agent.
Preferably, the agglutinant is solid powder or solution, and the mass ratio of agglutinant and flyash is：(0.4-2.5):
1。
Preferably, the calcination condition is：10min-2.5h is calcined at 500-950 DEG C.
Preferably, the microwave field leaching processing is under hydrochloric acid, sulfuric acid existence condition, and 2- is handled in microwave reactor
30min。
Preferably, the concentration of the hydrochloric acid is 5mol/L-7mol/L；The mass concentration of the sulfuric acid solution is 49%-
98%.
Preferably, the flyash and hydrochloric acid solution solid-to-liquid ratio are 1:3-1:10；Flyash is with sulfuric acid solution solid-to-liquid ratio
1:1-1:4。
Preferably, the microwave power of the microwave field is 1-1000W.
Present invention also offers the filtrate containing lithium of any above method extraction.
Present invention also offers potassium carbonate, potassium chloride, the single agglutinant of sodium acetate or potassium carbonate and sodium carbonate, potassium carbonate with
Application of the cesium carbonate mixed sintering agent in flyash leaches valuable element, the valuable element include：Lithium, silicon, aluminium, iron, gallium.
Beneficial effects of the present invention
(1) present invention realizes the efficient leaching of lithium metal in flyash, and raw material sources are cheap extensively, consumed when soaking lithium it is short and
Leaching rate is high.
(2) present invention process process is simple, and equipment requirement is low, and efficiency high is practical, easy to spread.
Brief description of the drawings
The Figure of description for forming the part of the application is used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its illustrate be used for explain the application, do not form the improper restriction to the application.
The action effect schematic diagram that Fig. 1 leaches for the mixed sintering agent of different potassium carbonate and ratio sodium carbonate to lithium；
Fig. 2 is several single agglutinants and agglutinant and coal ash mass ratio is respectively 0.5:1、1:1、1.5:The leaching of lithium when 1
Go out design sketch.
Embodiment
It is noted that described further below is all exemplary, it is intended to provides further instruction to the application.It is unless another
Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
A kind of method that lithium is leached from flyash, comprises the following steps：
A. the single agglutinant of potassium carbonate, potassium chloride, sodium acetate and potassium carbonate and sodium carbonate, potassium carbonate and cesium carbonate are prepared
Mixed sintering agent, potassium carbonate are 1%-40%, potassium carbonate and cesium carbonate with sodium carbonate mass content in sodium carbonate mixed sintering agent
Cesium carbonate mass content is 50%-99% in mixed sintering agent.
B. by agglutinant (0.4-2.5) in mass ratio:1 ratio is blended into flyash, will can be burnt to be well mixed it
The addition of agent wiring solution-forming is tied, mixing and dried sample are put into electric furnace heating 10min-2.5h.
C. hydrochloric acid or sulfuric acid leaching agent are added into the clinker after sintering, is put into microwave reactor and reacts 2-30min.
D. filter residue is filtered out with Suction filtration device, filtrate constant volume is obtained into filtrate containing lithium, it is former using inductively coupled plasma
Sub- emission spectrum (ICP-AES) or atomic absorption spectrum (AAS) measure lithium and leach content.
Present invention also offers a kind of method that lithium is leached from flyash, comprise the following steps：
A. potassium carbonate and sodium carbonate, the carbonic acid of potassium carbonate, potassium chloride, sodium acetate agglutinant and different mixing proportions are prepared
Potassium and cesium carbonate mixed sintering agent.
B. take 4g flyash to be well mixed with 2g-6g agglutinant in crucible, be then placed in 500-950 DEG C of Muffle furnace and add
Heat, heating response time are respectively set to 10min-2.5h.
C. the flyash after activation is mixed with 20ml hydrochloric acid solutions (6mol/L) or 6.4ml sulfuric acid solutions (98%), put
Enter and 2-30min is reacted in microwave reactor.
D. filter residue is filtered out with Suction filtration device, filtrate is settled to 100ml, obtain filtrate containing lithium.
Microwave after the mixed sintering agent calcining and activating of addition different ratio in flyash after certain western coal power station burning
As shown in Figure 1 (process conditions are same as Example 1), dotted line is to use carbon under the same terms to the leaching effect of acidleach lithium in Fig. 1
The leaching content of lithium when sour sodium agglutinant and potassium carbonate agglutinant.As shown in Figure 1, using mixed sintering agent microwave leaching considerably beyond
The leaching content of lithium when sodium carbonate and potassium carbonate are as agglutinant.Potassium carbonate and sodium carbonate mixed sintering agent, wherein, sodium carbonate quality
The leaching effect of lithium is preferable when fraction is 2%-30%, particularly 70% potassium carbonate and 30% sodium carbonate mixed sintering agent, fine coal
The leaching content of lithium is up to 279g/t in ash.
Fig. 2 is addition potassium carbonate, potassium chloride, potassium acetate and sodium acetate agglutinant and the mass ratio of agglutinant and flyash
Respectively 0.5:1、1:1、1.5:The leaching effect of lithium when 1 (process conditions are same as Example 1).The quality of potassium chloride and coal ash
Than for 1.5:Effect is best when 1, and potassium carbonate, the addition of sodium acetate are 1:Effect is best when 1.
Embodiment 1, take power station flyash after certain ground western coal combustion of 4g, with 4g agglutinants (0.4g sodium carbonate and
3.6g potassium carbonate) it is well mixed after be put into Muffle furnace and calcine 2h in 800 DEG C, the hydrochloric acid solution for then adding 20ml 6mol/L is micro-
Wave heating (microwave power 700W) 4min, lithium leaching content are 272g/t.
Embodiment 2, take power station flyash after certain ground western coal combustion of 4g, with 4g agglutinants (1.2g sodium carbonate and
2.8g potassium carbonate) it is well mixed after be put into Muffle furnace and calcine 2h in 800 DEG C, the hydrochloric acid solution for then adding 20ml 6mol/L is micro-
Wave heating (microwave power 700W) 4min, lithium leaching content are 279g/t.
Embodiment 3, power station flyash after certain ground western coal combustion of 4g is taken, with 4g agglutinants (2g sodium carbonate and 2g
Cesium carbonate) it is well mixed after be put into Muffle furnace and calcine 2h in 800 DEG C, the hydrochloric acid solution microwave for then adding 20ml 6mol/L adds
Heat (microwave power 700W) 4min, lithium leaching content are 114g/t.
Embodiment 4, take power station flyash after certain ground western coal combustion of 4g, with 4g agglutinants (0.4g cesium carbonates and
3.6g potassium carbonate) it is well mixed after be put into Muffle furnace and calcine 2h in 800 DEG C, the hydrochloric acid solution for then adding 20ml 6mol/L is micro-
Ripple (microwave power 700W) heats 4min, and lithium leaching content is 57g/t.
The preferred embodiment of the application is the foregoing is only, is not limited to the application, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of method that flyash leaches lithium, it is characterised in that including：
Lithium is leached using agglutinant calcining and activating-microwave field acidleach process integration；
Wherein, with potassium carbonate, potassium chloride, sodium acetate separately as agglutinant or potassium carbonate and sodium carbonate, potassium carbonate and cesium carbonate
Two kinds of mixing are used as agglutinant.
2. the method as described in claim 1, it is characterised in that the potassium carbonate and sodium carbonate matter in sodium carbonate mixed sintering agent
Amount fraction is 1%-40%, and potassium carbonate is 50%-99% with cesium carbonate mass fraction in cesium carbonate mixed sintering agent.
3. the method as described in claim 1, it is characterised in that the agglutinant is solid powder or solution, agglutinant and powder
Coal ash in mass ratio 0.4~2.5:1 blending calcining.
4. the method as described in claim 1, it is characterised in that the calcination condition is：10min- is calcined at 500-950 DEG C
2.5h。
5. the method as described in claim 1, it is characterised in that the microwave field acidleach processing is to add in clinker after firing
Add hydrochloric acid or sulfuric acid, 2-30min is handled in microwave reactor.
6. method as claimed in claim 5, it is characterised in that the concentration of the hydrochloric acid is 5mol/L-7mol/L；The sulfuric acid
The mass concentration of solution is 49%-98%.
7. method as claimed in claim 5, it is characterised in that clinker and hydrochloric acid solution solid-to-liquid ratio are 1 after the calcining:3-1:
10；Clinker and sulfuric acid solution solid-to-liquid ratio are 1 after calcining:1-1:4.
8. the method as described in claim 1, it is characterised in that the microwave power of the microwave field is 1-1000W.
9. the filtrate containing lithium of the method extraction described in claim any one of 1-8.
10. the application of potassium carbonate, sodium acetate, potassium acetate or potassium chloride as agglutinant in flyash leaches lithium.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110643832A (en) * | 2019-11-05 | 2020-01-03 | 广西中煤地质有限责任公司 | Method for extracting lithium from fly ash |
| CN113897486A (en) * | 2021-04-15 | 2022-01-07 | 江苏地质矿产设计研究院(中国煤炭地质总局检测中心) | Method for extracting lithium from coal |
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| CN103101935A (en) * | 2012-12-28 | 2013-05-15 | 中国神华能源股份有限公司 | Method for preparing lithium carbonate from coal ash |
| CN105692659A (en) * | 2016-01-26 | 2016-06-22 | 中国科学院过程工程研究所 | Method for extracting lithium from fly ash |
| CN106536767A (en) * | 2014-08-28 | 2017-03-22 | 韩国电力公社 | Method and apparatus for extracting lithium from coal ash |
| CN107130119A (en) * | 2017-07-18 | 2017-09-05 | 河北工程大学 | A kind of method that lithium is leached from flyash |
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2017
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| CN102583468A (en) * | 2012-03-08 | 2012-07-18 | 航天推进技术研究院 | Method for extracting aluminum oxide from fly ash based on ammonium sulfate activation process |
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| CN103101935A (en) * | 2012-12-28 | 2013-05-15 | 中国神华能源股份有限公司 | Method for preparing lithium carbonate from coal ash |
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| CN110643832A (en) * | 2019-11-05 | 2020-01-03 | 广西中煤地质有限责任公司 | Method for extracting lithium from fly ash |
| CN113897486A (en) * | 2021-04-15 | 2022-01-07 | 江苏地质矿产设计研究院(中国煤炭地质总局检测中心) | Method for extracting lithium from coal |
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