CN106673021A - Method for circularly extracting lithium from lithium mica as raw material - Google Patents
Method for circularly extracting lithium from lithium mica as raw material Download PDFInfo
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- CN106673021A CN106673021A CN201611206891.1A CN201611206891A CN106673021A CN 106673021 A CN106673021 A CN 106673021A CN 201611206891 A CN201611206891 A CN 201611206891A CN 106673021 A CN106673021 A CN 106673021A
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- lepidolite
- leaching
- lithium
- sodium fluoride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
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- Inorganic Chemistry (AREA)
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Abstract
The invention relates to a method for circularly extracting lithium from lithium mica as a raw material, belongs to the field of lithium resource leaching, and aims to overcome the defects of high energy consumption, high preparation cost and excessive release of poisonous gas in the process of extracting lithium from the lithium mica as the raw material in the prior art. In the method, the lithium mica is fluoridized and acidified by taking hydrochloric acid and sodium fluoride as an acidolysis solution; leach liquor can directly purify and precipitate lithium; leaching residues are filtered after being leached through sodium hydroxide; sodium fluoride obtained by reduced-pressure evaporation crystallization of filtrate can be recycled in lithium extraction. The method is safe and environment-friendly, is low in preparation cost, and has a good application prospect.
Description
Technical field
The present invention relates to a kind of method for extracting lithium as feedstock circulation with lepidolite, belong to lithium resource extraction field.
Background technology
Lithium has various excellent properties, is referred to as " energy metal of 21st century ", " industrial monosodium glutamate ", " space of tomorrow
Boat alloy ", strategic position is notable.The primary raw material for carrying lithium at present is salt lake bittern and solid lithium minerals, Chinese lepidolite and lithium
The rich reserves of pyroxene.Carried from lithium minerals the method for lithium mainly have sulfate process, chloride process, limestone-based process, sulfuric acid process with
And gas-solid reaction method.These methods are all that lithium minerals is carried out into high-temperature calcination, and then processing calcining slag with different methods enters one
Step produces lithium salts, and it is high to there is production cost, and energy consumption is big, and lithium recovery rate is low, and waste residue amount is big, and industrial significance is produced only using height
The outstanding problems such as grade spodumene.
Chinese invention patent ZL201010235150.2 is disclosed one kind and is decomposed with fluorochemical or mineral using sulfuric acid
Lepidolite, the method that the method for leaching that added water after evaporation spent acid extracts the lithium in lepidolite.This method high energy consumption, sour consumption
Greatly, and a large amount of toxic gases, such as SO can be discharged3、SO2、SiF4。
The content of the invention
In order to overcome in the prior art with lepidolite as raw material put forward lithium process present in energy consumption and preparation cost it is higher, have
Poisonous gas discharge excessive technical deficiency, and the present invention provides a kind of method for extracting lithium as feedstock circulation with lepidolite, and it is with salt
Acid and sodium fluoride carry out fluorination acidolysis to lepidolite for acid hydrolysis solution, and leachate can be with direct purification sinker, and leached mud passes through hydrogen
Sodium oxide molybdena leach after filter, the sodium fluoride that filtrate decompression evaporative crystallization is obtained can put into again carry lithium circulation among.The method
Safety and environmental protection, and preparation cost is cheap, there is application prospect higher.
The present invention is achieved through the following technical solutions above-mentioned technical purpose：
The present invention provides a kind of method for extracting lithium as feedstock circulation with lepidolite, and it comprises the steps：
1) lepidolite is leached：Sodium fluoride is added after hydrochloric acid solution is mixed with lepidolite, fluorination acidolysis is carried out, acidolysis terminates
After carry out solid-liquor separation, obtain leachate and leached mud, leachate is used to purify sinker；
2) purification of leaching liquor sinker：By leachate plus alkali causticization, regulation pH of leaching solution is dense by solution to 8.0~10.0
Contracting, filtering can obtain lithium product after precipitation lithium ion；
3) leached mud reclaims sodium fluoride：Leached mud is leached with NaOH solution, recrement and fluorine are filtrated to get after the completion of leaching again
Life liquid, fluorine regenerated liquid is evaporated under reduced pressure crystallization and can obtain sodium fluoride, and sodium fluoride can be reused for step 1) middle assistance acidolysis lithium cloud
It is female.
Described above to be extracted in the method for lithium by feedstock circulation of lepidolite, the step 1) in the concentration of hydrochloric acid solution be
5mol/L~10mol/L, it is 2.0 with the liquid-solid ratio of lepidolite：1~5.0：1.The step 1) in sodium fluoride addition with
The mass ratio of lepidolite is 0.55：1~0.8：1；The step 1) leaching temperature is 70 DEG C~108 DEG C in leaching process, leaching
Time is 2~6 hours；
It is described above with lepidolite as feedstock circulation extract lithium method in, the step 3) in NaOH consumptions be leached mud
In 2.5~3.2 times of total aluminium mole；Liquid-solid ratio is 10：1~15：1；The step 3) described in leaching temperature be 60 DEG C
~100 DEG C, leaching time is 10min~60min.
As a kind of implementation method preferred for this invention, the step 1) in hydrochloric acid solution concentration be 8mol/L, its
It is 3.5 with the liquid-solid ratio of lepidolite：1, the addition of sodium fluoride is 0.65 with the mass ratio of lepidolite：1, leached in leaching process
Temperature is 89 DEG C, and leaching time is 4 hours；The step 1) in leaching process leaching temperature be 70 DEG C~108 DEG C, during leaching
Between be 2~6 hours；The step 3) NaOH consumptions are 2.9 times of total aluminium mole in leached mud；Liquid-solid ratio is 12.5：1, state
Leaching temperature be 80 DEG C, leaching time is 35min.The recovery rate of lithium resource is most under this process conditions, in unit lepidolite
Height, preparation cost is minimum.
The present invention has following technical advantage compared with prior art：
1. destruction of the fluorine ion to sial key in lepidolite is utilized in extraction lithium method of the present invention, assist acid
Solution lepidolite, by low acid consumption, leaches lithium in the way of low energy consumption, and uses hydrochloric acid as acidolysis solution, during do not produce it is useless
Gas and other pollutants, safe preparation process environmental protection.
2. fluorine aluminium complex generation fluorine aluminium sodium salt is precipitated using sodium ion in extraction lithium method of the present invention, make leaching
The aluminium gone out in liquid is down to below 3g/L, and fluorine is down to below 1.5g/L；
3. using NaOH solution and leached mud reaction generation Al (OH) in extraction lithium method of the present invention3And NaF, make
NaF regenerates, and into production cycle, production cost can be greatly lowered.
Brief description of the drawings
The method that Fig. 1 present invention extracts lithium with lepidolite as feedstock circulation.
Specific embodiment
Technology contents of the invention are further illustrated below by way of specific embodiment, but the technical staff in the field should be able to
Know, the embodiment limits the protection domain of patent of the present invention never in any form.Those skilled in the art are basic herein
On the modification made or equivalent substitute, all should be included within this patent protection domain.
A kind of method for extracting lithium as feedstock circulation with lepidolite of embodiment 1
Described specifically includes following steps in the method that lepidolite extracts lithium as feedstock circulation：
1) lepidolite is leached：To sodium fluoride is added in hydrochloric acid solution, mix with lepidolite carries out fluorinated, acid solution, acidolysis afterwards
Solid-liquor separation is carried out after end, leachate and leached mud is obtained, leachate is used to purify sinker；The concentration of wherein hydrochloric acid solution is
5mol/L, it is 2.0 with the liquid-solid ratio of lepidolite：1, the addition of sodium fluoride is 0.55 with the mass ratio of lepidolite：1, leach
During leaching temperature be 70 DEG C, leaching time be 2 hours.
2) purification of leaching liquor sinker：Solution is concentrated, precipitated by leachate plus alkali causticization, regulation pH of leaching solution to 8.0
Filtering can obtain lithium product after lithium ion；
3) leached mud reclaims sodium fluoride：Leached mud is leached with NaOH solution, recrement and fluorine are filtrated to get after the completion of leaching again
Life liquid, fluorine regenerated liquid is evaporated under reduced pressure crystallization and can obtain sodium fluoride, and sodium fluoride can be reused for step 1) middle assistance acidolysis lithium cloud
It is female.Wherein NaOH consumptions are 2.5 times of total aluminium mole in leached mud；Liquid-solid ratio is 10：1.Described leaching temperature is 60 DEG C,
Leaching time is 10min.
A kind of method for extracting lithium as feedstock circulation with lepidolite of embodiment 2
Described specifically includes following steps in the method that lepidolite extracts lithium as feedstock circulation：
1) lepidolite is leached：To sodium fluoride is added in hydrochloric acid solution, mix with lepidolite carries out fluorinated, acid solution, acidolysis afterwards
Solid-liquor separation is carried out after end, leachate and leached mud is obtained, leachate is used to purify sinker；The concentration of wherein hydrochloric acid solution is
10mol/L, it is 5.0 with the liquid-solid ratio of lepidolite：1, the addition of sodium fluoride is 0.8 with the mass ratio of lepidolite：1, leach
During leaching temperature be 108 DEG C, leaching time be 6 hours.
2) purification of leaching liquor sinker：Solution is concentrated, sunk by leachate plus alkali causticization, regulation pH of leaching solution to 10.0
Filtering can obtain lithium product after the lithium ion of shallow lake；
3) leached mud reclaims sodium fluoride：Leached mud is leached with NaOH solution, recrement and fluorine are filtrated to get after the completion of leaching again
Life liquid, fluorine regenerated liquid is evaporated under reduced pressure crystallization and can obtain sodium fluoride, and sodium fluoride can be reused for step 1) middle assistance acidolysis lithium cloud
It is female.Wherein NaOH consumptions are 3.2 times of total aluminium mole in leached mud；Liquid-solid ratio is 15：1.Described leaching temperature is 100
DEG C, leaching time is 60min.
A kind of method for extracting lithium as feedstock circulation with lepidolite of embodiment 3
Described specifically includes following steps in the method that lepidolite extracts lithium as feedstock circulation：
1) lepidolite is leached：To sodium fluoride is added in hydrochloric acid solution, mix with lepidolite carries out fluorinated, acid solution, acidolysis afterwards
Solid-liquor separation is carried out after end, leachate and leached mud is obtained, leachate is used to purify sinker；The concentration of wherein hydrochloric acid solution is
8mol/L, it is 3.5 with the liquid-solid ratio of lepidolite：1, the addition of sodium fluoride is 0.65 with the mass ratio of lepidolite：1, leach
During leaching temperature be 89 DEG C, leaching time be 4 hours.
2) purification of leaching liquor sinker：Solution is concentrated, precipitated by leachate plus alkali causticization, regulation pH of leaching solution to 9.0
Filtering can obtain lithium product after lithium ion；
3) leached mud reclaims sodium fluoride：Leached mud is leached with NaOH solution, recrement and fluorine are filtrated to get after the completion of leaching again
Life liquid, fluorine regenerated liquid is evaporated under reduced pressure crystallization and can obtain sodium fluoride, and sodium fluoride can be reused for step 1) middle assistance acidolysis lithium cloud
It is female.Wherein NaOH consumptions are 2.9 times of total aluminium mole in leached mud；Liquid-solid ratio is 12.5：1.Described leaching temperature is 80
DEG C, leaching time is 35min.
A kind of method for extracting lithium as feedstock circulation with lepidolite of embodiment 4
Described specifically includes following steps in the method that lepidolite extracts lithium as feedstock circulation：
1) lepidolite is leached：To sodium fluoride is added in hydrochloric acid solution, mix with lepidolite carries out fluorinated, acid solution, acidolysis afterwards
Solid-liquor separation is carried out after end, leachate and leached mud is obtained, leachate is used to purify sinker；The concentration of wherein hydrochloric acid solution is
5mol/L, it is 5.0 with the liquid-solid ratio of lepidolite：1, the addition of sodium fluoride is 0.55 with the mass ratio of lepidolite：1, leach
During leaching temperature be 108 DEG C, leaching time be 2 hours.
2) purification of leaching liquor sinker：Solution is concentrated, sunk by leachate plus alkali causticization, regulation pH of leaching solution to 10.0
Filtering can obtain lithium product after the lithium ion of shallow lake；
3) leached mud reclaims sodium fluoride：Leached mud is leached with NaOH solution, recrement and fluorine are filtrated to get after the completion of leaching again
Life liquid, fluorine regenerated liquid is evaporated under reduced pressure crystallization and can obtain sodium fluoride, and sodium fluoride can be reused for step 1) middle assistance acidolysis lithium cloud
It is female.Wherein NaOH consumptions are 2.5 times of total aluminium mole in leached mud；Liquid-solid ratio is 15：1.Described leaching temperature is 60 DEG C
DEG C, leaching time is 60min.
A kind of method for extracting lithium as feedstock circulation with lepidolite of embodiment 5
Described specifically includes following steps in the method that lepidolite extracts lithium as feedstock circulation：
1) lepidolite is leached：To sodium fluoride is added in hydrochloric acid solution, mix with lepidolite carries out fluorinated, acid solution, acidolysis afterwards
Solid-liquor separation is carried out after end, leachate and leached mud is obtained, leachate is used to purify sinker；The concentration of wherein hydrochloric acid solution is
10mol/L, it is 2.0 with the liquid-solid ratio of lepidolite：1, the addition of sodium fluoride is 0.8 with the mass ratio of lepidolite：1, leach
During leaching temperature be 70 DEG C, leaching time be 6 hours.
2) purification of leaching liquor sinker：Solution is concentrated, precipitated by leachate plus alkali causticization, regulation pH of leaching solution to 8.0
Filtering can obtain lithium product after lithium ion；
3) leached mud reclaims sodium fluoride：Leached mud is leached with NaOH solution, recrement and fluorine are filtrated to get after the completion of leaching again
Life liquid, fluorine regenerated liquid is evaporated under reduced pressure crystallization and can obtain sodium fluoride, and sodium fluoride can be reused for step 1) middle assistance acidolysis lithium cloud
It is female.Wherein NaOH consumptions are 3.2 times of total aluminium mole in leached mud；Liquid-solid ratio is 10：1.Described leaching temperature is 100
DEG C, leaching time is 10min.
Claims (7)
1. it is a kind of with lepidolite as feedstock circulation extract lithium method, it comprises the steps：
1) lepidolite is leached：Sodium fluoride is added after hydrochloric acid solution is mixed with lepidolite, fluorination acidolysis is carried out, acidolysis terminates laggard
Row solid-liquor separation, obtains leachate and leached mud, and leachate is used to purify sinker；
2) purification of leaching liquor sinker：Solution is concentrated, sunk by leachate plus alkali causticization, regulation pH of leaching solution to 8.0~10.0
Filtering can obtain lithium product after the lithium ion of shallow lake；
3) leached mud reclaims sodium fluoride：Leached mud is leached with NaOH solution, recrement and fluorine regenerated liquid is filtrated to get after the completion of leaching,
Fluorine regenerated liquid is evaporated under reduced pressure crystallization and can obtain sodium fluoride, and sodium fluoride can be reused for step 1) middle assistance acidolysis lepidolite.
2. it is according to claim 1 with lepidolite as feedstock circulation extract lithium method, it is characterised in that the step 1)
The concentration of middle hydrochloric acid solution is 5mol/L~10mol/L, and it is 2.0 with the liquid-solid ratio of lepidolite：1~5.0：1.
3. it is according to claim 1 with lepidolite as feedstock circulation extract lithium method, it is characterised in that the step 1)
The addition of middle sodium fluoride is 0.55 with the mass ratio of lepidolite：1~0.8：1.
4. it is according to claim 1 with lepidolite as feedstock circulation extract lithium method, it is characterised in that the step 1)
Leaching temperature is 70 DEG C~108 DEG C in leaching process, and leaching time is 2~6 hours.
5. it is according to claim 1 with lepidolite as feedstock circulation extract lithium method, it is characterised in that the step 3)
Middle NaOH consumptions are 2.5~3.2 times of total aluminium mole in leached mud；Liquid-solid ratio is 10：1~15：1.
6. it is according to claim 1 with lepidolite as feedstock circulation extract lithium method, it is characterised in that the step 3)
Described in leaching temperature be 60 DEG C~100 DEG C, leaching time be 10min~60min.
7. it is according to claim 1 with lepidolite as feedstock circulation extract lithium method, it is characterised in that the step 1)
The concentration of middle hydrochloric acid solution is 8mol/L, and it is 3.5 with the liquid-solid ratio of lepidolite：1, the addition of sodium fluoride and the matter of lepidolite
Amount is than being 0.65：1, leaching temperature is 89 DEG C in leaching process, and leaching time is 4 hours；The step 1) in leaching process
Leaching temperature is 70 DEG C~108 DEG C, and leaching time is 2~6 hours；The step 3) NaOH consumptions are total aluminium mole in leached mud
2.9 times of amount；Liquid-solid ratio is 12.5：1, the leaching temperature stated is 80 DEG C, and leaching time is 35min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611206891.1A CN106673021A (en) | 2016-12-23 | 2016-12-23 | Method for circularly extracting lithium from lithium mica as raw material |
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| CN201611206891.1A CN106673021A (en) | 2016-12-23 | 2016-12-23 | Method for circularly extracting lithium from lithium mica as raw material |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885496A (en) * | 2010-07-23 | 2010-11-17 | 福州大学 | Process for extracting lithium from lithionite by fluorine chemistry |
| CN101974684A (en) * | 2010-11-26 | 2011-02-16 | 福州大学 | Process for removing impurities from lepidolite leaching solution |
| CN103601217A (en) * | 2013-11-26 | 2014-02-26 | 于岩 | Sodium fluoride production process and sodium fluoride mother liquor recycling process |
| WO2015155684A2 (en) * | 2014-04-09 | 2015-10-15 | Inis Biotech Llc | Process for obtaining lithium from aluminosilicates and intermediate compounds |
| CN105858676A (en) * | 2016-04-11 | 2016-08-17 | 福建瓮福蓝天氟化工有限公司 | Production method for coproducing sodium silicate and sodium fluoride |
-
2016
- 2016-12-23 CN CN201611206891.1A patent/CN106673021A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885496A (en) * | 2010-07-23 | 2010-11-17 | 福州大学 | Process for extracting lithium from lithionite by fluorine chemistry |
| CN101974684A (en) * | 2010-11-26 | 2011-02-16 | 福州大学 | Process for removing impurities from lepidolite leaching solution |
| CN103601217A (en) * | 2013-11-26 | 2014-02-26 | 于岩 | Sodium fluoride production process and sodium fluoride mother liquor recycling process |
| WO2015155684A2 (en) * | 2014-04-09 | 2015-10-15 | Inis Biotech Llc | Process for obtaining lithium from aluminosilicates and intermediate compounds |
| CN105858676A (en) * | 2016-04-11 | 2016-08-17 | 福建瓮福蓝天氟化工有限公司 | Production method for coproducing sodium silicate and sodium fluoride |
Non-Patent Citations (1)
| Title |
|---|
| SHI ZHONG-NING ET AL.: "Recovery of carbon and cryolite from spent pot lining of aluminium reduction cells by chemical leaching", 《TRANS. NONFERROUS MET. SOC. CHINA》 * |
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Application publication date: 20170517 |