CN108193058B - A method of extracting the ion liquid abstraction of lithium from salt lake - Google Patents
A method of extracting the ion liquid abstraction of lithium from salt lake Download PDFInfo
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- CN108193058B CN108193058B CN201711254492.7A CN201711254492A CN108193058B CN 108193058 B CN108193058 B CN 108193058B CN 201711254492 A CN201711254492 A CN 201711254492A CN 108193058 B CN108193058 B CN 108193058B
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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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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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
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
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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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/406—Mixtures at least one compound thereof being a heterocyclic compound
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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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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of from salt lake extract lithium ion liquid abstraction method, extracting process are as follows: (1) be concentrated, remove boron: salt lake bittern being concentrated by evaporation and introduces acidification pool, dinonyldiphenylamine and kerosene mixture is added after adjusting PH, obtains boron removal brine；(2) fractional extraction: organic phase and boron removal brine mixing-classifying are extracted；(3) ceramic membrane separation: load organic phases are separated by ceramic membrane；(4) demagging: being added concentrated ammonia liquor and remove the magnesium ion in lithium ion aqueous solution, the present invention according to different extraction concentration necessaries by extraction process be divided into primary extraction, it is advanced extract, quintessence takes, can satisfy different industrial requirements.In short, present invention process is reasonable, extraction yield is higher, extraction is with high purity, environmentally protective, it is suitble to different industrial productions with lithium processed.
Description
Technical field
The present invention relates to ion extractuin fields, and in particular to a kind of side for the ion liquid abstraction that lithium is extracted from salt lake
Method.
Background technique
Lithium is a kind of rare element, belongs to light metal class, Swede A Erfeitexun is sent out first in petalite within 1817
Existing lithium, produces lithium metal in 1855, just starts commercial scale lithium to the 1940s.The main character of lithium has: density
It is small, only 0.53 gram per centimeter3, it is most light metal；Fusing point is low (179 DEG C)；Lithium metal is very soft, and toughness is big, and ductility is good；Lithium has
Lithium6(Li6) and lithium6(Li7) two kinds of stable isotopes；The chemical activity of lithium is good.Lithium concentrate, lithiumation object and lithium metal have many
Advantageous property is widely applied in many departments.A small amount of lithium salts is added in aluminium cell, the physics of electrolyte can be substantially improved
Chemical property；Lithium concentrate or lithiumation object have biggish fluxing action when manufacturing glass；A small amount of lithiumation object is added in ceramics to drop
The sintering temperature of low ceramics-enamelware；A small amount of lithiumation object, which is added, can make thermal stability, mechanical stability and the change of lubricant
Learning stability is improved, therefore lithium concentrate or lithiumation object are largely used to the production of aluminium metallurgy, glass, china and pottery industry and lubricant
In.Lithium and lithiumation object can be used as high-energy fuel, lithium deuteride, and+and lithium tritide+is the important source material of hydrogen bomb, they are in nuclear energy and aerospace
Aspect plays an important role.Furthermore lithium and its compound are also used to synthetic rubber, alloy, high-energy battery, air-conditioning, medicine, welding
Etc..Scientists prophesy: lithium will play noticeable effect in terms of future source of energy (battery and nuclear fusion).Especially
It is the energy that 1g lithium is released by thermonuclear reaction in new energy field, is equivalent to more than 20,000 tons of high-quality coal combustion and is produced
Raw energy, lithium ion battery and nuclear fusion power generation are the hot spot directions nowadays studied, in view of it in atomic energy industry
Special performance, be otherwise known as " high-energy metals ".Many countries have made lithium from economic development needs and the consideration of national security angle
For strategic reserves substance and carry out extensive use technical research.
China is a big country with abundant lithium resource, and the lithium resource reserves that oneself verifies occupy the second in the world, especially
Liquid lithium ore resources are very rich, and the 87% of Zhan Quanguo gross reserves, it is mainly distributed on Qinghai, Tibet, Xinjiang and four, the Inner Mongol
Province, only the prospective reserves of Qinghai and Tibetan Salt Lakes brine lithium is just suitable with other countries, the world gross reserves that oneself verifies at present,
And have very high extraction value and huge potential economic benefit and the valuable source of China's Future Development lithium salts industry precious
Library.Therefore, it is necessary to reinforce the exploitation of China's brine lithium resource, promote the fast development of China's lithium salts industry.
In the prior art, Li Ye company in the U.S. proposes with -20% tributyl phosphate (TBP) of 80% diisobutyl ketone (DIBK)
The extraction system of composition extracts the method (US3537813) of lithium from high Mg/Li ratio brine, although diisobutyl ketone is for magnesium, lithium ion
Selectivity it is very strong, good separation, but the molten damage of diisobutyl ketone in water is serious and expensive.
In existing patent, a kind of method (CN103710549A) efficiently extracting lithium from salt lake bittern, provide it is a kind of from
Salt lake bittern efficiently extracts the method for mentioning lithium, method includes the following steps: (1) first forming extractant, co-extraction agent and diluent
Organic phase is extracted, then the extraction organic phase is mixed with salt lake bittern and is extracted, obtains organic phase；By step (1) in obtain
Organic phase mix and is stripped with back extraction acid solution, collecting water phase is the aqueous solution containing lithium ion, although this method step
It is rapid easy, using the cost of material is low, but in the aqueous solution containing lithium ion that is obtained by extraction of this method can containing a large amount of magnesium,
Boron plasma.
Summary of the invention
One kind that the technical problem to be solved by the present invention is to provide a kind of comprehensive recovery rates is higher, DNA purity is high is from salt lake
The method for extracting the ion liquid abstraction of lithium.
The technical solution of the present invention is as follows: a kind of method for the ion liquid abstraction that lithium is extracted from salt lake, including following step
It is rapid:
(1) it is concentrated, removes boron: the mode of salt lake bittern heating evaporation being concentrated, then draws the salt lake bittern after concentration
Enter acidification pool, addition and salt lake bittern volume ratio are the acidulant of 1:2~3 by brine pH value adjustment to 1~5, and body is then added
Boron ion is removed than the dinonyldiphenylamine and kerosene mixture that are 1:10, obtains boron removal brine by product；
(2) fractional extraction: the boron removal brine that step (1) is obtained introduces abstraction pool, is extracted by following steps
Extract operation:
Primary extraction: extractant, diluent are mixed into composition organic phase and boron removal brine and carried out with the volume ratio of 2~3:1
Mixing, the extractant account for the 80%~100% of organic phase total volume, the diluent account for organic phase total volume 0%~
20%, extraction times are 2 times, and single extraction time is 15min, and clarification is stood after the completion of extraction, and settling time 60min is clear
Isolated load organic phases A after clear；
Advanced extraction: by extractant, extraction agent, diluent is helped to mix composition organic phase and load organic phases A with 2~3:1's
Volume ratio is mixed, and the extractant accounts for the 20%~100% of organic phase total volume, described that extraction agent is helped to account for organic phase total volume
0%~30%, the diluent accounts for the 0%~50% of organic phase total volume, and extraction times are 6 times, and single extraction time is
25min stands clarification, settling time 60min, isolated load organic phases B after clarification after the completion of extraction；
(3) ceramic membrane separation: the obtained load organic phases B of step (2) is introduced into ceramic membrane separation device, then
Ceramic membrane separation device is sealed, open pressurizing device so that transmembrane pressure is reached 0.42MPa, using transmembrane pressure official post lithium ion,
By ceramic membrane, disengaging time 20min obtains water phase and organic phase cake layer, organic phase after the completion of separation for magnesium ion and water
Cake layer is reusable after recovery processing；
(4) demagging: the water phase obtained in step (3) is introduced into precipitating heating bath, concentrated ammonia liquor, the concentrated ammonia liquor is added
It is 3:1 with the volume ratio of water phase containing lithium, concentrated ammonia liquor is reacted with the magnesium ion in water phase containing lithium generates magnesium hydrate precipitate, by hydroxide
The filtering of magnesium magnesium precipitate removes the magnesium ion in water phase containing lithium, then by remaining heated aqueous containing lithium, evaporation is removed in water phase containing lithium
Ammonium chloride to get arrive the aqueous solution containing lithium ion.
Further, the acidulant in the step (1) is the hydrochloric acid and nitrate mixture that molar ratio is 3:1.
Further, the extractant in the step (2) is 1- phenylazo-beta naphthal, benzene that molar ratio is 3:4:3:1
The mixture of formyl acetone, thioyl trifluoroacetone and 1- ethyl-3-methylimidazole.
Further, in the step (2) helping extraction agent be molar ratio be 1:10:15 dimethyl sulfoxide, alkyl quaternary sulfonium
The mixture of salt and trioctylphosphine oxide.
Further, it is 4:2:1 o-dichlorohenzene, dodecane and sulfonated coal that the diluent in the step (2), which is molar ratio,
The mixture of oil.
Further, the ion adsorbent includes: 1%~5% microcosmic salt in percentage by weight, 13%~
15% hyperbranched polyamino, 20%~30%NSUL-2 adsorbent, 40%~45%TD-11 adsorbent, surplus are vermiculite, mixing
Adsorbent absorption can will in addition to lithium adsorption of metal ions, improve lithium ion solution purity, and it is at low cost, pollute small.
Further, step (1) is except being neutralized to 6.8~7.3 for brine pH value with sodium hydroxide after boron, later again into
Row extracting operation, when brine pH value is between 6.8~7.3, extraction efficiency highest.
Further, the method for the organic phase cake layer recovery processing in the step (3) is washing method, the washing used
Agent is saturated ammonium chloride, and organic phase is carried out recycling and reusing, both reduces production cost, also embodies green ring of the invention
It protects.
Further, the concentration for the concentrated ammonia liquor being added in the step (4) is 27%.
Further, the acidification pool, abstraction pool, ceramic membrane separation device, precipitating heating bath are all polytetrafluoroethylene (PTFE) one
System at, polytetrafluoroethylene (PTFE) have the characteristics that high-low temperature resistant, it is anticorrosive, insoluble in various organic solvents, be suitable as this most
The material of various equipment involved in invention.
Compared with prior art, the invention has the benefit that it is provided by the invention it is a kind of from salt lake extract lithium from
The method of sub- liquid extraction, using salt lake bittern → evaporation and concentration → acidification pool → abstraction pool → ceramic membrane separation device → precipitating
The step of heating bath, extracts lithium ion, is extracted again using first cleaning, then the method for reprecipitation, can be improved lithium from
The extraction purity of son, avoids the interference of other ions, and extraction series is divided into two primary extraction, advanced extraction steps, is improved
Then extraction purity is separated magnesium, lithium ion using Ceramic Membranes Separating Technique, the organic phase filter cake after separation by washing,
Can reuse, it is environmentally protective, compared with the existing technology in using the highly selective extraction lithium ion of expensive extractant side
Method, extractant, synergic reagent and the diluent that the present invention chooses all are that the cost performance selected while ensuring extraction efficiency is high
Material saves cost and time, has very big significance for industrial production.In short, present invention process rationally, extraction yield compared with
Height, extraction are with high purity, environmentally protective, are suitble to different industrial productions with lithium processed.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Embodiment 1
As shown in Figure 1, a kind of method for the ion liquid abstraction for extracting lithium from salt lake, comprising the following steps:
(1) it is concentrated, removes boron: the mode of salt lake bittern heating evaporation being concentrated, then draws the salt lake bittern after concentration
Enter acidification pool, acidification pool polytetrafluoroethylene (PTFE) is made into integration, polytetrafluoroethylene (PTFE) have high-low temperature resistant, it is anticorrosive, have insoluble in various
The characteristics of solvent, the material for being suitable as various equipment involved in the present invention the most, which is added with salt lake bittern volume ratio, is
For the acidulant of 1:2 by brine pH value adjustment to 1, acidulant is the hydrochloric acid and nitrate mixture that molar ratio is 3:1, and body is then added
Boron ion is removed than the dinonyldiphenylamine and kerosene mixture that are 1:10, obtains boron removal brine by product, with sodium hydroxide by halogen
Water pH value is neutralized to 6.8, carries out extracting operation again later；
(2) fractional extraction: the boron removal brine that step (1) is obtained introduces abstraction pool, is extracted by following steps
Extract operation:
Primary extraction: extractant, diluent are mixed into composition organic phase and mixed with boron removal brine with the volume ratio of 2:1
It closes, extractant is 1- phenylazo-beta naphthal, benzoyl acetone, thioyl trifluoroacetone and 1- that molar ratio is 3:4:3:1
The mixture of ethyl-3-methylimidazole, extractant account for the 80% of organic phase total volume, and diluent is that molar ratio is 4:2:1 neighbour two
The mixture of chlorobenzene, dodecane and sulfonated kerosene, diluent account for the 20% of organic phase total volume, and extraction times are 2 times, single extraction
Taking the time is 15min, stands clarification, settling time 60min, isolated load organic phases A after clarification after the completion of extraction；
Advanced extraction: by extractant, extraction agent, diluent is helped to mix composition organic phase and load organic phases A with the volume of 2:1
Than being mixed, extractant be molar ratio be 3:4:3:1 1- phenylazo-beta naphthal, benzoyl acetone, thenoyl trifluoro
The mixture of acetone and 1- ethyl-3-methylimidazole, extractant account for the 80% of organic phase total volume, and helping extraction agent be molar ratio is 1:
The mixture of the dimethyl sulfoxide of 10:15, alkyl quaternary sulfonium salt and trioctylphosphine oxide helps extraction agent to account for the 5% of organic phase total volume,
Diluent is the mixture that molar ratio is 4:2:1 o-dichlorohenzene, dodecane and sulfonated kerosene, and diluent accounts for organic phase total volume
15%, extraction times are 4 times, and single extraction time is 25min, and clarification is stood after the completion of extraction, and settling time 60min is clear
Isolated load organic phases B after clear；
(3) ceramic membrane separation: the obtained load organic phases B of step (2) is introduced into ceramic membrane separation device, then
Ceramic membrane separation device is sealed, open pressurizing device so that transmembrane pressure is reached 0.42MPa, using transmembrane pressure official post lithium ion,
By ceramic membrane, disengaging time 20min obtains water phase and organic phase cake layer, organic phase after the completion of separation for magnesium ion and water
Cake layer is reusable after recovery processing；
(4) demagging: water phase obtained in step (3) is introduced into precipitating heating bath, precipitating heating bath is polytetrafluoroethylene (PTFE) one
System at, concentrated ammonia liquor is added, the concentration of concentrated ammonia liquor is 27%, and concentrated ammonia liquor and the volume ratio of water phase containing lithium are 3:1, concentrated ammonia liquor with containing lithium
In water phase magnesium ion reaction generate magnesium hydrate precipitate, magnesium hydroxide magnesium precipitate is filtered, remove water phase containing lithium in magnesium from
Son, then by remaining heated aqueous containing lithium, evaporation removes the ammonium chloride in water phase containing lithium to get the aqueous solution containing lithium ion is arrived.
Embodiment 2
As shown in Figure 1, a kind of method for the ion liquid abstraction for extracting lithium from salt lake, comprising the following steps:
(1) it is concentrated, removes boron: the mode of salt lake bittern heating evaporation being concentrated, then draws the salt lake bittern after concentration
Enter acidification pool, acidification pool is made into integration for polytetrafluoroethylene (PTFE), polytetrafluoroethylene (PTFE) have high-low temperature resistant, it is anticorrosive, insoluble in various
The characteristics of organic solvent, the material for being suitable as various equipment involved in the present invention the most, which is added with salt lake bittern volume ratio, is
For the acidulant of 1:2.5 by brine pH value adjustment to 3, acidulant is the hydrochloric acid and nitrate mixture that molar ratio is 3:1, is then added
Volume ratio is the dinonyldiphenylamine and kerosene mixture of 1:10, and boron ion is removed, boron removal brine is obtained, will with sodium hydroxide
Brine pH value is neutralized to 7.0, carries out extracting operation again later；
(2) fractional extraction: the boron removal brine that step (1) is obtained introduces abstraction pool, is extracted by following steps
Extract operation:
Primary extraction: extractant, diluent are mixed into composition organic phase and mixed with boron removal brine with the volume ratio of 2:1
It closes, extractant is 1- phenylazo-beta naphthal, benzoyl acetone, thioyl trifluoroacetone and 1- that molar ratio is 3:4:3:1
The mixture of ethyl-3-methylimidazole, extractant account for the 90% of organic phase total volume, and diluent is that molar ratio is 4:2:1 neighbour two
The mixture of chlorobenzene, dodecane and sulfonated kerosene, diluent account for the 10% of organic phase total volume, and extraction times are 2 times, single extraction
Taking the time is 15min, stands clarification, settling time 60min, isolated load organic phases A after clarification after the completion of extraction；
Advanced extraction: by extractant, extraction agent, diluent is helped to mix composition organic phase and load organic phases A with the body of 2.5:1
Product ratio mixed, extractant be molar ratio be 3:4:3:1 1- phenylazo-beta naphthal, benzoyl acetone, thenoyl three
The mixture of fluorine acetone and 1- ethyl-3-methylimidazole, extractant account for the 50% of organic phase total volume, and helping extraction agent is that molar ratio is
The mixture of the dimethyl sulfoxide of 1:10:15, alkyl quaternary sulfonium salt and trioctylphosphine oxide helps extraction agent to account for organic phase total volume
25%, diluent is the mixture that molar ratio is 4:2:1 o-dichlorohenzene, dodecane and sulfonated kerosene, and it is total that diluent accounts for organic phase
The 25% of volume, extraction times are 4 times, and single extraction time is 25min, stand clarification after the completion of extraction, settling time is
60min, isolated load organic phases B after clarification；
(3) ceramic membrane separation: the obtained load organic phases B of step (2) is introduced into ceramic membrane separation device, then
Ceramic membrane separation device is sealed, open pressurizing device so that transmembrane pressure is reached 0.42MPa, using transmembrane pressure official post lithium ion,
By ceramic membrane, disengaging time 20min obtains water phase and organic phase cake layer, organic phase after the completion of separation for magnesium ion and water
Cake layer is reusable after recovery processing；
(4) demagging: water phase obtained in step (3) is introduced into precipitating heating bath, precipitating heating bath is polytetrafluoroethylene (PTFE) one
System at, concentrated ammonia liquor is added, the concentration of concentrated ammonia liquor is 27%, and concentrated ammonia liquor and the volume ratio of water phase containing lithium are 3:1, concentrated ammonia liquor with containing lithium
In water phase magnesium ion reaction generate magnesium hydrate precipitate, magnesium hydroxide magnesium precipitate is filtered, remove water phase containing lithium in magnesium from
Son, then by remaining heated aqueous containing lithium, evaporation removes the ammonium chloride in water phase containing lithium to get the aqueous solution containing lithium ion is arrived.
Embodiment 3
As shown in Figure 1, a kind of method for the ion liquid abstraction for extracting lithium from salt lake, comprising the following steps:
(1) it is concentrated, removes boron: the mode of salt lake bittern heating evaporation being concentrated, then draws the salt lake bittern after concentration
Enter acidification pool, acidification pool is made into integration for polytetrafluoroethylene (PTFE), polytetrafluoroethylene (PTFE) have high-low temperature resistant, it is anticorrosive, insoluble in various
The characteristics of organic solvent, the material for being suitable as various equipment involved in the present invention the most, which is added with salt lake bittern volume ratio, is
For the acidulant of 1:3 by brine pH value adjustment to 5, acidulant is the hydrochloric acid and nitrate mixture that molar ratio is 3:1, and body is then added
Boron ion is removed than the dinonyldiphenylamine and kerosene mixture that are 1:10, obtains boron removal brine by product, with sodium hydroxide by halogen
Water pH value is neutralized to 7.3, carries out extracting operation again later；
(2) fractional extraction: the boron removal brine that step (1) is obtained introduces abstraction pool, is extracted by following steps
Extract operation:
Primary extraction: extractant, diluent are mixed into composition organic phase and mixed with boron removal brine with the volume ratio of 2:1
It closes, extractant is 1- phenylazo-beta naphthal, benzoyl acetone, thioyl trifluoroacetone and 1- that molar ratio is 3:4:3:1
The mixture of ethyl-3-methylimidazole, extractant account for the 95% of organic phase total volume, and diluent is that molar ratio is 4:2:1 neighbour two
The mixture of chlorobenzene, dodecane and sulfonated kerosene, diluent account for the 5% of organic phase total volume, and extraction times are 2 times, single extraction
Taking the time is 15min, stands clarification, settling time 60min, isolated load organic phases A after clarification after the completion of extraction；
Advanced extraction: by extractant, extraction agent, diluent is helped to mix composition organic phase and load organic phases A with the volume of 3:1
Than being mixed, extractant be molar ratio be 3:4:3:1 1- phenylazo-beta naphthal, benzoyl acetone, thenoyl trifluoro
The mixture of acetone and 1- ethyl-3-methylimidazole, extractant account for the 30% of organic phase total volume, and helping extraction agent be molar ratio is 1:
The mixture of the dimethyl sulfoxide of 10:15, alkyl quaternary sulfonium salt and trioctylphosphine oxide helps extraction agent to account for organic phase total volume
30%, diluent is the mixture that molar ratio is 4:2:1 o-dichlorohenzene, dodecane and sulfonated kerosene, and it is total that diluent accounts for organic phase
The 40% of volume, extraction times are 4 times, and single extraction time is 25min, stand clarification after the completion of extraction, settling time is
60min, isolated load organic phases B after clarification；
(3) ceramic membrane separation: the obtained load organic phases B of step (2) is introduced into ceramic membrane separation device, then
Ceramic membrane separation device is sealed, open pressurizing device so that transmembrane pressure is reached 0.42MPa, using transmembrane pressure official post lithium ion,
By ceramic membrane, disengaging time 20min obtains water phase and organic phase cake layer, organic phase after the completion of separation for magnesium ion and water
Cake layer is reusable after recovery processing；
(4) demagging: water phase obtained in step (3) is introduced into precipitating heating bath, precipitating heating bath is polytetrafluoroethylene (PTFE) one
System at, concentrated ammonia liquor is added, the concentration of concentrated ammonia liquor is 27%, and concentrated ammonia liquor and the volume ratio of water phase containing lithium are 3:1, concentrated ammonia liquor with containing lithium
In water phase magnesium ion reaction generate magnesium hydrate precipitate, magnesium hydroxide magnesium precipitate is filtered, remove water phase containing lithium in magnesium from
Son, then by remaining heated aqueous containing lithium, evaporation removes the ammonium chloride in water phase containing lithium to get the aqueous solution containing lithium ion is arrived.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify to technical solution documented by previous embodiment or equivalent replacement of some of the technical features；And
These are modified or replaceed, the spirit and model of technical solution of the embodiment of the present invention that it does not separate the essence of the corresponding technical solution
It encloses.
Claims (5)
1. a kind of method for the ion liquid abstraction for extracting lithium from salt lake, which comprises the following steps:
(1) it is concentrated, removes boron: the mode of salt lake bittern heating evaporation is concentrated, the salt lake bittern after concentration is then introduced into acid
Change pond, addition and salt lake bittern volume ratio are the acidulant of 1:2~3 by brine pH value adjustment to 1~5, and volume ratio is then added
For the dinonyldiphenylamine and kerosene mixture of 1:10, boron ion is removed, obtains boron removal brine；
(2) fractional extraction: the boron removal brine that step (1) is obtained introduces abstraction pool, carries out extraction behaviour by following steps
Make:
Primary extraction: being mixed composition organic phase for extractant, diluent and mixed with boron removal brine with the volume ratio of 2~3:1,
The extractant accounts for the 80%~100% of organic phase total volume, and the diluent accounts for the 0%~20% of organic phase total volume, extraction
Taking number is 2 times, and single extraction time is 15min, stands clarification after the completion of extraction, settling time 60min is separated after clarification
Obtain load organic phases A；
Advanced extraction: by extractant, extraction agent, diluent is helped to mix composition organic phase and load organic phases A with the volume of 2~3:1
Than being mixed, the extractant accounts for the 20%~100% of organic phase total volume, described that extraction agent is helped to account for organic phase total volume
0%~30%, the diluent accounts for the 0%~50% of organic phase total volume, and extraction times are 6 times, and single extraction time is
25min stands clarification, settling time 60min, isolated load organic phases B after clarification after the completion of extraction；
(3) ceramic membrane separation: introducing ceramic membrane separation device for the obtained load organic phases B of step (2), then will pottery
Porcelain membrane separation plant sealing, open pressurizing device so that transmembrane pressure is reached 0.42MPa, using transmembrane pressure official post lithium ion, magnesium from
By ceramic membrane, disengaging time 20min obtains water phase and organic phase cake layer, organic phase filter cake after the completion of separation for son and water
Layer is reusable after recovery processing；
(4) demagging: by the water phase obtained in step (3) introduce precipitating heating bath, be added concentrated ammonia liquor, the concentrated ammonia liquor with contain
Lithium water phase volume ratio is 3:1, and concentrated ammonia liquor is reacted with the magnesium ion in water phase containing lithium generates magnesium hydrate precipitate, and magnesium hydroxide is sunk
It forms sediment and filters, remove the magnesium ion in water phase containing lithium, then by remaining heated aqueous containing lithium, evaporation removes the chlorination in water phase containing lithium
Ammonium to get arrive the aqueous solution containing lithium ion；
Acidulant in the step (1) is the hydrochloric acid and nitrate mixture that molar ratio is 3:1；
Extractant in the step (2) be molar ratio be 3:4:3:1 1- phenylazo-beta naphthal, benzoyl acetone, thiophene
The mixture of formyl trifluoroacetone and 1- ethyl-3-methylimidazole；
The extraction agent that helps in the step (2) is dimethyl sulfoxide, alkyl quaternary sulfonium salt and the trioctylphosphine oxidation that molar ratio is 1:10:15
The mixture of phosphorus；
Diluent in the step (2) is the mixture that molar ratio is 4:2:1 o-dichlorohenzene, dodecane and sulfonated kerosene.
2. a kind of method of ion liquid abstraction for extracting lithium from salt lake as described in claim 1, which is characterized in that step
(1) after removing boron, brine pH value is neutralized to 6.8~7.3 with sodium hydroxide, carries out extracting operation again later.
3. a kind of method of ion liquid abstraction for extracting lithium from salt lake as described in claim 1, which is characterized in that described
The method of organic phase cake layer recovery processing in step (3) is to be washed using saturated ammonium chloride.
4. a kind of method of ion liquid abstraction for extracting lithium from salt lake as described in claim 1, which is characterized in that described
The concentration for the concentrated ammonia liquor being added in step (4) is 27%.
5. a kind of method of ion liquid abstraction for extracting lithium from salt lake as described in claim 1, which is characterized in that described
Acidification pool, abstraction pool, separation equipment, precipitating heating bath are all made into integration for polytetrafluoroethylene (PTFE).
Priority Applications (1)
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| CN109355502B (en) * | 2018-11-16 | 2020-09-29 | 山西大学 | Method for extracting lithium ions from acid system |
| CN110527850B (en) * | 2019-10-08 | 2020-06-23 | 中国科学院过程工程研究所 | Method for extracting and separating lithium based on ketone group functionalized ionic liquid |
| CN115028149A (en) * | 2022-03-15 | 2022-09-09 | 瑜华科技(上海)有限公司 | Membrane method lithium extraction process for salt lake |
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| US7157065B2 (en) * | 1998-07-16 | 2007-01-02 | Chemetall Foote Corporation | Production of lithium compounds directly from lithium containing brines |
| US9034294B1 (en) * | 2009-04-24 | 2015-05-19 | Simbol, Inc. | Preparation of lithium carbonate from lithium chloride containing brines |
| WO2012005548A2 (en) * | 2010-07-09 | 2012-01-12 | Research Institute Of Industrial Science & Technology | Method for economical extraction of magnesium,boron and calcium from lithium bearing solution |
| AR083538A1 (en) * | 2011-10-24 | 2013-03-06 | Minera Exar S A | HIGH PURITY LITHIUM CARBONATE PRODUCTION BATTERY DEGREE FROM NATURAL OR INDUSTRIAL SALMUERAS |
| CN102491379A (en) * | 2011-12-10 | 2012-06-13 | 中南大学 | Method for preparing high-purity magnesium oxide with high boron salt lake brine |
| CN102633284B (en) * | 2012-05-08 | 2014-03-19 | 湘潭大学 | Method for separating magnesium and extracting lithium from salt lake brine with high magnesium-lithium ratio |
| WO2014078908A1 (en) * | 2012-11-23 | 2014-05-30 | Ady Resources Limited | Process for recovering lithium from a brine with reagent regeneration and low cost process for purifying lithium |
| CN103074502B (en) * | 2013-01-29 | 2014-04-23 | 中国科学院青海盐湖研究所 | Salt lake brine treatment method for separating lithium from high-magnesium-lithium-ratio salt lake brine |
| CN103710549B (en) * | 2013-12-13 | 2016-03-23 | 天津科技大学 | A kind of method efficiently extracting lithium from salt lake brine |
| CN104313348B (en) * | 2014-07-23 | 2017-08-08 | 江苏久吾高科技股份有限公司 | A kind of method that absorption method extracts Lithium from Salt Lake Brine |
| CN106337138A (en) * | 2016-11-03 | 2017-01-18 | 深圳市捷鑫资产管理有限公司 | Technology for preparing high-purity anhydrous lithium chloride through centrifugal extraction of salt lake brine |
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