CN106507816B - The method for extracting lithium from bittern - Google Patents
The method for extracting lithium from bitternInfo
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- CN106507816B CN106507816B CN200510097239.6A CN200510097239A CN106507816B CN 106507816 B CN106507816 B CN 106507816B CN 200510097239 A CN200510097239 A CN 200510097239A CN 106507816 B CN106507816 B CN 106507816B
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- lithium
- bittern
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- demagging
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Abstract
A kind of method for extracting lithium from bittern, is related to carry lithium in a kind of bittern from high Mg/Li ratio.Which is mainly characterized by comprising the steps of：First the solution of the bittern water or chloride containing lithium of high Mg/Li ratio is diluted, the lithium adsorbent that be mounted in post is run through again with selective absorption lithium, then rinsed with water or sodium chloride solution, to remove magnesium as far as possible, then with the lithium on lithium chloride solution or water wash adsorbent, by the demagging of leacheate depth and concentrate again, up to 20～120g/L, magnesium density is then less than 100mg/L to so obtained solution chlorination lithium concentration.With this method operation, cycle is short and economical and effective.The present invention is suitable for from former halogen and shining extraction lithium the old halogen of carnallite.
Description
Technical field
The present invention relates to a kind of method for carrying lithium in bittern from high Mg/Li ratio, and in particular to a kind of
By absorption and method of the desorption operations demagging effectively to reclaim lithium.
Background technology
Lithium as important rare element, its metal and compound chemical industry, metallurgy, the energy and
The fields such as material are widely used.Al-Li bianry alloys, Al-Mg-Li ternary alloy three-partalloys are new
The Aeronautics and Astronautics material of a generation, its isotope are thermonuclear materials, and following controlled fusion is anti-
The potential energy source of pile power generating is answered, therefore lithium becomes one of military project goods and materials with strategic importance, has
High strategic value.
China is a lithium resource reserves big country, and explored lithium resource commercial reserves is in the world
Bolivia is only second to, second is occupied, wherein bittern lithium accounts for 79%, and prospective reserves is more considerable.
The external bittern for carrying out carrying lithium is only limitted to the bittern relatively low containing magnesium density now, and Mg/Li ratio value is little
In 6: 1, and China's majority saline lake lithium resource Mg/Li ratio is up to 500: 1～1500: 1, put forward lithium work
Skill is relative complex, and there is presently no successful knowhow can use for reference.
High to more than one gram but most little up to per liter of hundreds of milligram of Qinghai Salt Lake lithium content
In 100mg/L, Qinghai potash fertilizer plant shines the lithium content of the old halogen of carnallite and is about 200mg/L, because
There is no the recovery technology of maturation, can only arrange outward, the lithium of annual thousands of tons of effectively cannot be reclaimed.
The method for extracting lithium from salt lake bittern has salting out method, roasting method, the precipitation method, ion to hand over
Change method, solvent extraction etc..To the bittern that lithium content is high, calcium-magnesium content is low, Na can be used2CO3
Step-by-step precipitation method produces Li2CO3, solvent extraction can use alkylphenol high molecular polymer,
TBP+FeCl3, the organic solvent such as crown ether or phosphate ester make extractant, use Na2CO3, NaHCO3
Or HCl back extraction.Extraction carries lithium and typically all adopts rich lithium bittern as raw materials for production, production
Raw material has limitation, causes equipment corrosion serious using HCl back extraction, and production cost is high.
Amberplex separation and recovery lithium is may also be employed, but cationic ion-exchange resin is not selected to lithium
Property, lithium cannot be separated from a large amount of alkali metal or alkaline-earth metal by exclusive use.The Chinese Academy of Sciences
" method of extracting lithium from salt lake brine by adsorption " (application of Qinghai Salt Lake research institute invention
Number it is 02145583.X) to disclose a kind of can be used for lithium being carried in the higher bittern of Mg/Li ratio
Method, but can see from its specific embodiment, and the method provided by the invention is being inhaled
Echo desorption phase and do not provide time of contact, time of contact studies and judges performance of the adsorbent quality
One of key parameter, from terms of the total residence time which is given, a cycle is got off, most short also will
Nearly 10 hours are too low for obvious efficiency in industrial production.In addition, in the invention operation
Also need to one again saturation the step of, this not only increased the complexity of operation so that production
Cycle is longer, and carries out saturation due to the LiCl solution with 2～2.5g/L free from foreign meter
Adsorb again, increase production process interior circulation.Therefore it provides a kind of with short production cycle and more
Economic method is necessary.
Content of the invention
It is an object of the invention to provide a kind of method for extracting lithium in bittern from high Mg/Li ratio, should
Method is with short production cycle compared with the conventional method, more economical, and possesses its all of effect and excellent
Point.
The present invention is implemented by：
1st, by pending bittern with containing solution that lithium concentration is 0～200mg/L dilution 5～
30%.
2nd, by dilution after bittern sedimentation or flow through a filter to remove suspended particulate therein
Thing.
3rd, by dilution after bittern flow through adsorption tower equipped with lithium adsorbent, adsorb time of contact
For 2～30 minutes.
4th, after adsorbent reaches displacement volume, adsorption tower is cut, with the chlorine of 0～300g/L
Change the magnesium in sodium solution drip washing adsorption column, time of contact is 1～20 minute.
5th, with the 0.1% sodium chloride solution wash-out adsorbent of chloride containing 0～1200mg/L of lithium
Lithium, time of contact are 3～30 minutes, obtain the drip washing that chlorination lithium content and purity all improve
Liquid.
In said method, step 5 can be replaced following operating procedure, during the contact of drip washing operation
Between be change, front 6 bed volumes are slow, and 12 bed volumes of back are then fast again.And
The eluent for being used is also change, and started is the lithium chloride solution of 1200mg/L,
Then the concentration of lithium chloride is gradually lowered, to being finally changed to use water wash.
Present invention additionally comprises follow-up operating procedure, i.e., qualified leacheate is carried out depth demagging,
The operation such as concentration.The demagging of qualified leacheate depth can adopt with ion-exchange demagging or with change
Precipitation method demagging is learned, concentration can be adopted and be concentrated with Pro-concentration with ion exchange process or reverse osmosis concentration or too
Positive energy natural evaporation concentration.Certainly, the present invention is also not excluded for other operations, as long as these
Operation is effective to removing magnesium and concentration lithium.
So, after follow-up demagging and concentration operation, the Chlorine in Solution lithium for obtaining is dense
Degree is up to 20～120g/L, and magnesium density is then less than 100mg/L, and these technical indicators are existing
There is the failed realization of technology.
The invention has the advantages that：
1st, this technique be the applied widely of bittern to adsorbing stoste, absorption stoste pH value for 4～
9, the pH value of acid or alkali de-regulation bittern need not be consumed.
2nd, the water lithium chloride solution using water and low concentration makees eluent, and reagent expense is low.
3rd, increase by a step before drip washing and wash magnesium operation so that magnesium density is lower in leacheate, from
And reduce the expense of depth demagging.
4th, whole production process is operated under near-neutral sulfite deinking, and operating condition is good, and equipment need not
Special preservative treatment, low equipment investment.
5th, carry in the bittern after lithium (i.e. adsorption tail liquid) and do not introduce other chemical substances, can
To be directly expelled back in concentraing pond, discarded object is not affected on environment.
Specific embodiment
With reference to embodiment, the present invention is described in detail.
In following illustrated embodiment, Ф 100 × 2000mm Organic glass columns are adopted, built-in
12 liters of lithium adsorbent, four posts are one group, three post series connection absorption, another post drip washing.
Certainly, according to operating procedure disclosed by the invention and having related parameter, those skilled in the art
The purpose of the present invention can be realized, and is not limited to using concrete according to the operating principle of this method
Adsorption column used in embodiment itself and its occupation mode.
Embodiment 1.
The total 300L of bittern for extracting lithium, Li concentration is 159mg/L, and Mg concentration is
79g/L.With water by dilution 5%, then be run through adsorption column, absorption time of contact is 20
Minute.Passed through 10 minutes with the speed of 1 minute time of contact with water after first post saturation, with to the greatest extent
Amount is except the magnesium of deentrainment.Then with 0.1% sodium chloride solution and water of chloride containing lithium 200mg/L
Substep drip washing lithium, the time of contact of drip washing lithium is 10 minutes.Through so operation, adsorb tail
33.3mg/L containing Li in liquid, the qualified leacheate of gained (6 bed volumes) 2400mg/L containing LiCl,
Mg720mg/L.Next demagging is precipitated to above-mentioned qualified leacheate sodium carbonate, then by steaming
Concentration is sent out, then can be obtained for directly preparing the lithium solution of lithium carbonate etc..
Embodiment 2.
240L is had for extracting the bittern of lithium, absorption bittern used is 252mg/L containing Li,
Mg concentration is 113g/L.With discharge in embodiment one wash magnesium liquid by dilution 17%, then make
By adsorption column, absorption time of contact is 5 minutes, with water with time of contact after first post saturation
The speed of 1 minute removed magnesium by 10 minutes to try one's best.Then chloride containing lithium 1000mg/L is used
0.1% sodium chloride solution and moisture step drip washing lithium, drip washing operation opened for substep speed change drip washing
The time of contact that begins when taking qualified leacheate is 10 minutes, then time of contact be changed to 5 minutes.
Through so operation, 102mg/L containing Li in adsorption tail liquid, the qualified leacheate of gained (6
Bed volume) 2322mg/L containing LiCl, Mg 860mg/L.
Next to above-mentioned qualified leacheate spent ion exchange resin demagging then dense by evaporating
Contracting, depth demagging of the Mg concentration less than 30mg/L is concentrated up to 60g/L to obtain LiCl concentration
Liquid, can be used to directly prepare lithium carbonate or lithium chloride.
Embodiment 3.
240L is had for extracting the bittern of lithium, absorption bittern used is 252mg/L containing Li,
Mg concentration is 113g/L.With discharge in embodiment two wash magnesium liquid by dilution 30%, then make
By adsorption column, absorption time of contact is 3 minutes, with the NaCl of 200g/L after first post saturation
Solution removes magnesium to try one's best with the speed of 10 minutes times of contact by 3 bed volumes.So
Afterwards with the 0.1% sodium chloride solution and moisture step drip washing lithium of chloride containing lithium 1200mg/L, drip washing
Operate as substep speed change drip washing, time of contact when starting to take qualified leacheate is 10 minutes,
Then time of contact is changed to 5 minutes.Through so operation, in adsorption tail liquid, contain Li120mg/L,
The qualified leacheate of gained (6 bed volumes) 2400mg/L containing LiCl, Mg 810mg/L.
Next to above-mentioned qualified leacheate spent ion exchange resin demagging, then pass through ion exchange
Resin concentration is concentrated, then can obtain for directly preparing the lithium solution of lithium carbonate etc..
Claims (3)
1. a kind of method for carrying lithium in bittern from high Mg/Li ratio, comprises the following steps：1. will treat
The bittern of process is with containing the solution dilution 5～30% that lithium concentration is 0～200mg/L；2. will be dilute
Bittern after releasing flows through a filter to remove suspended particulate substance therein；3. by filtration after
Bittern flows through the adsorption tower equipped with adsorbent, and absorption time of contact is 2～30 minutes；4. inhale
After attached dose reaches displacement volume, adsorption tower is cut, with the sodium chloride solution of 0～300g/L
The magnesium rinsed in adsorption tower, time of contact are 1～20 minute；5. then with chloride containing lithium 0～
Lithium on the 0.1% sodium chloride solution drip washing adsorbent of 1200mg/L, time of contact are 3～30
Minute, obtain the leacheate that chlorination lithium content and purity all improve；6. by qualified leacheate
Depth demagging is simultaneously concentrated.
2. method according to claim 1, it is characterised in that：5. step is replaced with
Following operating procedure, the time of contact of drip washing operation are to change, and front 6 bed volumes are slow,
12 bed volumes of back are then fast again, and the eluent for being used is also change, opens
Begun is the lithium chloride solution of 1200mg/L, is then gradually lowered the concentration of lithium chloride, arrives
Finally it is changed to use water wash.
3. method according to claim 1, it is characterised in that：Step 6. qualified leacheate
Depth demagging using ion-exchange demagging or uses chemical precipitation method demagging, concentrates and is handed over using ion
Change enrichment concentration or reverse osmosis concentration or solar energy is concentrated by evaporation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510097239.6A CN106507816B (en) | 2005-12-30 | 2005-12-30 | The method for extracting lithium from bittern |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510097239.6A CN106507816B (en) | 2005-12-30 | 2005-12-30 | The method for extracting lithium from bittern |
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| CN106507816B true CN106507816B (en) | 2010-09-08 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108996528A (en) * | 2018-09-27 | 2018-12-14 | 中蓝长化工程科技有限公司 | A kind of old halogen in salt pan proposes lithium method |
| CN109052435A (en) * | 2018-09-27 | 2018-12-21 | 中蓝长化工程科技有限公司 | A kind of adsorption tower group mentioning lithium for salt lake bittern |
| CN109354043A (en) * | 2018-11-14 | 2019-02-19 | 格尔木藏格锂业有限公司 | Clean the method for mentioning lithium from super low concentration brine containing lithium |
| CN113368537A (en) * | 2021-06-28 | 2021-09-10 | 青海盐湖工业股份有限公司 | Method and device for preparing high-lithium mother liquor by using old brine through adsorption method |
-
2005
- 2005-12-30 CN CN200510097239.6A patent/CN106507816B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108996528A (en) * | 2018-09-27 | 2018-12-14 | 中蓝长化工程科技有限公司 | A kind of old halogen in salt pan proposes lithium method |
| CN109052435A (en) * | 2018-09-27 | 2018-12-21 | 中蓝长化工程科技有限公司 | A kind of adsorption tower group mentioning lithium for salt lake bittern |
| CN108996528B (en) * | 2018-09-27 | 2019-08-09 | 中蓝长化工程科技有限公司 | A kind of old halogen in salt pan proposes lithium method |
| CN109354043A (en) * | 2018-11-14 | 2019-02-19 | 格尔木藏格锂业有限公司 | Clean the method for mentioning lithium from super low concentration brine containing lithium |
| CN109354043B (en) * | 2018-11-14 | 2021-03-23 | 格尔木藏格锂业有限公司 | Method for removing impurities and extracting lithium from ultra-low concentration lithium-containing brine |
| CN113368537A (en) * | 2021-06-28 | 2021-09-10 | 青海盐湖工业股份有限公司 | Method and device for preparing high-lithium mother liquor by using old brine through adsorption method |
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