CN102633284B - Method for separating magnesium and extracting lithium from salt lake brine with high magnesium-lithium ratio - Google Patents
Method for separating magnesium and extracting lithium from salt lake brine with high magnesium-lithium ratio Download PDFInfo
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- CN102633284B CN102633284B CN201210143879.6A CN201210143879A CN102633284B CN 102633284 B CN102633284 B CN 102633284B CN 201210143879 A CN201210143879 A CN 201210143879A CN 102633284 B CN102633284 B CN 102633284B
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Abstract
The invention discloses a method for separating magnesium and extracting lithium from salt lake brine with a high magnesium-lithium ratio. With adoption of the method, tributyl phosphate is taken as an extractant, number 200 solvent oil or kerosene is taken as a diluent, perchlorate is taken as a co-extraction agent, and water is taken as a stripping agent to form an extraction system; and lithium carbonate is prepared through extraction, reversed-phase extraction and deep magnesium removal by the salt lake brine. The method has the following beneficial effects: 1. the property of the co-extraction agent is stable, lithium magnesium separation can be carried out in neutral brine and the pH value of an aqueous phase needs not to be controlled; 2. the emulsification phenomenon doesn't exist and a third phase doesn't appear in the extraction process, two phases are easy to separate, the reversed-phase extraction is carried out by water and the device has little corrosion; and 3. the whole technique is simple in process, high in lithium extraction rate, good in separation effect and low in economic cost, is suitable for industrial production of the salt lake brine and is low in environmental damage degree because the co-extraction agent in water can be recycled.
Description
Technical field
The invention belongs to field of inorganic chemical engineering, relate to a kind of technology of extracting lithium from salt lake brine, refer more particularly to a kind of from high Mg/Li ratio bittern separating magnesium and extract the method for lithium.
Background technology
Recent two decades comes, lithium and compound thereof obtain increasingly extensive application because of its excellent properties, the whole world constantly increases the demand of lithium, and saline lake lithium resource accounts for 69% of world's lithium resource industrial reserves, and wherein first low Mg/Li ratio bittern Chile's Atacama type salt lake is developed.China Shi Yige salt lake resources big country, liquid lithium resource is very abundant, yet the most of salt lake of China has the high feature of magnesium lithium mass ratio, if the magnesium lithium mass ratio in the salt lakes such as large bavin dawn, Yi Liping, East Taijinaier, West Taijinar and Cha Er sweat is all more than 40～1800, the similarity of magnesium lithium character is brought difficulty to the exploitation of salt lake resources.Will from bittern, extract the necessary first separating magnesium of lithium, in bittern, the method for separating Li magnesium mainly contains at present: the precipitator method, calcination method, absorption method and extraction process etc.Wherein precipitator method alkali consumption is large, the lithium rate of recovery is low, is not suitable for processing bittern and the low lithium bittern containing a large amount of alkaline-earth metal.Calcination method is dry through spraying, roasting and leaching process, and water yield evaporation is large, energy consumption is high, equipment corrosion is serious, byproduct outlet is narrow.The key of absorption method is sorbent material, and lithium ion sieve type manganese oxygen, titanyl material come into one's own, but its actual adsorptive capacity is on the low side, poor permeability, has molten damage, granulation problem.By contrast, the advantage such as solvent extration has can operate continuously, concentration ratio is high, equipment is simple, turnout is large, key is the selection of extraction agent and determining of abstraction technique.Wherein tributyl phosphate (TBP) and FeCl
3extract altogether system once by primary study, described in document CN87103431A, its technique bottleneck is that bittern extraction will carry out under acidic conditions, Li
+back extraction require with 6～9mol/L hydrochloric acid soln, in extraction, have emulsion and third phase to occur, therefore so far there are no, and industrialization is reported.The people such as Zhou adopt ZnCl
2, CrCl
3extract altogether agent and under 3 kinds of thinners, the Extraction behavior of TBP studied, but do not obtain improvement effect (Zhou Z.-Y., Qin W., Fei W.-Y..J.Chem.Eng.Data, 2011,56,3518-3522).And when using TBP in document CN101698488A and CN102275956A, adopt acid amides, alcohol or ketone to help extraction agent, still adopt FeCl
3extract altogether back extraction under agent and acidic conditions and carry lithium, need make molysite reside in organic phase always, technological improvement degree has its limitation.
Summary of the invention
The object of the invention is for the deficiency existing in art methods, a kind of method of cost-effective separating magnesium and extraction lithium is provided.
Technical scheme provided by the invention and technological process are as follows:
A method for separating magnesium and extraction lithium from high Mg/Li ratio salt lake brine, comprises the following steps:
1) preparation of bittern: after concentrated to Exposure to Sunlight or the magnesium lithium mass ratio of sylvite after extracting be to add perchlorate to extract altogether agent in the bittern of 10: 1～500: 1, extracting altogether agent and lithium mol ratio is 0.5: 1～3: 1, brine ph is in 1～9 scope.
2) extraction: carry out bittern extraction with tributyl phosphate as organic phase, extraction phase compares V
o/ V
wbe 0.5: 1～3: 1,1～5 grade of extraction progression, single extraction time 1～30min, 0～60 ℃ of extraction temperature.
3) reversed phase extraction: use water as reverse-extraction agent, to carrying out reversed phase extraction containing lithium organic phase, V is compared in back extraction
w/ V
obe 0.02: 1～2: 1,1～5 grade of back extraction progression, single back extraction time 1～30min, 0～100 ℃ of back extraction temperature.
4) organic phase circulation: last step back extraction organic phase is transferred to the 1st grade of extraction plant, and extraction phase recycles.
5) degree of depth demagging: add sodium carbonate or caustic soda in strip aqueous, be settled out magnesiumcarbonate or magnesium hydroxide, control pH value of solution>=12, make Mg
2+precipitation is complete, filtering separation.
6) prepare Quilonum Retard: in the strip aqueous after degree of depth demagging, add sodium carbonate, produce Quilonum Retard precipitation, after filtering, being dried, make lithium carbonate product; After carrying lithium, strip aqueous is carried out internal recycling, extracts altogether the rear Reusability of agent recycling in water.
7) it is a kind of or its mixture in sodium perchlorate, potassium perchlorate, magnesium perchlorate and calcium perchlorate that the perchlorate that the present invention adopts extracts agent altogether; The organic phase thinner adopting is No. 200 solvent oils or kerosene, and its volumn concentration is less than 50%.
The present invention compared with prior art has the following advantages:
1) in solvent extraction process, use perchlorate to extract altogether agent, lipophilicity negatively charged ion perchlorate stable in properties, existence form is not subject to the impact of brine ph; Lithium ion enters organic phase by the microemulsion phase that comprises nanometer water core, presents special selectivity and high percentage extraction, and Separation of Li and Mg is respond well.
2) bittern extraction is carried out under neutrality, slightly acidic or weak basic condition, and pH subject range is wide; Two-phase is easily separated, without emulsion and third phase, occurs; Water replaces hydrochloric acid to make reverse-extraction agent, has fundamentally solved FeCl
3altogether in extraction process equipment corrosion and need in consumption alkali and etc. problem.
3) the method can be processed high Mg/Li ratio bittern such as boracic, containing sulfate radicals, and strong adaptability, Financial cost are low, can strictly control the discharge of magnesium-containing brine in production process, little to environmental disruption degree.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention will be further described:
Embodiment 1:
Technical process as shown in Figure 1.
1) get the bittern 50mL after concentrating, wherein contain: Li
+2.21g/L, Mg
2+100.71g/L, Na
+3.53g/L, K
+1.85g/L, magnesium lithium mass ratio is 45.6.
2) in bittern, add common extraction agent sodium perchlorate, consumption with
be as the criterion, stir at 25 ℃, dissolve, be extracted front aqueous salt brine, pH equals 5.
3) in adding organic phase TBP with the isopyknic ratio of water, carry out single extraction at 25 ℃, extraction time of vibration 10min, standing 15min, then two be separated.
4) with pure water, doing reverse-extraction agent, is to mix at 1: 1 by organic phase and water volume ratio, carries out back extraction at 25 ℃, back extraction time 10min, and standing 15min, then two is separated.
5) after back extraction, water regulates pH>=12 with caustic soda, and magnesium is with Mg (OH)
2form Precipitation, adds sodium carbonate solution to produce precipitation in water after filtering, after separated, dry lithium carbonate product.
After testing, lithium percentage extraction reaches 45.8%, magnesium percentage extraction is 5.3%, and lithium back extraction ratio reaches 64.1%, magnesium back extraction ratio is 69.2%, and in extraction and back-extraction process, magnesium lithium mass ratio drops to 5.7 by 45.6.
Embodiment 2:
1) get the bittern 50mL after concentrating, it consists of Li
+0.48g/L, Mg
2+96.21g/L, Na
+3.53g/L, K
+1.85g/L, magnesium lithium mass ratio is 200.4.
2) in bittern, add common extraction agent sodium perchlorate, consumption with
be as the criterion, stir at 25 ℃, dissolve, be extracted front aqueous salt brine, pH is adjusted to 7.
3) by oil phase and water volume ratio, be to add organic phase at 2: 1, organic phase is comprised of 80%TBP and 20% kerosene, carries out single extraction at 25 ℃, and extraction time of vibration 30min, standing 30min, then two be separated.
4) with pure water, doing reverse-extraction agent, is to mix at 1: 1 by organic phase and water volume ratio, carries out back extraction at 50 ℃, back extraction time 10min, and standing 30min, then two is separated.
5) after back extraction, water regulates pH>=12 with sodium carbonate and caustic soda, and magnesium is with MgCO
3and Mg (OH)
2form Precipitation, adds sodium carbonate solution to produce precipitation again in water after filtering, after separated, dry lithium carbonate product.
After testing, lithium percentage extraction reaches 46.2%, magnesium percentage extraction is 9.0%, and lithium back extraction ratio reaches 64.4%, magnesium back extraction ratio is 57.4%, and in extraction and back-extraction process, magnesium lithium mass ratio drops to 34.8 by 200.4.TBP solvent can extract lithium, Na in bittern from contain the bittern that lithium is low
+, K
+percentage extraction low, little to Separation of Li and Mg process influence.
Embodiment 3:
1) get the bittern 50mL of concentrated rear boracic, sulfate radical, it consists of: Li
+1.80g/L, Mg
2+90.51g/L, Na
+6.89g/L, K
+1.85g/L,
28.82g/L, B
2o
320.89g/L, magnesium lithium mass ratio is 50.3.
2) in bittern, add common extraction agent sodium perchlorate, consumption with
be as the criterion, stir at 25 ℃, dissolve, be extracted front aqueous salt brine.
3) by oil phase and water volume ratio, be to add organic phase TBP at 2: 1, carry out single extraction at 25 ℃, extraction time of vibration 10min, standing 30min, then two be separated.
4) with pure water, doing reverse-extraction agent, is to mix at 1: 1 by organic phase and water volume ratio, carries out back extraction at 60 ℃, back extraction time 10min, and standing 15min, then two is separated.
5) after back extraction, water regulates pH>=12 with sodium carbonate and caustic soda, and magnesium is with MgCO
3and Mg (OH)
2form Precipitation, adds sodium carbonate solution to produce precipitation again in water after filtering, after separated, dry lithium carbonate product.
After testing, lithium percentage extraction reaches 67.5%, magnesium percentage extraction is 8.3%, and lithium back extraction ratio reaches 83.6%, magnesium back extraction ratio is 89.4%, and in extraction and back-extraction process, magnesium lithium mass ratio drops to 6.6 by 50.3.Show that this system can extract lithium from the bittern of boracic and sulfate radical.
Embodiment 4:
1) get the bittern 50mL after concentrating, its composition is identical with embodiment 1.
2) in bittern, add common extraction agent sodium perchlorate, consumption with
be as the criterion, stir at 25 ℃, dissolve, be extracted front aqueous salt brine.
3) in adding organic phase TBP with the water volume ratio ratio of 1: 1, at 25 ℃, carry out 3 continuous extractions, add extraction agent after vibration time 10min, standing 15min at every turn, then two be separated.
4) organic phase of 3 continuous extractions being merged together, with pure water, doing reverse-extraction agent, is to mix at 1: 1 by organic phase and water volume ratio, carries out back extraction at 70 ℃, back extraction time 10min, and standing 30min, then two is separated.
5) after back extraction, water regulates pH>=12 with caustic soda, and magnesium is with Mg (OH)
2form Precipitation, adds sodium carbonate solution to produce precipitation again in water after filtering, after separated, dry lithium carbonate product.
After testing, lithium is continuous extracts that total percentage extraction reaches 88.2% for 3 times, extraction phase merge after lithium single back extraction ratio be 87.1%, magnesium is continuous extracts that total percentage extraction is 15.2%, magnesium single back extraction ratio is 93.3% for 3 times, and in extraction and back-extraction process, magnesium lithium mass ratio drops to 8.4 by 45.6.Separation of Li and Mg coefficient is 14.0.
Embodiment 5:
1) get the bittern 50mL after concentrating, its composition is identical with embodiment 1.
2) in bittern, add common extraction agent magnesium perchlorate, consumption with
be as the criterion, stir at 25 ℃, dissolve, be extracted front aqueous salt brine, pH equals 5, add magnesium perchlorate after solution Mg/Li ratio become 49.1.
3) by oil phase and water volume ratio, be to add organic phase TBP at 2: 1, carry out single extraction at 25 ℃, extraction time of vibration 10min, standing 30min, then two be separated.
4) with pure water, doing reverse-extraction agent, is to mix at 1: 1 by organic phase and water volume ratio, carries out back extraction at 50 ℃, back extraction time 10min, and standing 15min, then two is separated.
5) after back extraction, water regulates pH>=12 with caustic soda, and magnesium is with Mg (OH)
2form Precipitation, adds sodium carbonate solution to produce precipitation in water after filtering, after separated, dry lithium carbonate product.
After testing, lithium percentage extraction reaches 64.3%, magnesium percentage extraction is 12.6%, and lithium back extraction ratio reaches 85.9%, magnesium back extraction ratio is 75.9%, and in extraction and back-extraction process, magnesium lithium mass ratio drops to 8.5 by 49.1.
Claims (4)
1. separating magnesium and extract the method for lithium from high Mg/Li ratio salt lake brine, is characterized in that:
1) preparation of bittern: after concentrated to Exposure to Sunlight or the magnesium lithium mass ratio of sylvite after extracting be to add perchlorate to extract altogether agent in the salt lake brine of 10: 1～500: 1, extracting altogether agent and lithium mol ratio is 0.5: 1～3: 1, brine ph is in 1～9 scope;
2) extraction: carry out bittern extraction with tributyl phosphate as organic phase, extraction phase compares V
o/ V
wbe 0.5: 1～3: 1,1～5 grade of extraction progression, single extraction time 1～30min, 0～60 ℃ of extraction temperature;
3) reversed phase extraction: use water as reverse-extraction agent, to carrying out reversed phase extraction containing lithium organic phase, V is compared in back extraction
w/ V
obe 0.02: 1～2: 1,1～5 grade of back extraction progression, single back extraction time 1～30min, 0～100 ℃ of back extraction temperature;
4) degree of depth demagging: add sodium carbonate or caustic soda in strip aqueous, be settled out magnesiumcarbonate or magnesium hydroxide, control pH value of solution>=12, make Mg
2+precipitation is complete, filtering separation;
5) prepare Quilonum Retard: in the strip aqueous after degree of depth demagging, add sodium carbonate, produce Quilonum Retard precipitation, after filtering, being dried, make lithium carbonate product; After carrying lithium, strip aqueous is carried out internal recycling, extracts altogether the rear Reusability of agent recycling in water.
As claimed in claim 1 a kind of from high Mg/Li ratio salt lake brine separating magnesium and extract the method for lithium, it is characterized in that it is a kind of or its mixture in sodium perchlorate, potassium perchlorate, magnesium perchlorate, calcium perchlorate that perchlorate used extracts agent altogether.
As claimed in claim 1 a kind of from high Mg/Li ratio salt lake brine separating magnesium and extract the method for lithium, it is characterized in that organic phase used contains No. 200 solvent oils of thinner or kerosene, but its volumn concentration is less than 50%.
As claimed in claim 1 a kind of from high Mg/Li ratio salt lake brine separating magnesium and extract the method for lithium, it is characterized in that carrying out, after reversed phase extraction, the back extraction organic phase of last step is transferred to the 1st grade of extraction plant, directly reuse.
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| CN103898341B (en) * | 2014-03-06 | 2015-10-21 | 中国科学院青海盐湖研究所 | From the method for the rough separation and Extraction lithium of Lithium Sulphate |
| CN104232896A (en) * | 2014-09-18 | 2014-12-24 | 中国科学院青海盐湖研究所 | Method for separating lithium from salt lake brine |
| CN104232897A (en) * | 2014-09-18 | 2014-12-24 | 中国科学院青海盐湖研究所 | Lithium ion extraction system |
| CN104404268B (en) * | 2014-10-31 | 2017-05-17 | 天津科技大学 | Novel co-extraction system for extraction of lithium from high magnesium-lithium ratio bittern and co-extraction method using the same |
| CN105152190B (en) * | 2015-09-18 | 2017-04-05 | 湘潭大学 | A kind of method that separating magnesium from low lithium salt and enriching lithium produce lithium carbonate |
| CN105540624A (en) * | 2015-12-07 | 2016-05-04 | 上海实业振泰化工有限公司 | Preparation method of high purity acicular magnesium hydroxide |
| CN108193058B (en) * | 2017-11-29 | 2019-09-27 | 潍坊学院 | A method of extracting the ion liquid abstraction of lithium from salt lake |
| CN110817909B (en) * | 2019-11-19 | 2022-07-12 | 中国科学院过程工程研究所 | Lithium-magnesium separation method |
| CN111139356A (en) * | 2020-01-19 | 2020-05-12 | 意定(上海)信息科技有限公司 | Method for extracting lithium from lithium-containing low-magnesium brine |
| CN115477355A (en) * | 2022-09-30 | 2022-12-16 | 武汉工程大学 | Method for extracting lithium from lithium-containing wastewater by using TBP (tunnel boring machine) |
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