CN100343399C - Process for extracting lithium from salt lake brine by manganese dioxide - Google Patents

Process for extracting lithium from salt lake brine by manganese dioxide Download PDF

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Publication number
CN100343399C
CN100343399C CNB021455821A CN02145582A CN100343399C CN 100343399 C CN100343399 C CN 100343399C CN B021455821 A CNB021455821 A CN B021455821A CN 02145582 A CN02145582 A CN 02145582A CN 100343399 C CN100343399 C CN 100343399C
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lithium
salt lake
sieve
manganese dioxide
lake brine
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CN1511963A (en
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马培华
邓小川
李法强
温现民
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Qinghai Institute of Salt Lakes Research of CAS
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Qinghai Institute of Salt Lakes Research of CAS
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Abstract

The present invention relates to a method for extracting lithium from salt lake brine by a manganese dioxide ion sieve method, which is suitable for tsinghai lithium containing salt lake brine and salt field lithium containing concentrated old brine and the production processes for preparing lithium carbonate and lithium chloride from tsinghai salt lake brine. The method is aimed at lithium containing concentrated brine obtained by solarizing and evaporating a salt field, Li<+> is selectively absorbed by an MnO2 absorbing agent, and the absorbed Li<+> is eluted by a hydrochlric acid solution. An eluent is refined and concentrated, and the requirements of qualified raw materials needed by the preparation of the lithium carbonate or the lithium chloride are met.

Description

Manganese dioxide is put forward the method for lithium from salt lake brine
Technical field
The present invention relates to a kind of lithium that from solution, extracts, especially concentrate the technology of carrying lithium the old halogen of lithium with the manganese bioxide ionic sieve adsorbents adsorb that contains from containing lithium salts lake bittern water and salt pan.
Background technology
Lithium ion and a large amount of basic metal, alkaline-earth metal coexistence will reclaim lithium economically from natural polywater salt system high Mg/Li ratio salt lake brine, not only depend on to contain lithium concentration but also depend on to contain magnesium, calcium ion concn.Because magnesium is very similar to the chemical property of lithium, the magnesium lithium separates very difficult.The bittern of abroad having produced is carried lithium and is all only limited to contain the lower bittern of magnesium density now, the Mg/Li ratio value was less than 6: 1, and the Qinghai Salt Lake Bittern Mg/Li ratio was up to 300: 1, can not directly use the simple method of low Mg/Li ratio value bittern Exposure to Sunlight desalination precipitation Quilonum Retard, alkali charge is excessive when making with extra care bittern loses serious with lithium salts otherwise can cause.It is to solve magnesium lithium separation problem that the high Mg/Li ratio salt lake brine extracts the lithium salts matter of utmost importance.
In the world high Mg/Li ratio value bittern is put forward the existing many methods of lithium, as salting-out process, organic solvent extractionprocess, roasting method, the precipitator method etc.This several method respectively has characteristics at magnesium lithium isolation technique in the high Mg/Li ratio salt lake brine.The tbp extraction process adopt to concentrate rich lithium high-magnesium brine as raw materials for production, and the rate of recovery is than higher, but long flow path, equipment corrosion are serious, and the production cost height can't further be realized industrialization.Roasting method is wanted a large amount of hydrochloric acid of by-product and heavy MgO, and wherein heavy MgO faces the narrow problem in selling market, and hydrochloric acid is to the unusual serious problems of equipment corrosion, and whole process energy consumption height only carried out desk research work.Precipitator method feasible process, but long flow path, the material cycling amount is big, and repeatedly calcining is filtered, trivial operations, it is lower that hydrothermal decomposition or roasting leaching liquid contain lithium concentration, needs evaporated water bigger when concentrating.
Summary of the invention
The objective of the invention is in order to provide a kind of manganese dioxide from salt lake brine, to put forward the method for lithium, this method contains the concentrated old halogen of lithium that contains of lithium salts lake bittern water and salt pan from natural polywater salt system chloride type high Mg/Li ratio, solve bittern magnesium lithium and separate difficult problem, provide low Mg/Li ratio value, qualified rich lithium bittern for producing Quilonum Retard or lithium chloride.
Purpose of the present invention can realize by following measure:
A kind of manganese bioxide ionic sieve method is extracted the method for lithium from salt lake brine, comprise the steps:
(1) salt lake brine is sent into the absorption-desorption device, carried out absorption-desorption: dress MnO in the wherein said absorption-desorption device 2Sorbent material, by the sorbent material in the absorption-desorption device with the absorption of the lithium of salt lake brine after, again by acid solution with the lithium ion wash-out, lithium ion is separated with other foreign ion; Described manganese dioxide adsorbent is produced by following step: a, at first by manganous sulfate and sulphuric acid soln electrolysis system particulate MnO 2, soaking through lithium hydroxide solution, high temperature sintering carries out recrystallization, makes the manganese dioxide powder ion(ic)sieve; B, be to be suspended in 8: 1~15: 1 in the aqueous solution of acrylamide monomer by weight with the manganese dioxide powder ion(ic)sieve, add divinylbenzene, benzoyl peroxide again, wherein manganese dioxide powder ion(ic)sieve and linking agent weight ratio are 100: 1~130: 1; The weight ratio of manganese dioxide powder ion(ic)sieve and initiator is 10 3: 1~10 5: 1, through crosslinking polymerization, oven dry, pulverizing, screening, obtain Manganse Dioxide-polyacrylamide granular adsorption agent; (2) elutriant is refining, produce rich lithium bittern.
Described absorbent particles is a macroporous resin, and the particulate fineness is sieved at 80 orders<d by USS P<10 orders.
The used acid strength scope of described wash-out is 0.1~0.5mol/L.
The present invention has following advantage compared to existing technology:
1, the present invention uses the salt lake to carry the old halogen of potassium to be raw material, does not need the salt pan degree of depth to concentrate and carries boron, helps improving the utilization ratio of lithium.
2, the repeated use of pickle solution of the present invention has improved the concentration of lithium in the elutriant, and elutriant segmentation intercepting has reduced the acceptable solution foreign matter content, and pickle solution is the refining loss of having avoided lithium before concentrating, and electrodialysis concentrates has saved energy consumption.
3, the present invention carries behind the potassium old halogen and is different scales test, product Li with containing the lithium salts lake bittern water 2CO 3Purity is greater than 99%, and the lithium yield is greater than 80%.Prove a kind of viable process and technology of carrying lithium from salt lake brine.Advantages of simple technological process, easy to operate, have novelty.
Embodiment
The present invention also will be described in further detail in conjunction with the embodiments:
Salt lake brine or salt pan concentrated contain the old halogen of lithium and send into the absorption-desorption device continuously, dress particulate state MnO in this device 2The cylinder cylinder of sorbent material.Absorption-desorb is carried out with the counter-current fractionation way of contact, the MnO after the regeneration 2Sorbent material adsorbs next time.Absorption occurs in and contains lithium bittern contact sorbent material process, and lithium ion is adsorbed by selectivity; Desorb occurs in elution process, divides stage countercurrent to elute lithium ion with eluent, and lithium ion is separated with other foreign ion.Elutriant provides after electrodialysis concentrates and produces Quilonum Retard or the required qualified rich lithium bittern of lithium chloride through refining.
Described manganese dioxide adsorbent is produced by following step:
(1) at first by manganous sulfate and sulphuric acid soln electrolysis system particulate MnO 2, soaking through lithium hydroxide solution, high temperature sintering carries out recrystallization, makes the manganese dioxide powder ion(ic)sieve;
(2) be to be suspended at 11: 1 in the aqueous solution of acrylamide monomer by weight with the manganese dioxide powder ion(ic)sieve, add divinylbenzene, benzoyl peroxide again, wherein manganese dioxide powder ion(ic)sieve and divinylbenzene weight ratio are 120: 1; The weight ratio of manganese dioxide powder ion(ic)sieve and benzoyl peroxide is 10 4: 1, through crosslinking polymerization, oven dry, pulverizing, screening, obtain Manganse Dioxide-polyacrylamide granular adsorption agent.
Its specific embodiment is as follows:
Example one:
Intercrystalline bittern contains Li +0.14, Na +17.01, K +18.54, Mg 2+70.19, Cl -243.76, SO 4 2-, 7.43g/L regulates pH and is about 7.0 after pre-treatment, use 430gMnO 2Li in the ion(ic)sieve absorption bittern +, the Li that the back is adsorbed with 0.2mol/L HCl wash-out +Accept pickle solution and contain H +0.015, Li +1.74, Na +1.59, K +0.29, Mg 2+1.09, Cl -14.2, Mn 2+0.26g/L.
Example two:
Natural Exposure to Sunlight concentrated solution contains Li +0.22, Na +2.14, K +0.83, Mg 2+115.50, Cl -337.33, SO 4 2-, 6.27g/L regulates pH and is about 7.0 after pre-treatment, the Li that is adsorbed with 0.2mol/L HCl wash-out +Accept pickle solution and contain H +0.042, Li +1.51, Na +1.20, K +0.44, Mg 2+1.51, Cl -14.13, Mn 2+0.14g/L.Add Na respectively 2CO 3, CaO, NaOH remove impurity such as Ca, Mg, Mn, and refining back pickle solution Ca, Mg, Mn total amount are about 0.3mmol/L, and the Li yield is greater than 98.0%.
Example three:
With example two, refining pickle solution adopts electrodialysis to concentrate, and is concentrated to by the 1.44g/L lithium before concentrating to contain lithium 6.28g/L, closes LiCl38.4g/L, and the Li yield is greater than 97.2%.

Claims (3)

1, a kind of manganese bioxide ionic sieve method is extracted the method for lithium from salt lake brine, comprises the steps:
(1) salt lake brine is sent into the absorption-desorption device, carried out absorption-desorption: dress MnO in the wherein said absorption-desorption device 2Sorbent material, by the sorbent material in the absorption-desorption device with the absorption of the lithium of salt lake brine after, again by acid solution with the lithium ion wash-out, lithium ion is separated with other foreign ion; Described manganese dioxide adsorbent is produced by following step: a, at first by manganous sulfate and sulphuric acid soln electrolysis system particulate MnO 2, soaking through lithium hydroxide solution, high temperature sintering carries out recrystallization, makes the manganese dioxide powder ion(ic)sieve; B, be to be suspended in 8: 1~15: 1 in the aqueous solution of acrylamide monomer by weight with the manganese dioxide powder ion(ic)sieve, add divinylbenzene, benzoyl peroxide again, wherein manganese dioxide powder ion(ic)sieve and linking agent weight ratio are 100: 1~130: 1; The weight ratio of manganese dioxide powder ion(ic)sieve and initiator is 10 3: 1~10 5: 1, through crosslinking polymerization, oven dry, pulverizing, screening, obtain Manganse Dioxide-polyacrylamide granular adsorption agent; (2) elutriant is refining, produce rich lithium bittern.
2, manganese bioxide ionic sieve method as claimed in claim 1 is extracted the method for lithium from salt lake brine, it is characterized in that absorbent particles is a macroporous resin, and the particulate fineness is sieved at 80 orders<d by USS P<10 orders.
3, manganese bioxide ionic sieve method as claimed in claim 1 is extracted the method for lithium from salt lake brine, it is characterized in that the used acid strength scope of described wash-out is 0.1~0.5mol/L.
CNB021455821A 2002-12-27 2002-12-27 Process for extracting lithium from salt lake brine by manganese dioxide Active CN100343399C (en)

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CN102774860A (en) * 2012-08-22 2012-11-14 东莞市广华化工有限公司 Method for preparing lithium carbonate by brine

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CN102049237B (en) * 2010-11-19 2012-08-15 中南大学 Iron phosphate ion sieve for selectively extracting Li and application thereof
CN102049238B (en) * 2010-11-19 2012-08-15 中南大学 Ion sieve for selectively extracting lithium and application thereof
KR101047986B1 (en) * 2010-11-26 2011-07-13 한국지질자원연구원 Adsorption and desorption device of litium ion using counter current decantation process and method using the same
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
CN103498172B (en) * 2013-09-27 2016-04-20 中南大学 A kind of barium oxide for selective extraction lithium and application thereof
CN104689858B (en) * 2013-12-10 2017-06-27 上海空间电源研究所 A kind of application and preparation of mangaic acid lithium ion sieve seperation film
WO2015096549A1 (en) * 2013-12-26 2015-07-02 江苏久吾高科技股份有限公司 Process and apparatus for extracting battery grade lithium from brine
DE102015000872A1 (en) 2015-01-23 2016-07-28 K-Utec Ag Salt Technologies Method for recovering lithium chloride
CN106345394B (en) * 2016-11-02 2019-06-25 海西永正锂业有限公司 A method of it extracting lithium from brine and prepares high purity lithium dope
CN108439432A (en) * 2018-04-25 2018-08-24 西安蓝晓科技新材料股份有限公司 A kind of method of lithium sodium separation
CN108517421B (en) * 2018-07-02 2020-10-16 西安蓝晓科技新材料股份有限公司 Method for separating lithium and sodium in lithium and sodium-containing solution
CN111621640A (en) * 2020-07-13 2020-09-04 礼思(上海)材料科技有限公司 Adsorption tower for extracting lithium from salt lake brine and lithium extraction method
CN111809067A (en) * 2020-07-13 2020-10-23 礼思(上海)材料科技有限公司 Adsorption tower group for extracting lithium from salt lake brine and lithium extraction method
CN111826524A (en) * 2020-07-13 2020-10-27 礼思(上海)材料科技有限公司 Method for extracting lithium from salt lake brine by using adsorbent

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