CN1511963A - 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
CN1511963A
CN1511963A CNA021455821A CN02145582A CN1511963A CN 1511963 A CN1511963 A CN 1511963A CN A021455821 A CNA021455821 A CN A021455821A CN 02145582 A CN02145582 A CN 02145582A CN 1511963 A CN1511963 A CN 1511963A
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lithium
sieve
lake brine
salt lake
manganese dioxide
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CN100343399C (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 is manganese dioxide process of extracting lithium from salt lake brine, and the process is suitable for producing lithium carbonate and lithium chloride with lithium-containing Qinghai saline lake brine, including concentrated lithium-containing Qinghai saline lake brine. The process includes sun shining saline lake brine to obtain concentrated lithium containing brine, selective adsorption of lithium ion with MnO2 adsorbent, eluting adsorbed lithium ion with hydrochloric acid solution, and refining and concentrating the elutriant to obtain material for preparing lithium carbonate and lithium chloride.

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 absorption-desorption device, with counter-current fractionation way of contact absorption-desorption; Dress MnO in the wherein said absorption-desorption device 2Sorbent material after the lithium absorption of the sorbent material in the absorption-desorption device with salt lake brine, divides the stage countercurrent wash-out by acid solution with lithium ion again, and lithium ion is separated with other foreign ion; (2) elutriant is refining, promptly utilize electrodialyzer that elutriant is concentrated, produce rich lithium bittern.
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 thermodynamic recrystallization, makes the manganese dioxide powder ion(ic)sieve;
(2) 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 linking agent such as divinylbenzene, initiator such as 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.
Described absorbent particles is a macroporous resin, and the granular size scope is at 80 orders<d p<20 orders (USS sieve).
The saturated adsorption capacity of described manganese dioxide adsorbent is greater than 30.0mgLi +/ g.
The work loading capacity of described manganese dioxide adsorbent is 10.4~12.5mgLi +/ g, adsorption rate is greater than 89.0%.
Described wash-out acid strength scope 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 absorption-desorption device continuously, dress particulate state MnO in this device 2The cylinder cylinder of sorbent material.Absorption-desorption carries out with the counter-current fractionation way of contact, the MnO after the regeneration 2Sorbent material descends-inferior absorption.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, after pre-treatment, regulate pH and be about 7.0, use 430g MnO 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, after pre-treatment, regulate pH and be about 7.0, 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 (6)

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 absorption-desorption device, carry 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; (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 described manganese dioxide adsorbent 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 in 8: 1~15: 1 in the aqueous solution of acrylamide monomer by weight with the manganese dioxide powder ion(ic)sieve, add linking agent (as divinylbenzene), initiator (as 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.
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 absorbent particles is a macroporous resin, and the granular size scope is at 80 orders<d p<10 orders (USS sieve).
4, manganese bioxide ionic sieve method as claimed in claim 1 is extracted the method for lithium from salt lake brine, and the saturated adsorption capacity that it is characterized in that described manganese dioxide adsorbent is greater than 30.0mgLi +/ g.
5, manganese bioxide ionic sieve method as claimed in claim 1 is extracted the method for lithium from salt lake brine, and the work loading capacity that it is characterized in that described manganese dioxide adsorbent is 10.4~12.5mgLi +/ g.
6, 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 described wash-out acid strength scope 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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CN102049237A (en) * 2010-11-19 2011-05-11 中南大学 Iron phosphate ion sieve for selectively extracting Li and application thereof
CN102049238A (en) * 2010-11-19 2011-05-11 中南大学 Ion sieve for selectively extracting lithium and application thereof
CN102906287A (en) * 2010-04-22 2013-01-30 上原春男 Device and method for recovering lithium
CN102918170A (en) * 2010-11-26 2013-02-06 韩国地质资源研究院 Apparatus and method for adsorbing and desorbing lithium ions using a ccd process
CN103074502A (en) * 2013-01-29 2013-05-01 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
CN103498172A (en) * 2013-09-27 2014-01-08 中南大学 Vanadium oxide used for selectively extracting lithium and application thereof
CN104689858A (en) * 2013-12-10 2015-06-10 上海空间电源研究所 Preparation method of lithium manganate ion sieve separation membrane
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
CN106345394A (en) * 2016-11-02 2017-01-25 江苏旌凯中科超导高技术有限公司 Method for extracting lithium from bittern and preparing high-purity lithium concentrate
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
CN108517421A (en) * 2018-07-02 2018-09-11 西安蓝晓科技新材料股份有限公司 A method of separation is containing lithium sodium in lithium, sodium 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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CN1093517C (en) * 1999-04-20 2002-10-30 中国地质科学院盐湖与热水资源研究发展中心 Lithium salt extraction process from carbonate type bittern
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CN102906287A (en) * 2010-04-22 2013-01-30 上原春男 Device and method for recovering lithium
CN102049238A (en) * 2010-11-19 2011-05-11 中南大学 Ion sieve for selectively extracting lithium and application thereof
CN102049238B (en) * 2010-11-19 2012-08-15 中南大学 Ion sieve for selectively extracting lithium and application thereof
CN102049237A (en) * 2010-11-19 2011-05-11 中南大学 Iron phosphate ion sieve for selectively extracting Li and application thereof
CN102918170A (en) * 2010-11-26 2013-02-06 韩国地质资源研究院 Apparatus and method for adsorbing and desorbing lithium ions using a ccd process
CN102918170B (en) * 2010-11-26 2016-02-03 韩国地质资源研究院 Utilize the lithium ion adsorption/desorption devices and methods therefor of counter-current decantation technique
CN103074502A (en) * 2013-01-29 2013-05-01 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
CN103498172A (en) * 2013-09-27 2014-01-08 中南大学 Vanadium oxide used for selectively extracting lithium and application thereof
CN103498172B (en) * 2013-09-27 2016-04-20 中南大学 A kind of barium oxide for selective extraction lithium and application thereof
CN104689858A (en) * 2013-12-10 2015-06-10 上海空间电源研究所 Preparation method of lithium manganate ion sieve separation membrane
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
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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
CN108517421A (en) * 2018-07-02 2018-09-11 西安蓝晓科技新材料股份有限公司 A method of separation is containing lithium sodium in lithium, sodium 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
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