CN103435077A - Process for extracting lithium from brine - Google Patents

Process for extracting lithium from brine Download PDF

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Publication number
CN103435077A
CN103435077A CN2013103931227A CN201310393122A CN103435077A CN 103435077 A CN103435077 A CN 103435077A CN 2013103931227 A CN2013103931227 A CN 2013103931227A CN 201310393122 A CN201310393122 A CN 201310393122A CN 103435077 A CN103435077 A CN 103435077A
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China
Prior art keywords
lithium
magnesium
bittern
sulfate
extracting
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CN2013103931227A
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Chinese (zh)
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马迎曦
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Individual
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Individual
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Priority to CN2013103931227A priority Critical patent/CN103435077A/en
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Abstract

The invention discloses a process for extracting lithium from brine. The process comprises the following steps of: performing sulfuric acid acidification on original halogen; increasing the concentration of sulfate ions in the brine until sulfate is promoted to be crystallized while extracting boric acid; fully neutralizing excessive acid in the acidified brine after boron extraction; naturally evaporating and crystallizing the brine in a saline to obtain a mixture of lithium sulfate, magnesium sulfate and magnesium chloride; separating lithium salt from magnesium salt by using the physical characteristic that the density of lithium sulfate is greater than those of magnesium chloride and magnesium sulfate and using a heavy medium reselection principle in mineral processing technology to achieve the aim of separating magnesium and lithium; and then adopting sodium hydrate to deposit magnesium and sodium carbonate to deposit lithium so as to obtain a magnesium hydroxide product and a lithium carbonate product respectively. The process completely does not need spray drying and calcining process steps, so that the consumption of energy sources is greatly reduced, 70% of the production cost can be reduced; the process flow is simple and has less chemical reactions, so that the product quality cannot be difficult to control due to a complex flow, and the process is environment-friendly and pollution-free.

Description

A kind of technique of extracting lithium from bittern
Technical field
The present invention relates to a kind of lithium extraction process, specifically a kind of technique of extracting lithium from bittern.
Background technology
The magnesium lithium is in the consecutive position on diagonal lines in the periodic table of elements, and chemical property is basic identical, is difficult to separate by the pure chemistry method.Particularly, in the saline lake lithium resource leaching process, it is bottleneck problem that the magnesium lithium separates, and up to the present, still there is no the commercial run that effective cost is low.
The technique that current China extracts in salt lake lithium from bittern is mainly calcination method.This technical process is: bittern → salt pan spontaneous evaporation enrichment → hcl acidifying is carried boron → milk of lime removing sulfate → old halogen field and is continued evaporation enrichment → spray solidification → calcining → caustic soda demagging → soda ash sinker → Quilonum Retard finished product.
There is following problem in existing method:
1. energy consumption is high, is mainly manifested in spraying drying and two workshop sections of calcining, and spray drying section needs to carry out the spraying drying vaporize water containing the old halogen of lithium 10 grams per liters, obtains the solid mixture of magnesium chloride and lithium chloride; Calcining workshop section passes through the rotary calciner of 1200 ℃ by the solid mixture of magnesium chloride and lithium chloride, allows magnesium chloride resolve into water-fast magnesium oxide and hydrogen chloride gas.In producing at present, Quilonum Retard per ton needs electricity 6651 degree, by local electricity price, is converted into 5320 yuan, Sweet natural gas 7587 sides, and local inside the plan Gas Prices is 1.42 yuan/cubic metre and is converted into 10773 yuan, 2.42 yuan outside the plan are converted into 18360 yuan.
2. flow process complexity, quality product is difficult to be controlled.Inferior technical process complexity, must be with into a lot of detrimental impurity in process of production, affects quality product.
Summary of the invention
The object of the present invention is to provide a kind of technique of extracting lithium from bittern, to solve the problem proposed in the above-mentioned background technology.
For achieving the above object, the invention provides following technical scheme:
A kind of technique of extracting lithium from bittern comprises the following steps:
(1) former halogen is carried out to sulfuric acid acidation, when extracting boric acid, the sulfate concentration in bittern is increased, until impel sulphate crystal;
(2) fully the excess acid in boron acidifying bittern is later put forward in neutralization;
(3) allow bittern in salt pan spontaneous evaporation crystallization, crystallization goes out the mixture of Lithium Sulphate, sal epsom and magnesium chloride; Utilize density ratio sal epsom and the magnesium chloride of Lithium Sulphate all to want large physical property, use the dense medium gravity treatment principle in mineral dressing, lithium salts and magnesium salts are separated, to reach the purpose of separating magnesium and lithium;
(4) then adopt the heavy magnesium of caustic soda and soda ash sinker to obtain respectively magnesium hydroxide and lithium carbonate product.
As the further scheme of the present invention: former halogen described in step (1) is the mother liquor step after potash fertilizer has been carried in salt lake.
As the further scheme of the present invention: step (2) allows to be carried boron acidifying bittern later and drops down the Magnesium peroxide pond, fully in and excess acid.
Compared with prior art, the invention has the beneficial effects as follows: the present invention utilizes Lithium Sulphate and the sal epsom difference on physical properties, adopts physical method to be separated; At first increase the sulfate radical in former halogen, magnesium and lithium are crystallized out with the form of vitriol.Utilize density variation, sulfuric acid monohydrate lithium density is 2.21, and the density of magnesium sulfate heptahydrate is 1.7, the density of magnesium chloride hexahydrate is 1.6, use the dense medium gravity treatment principle in mineral dressing, lithium salts and magnesium salts are separated, do not need spraying drying and calcination procedure fully, greatly reduced the consumption of the energy, can reduce by 70% production cost, and technical process is simple, rare chemical reaction in process, can not be difficult to control because the flow process complexity causes quality product, and environment friendly and pollution-free.
The accompanying drawing explanation
Fig. 1 extracts the process flow sheet of lithium from bittern.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making under the creative work prerequisite the every other embodiment obtained, belong to the scope of protection of the invention.
Refer to Fig. 1, in the embodiment of the present invention, a kind of technique of extracting lithium from bittern comprises the following steps:
(1) former halogen is carried out to sulfuric acid acidation, when extracting boric acid, the sulfate concentration in bittern is increased, until impel sulphate crystal; Described former halogen is the mother liquor after potash fertilizer has been carried in salt lake;
(2) allow and carry boron acidifying bittern later and drop down the Magnesium peroxide pond, fully in and excess acid;
(3) allow bittern in salt pan spontaneous evaporation crystallization, crystallization goes out the mixture of Lithium Sulphate, sal epsom and magnesium chloride; Utilize density ratio sal epsom and the magnesium chloride of Lithium Sulphate all to want large physical property, use the dense medium gravity treatment principle in mineral dressing, lithium salts and magnesium salts are separated, to reach the purpose of separating magnesium and lithium;
(4) then adopt the heavy magnesium of caustic soda and soda ash sinker to obtain respectively magnesium hydroxide and lithium carbonate product.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned example embodiment, and in the situation that do not deviate from spirit of the present invention or essential characteristic, can realize the present invention with other specific form.Therefore, no matter from which point, all should regard embodiment as exemplary, and be nonrestrictive, scope of the present invention is limited by claims rather than above-mentioned explanation, therefore is intended to include in the present invention dropping on the implication that is equal to important document of claim and all changes in scope.Any Reference numeral in claim should be considered as limit related claim.
In addition, be to be understood that, although this specification sheets is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets is only for clarity sake, those skilled in the art should make specification sheets as a whole, and the technical scheme in each embodiment also can, through appropriate combination, form other embodiments that it will be appreciated by those skilled in the art that.

Claims (3)

1. a technique of extracting lithium from bittern, is characterized in that, comprises the following steps:
(1) former halogen is carried out to sulfuric acid acidation, when extracting boric acid, the sulfate concentration in bittern is increased, until impel sulphate crystal;
(2) fully the excess acid in boron acidifying bittern is later put forward in neutralization;
(3) allow bittern in salt pan spontaneous evaporation crystallization, crystallization goes out the mixture of Lithium Sulphate, sal epsom and magnesium chloride; Utilize density ratio sal epsom and the magnesium chloride of Lithium Sulphate all to want large physical property, use the dense medium gravity treatment principle in mineral dressing, lithium salts and magnesium salts are separated, to reach the purpose of separating magnesium and lithium;
(4) then adopt the heavy magnesium of caustic soda and soda ash sinker to obtain respectively magnesium hydroxide and lithium carbonate product.
2. the technique of extracting lithium from bittern according to claim 1, is characterized in that, former halogen described in step (1) is the mother liquor step after potash fertilizer has been carried in salt lake.
3. the technique of extracting lithium from bittern according to claim 1, is characterized in that, step (2) allows to be carried boron acidifying bittern later and drop down the Magnesium peroxide pond, fully in and excess acid.
CN2013103931227A 2013-09-03 2013-09-03 Process for extracting lithium from brine Pending CN103435077A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103898341A (en) * 2014-03-06 2014-07-02 中国科学院青海盐湖研究所 Method for separating and extracting lithium from lithium sulfate coarse ore
CN105329921A (en) * 2015-12-08 2016-02-17 汕头市泛世矿业有限公司 Three-in-one preparing technology for high-purity lithium carbonate
CN107986301A (en) * 2017-12-27 2018-05-04 江西赣锋锂业股份有限公司 A kind of method using battery-level lithium carbonate sinker mother liquor production LITHIUM BATTERY lithium hydroxide

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060115396A1 (en) * 1998-07-16 2006-06-01 Boryta Daniel A Production of lithium compounds directly from lithium containing brines
CN101691231A (en) * 2009-09-30 2010-04-07 达州市恒成能源(集团)有限责任公司 Method for preparing lithium carbonate by using high boric bittern saturated solution
KR20120070841A (en) * 2010-12-22 2012-07-02 재단법인 포항산업과학연구원 Method for preparing high purity lithium carbonate from brines

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060115396A1 (en) * 1998-07-16 2006-06-01 Boryta Daniel A Production of lithium compounds directly from lithium containing brines
CN101691231A (en) * 2009-09-30 2010-04-07 达州市恒成能源(集团)有限责任公司 Method for preparing lithium carbonate by using high boric bittern saturated solution
KR20120070841A (en) * 2010-12-22 2012-07-02 재단법인 포항산업과학연구원 Method for preparing high purity lithium carbonate from brines

Non-Patent Citations (2)

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Title
史恒欣等: "硼酸与硫酸镁分离的理论分析与实践", 《无机盐工业》, vol. 30, no. 5, 30 September 1998 (1998-09-30), pages 22 - 24 *
杨鑫等: "盐湖卤水硫酸法提取硼酸的工艺研究", 《湖南师范大学自然科学学报》, vol. 31, no. 1, 31 March 2008 (2008-03-31), pages 72 - 77 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103898341A (en) * 2014-03-06 2014-07-02 中国科学院青海盐湖研究所 Method for separating and extracting lithium from lithium sulfate coarse ore
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
CN105329921A (en) * 2015-12-08 2016-02-17 汕头市泛世矿业有限公司 Three-in-one preparing technology for high-purity lithium carbonate
WO2017096646A1 (en) * 2015-12-08 2017-06-15 范兵 Three-in-one preparation process for high-purity lithium carbonate
CN107986301A (en) * 2017-12-27 2018-05-04 江西赣锋锂业股份有限公司 A kind of method using battery-level lithium carbonate sinker mother liquor production LITHIUM BATTERY lithium hydroxide

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Application publication date: 20131211