CN102154563A - Flotation method for enriching lithium from brine of salt lake brine - Google Patents
Flotation method for enriching lithium from brine of salt lake brine Download PDFInfo
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- CN102154563A CN102154563A CN2010105797708A CN201010579770A CN102154563A CN 102154563 A CN102154563 A CN 102154563A CN 2010105797708 A CN2010105797708 A CN 2010105797708A CN 201010579770 A CN201010579770 A CN 201010579770A CN 102154563 A CN102154563 A CN 102154563A
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- Y02P10/20—Recycling
Abstract
The invention relates to an effective method for enriching lithium from salt lake brine, which comprises the following steps: taking TBP (tri-n-butyl phosphate) and FeCl3 as a trapping agent; wherein brine pH equals to 3.0-7.0; generating a stable LiFeCl4 nTBP associated matter by Li + and TBP and FeCl3; using a flotation device and adopting ethanol as a foaming agent; entering a kerosene medium through the floatation air; taking L-1HCl of 6.0mol as a stripping agent; and decomposing the LiFeCl4 nTBP associated matter so as to enable Li+ to enter a water phase. The one-step floatation extraction rate of Li+ can reach over 90%, and after the TBP and kerosene are circularly utilized for fifteen times, the floatation extraction rate of lithium salt basically keeps unchanged. Compared with the method for extracting the lithium salt from brine, the method disclosed by the invention utilizes the flotation method to enrich the lithium salt in the salt lake brine, so that labor intensity is low, the production cycle is short, the extraction efficiency and the recycling efficiency of raw auxiliary materials are high, and the production cost is low.
Description
Technical field
The invention belongs to the method for separating and concentrating of lithium in the salt lake brine, relate to technical field of inorganic chemical industry.
Background technology
Metallic lithium and various lithium compound are as important chemical material, be widely used in drying battery, pottery, glass, cooling agent, medicine or the like field, be described as " the resource metal that promotes world's process ", and will increase considerably in high capacity cell, aluminum base alloy, atomic scatterring type reactor fuel and other industrial aspect demand in the future metallic lithium and lithium compound.From China and world wide, the lithium resource of land is quite limited, and exploitation seawater, salt lake lithium resource are the common problems of paying close attention in countries in the world.About 1.466 * the 107t of whole world lithium resource total reserves, China is traditional lithium resource big country, explored lithium resource industrial reserves is only second to Bolivia in the world, occupy the second place of the world, wherein salt lake brine lithium reserves surpass 3 * 106t, account for 79%, occupy the third place in the world, have good resources supplIes and DEVELOPMENT PROSPECT.
The main method of lithium enrichment has solvent extration, the precipitator method, crystallization process, salting-out process, electroosmotic drainage, ion-exchange and absorption method etc. in the at present domestic and international bittern.Existing the whole bag of tricks all exists certain deficiency, for example precipitator method: the loss of lithium ion is bigger in the solution in leaching process, uses aluminium hydroxide, soda ash, Sodium phosphate dibasic is done precipitation agent, and the soda ash consumption is big, the lower (Wang Rigong of the rate of recovery of lithium, Wang Jun, WANG XIAOYAN etc., one step was extracted the method for Quilonum Retard, China from the high Mg/Li ratio salt lake brine, 1502557,2004-06-09).The key of absorption method is the sorbent material of development excellent property, and require sorbent material that lithium is had higher selective adsorption, so that can get rid of the interference of a large amount of basic metal of bittern and alkaline-earth metal ions, but the solution loss of sorbent material is bigger, the regeneration difficulty influences its practical application.(Zhang Shaocheng, Ran are extensively fragrant, and the absorption method salt lake brine is put forward the lithium technological test, salt lake research, and 1997,5 (1), 59-66).Salting-out process: though this method is feasible technically, technological process will be carried out under sealing condition, and equipment corrosion is serious, and the total yield of lithium is low, needs further to improve.Solvent extration: operation is easy to realize comparatively speaking, but its percentage extraction is not fully up to expectations, and technical process is comparatively loaded down with trivial details.
Extraction efficiency height of the present invention, the trapping agent relative loss factor is little, and easily effectively layering, the raw material and the equipment price that are adopted are cheap, and need not to regulate troublesome operation such as potential of hydrogen, improved the shortcoming that takes time and effort on the traditional extraction technology, easy to operation, be the extracting method of lithium in a kind of effective salt lake brine.
Summary of the invention
Main purpose of the present invention is to adopt flotation process to improve the bioaccumulation efficiency of lithium in the salt lake brine, one time the flotation extraction yield can reach more than 90%, and it is low to have improved traditional extraction method single extraction rate, and length consuming time, the shortcoming of complex operation step can effectively reduce the production cost of salt lake lithium salts.
Technical scheme of the present invention is undertaken by following operation steps:
(1) in the bittern that contains lithium 2～4mg/mL, be to add the organic phase that tributyl phosphate (TBP) and kerosene are formed, wherein TBP at 1: 3 in the ratio of water and organic phase: the kerosene volume ratio is 3: 2; Li
+With Fe
3+The ratio of amount of substance is 1: 2, adds iron trichloride; Add ethanol.
(2) open air compressor machine and regulate air flow quantity 10-50mL/min, flotation was left standstill after 3～10 minutes 3～10 minutes, and the organic phase water is separated fully.Emit water from the flotation column bottom, organic phase is stayed in flotation column.
(3) adding concentration is the hydrochloric acid of 3～6mol/L, adds ethanol, and opening air compressor machine and control air flow is 10-50mL/min, and flotation 5～10 minutes was left standstill 5～10 minutes, emitted water from flotation column, and organic phase is stayed in flotation column.
The advantage that the present invention has compared with prior art
(1) the present invention can reach more than 90% a flotation extraction yield of lithium, exceeds 50 percentage points of traditional solvent extraction technologies, can improve the utilization ratio of salt lake lithium resource widely.
What (2) the present invention adopted is flotation process, operate traditional relatively extraction process simply, save time, laborsaving.Since an extraction yield height, the utilization ratio height of raw and auxiliary materials such as trapping agent and kerosene, relative loss factor is little, and extracting cycle is short, and production cost is low.
(3) the present invention uses hydrochloric acid as reverse-extraction agent in strip stages, and back extraction ratio is apparently higher than traditional technology, and separation thoroughly.
Description of drawings
The used flotation unit of the present invention.
Embodiment
Embodiment 1:
Get the bittern 20mL that contains lithium 2mg/mL, add 3.1gFeCl
36H
2O, 40mL TBP, 26.7mL kerosene, 5mL ethanol is added to this mixing solutions in the flotation column.Control air flow 10mL/min, 5min is extracted in flotation, leaves standstill 5～10min.The single extraction rate is: 90.6%.
Embodiment 2
Get the bittern 30mL that contains lithium 2mg/mL, add 4.65g FeCl
36H
2O, 60mL TBP, 40mL kerosene, 7mL ethanol is added to this mixing solutions in the flotation column, control air flow 30mL/min, flotation extraction 5min leaves standstill 5～10min.The single extraction rate is 91.1%.
Embodiment 3
Get the bittern 20mL that contains lithium 2mg/mL, add 3.1g FeCl
36H
2O, 40mL TBP, 26.7mL kerosene, 5mL ethanol is added to this mixing solutions in the flotation cell, control air flow 30mL/min, flotation extraction 8～10min leaves standstill 5～10min.The single extraction rate is 91.2%.1: 1 ratio of hydrochloric acid volume ratio in organic phase and 6mol/L adds hydrochloric acid, and ethanol 5mL, control air flow 30mL/min, and flotation extraction 8min leaves standstill 5～10min.A back extraction ratio of lithium is 93%.
Claims (7)
1. the method for enriching lithium in the salt lake brine, its feature comprises: under (1) normal temperature and pressure, add trapping agent, ethanol and kerosene in the salt lake brine in flotation column respectively, open air compressor machine and regulate air flow quantity, air-blowing 3～10 minutes.Left standstill 3～10 minutes, and collected organic phase.(2) under the normal temperature and pressure, in flotation column, add certain density hydrochloric acid, ethanol, open air compressor machine and regulate air flow quantity, air-blowing 3～10 minutes.Left standstill 3～10 minutes, and collected water, obtain the concentrated solution of lithium.
2. lithium salts enriching method as claimed in claim 1 is characterized in that using air to be flotation gas, also can adopt sources of the gas such as nitrogen, argon gas.
3. lithium salts enriching method as claimed in claim 1 is characterized in that the used air of flotation is provided by oil-free air compressor, and the flow of air is 10-50mL/min.Also can adopt the air steel cylinder is source of the gas.
4. lithium salts enriching method as claimed in claim 1 is characterized in that selected trapping agent A kind is extensive: tributyl phosphate, trioctyl phosphine oxide, DBBP, propyl alcohol, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, 2-Ethylhexyl Alcohol, acetone, pimelinketone, methyl iso-butyl ketone (MIBK), hexanoyl acetone, two pivaloyl ketones, thenoyltrifluoroacetone, benzoyltrifluoroacetone, 1,1,2,2,3,3-fluoro heptyl-7,7-dimethyl-4,6-octyl group diketone, 14-hat-4 etc.These trapping agents can be a kind of separately, also two or more adapteds arbitrarily.
5. lithium salts enriching method as claimed in claim 1 is characterized in that selected trapping agent B can be: iron trichloride, thenoyltrifluoroacetone, o-phenanthroline, any one of trioctyl phosphine oxide, or two or more mixing utilization.
6. lithium salts enriching method as claimed in claim 1 is characterized in that selected organic solvent is a kerosene, gasoline, and the benzene class, chloroforms etc. can select for use any as organic phase.
7. lithium salts enriching method as claimed in claim 1 is characterized in that selected reverse-extraction agent is a hydrochloric acid, and its concentration is between 3～6mol/L.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671775A (en) * | 2012-06-11 | 2012-09-19 | 江南大学 | Chemical separation floatation column with high enrichment ratio |
| CN103523804A (en) * | 2012-11-16 | 2014-01-22 | 中国科学院上海有机化学研究所 | Method for extracting lithium salt from lithium-contained brine by using extraction process |
| CN103626207A (en) * | 2012-08-20 | 2014-03-12 | 宁波莲华环保科技股份有限公司 | Method and device for extracting lithium salt from lithium-containing salt lake bittern |
| CN105013620A (en) * | 2015-06-25 | 2015-11-04 | 西南科技大学 | Efficient combined collector for spodumene and preparation method and application thereof |
| CN105439176A (en) * | 2014-09-28 | 2016-03-30 | 中国科学院上海高等研究院 | Method for extracting high purity lithium salt from high-magnesium lithium-containing bittern |
| CN106975468A (en) * | 2017-04-20 | 2017-07-25 | 江门市长优实业有限公司 | Cellulosic material of lithium metal and preparation method thereof in a kind of recovery lithium ion battery |
| CN107779612A (en) * | 2017-12-08 | 2018-03-09 | 中国科学院青海盐湖研究所 | A kind of technique that lithium is extracted from alkaline bittern |
| CN107937734A (en) * | 2017-12-08 | 2018-04-20 | 中国科学院青海盐湖研究所 | The technique that lithium is extracted from the bittern of alkalescence containing lithium based on mixer-settler |
| CN108004420A (en) * | 2017-12-08 | 2018-05-08 | 中国科学院青海盐湖研究所 | The technique that lithium is extracted from the bittern of alkalescence containing lithium based on centrifugal extractor |
| CN108893604A (en) * | 2018-07-03 | 2018-11-27 | 山西大学 | A kind of extracting process for lithium in Strong acidic electrolyte solution system |
| CN112058090A (en) * | 2020-09-10 | 2020-12-11 | 中国科学院青海盐湖研究所 | System for separating lithium isotope by multi-stage air flotation extraction |
| CN112058087A (en) * | 2020-09-10 | 2020-12-11 | 中国科学院青海盐湖研究所 | Method for separating lithium isotope by multi-stage air flotation extraction |
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| CN101875497A (en) * | 2010-08-18 | 2010-11-03 | 化工部长沙设计研究院 | Production process for extracting lithium from raw brine of high magnesium-lithium ratio lithium salt-containing lake |
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| US6871743B2 (en) * | 2000-05-16 | 2005-03-29 | Mineral And Coal Technologies, Inc. | Methods of increasing flotation rate |
| JP2003272720A (en) * | 2002-03-15 | 2003-09-26 | Japan Science & Technology Corp | Recovery method for lithium cobaltate |
| CN1511964A (en) * | 2002-12-27 | 2004-07-14 | 中国科学院青海盐湖研究所 | Process for extracting lithium from salt lake brine by adsorptive method |
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671775A (en) * | 2012-06-11 | 2012-09-19 | 江南大学 | Chemical separation floatation column with high enrichment ratio |
| CN103626207A (en) * | 2012-08-20 | 2014-03-12 | 宁波莲华环保科技股份有限公司 | Method and device for extracting lithium salt from lithium-containing salt lake bittern |
| CN103626207B (en) * | 2012-08-20 | 2017-03-29 | 宁波莲华环保科技股份有限公司 | A kind of method and apparatus that lithium salts is extracted from lake bittern water containing lithium salts |
| CN103523804A (en) * | 2012-11-16 | 2014-01-22 | 中国科学院上海有机化学研究所 | Method for extracting lithium salt from lithium-contained brine by using extraction process |
| CN105439176A (en) * | 2014-09-28 | 2016-03-30 | 中国科学院上海高等研究院 | Method for extracting high purity lithium salt from high-magnesium lithium-containing bittern |
| CN105439176B (en) * | 2014-09-28 | 2017-10-13 | 中国科学院上海高等研究院 | It is a kind of that the process for preparing high-purity lithium salts is extracted from high-Mg Li-contained bittern |
| CN105013620A (en) * | 2015-06-25 | 2015-11-04 | 西南科技大学 | Efficient combined collector for spodumene and preparation method and application thereof |
| CN105013620B (en) * | 2015-06-25 | 2017-07-07 | 西南科技大学 | A kind of spodumene efficient combination collecting agent and its preparation method and application |
| CN106975468A (en) * | 2017-04-20 | 2017-07-25 | 江门市长优实业有限公司 | Cellulosic material of lithium metal and preparation method thereof in a kind of recovery lithium ion battery |
| CN106975468B (en) * | 2017-04-20 | 2019-08-27 | 江门市长优实业有限公司 | The cellulosic material and preparation method thereof of lithium metal in a kind of recycling lithium ion battery |
| CN107937734A (en) * | 2017-12-08 | 2018-04-20 | 中国科学院青海盐湖研究所 | The technique that lithium is extracted from the bittern of alkalescence containing lithium based on mixer-settler |
| CN108004420A (en) * | 2017-12-08 | 2018-05-08 | 中国科学院青海盐湖研究所 | The technique that lithium is extracted from the bittern of alkalescence containing lithium based on centrifugal extractor |
| CN107779612A (en) * | 2017-12-08 | 2018-03-09 | 中国科学院青海盐湖研究所 | A kind of technique that lithium is extracted from alkaline bittern |
| CN107779612B (en) * | 2017-12-08 | 2019-12-13 | 中国科学院青海盐湖研究所 | Process for extracting lithium from alkaline brine |
| CN108004420B (en) * | 2017-12-08 | 2020-04-28 | 中国科学院青海盐湖研究所 | Centrifugal extractor-based process for extracting lithium from lithium-containing alkaline brine |
| CN107937734B (en) * | 2017-12-08 | 2020-04-28 | 中国科学院青海盐湖研究所 | Process for extracting lithium from lithium-containing alkaline brine based on mixed clarifying tank |
| CN108893604A (en) * | 2018-07-03 | 2018-11-27 | 山西大学 | A kind of extracting process for lithium in Strong acidic electrolyte solution system |
| CN112058090A (en) * | 2020-09-10 | 2020-12-11 | 中国科学院青海盐湖研究所 | System for separating lithium isotope by multi-stage air flotation extraction |
| CN112058087A (en) * | 2020-09-10 | 2020-12-11 | 中国科学院青海盐湖研究所 | Method for separating lithium isotope by multi-stage air flotation extraction |
| CN112058087B (en) * | 2020-09-10 | 2024-04-09 | 中国科学院青海盐湖研究所 | Method for separating lithium isotopes by multistage air-floatation extraction |
| CN112058090B (en) * | 2020-09-10 | 2024-04-12 | 中国科学院青海盐湖研究所 | System for separating lithium isotopes by multistage air-floatation extraction |
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Application publication date: 20110817 |