CN106629790B - A method of separation is containing magnesium lithium in magnesium, lithium solution - Google Patents
A method of separation is containing magnesium lithium in magnesium, lithium solution Download PDFInfo
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- CN106629790B CN106629790B CN201610853866.6A CN201610853866A CN106629790B CN 106629790 B CN106629790 B CN 106629790B CN 201610853866 A CN201610853866 A CN 201610853866A CN 106629790 B CN106629790 B CN 106629790B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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Abstract
The method containing magnesium lithium in magnesium, lithium solution is efficiently separated the present invention relates to a kind of.The pH value containing magnesium, lithium solution is adjusted, soluble phytate is added to containing in magnesium, lithium solution, is made containing the Mg in magnesium, lithium solution2+Form complex compound sediment not soluble in water, and Li+It remains in solution；After separation of solid and liquid, contain Li+Solution it is concentrated after precipitation prepare lithium carbonate, after gained dissolving with hydrochloric acid containing magnesium precipitate, adsorb phytic acid radical ion therein with weakly-basic anion under weak acid environment, gained is containing Mg2+Friendship after liquid can be used for preparing magnesium salts；Regeneration is realized in load after having the resin of phytic acid radical ion to be desorbed with NaOH solution, stripping liquid is for subsequent cycle containing Mg in magnesium, lithium solution2+Precipitation.This method flow is short, easy to operate, can efficiently realize the separation containing magnesium lithium in magnesium, lithium solution, and phytate can recycle, production cost is low, is easy to industrial applications.
Description
Technical field
The invention belongs to separating magnesium and lithium technical fields in salt lake bittern, it particularly relates to which one kind is efficiently separated containing magnesium, lithium
The method of magnesium lithium in solution.
Background technology
Lithium becomes more and more important in modern industry, is known as " the new energy metal of 21 century ".Obama appears on the stage her
Lithium is just positioned at the American National strategic materials of equal importance with oil by the beginning.With the fast development of New Energy Industry, lithium
The market demand drastically expands, and the exploitation of lithium resource seems more important.
In nature, lithium resource is primarily present in brine especially salt lake bittern, and reserves account for whole lithium resource reserves
80% or more.The lithium product in 85% or more the whole world comes from salt lake bittern at present, and mostly by Chilean SQM, Germany Chemtall
It monopolizes and produces with tri- companies of U.S. FMC, this possesses low Mg/Li ratio (≤6 dependent on it:1) high-quality salt lake bittern.China's salt
Lake lithium resource is very abundant, finds out reserves up to 6,000,000 tons or more, but the Mg/Li ratio in most salt lake bitterns is all 40:1 with
On, up to 1837:1, it is far above commercial mining standard (Mg/Li ratio≤6:1).Due to the chemistry of magnesium and lithium in salt lake bittern
Property is closely similar, and separating magnesium and lithium is extremely difficult, and production cost is high, the serious exploitation profit for restricting China's salt lake resources
With how economical and efficient realizes that the separating magnesium and lithium in salt lake bittern becomes a global problem.Researchers using the precipitation method,
Ion-exchange, solvent extraction, carbonizatin method etc. extract the lithium resource in brine, but the most process of these methods is complicated, examination
Agent consumption is big, severe corrosion to equipment, and production cost is high, it is difficult to large-scale industrial production.
Based on the above situation, the present invention proposes a kind of new thinking, and halogen is precipitated using a kind of novel organic precipitant
Mg in water2+, then realize by the means of sour molten-ion exchange the regeneration of organic precipitant.So, halogen is not only realized
Magnesium lithium efficiently separates in water, and overcome traditional precipitation method separating magnesium and lithium be not thorough, reagent consumption it is big, it is of high cost
Disadvantage.
Invention content
It is an object of the present invention to propose it is a kind of efficiently separate the method containing magnesium lithium in magnesium, lithium solution, realize salt lake bittern
Magnesium lithium efficiently separates especially in salt lake brine with high magnesium-lithium ratio.This method flow is short, easy to operate, and medicament recycles, raw
It produces at low cost, is easy to industrial applications.
A method of separation containing magnesium lithium in magnesium, lithium solution, by phytate be added to containing precipitated in magnesium, lithium solution magnesium from
Son, to separating magnesium lithium；Described is arbitrarily to contain Li containing magnesium, lithium solution+And Mg2+Solution, including：Original in arbitrary salt lake
Beginning brine either its evaporation and concentration after brine or its propose the mixing of one or more of old halogen after potassium.
The soluble phytate is the mixing of one or more of phytic acid lithium, sodium phytate, POTASSIUM PHYTATE, phytic acid ammonium
Object.Soluble phytate presses magnesium ion:Phytic acid root molar ratio=(1~5):1 ratio addition.
Method of the separation containing magnesium lithium in magnesium, lithium solution, is adjusted to 5~8 by the pH value containing magnesium, lithium solution and adds
Phytate.
Method of the separation containing magnesium lithium in magnesium, lithium solution, phytate solution is added to containing in magnesium, lithium solution, in room
It is stirred to react 30~120min under temperature.
Method of the separation containing magnesium lithium in magnesium, lithium solution is used after precipitating the filtered concentrating filter liquor of magnesium ion
Na2CO3Precipitation prepares lithium carbonate.
Method of the separation containing magnesium lithium in magnesium, lithium solution precipitates the filter residue diluted hydrochloric acid dissolution obtained by magnesium ion, will
Dissolved solution flows through weak-base anion-exchange resin to adsorb phytic acid radical ion therein.
Method of the separation containing magnesium lithium in magnesium, lithium solution, with diluted hydrochloric acid dissolution filter residue control reaction end pH be 1~
3；Dissolved solution is flowed through into weak-base anion-exchange resin to adsorb it with the linear velocity of 1~12cm/min at room temperature
In phytic acid radical ion；The weak-base anion-exchange resin is macroporous type weak-base anion-exchange resin.
Method of the separation containing magnesium lithium in magnesium, lithium solution, with NaOH solution desorption and regeneration loaded resin, gained contains can
It is returned after the stripping liquid hydrochloric acid adjustment pH value of dissolubility phytate for precipitating Mg2+。
Method of the separation containing magnesium lithium in magnesium, lithium solution, with water by ion exchange column elution it is clean after, with 0.1~
The NaOH solution desorption and regeneration loaded resin of 0.5mol/L, stripping liquid of the gained containing soluble phytate adjust pH value 5 with hydrochloric acid
It is returned after~7 for precipitating Mg2+。
The invention has the advantages that：
1, organic precipitant has extraordinary selectivity to magnesium, can form the low-down complex compound sediment of solubility with magnesium,
Separating magnesium and lithium is very thorough；
2, the method can handle the brine of different Mg/Li ratios, can also handle for example original brine of different types of brine and
Old halogen after concentration etc. is particularly suitable for depth demagging；
3, the method can realize the regeneration of organic precipitant, and reagent consumption is few, and production cost is low, easy to operate, be easy to
Large-scale production.
Specific implementation mode
In order to which the present invention is explained in greater detail, enumerates following embodiment and illustrate, but the present invention is not limited to these realities
Apply example.
Embodiment 1
It is tested using the original brine in certain domestic western salt lake, main component and the content such as following table institute of salt lake bittern
Show：
| Ingredient | Concentration (mg/L) |
| Li+ | 280 |
| Na+ | 2350 |
| Mg2+ | 15600 |
| K+ | 1050 |
| Ca2+ | 120 |
The 1L pH original brine for being 6.8 is added in stirred reactor, the sodium phytate for adding 200ml 500g/L is molten
Reaction 60min is stirred at room temperature in liquid；After separation of solid and liquid, Mg in filtrate2+A concentration of 20mg/L, Li+A concentration of 233mg/L,
Mg2+And Li+Rate of deposition be respectively 99.8% and 0.1%；By the dissolving with hydrochloric acid of filter residue 10g/L, it is diluted to deionized water
PH is 3, and dilution is flowed through D301 resins with the linear velocity of 1cm/min at room temperature, is cleaned loaded resin with deionized water
Totally, then with the NaOH solution of 0.5mol/L loaded resin is desorbed, gained stripping liquid is with the hydrochloric acid of 50g/L adjustment pH
After 7, the precipitation for magnesium in next batch brine is returned.
Embodiment 2
It is tested using low Mg/Li ratio salt lake bittern, the main component and content of salt lake bittern are as shown in the table：
| Ingredient | Concentration (mg/L) |
| Li+ | 200 |
| Na+ | 2580 |
| Mg2+ | 1260 |
| K+ | 780 |
The 1L pH original brine for being 7.82 is added in stirred reactor, the POTASSIUM PHYTATE for adding 20ml 500g/L is molten
Reaction 120min is stirred at room temperature in liquid；After separation of solid and liquid, Mg in filtrate2+A concentration of 18mg/L, Li+A concentration of 195mg/
L, Mg2+And Li+Rate of deposition be respectively 98.5% and 0.55%；By the dissolving with hydrochloric acid of filter residue 10g/L, diluted with deionized water
It is 2 to pH, dilution is flowed through into D301 resins with the linear velocity of 12cm/min at room temperature, it is with deionized water that loaded resin is clear
Wash clean, then loaded resin is desorbed with the NaOH solution of 0.1mol/L, gained stripping liquid adjusts pH with the hydrochloric acid of 50g/L
After 7, the precipitation for magnesium in next batch brine is returned.
Embodiment 3
It is tested using the old halogen in domestic Qinghai East Platform salt lake, the main component and content of old halogen are as shown in the table：
| Ingredient | Concentration (mg/L) |
| Li+ | 5670 |
| Na+ | 2390 |
| Mg2+ | 121126 |
| K+ | 2339 |
| Ca2+ | 236 |
| Cl- | 248534 |
The 1L pH old halogen for being 4.67 is added in stirred reactor, is adjusted its pH to 6.8 with NaOH solution, then add
Reaction 120min is stirred at room temperature in the sodium phytate particle for entering 780g；After separation of solid and liquid, Mg in filtrate2+A concentration of 22mg/L,
Li+A concentration of 5638mg/L, Mg2+And Li+Rate of deposition be respectively 99.9% and 0.56%；Filter residue is molten with the hydrochloric acid of 30g/L
Solution, with deionized water be diluted to pH be 1, dilution is flowed through into D314 resins with the linear velocity of 5cm/min at room temperature, spend from
Sub- water cleans up loaded resin, then is desorbed to loaded resin with the NaOH solution of 0.5mol/L, and gained stripping liquid is used
After the hydrochloric acid adjustment pH of 100g/L is 5, the precipitation for magnesium in next batch brine is returned.
Embodiment 4
It is tested using the original brine in certain western salt lake, the main component and content of brine are as shown in the table：
| Ingredient | Concentration (mg/L) |
| Li+ | 198 |
| Na+ | 91214 |
| Mg2+ | 16735 |
| K+ | 8508 |
| Ca2+ | 280 |
| Cl- | 191111 |
The 1L pH original brine for being 7.67 is added in stirred reactor, the phytic acid ammonium powder of 110g is added, in room
It is stirred to react 120min under temperature；After separation of solid and liquid, Mg in filtrate2+A concentration of 21mg/L, Li+A concentration of 195mg/L, Mg2+With
Li+Rate of deposition be respectively 99.8% and 0.45%；By the dissolving with hydrochloric acid of filter residue 20g/L, being diluted to pH with deionized water is
1, dilution is flowed through into D314 resins with the linear velocity of 10cm/min at room temperature, loaded resin is cleaned with deionized water and is done
Only, then with the NaOH solution of 0.3mol/L loaded resin is desorbed, gained stripping liquid is 5 with the hydrochloric acid adjustment pH of 50g/L
Afterwards, the precipitation for magnesium in next batch brine is returned.
Claims (10)
1. a kind of method containing separating magnesium lithium in magnesium, lithium solution, which is characterized in that being added to soluble phytate containing magnesium, lithium
Magnesium ion is precipitated in solution, to separating magnesium lithium；Described is arbitrarily to contain Li containing magnesium, lithium solution+And Mg2+Solution, including：
Original brine in arbitrary salt lake either the brine after its evaporation and concentration or its carry one or more of old halogen after potassium
Mixing.
2. method of the separation containing magnesium lithium in magnesium, lithium solution according to claim 1, which is characterized in that the solubility
Phytate is the mixture of one or more of phytic acid lithium, sodium phytate, POTASSIUM PHYTATE, phytic acid ammonium.
3. method of the separation containing magnesium lithium in magnesium, lithium solution according to claim 1 or 2, which is characterized in that soluble phytic acid
Salt presses magnesium ion:Phytic acid root molar ratio=(1~5):1 ratio addition.
4. method of the separation containing magnesium lithium in magnesium, lithium solution according to claim 1, which is characterized in that magnesium, lithium solution will be contained
PH value be adjusted to 5~8 and add phytate.
5. method of the separation containing magnesium lithium in magnesium, lithium solution according to claim 1 or 4, which is characterized in that phytate solution
It is added to containing in magnesium, lithium solution, 30~120min of reaction is stirred at room temperature.
6. method of the separation containing magnesium lithium in magnesium, lithium solution according to claim 1, which is characterized in that precipitation magnesium ion mistake
Na is used after concentrating filter liquor after filter2CO3Precipitation prepares lithium carbonate.
7. method of the separation containing magnesium lithium in magnesium, lithium solution according to claim 1, which is characterized in that precipitation magnesium ion institute
The filter residue diluted hydrochloric acid dissolution obtained, flows through weak-base anion-exchange resin to adsorb phytic acid root therein by dissolved solution
Ion.
8. method of the separation containing magnesium lithium in magnesium, lithium solution according to claim 7, which is characterized in that use diluted hydrochloric acid dissolution
It is 1~3 that filter residue, which controls reaction end pH,；Dissolved solution is flowed through into weak base with the linear velocity of 1~12cm/min at room temperature
Property anion exchange resin is to adsorb phytic acid radical ion therein；The weak-base anion-exchange resin is macroporous type weak base
Property anion exchange resin.
9. method of the separation containing magnesium lithium in magnesium, lithium solution according to claim 7, which is characterized in that with NaOH solution solution
Regeneration duties resin is inhaled, gained returns after the stripping liquid hydrochloric acid adjustment pH value containing soluble phytate for precipitating Mg2+。
10. method of the separation containing magnesium lithium in magnesium, lithium solution according to claim 9, which is characterized in that handed over ion with water
After changing column elution totally, with the NaOH solution desorption and regeneration loaded resin of 0.1~0.5mol/L, gained is containing soluble phytate
Stripping liquid hydrochloric acid returns after adjusting pH value 5~7 for precipitating Mg2+。
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| CN107986298A (en) * | 2017-12-13 | 2018-05-04 | 成都理工大学 | A kind of salt lake bittern separating magnesium and lithium method |
| CN110615453B (en) * | 2019-09-26 | 2022-02-08 | 黄冈师范学院 | Method for directly preparing battery-grade lithium carbonate |
| CN115318446B (en) * | 2022-08-05 | 2024-04-12 | 中国地质科学院矿产综合利用研究所 | Flotation reagent system for refractory low-grade nickel-cobalt sulfide ores and application thereof |
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| JP2729805B2 (en) * | 1988-07-08 | 1998-03-18 | 日本製粉株式会社 | Transformation promoter and transformation promotion method |
| CN104803399B (en) * | 2015-04-01 | 2017-04-12 | 长沙矿冶研究院有限责任公司 | Method for preparing high-purity magnesium oxalate, lithium carbonate and high-purity nanometer magnesia from salt lake brine of high magnesium-lithium ratio |
| CN104962757B (en) * | 2015-06-18 | 2017-05-10 | 中南大学 | Method for deeply removing magnesium from lithium chloride solution |
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