CN106044803A - Method of extracting lithium chloride from sulfate-type salt lake brine - Google Patents
Method of extracting lithium chloride from sulfate-type salt lake brine Download PDFInfo
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- CN106044803A CN106044803A CN201610419425.5A CN201610419425A CN106044803A CN 106044803 A CN106044803 A CN 106044803A CN 201610419425 A CN201610419425 A CN 201610419425A CN 106044803 A CN106044803 A CN 106044803A
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- lithium chloride
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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
- C01D15/04—Halides
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Abstract
The invention provides a method of extracting lithium chloride from sulfate-type salt lake brine. An extraction system comprises an extractor, a co-extractor and a diluent, and the extractor is a mixture of an unsaturated hydrocarbon amide compound and tributyl phosphate. The extractor used in the method contains unsaturated hydrocarbon, and a 1, 4-conjugated system is formed between carbon-carbon double bond and carbon-oxygen double bond when double bonds of are directly connected with carbonyl; electric charge density on carbonyl oxygen is increased under action that carbonyl absorbs electrons, so that capability, in coordination with metal ions, of carbonyl is enhanced, and yield of extracted lithium is increased.
Description
Technical field
The method that the present invention relates to use solvent extraction to extract lithium chloride from sulfate type salt lake brine.
Background technology
Lithium chloride is in the field such as biology, medical science also extensive application, and additionally the former of lithium metal still produced by lithium chloride
The raw material of the nonlinear optical material in material, the welding compound of aluminum, air conditioner dehumidification agent, optic communication, its demand is increasing, thus
The production making lithium chloride demonstrates unprecedented good prospect.The production method of lithium chloride is mainly lithium carbonate or hydrogen at present
Lithium oxide and hydrochloric acid reaction, along with lithium carbonate, the rise at full speed of Lithium hydrate price, using the method to produce lithium chloride does not has
Economic benefit.The present invention uses extraction to extract lithium chloride, and its technique is simple, and easy to operate, cost is relatively low, product lithium chloride
Reach primes requirement.
The system of the extraction lithium the most reported mainly has: alcohols, ketone (diketone) class, organic phosphine class, quaternary amine
Salt azo ion chelating association class, crown ether-like.Nineteen thirty-seven Bardet et al. is from the sea water containing lithium 200 micrograms per litre, with penta
Alcohol is extract and separate lithium from NaCl solution, has the drawback that amylalcohol is soluble in water and is not suitable for commercial production.Nineteen sixty-eight the U.S.
Lithium company J.R.Neille et al. has invented the 80% diisobutyl ketone 20%TBP method from high-magnesium brine extraction lithium, and the method is deposited
The shortcomings such as in, water high in diisobutyl ketone price molten damage is serious and lithium extraction yield is low, and the commercial Application of reality cannot be realized.2015
Nian Shidong et al. has invented a kind of extraction lithium ion or alkaline-earth metal ions extraction system, and the extractant of this extraction system is diketone
Compound, synergic reagent is neutral phosphor oxygen compound.Although avoid use synergic reagent ferric chloride, but cannot realize magnesium, lithium point
From, thus may not apply to the sulfate type salt lake that Mg/Li ratio is higher.Organic phosphinic extractant is applied at the higher salt of lithium magnesium
In lake bittern water, effect is preferable, wherein, is most commonly used that neutral phosphorus extractant: tributyl phosphate (TBP), trioctylphosphine oxygen phosphorus
And butyl phosphoric acid dibutyl ester (DBBP) (TOPO), effect of extracting most preferably tributyl phosphate (TBP) extractant, 1979,
Qinghai Yanhu Inst., Chinese Academy of Sciences proposes the technique of 80%TBP-20% kerosene system extraction lithium, and uses big bavin denier salt lake
Salt has carried out expanding test, owing in this system, tributyl phosphate concentration is higher, extremely strong to the corrosivity of extraction equipment, and
Salt dissolubility in organic facies is relatively big, and product purity only has about 98.5%, the most non-large-scale industrial production.Quaternary amine
Salt azo ion chelating-association class, Chinese Academy of Sciences's Shanghai organic chemistry have studied 20%N-503 [N, N-bis-in 1979
(1-methylheptyl) acetamide] 20%TBP-60%200# kerosene extracts system and the method for lithium from the bromine mother solution of Zi Gong,
Extracting through four-stage counter-current, the yield of Li is up to 90%.Shanghai organic chemistry institutes of the Chinese Academy of Sciences in 2012 and the Chinese Academy of Sciences are blue or green
Sea salt lake institute have studied 20% N523 (N, N-bis-(2-ethylhexyl) acetamide)-30%TBP-50% sulfonated kerosene system
The technique extracting lithium from the salt lake brine with high magnesium-lithium ratio of Qinghai.The extraction yield of three stage countercurrent extraction cascade experiment result display lithiums reaches
96%, have no three-phase and emulsion.Crown ether-like extractant, according to size and the Lewis acid-base theoryby in crown ether hole, crown ether is to certain
The when that a little metal ions having the hole size of higher selectivity, i.e. crown ether suitable with the radius of some metal ion, metal
Ion just can enter crown ether hole and chelate therewith.The crown ether cycle being best suitable for extracting lithium is 14 hats 4, due to this kind of extractants price
Higher, there is no the report of commercial Application at present.
Summary of the invention
Extract from sulfate type salt lake brine for the solvent extraction of existing use present in the method for lithium chloride
Deficiency strong to equipment corrosion, that extraction yield is low, the present invention provides a kind of and can reduce the corrosivity to equipment and improve extraction yield
Method, be suitable for industrialized production.
It is as follows that the present invention realizes process:
A kind of method extracting lithium chloride from sulfate type salt lake brine, its extraction system includes extractant, altogether extraction agent and dilute
Releasing agent, described extractant is the mixture of tributyl phosphate and the unsaturated hydro carbons amide compound shown in structure formula (I),
The structural formula of described unsaturated hydro carbons amide compound is:
In formula, R1、R2And R3Independently selected from the alkyl of H, C1-C5, cycloalkyl, phenyl, pyridine radicals, piperidyl, pyrrole radicals, thiophene
Fen base；R4And R5Independently selected from the alkyl of C4-C12, the alkyl of the C1-C4 of cycloalkyl substituted.
The agent of above-mentioned extraction altogether is ferric chloride；Diluent is 200# industrial naptha, sulfonated kerosene；Unsaturated hydro carbons in extractant
Amide compound is (0.2～5) with the volume ratio of tributyl phosphate: 1.
During extraction, organic facies is (0.8～5) with the volume ratio of aqueous phase: 1, and lithium concentration is (0.5～8) g/L, salt lake bittern
In in, the mass ratio of magnesium elemental lithium is (8～200): 1, and extraction agent ferric chloride with the mol ratio of Lithium from Salt Lake Brine ion is altogether
(1～1.5): 1, diluent is (0.5～2) with the volume ratio of extractant: 1.
Advantages of the present invention:
1. devising the extractant-unsaturation hydro carbons amide compound of a kind of brand-new lithium, such material double bond is direct with carbonyl
When being connected, between carbon-carbon double bond and C=O bond, form an Isosorbide-5-Nitrae-conjugated system, ketonic oxygen under the electrophilic effect of carbonyl
On charge density raise, and then strengthen the coordination ability of itself and metal ion；
2. this kind of extractants synthetic reaction route is simple, and reaction raw materials is easy to get, and reaction yield is high, has the highest potential industry raw
Produce and be worth；
3., due to the minimizing of TBP content, reduce the corrosion of organic relative device.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described, the table 1 high Mg/Li ratio salt lake halogen used by experiment
Water forms, and the effect of extracting process of the present invention in specific embodiment is described.
The synthetic route of unsaturation hydro carbons amide compound of the present invention: will be with R4, the amine of R5 joins in there-necked flask,
Adding the triethylamine of 1.1equiv equivalent, addition dichloromethane is as solvent, and system temperature drops to-5 DEG C ~ 0 DEG C, drips structure
Acyl chlorides/dichloromethane solution shown in formula (II), control system temperature, at 0 DEG C, reacts 2h, and add water separatory, collects organic facies, rotation
Do to obtain target product.
Embodiment 1
Extractant is TBP and amides compound N, N-bis-(2-ethylhexyl) acrylamide, and its structural formula is as follows:
Its synthetic method is as follows: will be with N, and N-bis--(2-ethylhexyl) amine joins in there-necked flask, adds 1.1 equivalents
Triethylamine, add dichloromethane as solvent, system temperature drops to-5 DEG C ~ 0 DEG C, dropping with acryloyl chloride/dichloromethane
Solution, control system temperature, at 0 DEG C, reacts 2h, and add water separatory, collects organic facies, is spin-dried for obtaining target product.
In a separatory funnel, add the salt lake bittern as shown in table 1 of 1 volume, add a certain amount of FeCl3
(FeCl3With Li in salt+Mol ratio be 1:1.3) as extracting agent altogether, shake is allowed to dissolve.Add 2 volumes organic facies (
Compare O/A=2), wherein N, N-bis-(2-ethylhexyl) acrylamide, the volume ratio of TBP and 200# industrial naptha are 3:2:5,
Static layering after vibrating 5 minutes.Measure Li in balance aqueous phase+Concentration, the single extraction yield calculating lithium is 85.53%, through three
After secondary counter-current extraction, yield reaches 97.85%.
Comparing result: synthesis obtains the amide compound extractant shown in following structural formula, uses above-mentioned same procedure, warp
After three counter-current extractions, yield reaches 82.56%.
Embodiment 2
Extractant is TBP and amides compound N-(1-methyl butyl)-N-hexamethylene methylene-3-methyl-2-butene amide, its
Structural formula is as follows:
In a separatory funnel, add the salt lake bittern as shown in table 1 of 1 volume, add a certain amount of FeCl3(FeCl3With
Li in salt+Mol ratio be 1:1.5) as extracting agent altogether, shake is allowed to dissolve.The organic facies adding 5 volumes (compares O/A
=5), wherein N-(1-methyl butyl)-N-hexamethylene methylene-3-methyl-2-butene amide, TBP and the volume ratio of sulfonated kerosene
For 2:1:2, static layering after vibrating 10 minutes.Measure Li in balance aqueous phase+Concentration, the single extraction yield calculating lithium is
88.01%, after three counter-current extractions, yield reaches 98.67%.
Comparing result: synthesis obtains the amide compound extractant shown in following structural formula, uses above-mentioned same procedure, warp
After three counter-current extractions, yield reaches 83.17%.
Embodiment 3
Extractant is TBP and amides compound N, N-dibutyl-2-methyl-2-butene amide, and its structural formula is as follows:
In a separatory funnel, add the salt lake bittern as shown in table 1 of 1 volume, add a certain amount of FeCl3(FeCl3With
Li in salt+Mol ratio be 1:1) as extracting agent altogether, shake is allowed to dissolve.The organic facies adding 2 volumes (compares O/A=
0.8), the volume ratio of wherein N, N-dibutyl-2-methyl-2-butene amide, TBP and sulfonated kerosene is 1:1:2, vibrates 10 minutes
Static layering afterwards.Measure Li in balance aqueous phase+Concentration, the extraction yield calculating lithium is 82.15%, receives after three counter-current extractions
Rate reaches 96.70%.
Comparing result: synthesis obtains the amide compound extractant shown in following structural formula, uses above-mentioned same procedure, warp
After three counter-current extractions, yield reaches 81.28%.
Claims (9)
1. the method extracting lithium chloride from sulfate type salt lake brine, it is characterised in that: extraction system include extractant,
Extraction agent and diluent altogether, described extractant is tributyl phosphate and the unsaturated hydro carbons amide compound shown in structure formula (I)
Mixture,
The structural formula of described unsaturated hydro carbons amide compound is:
In formula, R1、R2And R3Independently selected from the alkyl of H, C1-C5, cycloalkyl, phenyl, pyridine radicals, piperidyl, pyrrole radicals, thiophene
Fen base；R4And R5Independently selected from the alkyl of C4-C12, the alkyl of the C1-C4 of cycloalkyl substituted.
2. according to the method extracting lithium chloride described in claim 1, it is characterised in that: described common extraction agent is ferric chloride.
3. according to the method extracting lithium chloride described in claim 1, it is characterised in that: described diluent is 200# solvent vapour
Oil, sulfonated kerosene.
4. according to the method extracting lithium chloride described in claim 1, it is characterised in that: unsaturated hydro carbons amidatioon in extractant
Compound is (0.2～5) with the volume ratio of tributyl phosphate: 1.
5. according to the method extracting lithium chloride described in claim 1, it is characterised in that: during extraction, organic facies and the volume of aqueous phase
Than being (0.8～5): 1.
6. according to the method extracting lithium chloride described in claim 1, it is characterised in that: described lithium concentration is (0.5～8) g/L.
7. according to the method extracting lithium chloride described in claim 1, it is characterised in that: magnesium elemental lithium in described salt lake bittern
Mass ratio be (8～200): 1.
8. according to the method extracting lithium chloride described in claim 1, it is characterised in that: extraction agent ferric chloride and salt lake bittern altogether
The mol ratio of middle lithium ion is (1～1.5): 1.
9. according to the method extracting lithium chloride described in claim 1, it is characterised in that: diluent with the volume ratio of extractant is
(0.5～2): 1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4661634A (en) * | 1985-09-16 | 1987-04-28 | The Dow Chemical Company | Removal of impurities from amines |
| CN102001692A (en) * | 2010-12-03 | 2011-04-06 | 中国科学院青海盐湖研究所 | Coordinate extracting system for extracting lithium from salt lake brine with extraction method |
| CN103055538A (en) * | 2012-05-24 | 2013-04-24 | 中国科学院上海有机化学研究所 | Method for extracting lithium salts in lithium-containing brine through extraction method |
| CN103055539A (en) * | 2012-05-24 | 2013-04-24 | 中国科学院上海有机化学研究所 | Method for extracting lithium salts in lithium-containing brine |
| 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 |
-
2016
- 2016-06-14 CN CN201610419425.5A patent/CN106044803B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4661634A (en) * | 1985-09-16 | 1987-04-28 | The Dow Chemical Company | Removal of impurities from amines |
| CN102001692A (en) * | 2010-12-03 | 2011-04-06 | 中国科学院青海盐湖研究所 | Coordinate extracting system for extracting lithium from salt lake brine with extraction method |
| CN103055538A (en) * | 2012-05-24 | 2013-04-24 | 中国科学院上海有机化学研究所 | Method for extracting lithium salts in lithium-containing brine through extraction method |
| CN103055539A (en) * | 2012-05-24 | 2013-04-24 | 中国科学院上海有机化学研究所 | Method for extracting lithium salts in lithium-containing brine |
| 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 |
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