CN110240183A - A kind of preparation method of lithium carbonate - Google Patents
A kind of preparation method of lithium carbonate Download PDFInfo
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- CN110240183A CN110240183A CN201910713835.4A CN201910713835A CN110240183A CN 110240183 A CN110240183 A CN 110240183A CN 201910713835 A CN201910713835 A CN 201910713835A CN 110240183 A CN110240183 A CN 110240183A
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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
Abstract
The present invention is suitable for chemical field, provides a kind of preparation method of lithium carbonate, comprising: by extraction organic phase and lithium-containing solution, 1:1 ~ 10 are mixed to form alkaline extraction system by volume, extract 1 ~ 3 time, and single extraction time is 1 ~ 15 minute, obtain organic phase containing lithium；Lithium organic phase will be contained, and 1:1 ~ 10 mix by volume with stripping solution, are stripped 1 ~ 3 time, and single back-extraction time is 1 ~ 15 minute, collect the lithium bicarbonate aqueous solution containing lithium ion；Stripping workshop is that carbon dioxide is passed through aqueous solution made from one of pure water, alkaline metal salt or ammonium salt aqueous solution or any combination thereof；Lithium bicarbonate aqueous solution containing lithium ion is heated, the lithium bicarbonate in the aqueous solution is crystallized and is precipitated, and thermally decomposed to yield lithium carbonate.This method extraction efficiency is high, lithium ion can be extracted directly in alkaline brine or aqueous solution and prepare lithium carbonate, small to the corrosivity of production equipment, production cost is low and environmentally friendly.
Description
Technical field
The invention belongs to chemical field more particularly to a kind of preparation methods of lithium carbonate.
Background technique
Lithium is the important rare element for promoting the development of the related industries such as modernization construction and science and technology, is most potential
One of a kind of new energy and strategic resource are widely used in high power lithium battery, rubber industry, aerospace, ceramics, swash
The numerous areas such as light, medicine, welding, explosive, cement, smelting and new energy are known as " energy metal of 21 century " by reputation.Especially
It is the energy that l grams of lithium is released by thermonuclear reaction in new energy field, is equivalent to more than 20,000 tons of high-quality coal combustion and is produced
Raw energy, lithium ion battery and nuclear fusion power generation are the hot spot directions nowadays studied, in view of it in atomic energy industry
Special performance, be otherwise known as " high-energy metals ".Many countries have made lithium from economic development needs and the consideration of national security angle
For strategic reserves substance and carry out extensive use technical research.
China is a big country with abundant lithium resource, and the lithium resource reserves that oneself verifies occupy the second in the world, especially
Liquid lithium ore resources are very rich, and the 87% of Zhan Quanguo gross reserves, it is mainly distributed on Qinghai, the Tibet province Liang Ge, Qinghai and Tibet
The prospective reserves of salt lake bittern lithium is just suitable with other countries, the world gross reserves that oneself verifies at present, and has very high exploitation valence
Value and huge potential economic benefit and the valuable source treasure-house of China's Future Development lithium salts industry.Wherein Tibetan Salt Lakes master
In the majority for alkaline salt lake, lake water pH value is between 7 ~ 10.There is carbonate, Sulfates, borate family and chloride etc. four
Big type.Tibet plateau salt lake spreads all over the place, and is that China salt lake is distributed most intensive one of area, and height above sea level is most in the world
Height, range are maximum, quantity is most, complete types plateau salt lake distributed areas.Tibet plateau has nearly 500 of salt lake, the lake Zhan Xizang
Moor the 1/4 of total quantity；Salt lake area about 8225km2(brine lake area), the 30.46% of the lake the Zhan Xizang gross area.In addition ore
The lithium carbonate of method output needs to roast, it is big, at high cost to pollute.The sinker mother liquor for preparing lithium carbonate generation, containing a large amount of lithium,
Extraction cost is also higher.The lithium product especially lithium carbonate in China still depends on import at present, therefore, it is necessary to reinforce me
The exploitation of state's brine lithium resource promotes the fast development of China's lithium salts industry.
In addition, existing lithium carbonate preparation method still have such as extraction efficiency it is low, can not be in alkaline brine or water
Lithium ion is directly mentioned in solution and prepares lithium carbonate, and the problems such as equipment seriously corroded, high production cost and environmental pollution.
Summary of the invention
The embodiment of the present invention provides a kind of preparation method of lithium carbonate, it is intended to solve existing lithium carbonate preparation method still
It is low in the presence of such as extraction efficiency, can not directly mention lithium ion in alkaline brine or aqueous solution and prepare lithium carbonate, and equipment is rotten
The problem of losing serious, high production cost and environmental pollution.
The embodiments of the present invention are implemented as follows, and a kind of preparation method of lithium carbonate, described method includes following steps:
Organic phase will be extracted, and 1:1 ~ 10 mix by volume with lithium-containing solution, extract 1 ~ 3 time, and single extraction time is 1 ~ 15
Minute, obtain organic phase containing lithium；
By the organic phase containing lithium, 1:1 ~ 10 are mixed by volume with stripping solution, are stripped 1 ~ 3 time, single back extraction
Time is 1 ~ 15 minute, collects lithium bicarbonate aqueous solution；Wherein, the stripping workshop is that carbon dioxide is passed through pure water, alkalinity
Aqueous solution made from one of metal salt or ammonium salt aqueous solution or any combination thereof；
The lithium bicarbonate aqueous solution is heated, so that the lithium bicarbonate in the lithium bicarbonate aqueous solution containing lithium ion
Crystallization is precipitated, and is thermally decomposed to yield lithium carbonate.
The preparation method of lithium carbonate provided in an embodiment of the present invention, first, the extraction organic phase abundant raw material used, water-soluble
Property small, small toxicity, and it is cheap, it is high to the extraction yield of lithium ion, the recovery rate to the lithium ion in lithium-containing solution can be improved；
Second, the extraction of this method and strip stage carry out under alkaline condition, therefore can avoid rotten to the acidity of production equipment
Erosion；Third, in strip stage, using one be passed through carbon dioxide in pure water, alkaline metal salt or ammonium salt aqueous solution
Kind or any combination thereof made from aqueous solution as stripping solution, the back extraction system that is mixed to form with organic phase containing lithium
Acidity is lower than 6 ~ 9moL/L, and directly can convert lithium bicarbonate for the lithium ion in organic phase containing lithium under alkaline environment,
The lithium bicarbonate aqueous solution containing lithium ion of collection is heated, that is, may make in the lithium bicarbonate aqueous solution containing lithium ion
Lithium bicarbonate crystallization is precipitated, and is thermally decomposed to yield lithium carbonate, and which not only improves the purity of lithium carbonate, but also greatly drop
Low production cost, avoids environmental pollution.Lithium carbonate provided in an embodiment of the present invention is used using ICP-0ES assay
Preparation method prepare each ion concentration in the extract liquors and anti-stripping agent at different levels generated during lithium carbonate, be computed analysis knot
Fruit shows, can reach 86.83% ~ 99.53% to the overall recovery of the lithium in lithium-containing solution.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not
For limiting the present invention.
The embodiment of the invention provides a kind of preparation method of lithium carbonate, this method is using water-soluble small, small toxicity, price
It is cheap and there is the extraction organic phase of high extraction yield and lithium-containing solution to form alkaline extraction system lithium ion, it not only increases pair
The recovery rate of lithium ion in lithium-containing solution, and can avoid the sour corrosion to production equipment；Meanwhile leading to using by carbon dioxide
It is molten as being stripped to enter aqueous solution made from one of pure water, alkaline metal salt or ammonium salt aqueous solution or any combination thereof
Liquid, the acidity for the back extraction system being mixed to form with organic phase containing lithium are lower than 6 ~ 9moL/L, and can be under alkaline environment directly
Lithium bicarbonate is converted by the lithium ion in organic phase containing lithium, the lithium bicarbonate aqueous solution containing lithium ion of collection is added
Heat may make lithium bicarbonate in the lithium bicarbonate aqueous solution containing lithium ion crystallizes to be precipitated, and thermally decomposed to yield lithium carbonate,
Which not only improves the purity of lithium carbonate, but also significantly reduce production cost, avoid environmental pollution.
The embodiment of the invention provides a kind of preparation methods of lithium carbonate, and described method includes following steps:
Organic phase and lithium-containing solution will be extracted, and 1:1 ~ 10 are mixed to form alkaline extraction system by volume, extract 1 ~ 3 time, single extraction
Taking the time is 1 ~ 15 minute, obtains organic phase containing lithium.
By the organic phase containing lithium, 1:1 ~ 10 are mixed by volume with stripping solution, are stripped 1 ~ 3 time, single is anti-
Extraction time is 1 ~ 15 minute, collects the lithium bicarbonate aqueous solution containing lithium ion；Wherein, the stripping workshop is by carbon dioxide
It is passed through aqueous solution made from one of pure water, alkaline metal salt or ammonium salt aqueous solution or any combination thereof.Wherein, the alkali
Metallic element includes lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), francium (Fr), and ammonium salt includes inorganic ammonium salt, quaternary ammonium salt.
Alkaline metal salt includes halide ion salt, sulfate, nitrate, carbonate, bicarbonate.Carbon dioxide is by gaseous state titanium dioxide
Carbon is squeezed into later using compressor boosting, or the carbon dioxide filled with the steel cylinder per se with pressure.In addition, to carbonic acid
Hydrogen lithium aqueous solution is heated, and lithium bicarbonate crystallization is precipitated and the carbon dioxide generated after being thermally decomposed can recycle.When
So, carbon dioxide gas also can be used directly, and perhaps the salt decomposition containing bicarbonate radical is produced or using carbonate as waste
Carbon dioxide.
The lithium bicarbonate aqueous solution containing lithium ion is heated, so that the lithium bicarbonate containing lithium ion is water-soluble
Lithium bicarbonate in liquid, which crystallizes, to be precipitated, and is thermally decomposed to yield lithium carbonate.
As an embodiment of the present invention, in extraction stages, lithium-containing solution and extractant can be pressed preset volume ratio
Mixing is extracted, and by obtained organic phase containing lithium and stripping solution (e.g., the mixture of carbon dioxide and pure water) by pre-
If volume ratio mixing is stripped, the extractant separated in the back extraction stage, which can enter extraction stages, which carries out circulation, makes
With, and after the isolated lithium bicarbonate aqueous solution containing lithium ion is heated in the back extraction stage, lithium bicarbonate therein
Crystallization is precipitated, and by the lithium carbonate and carbon dioxide for thermally decomposing to yield high-purity, which can enter the back extraction stage
It is recycled, remaining mixed liquor is separated, obtain the lithium carbonate and sinker mother liquor of high-purity, which can
It enters in the back extraction stage and is recycled, or extraction stages can be entered as lithium-containing solution and carry out cycling extraction, from
And improve the rate of recovery to the lithium ion of lithium-containing solution.
In embodiments of the present invention, in extraction stages, the reaction equation for extracting organic phase and lithium-containing solution can be expressed
It is as follows: S+Li+→SLi+, wherein S indicates extraction organic phase.
In the back extraction stage, the reaction equation of back extraction is expressed as follows:
H2O+CO2→H2CO3
SLi++H2CO3→SH++LiHCO3
SH++OH-→S+H2O
Due to the solubility with temperature of lithium bicarbonate raising and reduce, so after lithium bicarbonate aqueous solution is heated,
Lithium bicarbonate therein is crystallized from aqueous solution and is precipitated, and is heated and is decomposed into lithium carbonate, carbon dioxide and water, the equation of reaction
Formula is as follows:
2LiHCO3→Li2CO3↓+CO2↑+H2O
In the process, lithium carbonate obtains after directly being thermally decomposed from lithium bicarbonate, and non-added carbonate deposition, therefore is obtained
Lithium carbonate be pure Lithium Carbonate, purity can reach 99.9%, can be directly used for lithium battery etc..In addition, without dividing in extraction process
Form corresponding bicarbonate after back extraction from impurity such as the sodium, potassium, boron ion fallen, and the solubility of these bicarbonates with
The raising of temperature and increase, therefore the impurity will not crystallize and be precipitated and influence the high-purity of lithium carbonate, therefore high-purity can be made
Lithium carbonate.
Preferably, the lithium-containing solution is salt lake bittern, the aqueous solution containing lithium leached in ore, sinker mother liquor, battery time
One of lithium solution of receipts or alkaline aqueous solution containing lithium or any combination thereof.
Preferably, lithium organic salt and/or inorganic salts are contained in the lithium-containing solution；The lithium organic salt includes: lithium formate
And/or lithium acetate；The lithium inorganic salts include: one of lithium chloride, lithium sulfate, lithium carbonate, lithium bicarbonate or lithium nitrate or
Any combination thereof.
Preferably, the lithium-containing solution is the faintly acid, neutrality or alkaline aqueous solution containing lithium of 6 or more pH value.
Preferably, the extraction organic phase is made of extractant and diluent；The extractant accounts for the extraction organic phase
Weight percent be 5% ~ 100%.The weight percent amount ranges of diluent are up to 95%, and can be dropped using diluent
The viscosity of low extractant accelerates the split-phase time.
Preferably, the extractant is three oxygen thiophene oxides, trialkylphosphate, phosphate dialkyl ester, trialkyl oxygen
Phosphine, the fluoro- 5,5- dimethyl -2,4- acetyl butyryl of 1,1,1- tri-, the fluoro- 6,6 dimethyl -3,5- heptadione of 1,1,1,2,2- five, 1,1,
The fluoro- 7,7- dimethyl -4,6- acetyl caproyl of 1,2,2,3,3- seven, benzoyltrifluoroacetone, cyclohexanone, hexone, β -
Diketone, primary alconol, 4 ether dibutyl-butylphosphonate of 14- crown-, dibutylphosphoric acid butyl ester or 1- hydroxyethyl -3- methylimidazole bis- (three
Methyl fluoride sulfonyl) one of acid imide or any combination thereof mixture.Extractant selected by the embodiment of the present invention comes
Source is extensive, abundant raw material, and water solubility is small, toxicity is low, cheap, and to the extraction yield of lithium height.
Preferably, dilute diluent is n-hexane, n-dodecane, hexamethylene, cyclohexanone, methyl-isobutyl first
The mixing of one of ketone, isobutyrone, solvent naphtha, common kerosene, aviation kerosine or sulfonated kerosene or any combination thereof
Object.
Further, increase due to the solubility of carbon dioxide with the raising of pressure, so needing to guarantee the present invention
The volume of the carbon dioxide dissolved in stripping workshop in embodiment and the volume ratio of stripping workshop are 1:1 or more.
Further, described by the organic phase containing lithium, 1:1 ~ 10 are mixed by volume with stripping solution, back extraction
It takes 1 ~ 3 time, single back-extraction time is 1 ~ 15 minute, the step of collecting lithium bicarbonate aqueous solution containing lithium ion, comprising: by institute
Stating organic phase containing lithium, 1:1 is mixed by volume with stripping solution, and volume ratio 1:1 mixing more can be counted intuitively and accurately
Extraction yield, stripping rate and total extraction yield are calculated, operation is facilitated.Back extraction 1 ~ 3 time, single back-extraction time are 1 ~ 15 point
Clock collects the lithium bicarbonate aqueous solution containing lithium ion.
Further, described by the organic phase containing lithium, 1:1 ~ 10 are mixed by volume with stripping solution, back extraction
It taking 1 ~ 3 time, single back-extraction time is 1 ~ 15 minute, the step of collecting lithium bicarbonate aqueous solution containing lithium ion, specifically: it will
1:1 ~ 10 are mixed the organic phase containing lithium by volume with stripping solution, are 0.01 ~ 10MPa in pressure, temperature is -30
It under conditions of ~ 120 degrees Celsius, is stripped 1 ~ 3 time, single back-extraction time is 1 ~ 15 minute, collects the bicarbonate containing lithium ion
Lithium aqueous solution.
Technical solution of the present invention and technical effect are described further below by way of specific embodiment.
Embodiment 1,
The embodiment of the invention provides a kind of preparation methods of lithium carbonate, include the following steps:
It is 0.26g/L salt lake bittern, pH value 9 that lithium-containing solution, which is chosen containing lithium,.
Extraction stages: extractant (benzoyltrifluoroacetone 10mL, trioctyl phosphine oxide 10mL) 20mL, dilution is measured respectively
Agent (common kerosene) 90mL is uniformly mixed in separatory funnel, adds salt lake bittern 390mL, is controlled temperature at 5 DEG C, is vibrated l
Water phase and organic phase containing lithium are isolated after minute, repeat above-mentioned extracting operation three times.
The back extraction stage: stripping solution uses carbon dioxide and mass concentration for 2% sodium bicarbonate aqueous solution, will be upper
It states the isolated organic phase containing lithium of extraction stages to mix with the strip liquor of brine equal volume 390mL, is then in pressure
0.1MPa, temperature are stripped three times under conditions of being -30 degrees Celsius, and the time of single back extraction is 10 minutes, are collected and are divided
Water phase from after, i.e. the lithium bicarbonate aqueous solution containing lithium ion.
Crystallization is precipitated and the heat resolve stage: the isolated lithium bicarbonate containing lithium ion of above-mentioned strip stages is water-soluble
Liquid is heated to 85 degrees Celsius, is precipitated so that the lithium bicarbonate in the lithium bicarbonate aqueous solution containing lithium ion crystallizes, and thermally decomposed
For lithium carbonate and carbon dioxide, wherein carbon dioxide can be recycled into the back extraction stage.Lithium carbonate obtained it is pure
Degree is up to 99.7%.
Using the content of various ions in the brine after ICP-0ES assay every time extraction/back extraction, and pass through
Analytical calculation obtains: brine brine 0.129g/L containing lithium after single extraction, and single extraction rate is 50.3%；After reextraction
Brine 0.061g/L containing lithium, reextraction rate 76.5%；Three times extract after brine 0.030g/L containing lithium, three times extraction yield be
88.34%；Anti-stripping agent lithium content 0.219g/L after primary back extraction, a stripping rate are 95.37%；It is stripped after secondary back extraction
Liquid lithium content 0.226g/L, secondary stripping rate are 98.38%；Anti-stripping agent lithium content 0.223g/L after being stripped three times, three times instead
Extraction yield is 99.96%；The overall recovery of lithium is up to 86.83%.
Embodiment 2,
The embodiment of the invention provides a kind of preparation methods of lithium carbonate, include the following steps:
The salt lake concentrated brine that it is 2.2g/L containing lithium that lithium-containing solution, which is chosen, pH value 11.
Extraction stages: extractant (benzoyltrifluoroacetone 5mL, three hexyl phosphine oxide 5mL) 10mL, diluent is measured respectively
(common kerosene) 650mL is uniformly mixed in separatory funnel, adds salt lake concentrated brine 2000mL, controls temperature at 25 DEG C,
Water phase and organic phase containing lithium are isolated in oscillation after l0 minutes, repeat above-mentioned extracting operation three times.
The back extraction stage: stripping solution uses carbon dioxide and mass concentration for 2% potassium bicarbonate aqueous solution, will be upper
It states the isolated organic phase containing lithium of extraction stages to mix with 2000mL strip liquor, is then 0.5MPa, temperature 50 in pressure
It is stripped under conditions of degree Celsius three times, the time of single back extraction is 5 minutes, the water phase after collecting separation contains lithium
The lithium bicarbonate aqueous solution of ion.
Crystallization is precipitated and the heat resolve stage: the isolated lithium bicarbonate containing lithium ion of above-mentioned strip stages is water-soluble
Liquid is heated to 90 degrees Celsius, is precipitated so that the lithium bicarbonate in the lithium bicarbonate aqueous solution containing lithium ion crystallizes, and thermally decomposed
For lithium carbonate and carbon dioxide, wherein carbon dioxide can be recycled into the back extraction stage.Lithium carbonate obtained it is pure
Degree is up to 99.8%.
Using the content of various ions in the brine after ICP-0ES assay every time extraction/back extraction, and pass through
Analytical calculation obtains: the single extraction rate of lithium is 85.71% in the brine；Reextraction rate 98.80%；Extraction yield is three times
99.57%；Back extraction ratio is 88.61%；Secondary back extraction ratio is 98.25%；Back extraction ratio is 99.96% three times；The overall recovery of lithium
Up to 99.53%.
Embodiment 3,
The embodiment of the invention provides a kind of preparation methods of lithium carbonate, include the following steps:
The sinker mother liquor that it is 1.5g/L containing lithium that lithium-containing solution, which is chosen, pH value 11.
Extraction stages: extractant (benzoyl trifluoro decanone 75mL, three hexyl phosphine oxide 75mL) 150mL, dilute is measured respectively
It releases agent (sulfonated kerosene) 1200mL to be uniformly mixed in separatory funnel, adds lithium-containing solution 4000mL, control temperature at 45 DEG C,
Water phase and organic phase containing lithium are isolated in oscillation after ten minutes, repeat above-mentioned extracting operation three times.
The back extraction stage: stripping solution uses carbon dioxide and mass concentration for 1% aqueous sodium carbonate, will be above-mentioned
The isolated organic phase containing lithium of extraction stages is mixed with 4000mL strip liquor, is then 0.2MPa in pressure, temperature is taken the photograph for 120
Be stripped under conditions of family name's degree three times, single back extraction time be 1 minute, collect separation after water phase, i.e., containing lithium from
The lithium bicarbonate aqueous solution of son.
Crystallization is precipitated and the heat resolve stage: the isolated lithium bicarbonate containing lithium ion of above-mentioned strip stages is water-soluble
Liquid is heated to 90 degrees Celsius, is precipitated so that the lithium bicarbonate in the lithium bicarbonate aqueous solution containing lithium ion crystallizes, and thermally decomposed
For lithium carbonate and carbon dioxide, wherein carbon dioxide can be recycled into the back extraction stage.Lithium carbonate obtained it is pure
Degree is up to 99.7%.
Using the content of various ions in the brine after ICP-0ES assay every time extraction/back extraction, and pass through
Analytical calculation obtains: the single extraction rate of lithium is 80.81% in the brine；Reextraction rate 97.39%；Extraction yield is three times
99.59%；Back extraction ratio is 83.85%；Secondary back extraction ratio is 98.20%；Back extraction ratio is 99.93% three times；The overall recovery of lithium
Up to 99.52%.
Embodiment 4,
The embodiment of the invention provides a kind of preparation methods of lithium carbonate, include the following steps:
Lithium-containing solution chooses the lithium solution containing the battery recycling that lithium is 1.5g/L, pH value 10.
Extraction stages: extractant (the fluoro- 5,5- dimethyl -2,4- acetyl butyryl 25mL of 1,1,1- tri-, three hexyl oxygen are measured respectively
Change phosphine 75mL) 100mL, diluent (n-hexane 500mL and hexamethylene 700mL) 1200mL in separatory funnel be uniformly mixed, then
Lithium-containing solution 6500mL is added, controls temperature at 35 DEG C, water phase and organic phase containing lithium are isolated in oscillation after 3 minutes, repeated above-mentioned
Extracting operation is three times.
The back extraction stage: stripping solution uses carbon dioxide and quaternary ammonium salt aqueous solution, and above-mentioned extraction stages are separated
The organic phase containing lithium arrived is mixed with 6500mL strip liquor, is then 10MPa in pressure, temperature carries out under conditions of being 0 degree Celsius
Three times, the time of single back extraction is 5 minutes, the water phase after collecting separation for back extraction, i.e. the lithium bicarbonate containing lithium ion is water-soluble
Liquid.
Crystallization is precipitated and the heat resolve stage: the isolated lithium bicarbonate containing lithium ion of above-mentioned strip stages is water-soluble
Liquid is heated to 90 degrees Celsius, is precipitated so that the lithium bicarbonate in the lithium bicarbonate aqueous solution containing lithium ion crystallizes, and thermally decomposed
For lithium carbonate and carbon dioxide, wherein carbon dioxide can be recycled into the back extraction stage.Lithium carbonate obtained it is pure
Degree is up to 99.6%.
Using the content of various ions in the brine after ICP-0ES assay every time extraction/back extraction, and pass through
Analytical calculation obtains: brine 1.353g/L containing lithium after the single extraction of lithium in the brine, and primary rate is 90.2%；After reextraction
Brine 1.434g/L containing lithium, reextraction rate 95.6%；Three times extract after brine 1.478g/L containing lithium, three times extraction yield be
98.5%；Strip liquor 1.411g/L containing lithium after primary back extraction, a back extraction ratio are 95.5%；Strip liquor contains lithium after secondary back extraction
1.458g/L, secondary back extraction ratio are 98.7%；Strip liquor 1.476g/L containing lithium after being stripped three times, back extraction ratio is 99.9% three times；
The overall recovery of lithium is up to 98.4%.
Embodiment 5,
Lithium-containing solution is chosen containing the aqueous solution containing lithium leached in the ore that lithium is 1.7g/L, pH value 11.
Extraction stages: extractant (phosphate dialkyl ester 35mL, three oxygen thiophene oxide 100mL) 135mL, dilute is measured respectively
It releases agent (aviation kerosine) 600mL to be uniformly mixed in separatory funnel, adds lithium-containing solution 2205mL, control temperature at 45 DEG C,
Water phase and organic phase containing lithium are isolated in oscillation after 15 minutes, repeat above-mentioned extracting operation three times.
The back extraction stage: stripping solution uses carbon dioxide and quaternary ammonium salt aqueous solution, and above-mentioned extraction stages are separated
The organic phase containing lithium arrived is that 1:8 is mixed according to volume ratio with stripping solution, is then 1MPa in pressure, temperature is 100 Celsius
It is stripped under conditions of degree three times, the time of single back extraction is 15 minutes, the water phase after collecting separation contains lithium ion
Lithium bicarbonate aqueous solution.
Crystallization is precipitated and the heat resolve stage: the isolated lithium bicarbonate containing lithium ion of above-mentioned strip stages is water-soluble
Liquid is heated to 85 degrees Celsius, is precipitated so that the lithium bicarbonate in the lithium bicarbonate aqueous solution containing lithium ion crystallizes, and thermally decomposed
For lithium carbonate and carbon dioxide, wherein carbon dioxide can be recycled into the back extraction stage.Lithium carbonate obtained it is pure
Degree is up to 99.6%.
Using the content of various ions in the brine after ICP-0ES assay every time extraction/back extraction, and pass through
Analytical calculation obtains: brine 1.328g/L containing lithium after lithium single extraction in the brine, and single extraction rate is 78.1%；Reextraction
Brine 1.522g/L containing lithium afterwards, reextraction rate 89.5%；Three times extract after brine 1.569g/L containing lithium, three times extraction yield be
92.3%；1.182g/L containing lithium after primary back extraction strip liquor, a back extraction ratio are 75.3%；Contain lithium after secondary back extraction strip liquor
Bis- back extraction ratios of 1.360g/L are 86.7%；1.483g/L containing lithium after back extraction strip liquor three times, back extraction ratio is 94.5% three times；Lithium
Overall recovery up to 87.2%.
Embodiment 6,
Lithium-containing solution chooses the mixture containing salt lake bittern and sinker mother liquor that lithium is 2.2g/L, pH value 12.
Extraction stages: respectively measure extractant (benzoyltrifluoroacetone) 200mL, diluent (solvent naphtha) 600mL in point
Be uniformly mixed in liquid funnel, add lithium-containing solution 8000mL, control temperature at 35 DEG C, oscillation isolate after ten minutes water phase and
Organic phase containing lithium repeats above-mentioned extracting operation three times.
The back extraction stage: stripping solution uses carbon dioxide and sodium nitrate aqueous solution, and above-mentioned extraction stages are separated
The organic phase containing lithium arrived is that 1:1 is mixed according to volume ratio with stripping solution, is then 2.5MPa in pressure, temperature is 60 Celsius
It is stripped under conditions of degree three times, the time of single back extraction is 15 minutes, the water phase after collecting separation contains lithium ion
Lithium bicarbonate aqueous solution.
Crystallization is precipitated and the heat resolve stage: the isolated lithium bicarbonate containing lithium ion of above-mentioned strip stages is water-soluble
Liquid is heated to 90 degrees Celsius, is precipitated so that the lithium bicarbonate in the lithium bicarbonate aqueous solution containing lithium ion crystallizes, and thermally decomposed
For lithium carbonate and carbon dioxide, wherein carbon dioxide can be recycled into the back extraction stage.Lithium carbonate obtained it is pure
Degree is up to 99.3%.
Using the content of various ions in the brine after ICP-0ES assay every time extraction/back extraction, and pass through
Analytical calculation obtains: brine 1.874g/L containing lithium after the single extraction of lithium in the brine, and single extraction rate is 85.2%；Secondary extraction
Take rear brine 1.960g/L containing lithium, reextraction rate 89.1%；Extraction yield is brine 2.088g/L containing lithium three times after extracting three times
94.9%；Primary extraction is counter to take rear strip liquor 1.583g/L containing lithium, and a back extraction ratio is 75.8%；Secondary extraction is counter to take rear strip liquor containing lithium
1.794g/L, secondary back extraction ratio are 85.9%；Extract three times it is counter take rear strip liquor 1.877g/L containing lithium, three times back extraction ratio be 89.9%；
The overall recovery of lithium is up to 85.31%.
It should be noted that in embodiments of the present invention, extractant can for three oxygen thiophene oxides, trialkylphosphate,
Phosphate dialkyl ester, trialkylphosphine oxide, the fluoro- 5,5- dimethyl -2,4- acetyl butyryl of 1,1,1- tri-, 1,1,1,2,2- five fluoro- 6,6 2
Methyl -3,5- heptadione, the fluoro- 7,7- dimethyl -4,6- acetyl caproyl of 1,1,1,2,2,3,3- seven, benzoyltrifluoroacetone, hexamethylene
Ketone, hexone, beta-diketon, primary alconol, 4 ether dibutyl-butylphosphonate of 14- crown-, dibutylphosphoric acid butyl ester or 1- hydroxyl
The mixture of one of bis- (trifluoromethyl sulfonyl) acid imides of ethyl-3-methylimidazole or any combination thereof.Convenient for saying
Bright, above embodiments only show several optimum organization modes therein.In practical applications, said components can arbitrarily be selected
One of or any several combination as extractant, one of the various combinations numerous to list herein.
Based on above-mentioned identical reason, diluent involved in the embodiment of the present invention is n-hexane, n-dodecane, hexamethylene
In alkane, cyclohexanone, hexone, isobutyrone, solvent naphtha, common kerosene, aviation kerosine or sulfonated kerosene
A kind of or any combination thereof mixture.The lithium-containing solution is salt lake bittern, the aqueous solution containing lithium leached in ore, sinker mother
One of liquid, the lithium solution of battery recycling or alkaline aqueous solution containing lithium or any combination thereof.These above-mentioned components it is various
Combination does not also enumerate herein.
Test one,
It is carried out using mass percent dosage of the single factor experiment method to extractant and diluent in the embodiment of the present invention 2 excellent
Choosing.Fixed others process conditions are constant, and the mass percent for changing extractant and diluent is 0:100；5:95；10:90；
30:70；40:60；50:50；60:40；70:30；95:5 and 100:0, prepares lithium carbonate under the above conditions respectively.Using ICP-
Each test group of 0ES assay every time in the brine after extraction/back extraction various ions content, and be calculated analytically
The test result for obtaining each group test group, is detailed in the following table 1.
Table 1
It can be seen that from the test result of upper table 1
Test two,
The back extraction pressure in the back extraction stage in the embodiment of the present invention 2 is carried out using single factor experiment method preferred.It is fixed
Other process conditions are constant, the back extraction pressure for changing strip stages is respectively 0,0.1,0.2,0.4,1,3,5,8,10,
10.5MPa prepares lithium carbonate under the above conditions respectively.Using the extraction/back extraction every time of each test group of ICP-0ES assay
The content of various ions in brine after taking, and it is calculated analytically the test result for obtaining each group test group, it is detailed in following table
2。
Table 2
| It is stripped pressure (MPa) | The extraction yield (%) of single extraction | The extraction yield (%) of reextraction | The extraction yield extracted three times (%) | The extraction yield being once stripped (%) | The extraction yield (%) of secondary back extraction | The extraction yield being stripped three times (%) | Total lithium rate of recovery (%) |
| 0 | 76.24 | 88.51 | 95.88 | 11.5 | 12.1 | 12.8 | 12.1 |
| 0.1 | 76.24 | 88.51 | 95.88 | 81.43 | 90.80 | 97.22 | 93.21 |
| 0.2 | 76.24 | 88.51 | 95.88 | 92.88 | 97.61 | 99.00 | 95.0 |
| 0.4 | 76.24 | 88.51 | 95.88 | 94.09 | 98.25 | 99.96 | 95.49 |
| 1 | 76.24 | 88.51 | 95.88 | 94.66 | 98.75 | 99.97 | 95.86 |
| 3 | 76.24 | 88.51 | 95.88 | 94.87 | 98.52 | 99.97 | 95.86 |
| 5 | 76.24 | 88.51 | 95.88 | 95.06 | 98.54 | 99.98 | 95.86 |
| 8 | 76.24 | 88.51 | 95.88 | 95.25 | 98.31 | 99.98 | 95.86 |
| 10 | 76.24 | 88.51 | 95.88 | 95.99 | 98.87 | 99.98 | 95.86 |
| 10.5 | 76.24 | 88.51 | 95.88 | 95.78 | 98.90 | 99.98 | 95.86 |
By the test result of upper table 2 it is known that
Test three,
It is preferred to temperature progress is stripped in the back extraction stage in the embodiment of the present invention 2 using single factor experiment method.Fix it
His condition is constant, and the back extraction temperature for changing strip stages is respectively -40, -30, -10,0,25,45,60,80,100,120,130
Degree Celsius, prepare lithium carbonate under the above conditions respectively.Using the extraction/back extraction every time of each test group of ICP-0ES assay
The content of various ions in brine after taking, and it is calculated analytically the test result for obtaining each group test group, it is detailed in following table
3。
Table 3
| It is stripped temperature (degree Celsius) | The extraction yield of single extraction (%) | The extraction yield of reextraction (%) | The extraction yield extracted three times (%) | The extraction yield being once stripped (%) | The extraction yield of secondary back extraction (%) | The extraction yield (%) being stripped three times | Total lithium rate of recovery (%) |
| -30 | 75.21 | 88.82 | 94.53 | 82.56 | 88.34 | 92.01 | 86.97 |
| -10 | 78.21 | 90.82 | 96.53 | 92.88 | 98.61 | 99.01 | 95.56 |
| 0 | 78.21 | 89.35 | 96.87 | 92.88 | 98.61 | 99.00 | 95.0 |
| 25 | 85.71 | 98.80 | 99.57 | 88.61 | 98.25 | 99.96 | 99.47 |
| 45 | 84.71 | 97.52 | 99.55 | 80.61 | 97.53 | 97.25 | 96.81 |
| 60 | 82.71 | 98.49 | 99.32 | 81.61 | 97.72 | 96.74 | 96.08 |
| 80 | 75.21 | 85.56 | 95.33 | 80.56 | 85.78 | 92.01 | 87.70 |
| 100 | 75.21 | 83.43 | 94.53 | 81.36 | 88.34 | 91.91 | 86.97 |
| 120 | 55.891 | 65.47 | 76.55 | 72.58 | 80.73 | 90.85 | 69.54 |
It can be seen that from the test result of upper table 3
Test four,
Comparative example 1, the comparative example and the difference of above-described embodiment 2 are only that, the extraction organic phase used in extraction stages is replaced
It is changed to the extraction organic phase of isometric tributyl phosphate, ferric trichloride and 200# solvent kerosene composition.
Comparative example 2, the comparative example and the difference of above-described embodiment 2 are only that, the extraction used in extraction stages is organic
Mutually replace with the extraction organic phase of isometric iron chloride, diisobutyl ketone and tributyl phosphate composition.
Comparative example 3, the comparative example and the difference of above-described embodiment 2 are only that, the extraction used in extraction stages is organic
The extraction for replacing with isometric tributyl phosphate, C atomicity mutually as 2 ~ 10 amide, 200# kerosene and iron chloride composition is organic
Phase.
Comparative example 4, the comparative example and the difference of above-described embodiment 2 be only that, the back extraction that will be used in the back extraction stage
Solution replaces with the hydrochloric acid solution that the concentration of equivalent is 3moL.
Lithium carbonate is prepared under the above conditions respectively, using the extraction/back extraction every time of each test group of ICP-0ES assay
The content of various ions in brine after taking, and it is calculated analytically the test result for obtaining each group test group, it is detailed in following table
4。
Table 4
| Test example | The extraction yield (%) of single extraction | The extraction yield (%) of reextraction | The extraction yield (%) extracted three times | The extraction yield (%) being once stripped | The extraction yield (%) of secondary back extraction | The extraction yield (%) being stripped three times | Total lithium rate of recovery (%) |
| Embodiment 2 | 85.71 | 98.80 | 99.57 | 88.61 | 98.25 | 99.96 | 99.53 |
| Comparative example 1 | 15.2 | 18.5 | 20.5 | 77.53 | 88.56 | 95.75 | 19.6 |
| Comparative example 2 | 17.2 | 20.5 | 23.5 | 67.57 | 78.94 | 85.42 | 20 |
| Comparative example 3 | 5.6 | 8.5 | 12.6 | 70.75 | 75.68 | 80.11 | 10.1 |
| Comparative example 4 | 85.71 | 98.80 | 99.57 | 92.55 | 98.67 | 99.98 | 99.55 |
It can be seen that from the test result of upper table 4
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within principle.
Claims (10)
1. a kind of preparation method of lithium carbonate, which is characterized in that described method includes following steps:
Organic phase and lithium-containing solution will be extracted, and 1:1 ~ 10 are mixed to form alkaline extraction system by volume, extract 1 ~ 3 time, single extraction
Taking the time is 1 ~ 15 minute, obtains organic phase containing lithium；
By the organic phase containing lithium, 1:1 ~ 10 are mixed by volume with stripping solution, are stripped 1 ~ 3 time, single back extraction
Time is 1 ~ 15 minute, collects the lithium bicarbonate aqueous solution containing lithium ion；Wherein, the stripping workshop is to be passed through carbon dioxide
Aqueous solution made from one of pure water, alkaline metal salt or ammonium salt aqueous solution or any combination thereof；
The lithium bicarbonate aqueous solution containing lithium ion is heated, so that in the lithium bicarbonate aqueous solution containing lithium ion
Lithium bicarbonate crystallize and be precipitated, and thermally decomposed to yield lithium carbonate.
2. the preparation method of lithium carbonate as described in claim 1, which is characterized in that the lithium-containing solution is salt lake bittern, mine
One of the aqueous solution containing lithium that is leached in stone, sinker mother liquor, the lithium solution of battery recycling or alkaline aqueous solution containing lithium or its
Meaning combination.
3. the preparation method of lithium carbonate as described in claim 1, which is characterized in that contain lithium organic salt in the lithium-containing solution
And/or inorganic salts；
The lithium organic salt includes: lithium formate and/or lithium acetate；
The lithium inorganic salts include: one of lithium chloride, lithium sulfate, lithium carbonate, lithium bicarbonate or lithium nitrate or its any group
It closes.
4. the preparation method of lithium carbonate as described in claim 1, which is characterized in that the lithium-containing solution is 6 or more pH value
Faintly acid, neutrality or alkaline aqueous solution containing lithium.
5. the preparation method of lithium carbonate as described in claim 1, which is characterized in that the extraction organic phase is by extractant and dilute
Release agent composition；
The weight percent that the extractant accounts for the extraction organic phase is 5% ~ 100%.
6. the preparation method of lithium carbonate as described in claim 1, which is characterized in that the extractant is the oxidation of three oxygen thiophene
Object, trialkylphosphate, phosphate dialkyl ester, trialkylphosphine oxide, the fluoro- 5,5- dimethyl -2,4- acetyl butyryl of 1,1,1- tri-, 1,1,
The fluoro- 6,6 dimethyl -3,5- heptadione of 1,2,2- five, the fluoro- 7,7- dimethyl -4,6- acetyl caproyl of 1,1,1,2,2,3,3- seven, benzene first
Acyl trifluoroacetone, cyclohexanone, hexone, beta-diketon, primary alconol, 4 ether dibutyl-butylphosphonate of 14- crown-, dibutyl phosphorus
One of acid butyl ester or bis- (trifluoromethyl sulfonyl) acid imides of 1- hydroxyethyl -3- methylimidazole or any combination thereof mix
Close object.
7. the preparation method of lithium carbonate as described in claim 1, which is characterized in that dilute diluent be n-hexane,
N-dodecane, hexamethylene, cyclohexanone, hexone, isobutyrone, solvent naphtha, common kerosene, aviation kerosine or
The mixture of one of sulfonated kerosene or any combination thereof.
8. the preparation method of lithium carbonate as described in claim 1, which is characterized in that the titanium dioxide dissolved in the stripping workshop
The volume of carbon and the volume ratio of stripping workshop are 1:1 or more.
9. the preparation method of lithium carbonate as described in claim 1, which is characterized in that described by the organic phase containing lithium and back extraction
Taking solution, 1:1 ~ 10 are mixed by volume, be stripped 1 ~ 3 time, single back-extraction time be 1 ~ 15 minute, collect containing lithium from
The step of lithium bicarbonate aqueous solution of son, comprising:
By the organic phase containing lithium, 1:1 is mixed by volume with stripping solution, is stripped 1 ~ 3 time, when single is stripped
Between be 1 ~ 15 minute, collect the lithium bicarbonate aqueous solution containing lithium ion.
10. the preparation method of lithium carbonate as described in claim 1, which is characterized in that described by the organic phase containing lithium and anti-
1:1 ~ 10 are mixed extraction solution by volume, are stripped 1 ~ 3 time, and single back-extraction time is 1 ~ 15 minute, are collected and are contained lithium
The step of lithium bicarbonate aqueous solution of ion, specifically:
By the organic phase containing lithium, 1:1 ~ 10 are mixed by volume with stripping solution, are 0.01 ~ 10MPa, temperature in pressure
It under conditions of degree is -30 ~ 120 degrees Celsius, is stripped 1 ~ 3 time, single back-extraction time is 1 ~ 15 minute, is collected containing lithium ion
Lithium bicarbonate aqueous solution.
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