CN102225774A - Method for extracting lithium carbonate from lepidolite raw material and removing aluminium - Google Patents
Method for extracting lithium carbonate from lepidolite raw material and removing aluminium Download PDFInfo
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- CN102225774A CN102225774A CN2011100753252A CN201110075325A CN102225774A CN 102225774 A CN102225774 A CN 102225774A CN 2011100753252 A CN2011100753252 A CN 2011100753252A CN 201110075325 A CN201110075325 A CN 201110075325A CN 102225774 A CN102225774 A CN 102225774A
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Abstract
The invention discloses a method for extracting lithium carbonate from a lepidolite raw material and removing aluminium, which comprises the following process steps: (1) fluorine removal by reaction, that is, soaking lepidolite powder with a sulfuric acid solution for reaction to remove fluorine so as to obtain a solid-liquid mixed solution; (2) separation and refrigeration processing, that is, filtering the mixed solution, separating to remove filter residues to obtain a filtrate mother liquor 1, controlling the mother liquor 1 to obtain a K+ and Al3+ saturated solution, performing refrigeration, cooling, filtration, and separation, removing residues to obtain a filtrate mother liquor 2; (3) neutralization for aluminium removal, that is, cooling and refrigerating the mother liquor 2, filtering and separating to obtain a filtrate solution, adding a divalent metal oxide to obtain a mother liquor 3, precipitating and filtering the mother liquor 3 to remove residues, separating to obtain a mother liquor 4; (4) filtration and concentration to prepare a product, that is, concentrating the mother liquor 4, filtering, adding a sodium carbonate solution into the filtrate for reaction, filtering and separating, recovering the filtrate, wherein the filter residue is lithium carbonate. The extraction of lithium carbonate from a lepidolite raw material has a high aluminium-removing rate and low energy consumption, improves the yield of lithium carbonate, has a high recovery utilization rate of aluminium, and therefore the production cost is decreased greatly.
Description
Technical field: the present invention relates to a kind of method of from the lithionite raw material, removing aluminium, particularly from the lithionite raw material, extract the method that Quilonum Retard removes aluminium.
Background technology: lithionite is a kind of important Mineral resources, and it contains abundant Rare Metals Materials, as lithium, sodium, potassium, rubidium, caesium, aluminium etc.The tantalum niobium lithium ore deposit of Yichuan is the tantalum niobium lithium ore deposit of present Asia maximum, Li in the lithionite raw material
2The content of O reaches 4.5%, and alumina content carries out comprehensive development and utilization to it and has very important economy and strategic value about 23%.
Along with the growing tension of world energy sources, especially be the energy worsening shortages of raw material with the oil, the development and use new forms of energy are the common issue in the world.One of important industry that lithium electric energy new forms of energy develop as current new forms of energy is more and more paid attention to by various countries, and Quilonum Retard has bigger development prospect as the basic material of lithium electricity new forms of energy industry.
From the lithionite raw material, extract the method for Quilonum Retard at present, mainly contain solid ore deposit and liquid ore deposit from raw material, the liquid ore deposit mainly is to be that raw material extracts with the salt lake saline, the solid ore deposit is to be that raw material mainly is to be that raw material extracts with lithionite or triphane with the ore, adopt high-temperature calcination, temperature generally about 1000 ℃, reaches other chemical process such as sulfuric acid impregnating.With the solid ore deposit is the method for raw material, no matter high-temperature calcination, still chemical process all must remove and recycle the aluminium in the lithionite raw material, in the existing production process of from the lithionite raw material, extracting Quilonum Retard, removing aluminium is to adopt simple freezing to handle, and the compound of aluminium in the solution is promptly removed in centrifugation then.This method only can tentatively be removed aluminum ion in the solution, and this just influences the yield of Quilonum Retard greatly, even causes the success or failure of extraction process, and the content of the Quilonum Retard that extracts is not high.Be that the lithionite powder is removed aluminium through calcining in addition.Aluminium reclaims difficulty, has wasted resource, also will pass through high-temperature calcination, and energy consumption is also big.
Summary of the invention: purpose of the present invention is exactly that a kind of method that Quilonum Retard removes aluminium of extracting from the lithionite raw material will be provided, with the lithionite is that raw material extracts Quilonum Retard except that aluminium rate height, energy consumption is little, has improved the yield and the aluminium recovery utilization rate height of system Quilonum Retard, thereby has significantly reduced its production cost.
Technical scheme of the present invention is achieved like this, and comprises following processing step:
(1) the reaction defluorination places reaction unit with 80-300 purpose lithionite powder, impregnated in to react under 100～130 ℃ of temperature with sulphuric acid soln and separates defluorination in 4～10 hours, gets the solid-liquid mixing solutions;
(2) separate freezing treatment, described mixing solutions filtering separation is removed filter residue, get filtrate mother liquor 1, control mother liquor 1 is K
+, Al
3+Saturated solution, frozen cooling to 0～40 ℃ refilter separation, remove the gred filtrate mother liquor 2;
(3) neutralization removes aluminium, mother liquor 2 is stirred and lowers the temperature be refrigerated to 0～-30 ℃, and filtering separation gets filtrate solution and forms mother liquor 3 to wherein adding bivalent metal oxide or oxyhydroxide, with the slagging-off of mother liquor 3 sedimentation and filtrations, and Al in the controlled filter liquid
3+Concentration≤0.008 g/l, filtering separation gets mother liquor 4;
(4) filtering and concentrating system product concentrates and controls Li in the solution with mother liquor 4
+Concentration refilters at 20～45 g/l, adds sodium carbonate solution reaction filtering separation in filtrate, and filtrate is reclaimed, and filter residue is a Quilonum Retard.
Sulphuric acid soln concentration of the present invention is preferably 40～60Wt ﹪, and the mass ratio of lithionite and sulphuric acid soln is 1:2-4.
Step of the present invention (2) is to add Al in mother liquor 1
2(SO
4)
3Or Al(OH)
3, make K in the mother liquor 1
+, Al
3+Concentration is in state of saturation and forms K
+, Al
3+Saturated solution.
Bivalent metal oxide of the present invention or oxyhydroxide are preferably calcium oxide or calcium hydroxide.
Each chemical material components quality is Li than content in the present invention's control (2) step filter residue
2O 0.55-0.62%, K
2O 0.9-1.08%, Na
2O 0.4-0.45%, Al
2O
38-8.01%, SiO
288.9-89.74%, Rb
2O 0.11-0.123%, CS
2O 0.015-0.018%.
Adopt the present invention from the lithionite raw material, to extract the method that Quilonum Retard removes aluminium, adopt the process of the Quilonum Retard in the low temperature acid leaching extraction lithionite raw material, analyse after sinker removes the aluminium operation through freezing, aluminium in the leaching liquid is removed clean, the content and the yield of Quilonum Retard have significantly been improved, improved quality product, Pb+Zn+Al content in the product has reduced production cost less than 0.0008%, has the processing condition gentleness, operating process is stable, with short production cycle, the plant factor height, three waste discharge is few, thereby the bigger overall economic efficiency that improves lithionite, and the environmental protection three waste discharge is little.
Utilize Quilonum Retard that the inventive method produces after testing purity reach more than 99.5% technical indicator such as table 1
| Li 2CO 3 | 99.5% |
| Na + | 0.025% |
| K + | 0.001% |
| Fe 3+ | 0.002% |
| Ca 2+ | 0.005% |
| Mg 2+ | 0.002% |
| SO 4 2- | 0.05% |
| Cl - | 0.005% |
| Cu 2+ | 0.001% |
| Si | 0.005% |
| H 2O | 0.4% |
| Pb+Zn+Al | 0.0008% |
In the production process of the present invention, the main chemical reactions equation that relates to:
Li
2O+H
2SO
4→Li
2SO
4+H
2O K
2O+H
2SO
4→K
2SO
4+H
2O Na
2O+H
2SO
4→Na
2SO
4+H
2O
Al
2O
3+3H
2SO
4→AL
2(SO
4)
3+3H
2O Rb
2O
3+3H
2SO
4→Rb
2(SO
4)
3+3H
2O
Cs
2O+H
2SO
4→Cs
2SO
4+H
2O Li
2SO
4+Ca(OH)
2→2LiOH+CaSO
4
2LiOH+Na
2CO
3→LiCO
3+2NaOH 。
Embodiment: relating to concentration among the embodiment and be mass concentration, now is that the technological process of raw material extraction Quilonum Retard illustrates aluminum removing method from lithionite with the lithionite.
Embodiment 1
(1) filler is crushed to the 80-200 order with lithionite, places reaction unit, main chemical compositions in the raw material lithionite powder such as following table (wt%)
| Li 2O | K 2O+Na 2O | Al 2O 3 | SiO 2 | Fe 2O 3 | Rb 2O | Cs 2O | F |
| 4.0% | 8.5% | 23.0% | 53.57% | 0.19% | 1.30% | 0.20% | 4.1% |
(2) acidleach defluorination: get the lithionite powder, by certain solid, liquid mass ratio, the adding dilute sulphuric acid is knocked down to boil in the reactor and is boiled, and constantly stirs in the process of boiling of boiling, fully reaction.Simultaneously the hydrofluoric acid water vapour that contains in the reactor is extracted out, liquefy solution after condensation reclaims;
The processing condition that this step of present embodiment adopts are:
Lithionite and 50% dilute sulphuric acid solid, liquid mass ratio are 1:3,
Temperature of reaction is 120 ℃,
Reaction times is 6h,
(3) separate: the Li that contains behind (2) step defluorination
+Vitriol solid-liquid mixed solution carry out filtering separation, temperature is at 100 ℃, and in sepn process, is 80 ℃ hot wash to isolated solid filter residue temperature, detects that each composition content is respectively Li in this filter residue of control
2O 0.61%; K
2O 1.07%, Na
2O 0.45%, Al
2O
38.01%, SiO
289.74%, Fe
2O
3, Rb
2O 0.123%, Cs0.018%; Isolating filter residue reclaims; Washings and the solution that filters to isolate are mother liquor 1, enter mother liquor tank in the lump;
(4) subzero fractionation: be that refrigerated cylinder is injected in mother liquor 1 dilution back, and add Al
2(SO
4)
3, make K in the mother liquor 1
+, Al
3+Concentration is in state of saturation, forms K
+, Al
3+Saturated solution.Under the agitation condition that does not stop, when temperature is reduced to 0～40 ℃, rubidium, caesium, the arcanite mixed solution of separating out; Mixed solution separates after filtration, and filter residue reclaims, and filtrate is mother liquor 2;
(5) neutralize except that aluminium: mother liquor 2 is stirred be cooled to 0～-30 ℃, separate after filtration, filter residue reclaims, and gets filtrate solution, adds calcium hydroxide emulsion in filtrate solution, and under agitation adjusting pH value is 7～8; Form mixing solutions mother liquor 3;
(6) separate: mother liquor 3 is filtered, separate the Al in the controlled filter liquid
3+≤ 0.008g/l gets filtered liquid mother liquor 4;
(7) concentrate, filter: mother liquor 4 is concentrated to Li
+Concentration is 20～45g/L, filters;
(8) sinker: with the mother liquor 4 after the filtration of (7) step, add sodium carbonate solution under 85 ℃ of temperature, carry out sinker reaction 50 minutes;
(9) separate the system product: (8) step sinker reacted solution is carried out centrifugation get the Quilonum Retard crude product, carry out drying after the drip washing, promptly get lithium carbonate product with pure water.Solution after the filtration is washed lithium water and is returned the preparation sodium carbonate solution through recycling once more after treatment.
All the other are identical to adding K in the aluminium hydroxide control mixing solutions in the mixing solutions of subzero fractionation with processing condition and example 1 except that the following describes for embodiment 2
+, Al
3+Concentration is in state of saturation.(5) in the step and the time add calcium oxide solution.
Remove the Quilonum Retard purity height of producing behind the aluminium through above-mentioned technology, aluminium content is few in the product.
Claims (5)
1. one kind is extracted the method that Quilonum Retard removes aluminium from the lithionite raw material, comprises following processing step:
(1) the reaction defluorination places reaction unit with 80-300 purpose lithionite powder, with the sulphuric acid soln dipping, reacts 4～10 hours under 100～130 ℃ of temperature, separates defluorination, gets the solid-liquid mixing solutions;
(2) separate freezing treatment, described mixing solutions filtering separation is removed filter residue, get filtrate mother liquor 1, control mother liquor 1 is K
+, Al
3+Saturated solution, frozen cooling to 0～40 ℃ refilter separation, slagging-off, filtrate mother liquor 2;
(3) neutralization, remove aluminium, mother liquor 2 stirred and cooling is refrigerated to 0～-30 ℃, filtering separation, filtrate solution and form mother liquor 3 to wherein adding bivalent metal oxide or oxyhydroxide, with the slagging-off of mother liquor 3 sedimentation and filtrations, and Al in the controlled filter liquid
3+Concentration≤0.008 g/l, filtering separation gets mother liquor 4;
(4) filtering and concentrating concentrates and controls Li in the solution with mother liquor 4
+Concentration refilters at 20～45 g/l, adds sodium carbonate solution reaction filtering separation in filtrate, and filtrate is reclaimed, and filter residue is a Quilonum Retard.
2. according to the described method of Quilonum Retard except that aluminium of extracting from the lithionite raw material of claim 1, it is that described sulphuric acid soln concentration is 40～60Wt ﹪ that its grade is levied, and the mass ratio of lithionite and sulphuric acid soln is 1:2-4.
3. according to the described method of Quilonum Retard except that aluminium of extracting from the lithionite raw material of claim 1, it is that described step (2) adds Al in mother liquor 1 that its grade is levied
2(SO
4)
3Or Al(OH)
3, make K in the mother liquor 1
+, Al
3+Concentration is in state of saturation and forms saturated solution.
4. according to the described method of Quilonum Retard except that aluminium of extracting from the lithionite raw material of claim 1, it is that described bivalent metal oxide or oxyhydroxide are calcium oxide or calcium hydroxide that its grade is levied.
5. according to the described method of Quilonum Retard except that aluminium of extracting from the lithionite raw material of claim 1, it is that each chemical material components quality is Li than content in control (2) the step filter residue that its grade is levied
2O 0.55-0.62%, K
2O 0.9-1.08%, Na
2O 0.4-0.45%, Al
2O
38-8.01%, SiO
288.9-89.74%, Rb
2O 0.11-0.123%, CS
2O 0.015-0.018%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100753252A CN102225774A (en) | 2011-03-28 | 2011-03-28 | Method for extracting lithium carbonate from lepidolite raw material and removing aluminium |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100753252A CN102225774A (en) | 2011-03-28 | 2011-03-28 | Method for extracting lithium carbonate from lepidolite raw material and removing aluminium |
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|---|---|
| CN102225774A true CN102225774A (en) | 2011-10-26 |
Family
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|---|---|---|---|
| CN2011100753252A Pending CN102225774A (en) | 2011-03-28 | 2011-03-28 | Method for extracting lithium carbonate from lepidolite raw material and removing aluminium |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718234A (en) * | 2012-07-12 | 2012-10-10 | 张勇 | Method for extracting lithium carbonate from lepidolite |
| CN107344725A (en) * | 2017-06-29 | 2017-11-14 | 周宇 | The preparation technology of elemental lithium in sulfuric acid straight dipping process extraction lithium ore |
| CN112142081A (en) * | 2020-09-28 | 2020-12-29 | 江西永兴特钢新能源科技有限公司 | Method for preparing battery-grade lithium carbonate by using lepidolite |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3189407A (en) * | 1960-02-11 | 1965-06-15 | Saint Gobain | Method of recovering lithium from lepidolite |
| CA1297265C (en) * | 1986-07-02 | 1992-03-17 | Paul Brodermann | Process of producing lithium carbonate |
| CN101186968A (en) * | 2006-11-24 | 2008-05-28 | 江西赣锋锂业有限公司 | Method for producing refined lithium sulfate solution used in lepidolite lithium-extracting technique by sulfuric acid process |
| CN101955211A (en) * | 2010-10-29 | 2011-01-26 | 江西本源新材料科技有限公司 | Method for extracting lithium carbonate from lepidolite |
-
2011
- 2011-03-28 CN CN2011100753252A patent/CN102225774A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3189407A (en) * | 1960-02-11 | 1965-06-15 | Saint Gobain | Method of recovering lithium from lepidolite |
| CA1297265C (en) * | 1986-07-02 | 1992-03-17 | Paul Brodermann | Process of producing lithium carbonate |
| CN101186968A (en) * | 2006-11-24 | 2008-05-28 | 江西赣锋锂业有限公司 | Method for producing refined lithium sulfate solution used in lepidolite lithium-extracting technique by sulfuric acid process |
| CN101955211A (en) * | 2010-10-29 | 2011-01-26 | 江西本源新材料科技有限公司 | Method for extracting lithium carbonate from lepidolite |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718234A (en) * | 2012-07-12 | 2012-10-10 | 张勇 | Method for extracting lithium carbonate from lepidolite |
| CN102718234B (en) * | 2012-07-12 | 2014-05-14 | 张勇 | Method for extracting lithium carbonate from lepidolite |
| CN107344725A (en) * | 2017-06-29 | 2017-11-14 | 周宇 | The preparation technology of elemental lithium in sulfuric acid straight dipping process extraction lithium ore |
| CN112142081A (en) * | 2020-09-28 | 2020-12-29 | 江西永兴特钢新能源科技有限公司 | Method for preparing battery-grade lithium carbonate by using lepidolite |
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Application publication date: 20111026 |