CN102502721B - Method for preparing lithium carbonate through extracting lithium from lithium ore - Google Patents
Method for preparing lithium carbonate through extracting lithium from lithium ore Download PDFInfo
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- CN102502721B CN102502721B CN201110361621.9A CN201110361621A CN102502721B CN 102502721 B CN102502721 B CN 102502721B CN 201110361621 A CN201110361621 A CN 201110361621A CN 102502721 B CN102502721 B CN 102502721B
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Abstract
The invention relates to a method for preparing lithium carbonate through extracting lithium from lithium ore. The method comprises the following steps: 1, reacting the lithium ore with fluosilicic acid; 2, filtering; 3, carrying out a fluorine removal reaction; 4, adding water, and dissolving; 5, carrying out a neutralization reaction; and 6, carbonizing to precipitate lithium. The method which allows high energy consumption processes of high temperature roasting and pressurization reacting of the lithium ore in traditional technologies to be not needed and is a method for extracting lithium from the lithium ore through a low temperature process has the characteristics of simple process, low energy consumption and high extraction rate, and makes the comprehensive utilization rate of byproducts be high and the production cost be substantially reduced.
Description
Technical field
The present invention relates to lithium ore comprehensive development and utilization technical field, relate in particular to a kind of low temperature wet method that adopts and from lithium ore, put forward the method that lithium is prepared Quilonum Retard.
Background technology
Lithium is a kind of important strategic resources material, is the indispensable important raw and processed materials of modern high technology product.The main raw material that extracts lithium is triphane, lithionite, lithium sanidine and salt lake brine.According to different raw materials, the extraction of lithium is divided into from lithium ore and salt lake brine extracts two kinds of methods.
The method that current ore is carried lithium has:
(1) lime sinter process.This method is that lithium ore and Wingdale are prepared burden by 1: 3 (mass ratio), and high-temperature roasting at 850-950 ℃, ball milling, water logging go out, and obtains containing LiO
2the LiOH solution of 3～4g/l, then by sedimentation, filtration, purification, removal of impurities, evaporation, crystallization, the dry lithium hydroxide that obtains.This is current main industrial process, this method raw material is easy to get, cheap, wide material sources, production technique is simple, but Wingdale proportioning is high, need in rotary kiln, decompose a large amount of Wingdales, energy consumption is high, and mass flow is large, equipment capacity low (the design production capacity of 2.07 * 45 meters of rotary kilns of Φ is 800 tons/year), the quantity of slag large (42 tons of slag/ton products), the rate of recovery low (67% left and right).
(2) sulphate process.This method is that lithium ore is mixed with auxiliary materials such as potassium sulfate, high-temperature roasting, ball milling, leaching, purification, evaporation, precipitation Quilonum Retard processed.Although this method is better than lime sinter process, but still there is following problem: the one, potassium sulfate consumption is large, and the cost of potassium sulfate is 4～5 times of Wingdale, causes production cost higher; The 2nd, due to adding of potassium sulfate, make furnace charge melting point depression, very easily there is partial melting and sintering, the leaching yield of lithium is reduced greatly.
(3) chlorinating roasting.This method is lithium and other alkali metal and the chlorizating agent generation chlorination reaction making under maturing temperature in lithium ore, generates corresponding muriate, then from these muriates, extracts respectively various alkali metal compound products.Technical process mainly comprises batching ball processed, chloridizing roasting, diafiltration stripping, solution purification, condensing crystal, crystallisation by cooling, Quilonum Retard precipitation and washing and drying etc.
(4) basic pressure digestion method.This method is by after lithium grinde ore, directly adds water adding calcium hydroxide and presses and boil in autoclave, and pressing and boiling temperature is 240～260 ℃, and pressure is 2.8Mpa, reacts 4 hours, and the rate of decomposition of lithium ore can reach 95%.But this method calcium hydroxide consumption is large, and energy-saving effect is not remarkable, press temperature, pressure while boiling all very high, and the cost of high pressure leaching plant is also very high.
Through the literature search of prior art is found, due to the importance of lithium, at present ore is proposed to the research of lithium very active.As Huang Jifen, the people such as Tang Xianliu disclose a kind of technology of pressurized boiling process for preparing lithium carbonate with lithium mica ore and mixed base in patent CN1067028, concentrate to be passed into water vapor carry out roasting, then roasting material is allocated into mixed base (as calcium oxide, sodium carbonate or sodium hydroxide) grind size mixing, solution purification, evaporation concentration, carbonating carry lithium, mixed base recycling use, potassium, rubidium, caesium comprehensively reclaim.
Xu Longquan, great-grandfather is bright waits people in patent CN1267636, to disclose a kind of method of sulfuric acid process to produce battery-level lithium carbonate, is make the transition roasting, acidizing fired, leaching, purifying treatment, concentration, sinker processing, cleaning, drying treatment, pulverizing, package processing of lithium concentrate formed.The features such as the method has constant product quality, and production technique is simple, makes full use of resource, and cost is low.The raw-material production application of suitable lithium ion battery.
Zhong Hui, Xu Hui discloses a kind of lithium Li processed that extracts from lithionite in patent CN1827527
2cO
3method, its basic working procedure is: lepidolite ore is added to CaF, CaSO
4, Na
2sO
4deng auxiliary material, under certain temperature, carry out after modification by calcination, ball milling, leaching, filtration, then leach liquor is added to Na
2cO
3precipitation Li
+, form Li
2cO
3precipitation, filters the solid obtaining and is Li through washing, being dried
2cO
3product, filtrated stock returns and is circulated in precipitation Li
+process, after 2 circulations, this filtrated stock, through crystallisation by cooling, is separated out K
2sO
4, Na
2sO
4mixing salt, returns to this mixing salt part to do auxiliary material and the baking mixed recycle of lepidolite ore, and another part can be used as the raw material of potassium sulfate making.
Can find out, what at present both at home and abroad from ore, carry that the method for lithium adopts is all at high temperature roasting, then leaches the technique of crystallization, all has that energy consumption is high, the feature of complex process.
Summary of the invention
For the deficiencies in the prior art, the present invention aims to provide a kind of method of extracting lithium from lithium ore deposit, and it is simple that the method has technique, do not need pyroreaction, and energy consumption is low, and the extraction yield of lithium is high, greatly reduces production cost.
The technical solution used in the present invention is:
From lithium ore, carry lithium and prepare a method for Quilonum Retard, it is characterized in that, said method comprising the steps of:
(1) lithium ore reacts with silicofluoric acid: the lithium ore powder after pulverizing is put into reactor, ratio=1 in quality (g) with volume (ml): 1～1: 10 ratio adds silicofluoric acid, heated and stirred reaction 1.0-3.0 hour;
(2) filter: step (1) gained reaction product is filtered, gained solid is joined in defluorination reactor;
(3) defluorination reaction: add sulfuric acid to carry out defluorination reaction in defluorination reactor, the mass ratio of above-mentioned solid reactant and sulfuric acid is 1: 0.1-1: 0.8, the reaction times is 0.5-4 hour;
(4) be dissolved in water: step (3) gained reaction product is filtered, and gained solid joins in dissolution kettle, and the ratio of 1: 1 in mass ratio～1: 5 adds water, be heated to boiling, stirring and dissolving 2-30 minute;
(5) neutralization reaction: step (4) gained reaction product is filtered, and gained filtrate is sent into neutralization tank, adds ammoniacal liquor to regulate pH value to 4～10;
(6) carbonization sinker: step (5) gained reaction product is filtered, add soluble carbonate salt in gained filtrate, stirring reaction 2-20 minute, then ageing 0.5-2 hour, filters, and gained solid product is Crude lithium Carbonate, Crude lithium Carbonate back washing is dry, obtain product Quilonum Retard.
Preferably, the granularity of the lithium ore powder in step (1) is 80～200 orders.
Preferably, the mass percent concentration of the silicofluoric acid in step (1) is 10%～50%.
Preferably, the temperature of reaction in step (1) is 90 ℃-140 ℃.
Preferably, the mass percent concentration of the sulfuric acid in step (3) is 50%-98%.
Preferably, the mass percent concentration of step (4) ammoniacal liquor used is 5%～30%.
Preferably, described in step (6), soluble carbonate salt is volatile salt.
Preferably, in step (6), the mass ratio of filtrate and soluble carbonate salt is 3: 0.02～3: 1.
The present invention overcome in traditional technology by the high-temperature roasting of lithium ore, the high energy consumption techniques such as compressive reaction, that a kind of low temperature wet method that adopts is extracted the method for lithium from lithium ore, have the advantages that technique is simple, energy consumption is low, extraction yield is high, and byproduct comprehensive utilization ratio is high, greatly reduces production cost.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that extracts the method for lithium from lithium ore deposit of the present invention.
Embodiment
Embodiment 1
(1) will be crushed to 80～200 object triphane powder 1000g and put into reactor, adding 1000ml mass percent concentration is 50% silicofluoric acid, is heated to 90 ℃, reacts 1 hour;
(2) reaction product of step (1) is filtered, filter gained solid and join in defluorination reactor;
(3) to adding mass percent concentration in defluorination reactor, be that 50% sulfuric acid carries out defluorination reaction, and the mass ratio of solid reactant and sulfuric acid is 1: 0.8, the reaction times is 4 hours;
(4) step (3) gained reaction product is filtered, gained solid joins in dissolution kettle, and the ratio of 1: 1 adds water in mass ratio, is heated to boiling, stirring and dissolving 30 minutes;
(5) by step (4) gained reaction product Filter Press, gained filtrate is sent into neutralization tank, and adding mass percent concentration is that 5% ammoniacal liquor regulates pH value to 4;
(6) step (5) gained reaction product is filtered, in gained filtrate, add volatile salt, and the mass ratio of filtrate and volatile salt is 3: 1, stirring reaction 20 minutes, then ageing is 0.5 hour, and with Filter Press, gained solid product is Crude lithium Carbonate, Crude lithium Carbonate back washing is dry, obtain product Quilonum Retard.
Embodiment 2
(1) will be crushed to 80～200 object lithionite powder 1000g and put into reactor, adding 10000ml mass percent concentration is 10% silicofluoric acid, is heated to 120 ℃, reacts 3 hours;
(2) reaction product of step (1) is filtered, filter gained solid and join in defluorination reactor;
(3) to adding mass percent concentration in defluorination reactor, be that 98% sulfuric acid carries out defluorination reaction, and the mass ratio of solid reactant and sulfuric acid is 1: 0.1, the reaction times is 0.5 hour;
(4) step (3) gained reaction product is filtered, gained solid joins in dissolution kettle, and the ratio of 1: 5 adds water in mass ratio, is heated to boiling, stirring and dissolving 2 minutes;
(5) by step (4) gained reaction product Filter Press, gained filtrate is sent into neutralization tank, and adding mass percent concentration is that 30% ammoniacal liquor regulates pH value to 6;
(6) step (5) gained reaction product is filtered, in gained filtrate, add volatile salt, and the mass ratio of filtrate and sodium carbonate is 3: 0.02, stirring reaction 2 minutes, then ageing is 2 hours, and with Filter Press, gained solid product is Crude lithium Carbonate, Crude lithium Carbonate back washing is dry, obtain product Quilonum Retard.
Embodiment 3
(1) will be crushed to 80～200 object lithium Feldspar Powder 1000g and put into reactor, adding 3000ml mass percent concentration is 40% silicofluoric acid, is heated to 100 ℃, reacts 1.5 hours;
(2) reaction product of step (1) is filtered, filter gained solid and join in defluorination reactor;
(3) to adding mass percent concentration in defluorination reactor, be that 65% sulfuric acid carries out defluorination reaction, and the mass ratio of solid reactant and sulfuric acid is 1: 0.6, the reaction times is 2 hours;
(4) step (3) gained reaction product is filtered, gained solid joins in dissolution kettle, and the ratio of 1: 2 adds water in mass ratio, is heated to boiling, stirring and dissolving 20 minutes;
(5) by step (4) gained reaction product Filter Press, gained filtrate is sent into neutralization tank, and adding mass percent concentration is that 15% ammoniacal liquor regulates pH value to 8;
(6) step (5) gained reaction product is filtered, in gained filtrate, add volatile salt, and the mass ratio of filtrate and volatile salt is 3: 0.1, stirring reaction 10 minutes, then ageing is 1 hour, and with Filter Press, gained solid product is Crude lithium Carbonate, Crude lithium Carbonate back washing is dry, obtain product Quilonum Retard.
Embodiment 4
(1) will be crushed to 80～200 object triphane powder 1000g and put into reactor, adding 5000ml mass percent concentration is 30% silicofluoric acid, is heated to 140 ℃, reacts 2 hours;
(2) reaction product of step (1) is filtered, filter gained solid and join in defluorination reactor;
(3) to adding mass percent concentration in defluorination reactor, be that 70% sulfuric acid carries out defluorination reaction, and the mass ratio of solid reactant and sulfuric acid is 1: 0.4, the reaction times is 2 hours;
(4) step (3) gained reaction product is filtered, gained solid joins in dissolution kettle, and the ratio of 1: 3 adds water in mass ratio, is heated to boiling, stirring and dissolving 10 minutes;
(5) by step (4) gained reaction product Filter Press, gained filtrate is sent into neutralization tank, and adding mass percent concentration is that 25% ammoniacal liquor regulates pH value to 10;
(6) step (5) gained reaction product is filtered, in gained filtrate, add sodium carbonate, and the mass ratio of filtrate and volatile salt is 3: 0.5, stirring reaction 15 minutes, then ageing is 1.5 hours, and with Filter Press, gained solid product is Crude lithium Carbonate, Crude lithium Carbonate back washing is dry, obtain product Quilonum Retard.
Embodiment 1～5 gained Quilonum Retard is detected, and the mass percentage content of each composition is in Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Li 2C O3 | 99.51 | 99.57 | 99.61 | 99.67 |
| Na + | 0.025 | 0.020 | 0.023 | 0.031 |
| K + | 0.001 | 0.002 | 0.002 | 0.003 |
| Fe 3+ | 0.002 | 0.002 | 0.001 | 0.002 |
| Ca 2+ | 0.005 | 0.004 | 0.006 | 0.005 |
| Mg 2+ | 0.002 | 0.001 | 0.001 | 0.002 |
| S0 4 2- | 0.04 | 0.05 | 0.06 | 0.07 |
| Cl - | 0.005 | 0.006 | 0.004 | 0.008 |
As can be seen from Table 1, the purity of Quilonum Retard of the present invention is all more than 99.5%.
Claims (8)
1. from lithium ore, put forward the method that lithium is prepared Quilonum Retard, it is characterized in that, said method comprising the steps of:
(1) lithium ore reacts with silicofluoric acid: the lithium ore powder after pulverizing is put into reactor, ratio=1 in quality (g) with volume (mL): 1～1: 10 ratio adds silicofluoric acid, heated and stirred reaction 1.0-3.0 hour;
(2) filter: step (1) gained reaction product is filtered, gained solid is joined in defluorination reactor;
(3) defluorination reaction: add sulfuric acid to carry out defluorination reaction in defluorination reactor, the mass ratio of above-mentioned solid reactant and sulfuric acid is 1: 0.1-1: 0.8, the reaction times is 0.5-4 hour, sulfuric acid mass percent concentration is 65%-98%;
(4) be dissolved in water: step (3) gained reaction product is filtered, and gained solid joins in dissolution kettle, and the ratio of 1: 1 in mass ratio～1: 5 adds water, be heated to boiling, stirring and dissolving 2-30 minute;
(5) neutralization reaction: step (4) gained reaction product is filtered, and gained filtrate is sent into neutralization tank, adds ammoniacal liquor to regulate pH value to 4～10;
(6) carbonization sinker: step (5) gained reaction product is filtered, add soluble carbonate salt in gained filtrate, stirring reaction 2-20 minute, then ageing 0.5-2 hour, filters, and gained solid product is Crude lithium Carbonate, Crude lithium Carbonate back washing is dry, obtain product Quilonum Retard.
2. as claimed in claim 1ly from lithium ore, put forward the method that lithium is prepared Quilonum Retard, it is characterized in that, the granularity of the lithium ore powder in step (1) is 80～200 orders.
3. as claimed in claim 1ly from lithium ore, put forward the method that lithium is prepared Quilonum Retard, it is characterized in that, the mass percent concentration of the silicofluoric acid in step (1) is 10%～50%.
4. as claimed in claim 1ly from lithium ore, put forward the method that lithium is prepared Quilonum Retard, it is characterized in that, the temperature of reaction in step (1) is 90 ℃-140 ℃.
5. as claimed in claim 1ly from lithium ore, put forward the method that lithium is prepared Quilonum Retard, it is characterized in that, the mass percent concentration of the sulfuric acid in step (3) is 50%-98%.
6. as claimed in claim 1ly from lithium ore, put forward the method that lithium is prepared Quilonum Retard, it is characterized in that, the mass percent concentration of step (4) ammoniacal liquor used is 5%～30%.
7. as claimed in claim 1ly from lithium ore, put forward the method that lithium is prepared Quilonum Retard, it is characterized in that, described in step (6), soluble carbonate salt is volatile salt.
8. as claimed in claim 1ly from lithium ore, put forward the method that lithium is prepared Quilonum Retard, it is characterized in that, in step (6), the mass ratio of filtrate and soluble carbonate salt is 3: 0.02～3: 1.
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| CN104591232A (en) * | 2014-12-29 | 2015-05-06 | 宜春市科远化工有限公司 | Method for extracting lithium carbonate from Yichun tantalum niobium tailings lithium mica and obtaining by-product |
| CN104495880A (en) * | 2014-12-29 | 2015-04-08 | 宜春市科远化工有限公司 | Method for preparing lithium chloride and byproducts of lithium chloride from lepidolite |
| CN105152188A (en) * | 2015-08-06 | 2015-12-16 | 昊青薪材（北京）技术有限公司 | Method for preparing lithium carbonate and potassium sulfate by using zinnwaldite |
| CN105329921A (en) * | 2015-12-08 | 2016-02-17 | 汕头市泛世矿业有限公司 | Three-in-one preparing technology for high-purity lithium carbonate |
| CN106044804B (en) * | 2016-05-26 | 2017-10-24 | 四川思达能环保科技有限公司 | A kind of sulfuric acid process lithium salts production new technique |
| CN107344725B (en) * | 2017-06-29 | 2019-02-26 | 周宇 | Sulfuric acid straight dipping process extracts the preparation process of elemental lithium in lithium ore |
| CN107162024A (en) * | 2017-07-15 | 2017-09-15 | 汕头市泛世矿产资源股份有限公司 | The technique that a kind of acidization extracts lithium carbonate from amblygonite |
| CN110526250B (en) * | 2019-09-27 | 2023-01-10 | 福州大学 | Comprehensive utilization method for directly extracting lithium from silicate lithium-containing ore by acid process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059702A (en) * | 1990-09-10 | 1992-03-25 | 新疆有色金属研究所 | The method for preparing Quilonum Retard with the volatile salt precipitation |
| CN101948115A (en) * | 2010-09-14 | 2011-01-19 | 薛彦辉 | Method for processing potassium-containing rocks |
| 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 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059702A (en) * | 1990-09-10 | 1992-03-25 | 新疆有色金属研究所 | The method for preparing Quilonum Retard with the volatile salt precipitation |
| CN101948115A (en) * | 2010-09-14 | 2011-01-19 | 薛彦辉 | Method for processing potassium-containing rocks |
| 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 |
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