CN102010992A - Method for removing fluorine from lithium mica raw material - Google Patents
Method for removing fluorine from lithium mica raw material Download PDFInfo
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- CN102010992A CN102010992A CN2010105246207A CN201010524620A CN102010992A CN 102010992 A CN102010992 A CN 102010992A CN 2010105246207 A CN2010105246207 A CN 2010105246207A CN 201010524620 A CN201010524620 A CN 201010524620A CN 102010992 A CN102010992 A CN 102010992A
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- defluorination
- acidleach
- raw material
- lithionite
- fluorine
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for removing fluorine from a lithium mica raw material. A method for removing the fluorine by acid leaching or a method for removing the fluorine by acid leaching and neutralizing is adopted. The method for removing the fluorine by acid leaching comprises the following steps of: reacting lithium mica powder with 20 to 60 weight percent solution of sulfuric acid in a solid to liquid mass ratio of 1:3-5 at the temperature of between 60 and 150 DEG C for 6 to 9 hours so as to generate hydrofluoric acid; and vacuumizing and separating the generated hydrofluoric acid. The method for removing the fluorine by acid leaching and neutralizing comprises the following step of: neutralizing mixed solution from which the fluorine is removed by acid leaching so as to remove the fluorine. The method has a mild process condition, high equipment utilization ratio, low energy consumption, high metal recovery rate of the lithium mica raw material, low production cost, environment friendliness and low three-waste emission.
Description
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Technical field:The present invention relates to a kind of from the lithionite raw material method of defluorination.
Lithionite is a kind of important Mineral resources, and it contains multiple metallic elements such as lithium, sodium, potassium, rubidium, caesium and as non-metallic elements such as silicon-dioxide, has developed the lithionite breeze and had grand strategy and economic worth.
From the lithionite raw material, all must remove the fluorine in the lithionite raw material in the process of its metal that contains of extraction and salt thereof.Traditional defluorinating process is generally used the method for high-temperature roasting, and temperature is carried out defluorination about 1000 ℃, volatilizees because of the fluorine in the lithionite generates hydrogen fluoride under high-temperature roasting.As China Patent No. is that 85101989 " preparation of Li 2 CO 3 by treating lithium-loaded mica with K 2 SO 4 processing methodes " and Chinese patent application number are that 201010001287.1 " a kind of method of carrying lithium from lithionite " all is to adopt the high temperature sintering method to carry out defluorination, adopt this method defluorination, energy consumption is high, and very easily cause the loss of some metallic elements, as rubidium, the rate of recovery of raw metals such as caesium is low, thereby the comprehensive development and utilization rate that has significantly reduced the lithionite ore deposit is worth, also improved its production cost, particularly be that raw material extracts in the process of metallic lithium and Quilonum Retard with the lithionite, adopt calcining method roasting defluorination, rubidium, caesium runs off big, the rate of recovery is low, significantly improve the production cost of carrying lithium and Quilonum Retard, thereby may cause forfeiture to adopt the economic worth of from the lithionite raw material, extracting lithium and Quilonum Retard, caused the wasting of resources.
Summary of the invention:The present invention be exactly to provide a kind of from the lithionite raw material method of defluorination, adopt the low temperature process acidleach and in and defluorination method, the manufacturing condition gentleness, the plant factor height, energy consumption is low, the metal recovery rate height, the environmental protection three waste discharge is little.
Technical scheme of the present invention be achieved like this adopt acidleach defluorination or acidleach and in and defluorination method; Described acidleach defluorination is to be the sulphuric acid soln of 20～60wt% with lithionite powder and concentration, presses solid, liquid mass ratio 1:3～5, reacts 6～9h under 60～150 ℃ of temperature, and the hydrofluoric acid of generation vacuumizes separation; Described acidleach and in and defluorination be during mixing solutions behind the acidleach defluorination carries out again and defluorination.
In of the present invention and defluorination be that mixing solutions behind the acidleach defluorination removes the gred after filtration and adds alkaline earth metal oxide and/or oxyhydroxide in the solution that the back obtains, PH is 9～12 in the control solution.
In of the present invention and defluorination be after adding water filtration slagging-off in the mixing solutions behind the acidleach defluorination, to add alkaline earth metal oxide and/or oxyhydroxide again.
In of the present invention and defluorination preferably add in the mixing solutions behind the acidleach defluorination in the solution of the water after-filtration slagging-off suitable and add alkaline earth metal oxide and/or oxyhydroxide again with vacuumizing isolated hydrofluoric acid solution.
The alkaline earth metal oxide and/or the oxyhydroxide that add with defluorination in of the present invention are calcium oxide and/or calcium hydroxide.
Among the present invention and the described calcium hydroxide of defluorination be calcium hydroxide emulsion.
The method of the present invention's defluorination from the lithionite raw material, the mode that adopts the neutralization of acidleach or acidleach and alkali to combine carries out defluorination, avoided 1000 ℃ of Yin Gaowen that the lithionite raw material is calcined and causes some rare metals in the lithionite raw material such as the loss of rubidium, caesium etc. significantly to improve its recovery utilization rate; Solution can continue to utilize after isolated hydrofluoric acid reclaims because of the hydrofluoric acid that the mode that adopts negative pressure and vacuumize generates in to reaction unit separates after acidleach defluorination operation, can prepare lithium fluoride etc. after adding LiOH solution.Significantly cut down the consumption of energy, reduce environmental pollution, three waste discharge is little.
Embodiment:The present invention is described in further detail below in conjunction with embodiment.
The lithionite ore deposit that the embodiment of the invention is selected for use is adopted and is originated from tantalum niobium lithium ore deposit, Yichuan, its each main chemical such as following table wt%.
| Li 2O | K 2O+Na 2O | AL 2O 3 | Si 2O | Fe 2O 3 | Rb 2O | Cs 2O | F |
| 4.5% | 9.0% | 23.5% | 52.87% | 0.18% | 1.45% | 0.22% | 4.2% |
Embodiment 1
The defluorination mode that adopts the neutralization of acidleach and alkali to combine: acidleach defluorination, be earlier lithionite to be crushed to 100 orders, place reaction unit, and add the lithionite powder and concentration is the dilution heat of sulfuric acid of 45wt% in the ratio of solid, liquid mass ratio 1:3, progressively heating, make lithionite and dilute sulphuric acid mixing solutions temperature reach 80 ℃, and under constantly stirring, react 6h; Vacuumize simultaneously and separate hydrofluoric acid and the water vapor of removing lithionite and dilute sulphuric acid reaction back generation; Remaining solid, liquid mixing solutions promptly resides in the reaction unit; After condensation, become liquid hydrofluoric acid aqueous solution and vacuumize hydrofluoric acid and the water vapor separated, recyclable utilization; To remaining in solid, liquid mixing solutions in the reaction unit after adding water, amount of makeup water is that to extract the amount of removing to generate hydrofluoric acid and water vapor solution when vacuumizing out suitable, then to solid, liquid mixing solutions filtering separation; The fluorine that contains 1.8wt% in the filtering solution behind above-mentioned acidleach defluorinating process approximately is in carrying out and defluorination again.Add calcium hydroxide emulsion in the filtering solution behind the acidleach defluorinating process, the PH in the control solution is 10; And then carry out centrifuging and separate, the solution after separation fluorine content≤0.03wt% is after testing promptly finished defluorination; Solution behind defluorination promptly continues on for extracting products such as other metallic element such as lithium, caesium, rubidium, potassium.
Embodiment 2
The mode of acidleach defluorination: lithionite is crushed to 200 orders, place reaction unit, and add the lithionite powder and concentration is the dilution heat of sulfuric acid of 50wt% in the ratio of solid, liquid mass ratio 1:4, progressively heating, make lithionite and dilute sulphuric acid mixing solutions temperature reach 120 ℃, and under constantly stirring, react 9h; Other processing step and condition are identical with the step of acidleach defluorination among the embodiment 1, and the solution behind the acidleach defluorination is fluorine content≤0.1wt% after testing.
All the other are identical with embodiment 1 except that the situation of following explanation for embodiment 3
The acidleach defluorination is earlier lithionite to be crushed to 180 orders, places reaction unit, and add the lithionite powder and concentration is the dilution heat of sulfuric acid of 40wt% in the ratio of solid, liquid mass ratio 1:5, progressively heating makes lithionite and dilute sulphuric acid mixing solutions temperature reach 140 ℃, and reacts 9h under constantly stirring; Beginning when filling with substance simultaneously promptly starts and vacuumizes tripping device and separate hydrofluoric acid and the water vapor remove lithionite and dilute sulphuric acid reaction back generation; Remaining solid, liquid mixing solutions promptly resides in the reaction unit; To remaining in the solid, liquid mixing solutions filtering separation in the reaction unit; The fluorine that contains 1.2wt% in the solution after the filtering separation behind above-mentioned acidleach defluorinating process approximately is in carrying out and defluorination again; Add calcium oxide liquid in the filtering solution behind the acidleach defluorinating process, the PH in the control solution is 11; And then carry out centrifuging and separate, the solution after separation fluorine content≤0.05wt% is after testing promptly finished defluorination; Solution behind defluorination promptly continues on for extracting products such as other metallic element such as lithium, caesium, rubidium, potassium.
Claims (7)
1. the method for a defluorination from the lithionite raw material, adopt acidleach defluorination or acidleach and in and defluorination method; Described acidleach defluorination is to be the sulphuric acid soln of 20～60wt% with lithionite powder and concentration, presses solid, liquid mass ratio 1:3～5, reacts 6～9h under 60～150 ℃ of temperature, and the hydrofluoric acid of generation vacuumizes separation; Described acidleach and in and defluorination be during mixing solutions behind the acidleach defluorination carries out again and defluorination.
According to claim 1 described from the lithionite raw material method of defluorination, it is characterized in that described in and defluorination be that mixing solutions behind the acidleach defluorination removes the gred after filtration and adds alkaline earth metal oxide and/or oxyhydroxide in the solution that the back obtains, PH is 9～12 in the control solution.
According to claim 1 described from the lithionite raw material method of defluorination, it is characterized in that described in and defluorination be after adding the water filtration slagging-off in the mixing solutions behind the acidleach defluorination, to add alkaline earth metal oxide and/or oxyhydroxide again.
According to claim 1 described from the lithionite raw material method of defluorination, it is characterized in that described in and defluorination be to add alkaline earth metal oxide and/or oxyhydroxide again in the solution that adds in the mixing solutions behind the acidleach defluorination after the water after-filtration slagging-off suitable with vacuumizing isolated hydrofluoric acid solution.
According to claim 2,3 or 4 described from the lithionite raw material method of defluorination, it is characterized in that described in and the defluorination alkaline earth metal oxide and/or the oxyhydroxide that add be calcium oxide and/or calcium hydroxide.
According to claim 5 described from the lithionite raw material method of defluorination, it is characterized in that described calcium hydroxide is calcium hydroxide emulsion.
According to claim 1 described from the lithionite raw material method of defluorination, it is characterized in that described acidleach defluorination hydrofluoric acid vacuumizes that to separate be promptly to start in raw material filling process or after finishing to vacuumize tripping device.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010105246207A CN102010992A (en) | 2010-10-29 | 2010-10-29 | Method for removing fluorine from lithium mica raw material |
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| CN2010105246207A CN102010992A (en) | 2010-10-29 | 2010-10-29 | Method for removing fluorine from lithium mica raw material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690961A (en) * | 2012-06-28 | 2012-09-26 | 贵州开磷（集团）有限责任公司 | Method for directly extracting lithium by utilizing low-grade alpha-spodumene as raw material |
| CN104419826A (en) * | 2013-08-26 | 2015-03-18 | 四川宏达股份有限公司 | Method for preparing electrodeposited zinc by ammonia leaching of zinc oxide |
| CN106086471A (en) * | 2016-06-15 | 2016-11-09 | 湖南有色金属研究院 | A kind of method that lepidolite defluorinate and valuable metal leach |
| CN106115746A (en) * | 2016-02-05 | 2016-11-16 | 山东瑞福锂业有限公司 | The technique that a kind of lepidolite prepares lithium fluoride |
| CN107012323A (en) * | 2016-12-21 | 2017-08-04 | 江苏常州酞青新材料科技有限公司 | A kind of extracting method of potassium rubidium cesium alum |
| CN108570566A (en) * | 2018-05-21 | 2018-09-25 | 江西南氏锂电新材料有限公司 | The technique that lepidolite raw material Roasting And Leaching extracts lithium |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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- 2010-10-29 CN CN2010105246207A patent/CN102010992A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690961A (en) * | 2012-06-28 | 2012-09-26 | 贵州开磷（集团）有限责任公司 | Method for directly extracting lithium by utilizing low-grade alpha-spodumene as raw material |
| CN104419826A (en) * | 2013-08-26 | 2015-03-18 | 四川宏达股份有限公司 | Method for preparing electrodeposited zinc by ammonia leaching of zinc oxide |
| CN104419826B (en) * | 2013-08-26 | 2017-03-29 | 四川宏达股份有限公司 | The method that ammonia soaks Zinc Oxide electrowinning zinc |
| CN106115746A (en) * | 2016-02-05 | 2016-11-16 | 山东瑞福锂业有限公司 | The technique that a kind of lepidolite prepares lithium fluoride |
| CN106086471A (en) * | 2016-06-15 | 2016-11-09 | 湖南有色金属研究院 | A kind of method that lepidolite defluorinate and valuable metal leach |
| CN106086471B (en) * | 2016-06-15 | 2018-06-08 | 湖南有色金属研究院 | A kind of method that lepidolite defluorinate and valuable metal leach |
| CN107012323A (en) * | 2016-12-21 | 2017-08-04 | 江苏常州酞青新材料科技有限公司 | A kind of extracting method of potassium rubidium cesium alum |
| CN108570566A (en) * | 2018-05-21 | 2018-09-25 | 江西南氏锂电新材料有限公司 | The technique that lepidolite raw material Roasting And Leaching extracts lithium |
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Application publication date: 20110413 |