CN106882822A - A kind of method that lithium is recycled into battery-level lithium carbonate in sinker mother liquor - Google Patents
A kind of method that lithium is recycled into battery-level lithium carbonate in sinker mother liquor Download PDFInfo
- Publication number
- CN106882822A CN106882822A CN201710152049.2A CN201710152049A CN106882822A CN 106882822 A CN106882822 A CN 106882822A CN 201710152049 A CN201710152049 A CN 201710152049A CN 106882822 A CN106882822 A CN 106882822A
- Authority
- CN
- China
- Prior art keywords
- lithium carbonate
- lithium
- mother liquor
- sinker
- carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to the method that lithium in a kind of sinker mother liquor is recycled into battery-level lithium carbonate, it includes step successively：To being that the sinker mother liquor produced when raw material reacts and produce lithium carbonate with sodium carbonate first carries out freezing analysis salt refined filtration process step, concentration sinker step, washing step, concentration Mother liquor return freezing analysis salt step with lithium sulfate.It is an advantage of the invention that：Reclaim resulting lithium carbonate and be the battery-level lithium carbonate of high-purity, and sulfuric acid need not be consumed and neutralized, be also not required to consume sodium carbonate again carry out sinker again, production cost is also reduced while high-purity battery-level lithium carbonate is obtained.
Description
Technical field
The present invention relates to the preparing technical field of lithium salts, and in particular to lithium is recycled into LITHIUM BATTERY carbonic acid in a kind of sinker mother liquor
The method of lithium.
Background technology
With continuing to develop for new energy, the demand of lithium carbonate is increasing, the production source of the current lithium carbonate of China
Mostly come from the production of spodumene ore method.Spodumene sulfuric acid leaching lithium obtains lithium sulfate solution, then lithium sulfate solution with
Sodium carbonate reaction obtains lithium carbonate and sinker mother liquor, and the method for the traditional recovery lithium therein of the sinker mother liquor to obtaining is first to use
Sulfuric acid carries out neutralisation treatment removal carbonate to sinker mother liquor, and being then evaporated concentration to the sinker mother liquor after neutralization again separates out
Anhydrous sodium sulfate solid, then anhydrous sodium sulfate solid is separated, so as to obtain the mixed solution of lithium sulfate and sodium sulphate, so
The mixed solution and sodium carbonate liquor are carried out sinker reaction afterwards and obtains lithium carbonate solid, the lithium carbonate solid that the recovery is obtained is pure
Degree only reaches industrial seconds lithium carbonate quality requirements 98% or so.And the method reclaims the seconds lithium carbonate amount for obtaining and accounts for
The accounting of 20% or so of whole lithium sulfate method production lithium carbonate total amount, the price of technical grade seconds lithium carbonate is than LITHIUM BATTERY carbon
The price of sour lithium is much lower, so how to improve raising of the lithium carbonate quality of sinker mother liquor lithium recovery to productivity effect having
Highly important meaning.
The content of the invention
The method that lithium is recycled into battery-level lithium carbonate in a kind of sinker mother liquor of present invention offer, the method reclaims sinker mother liquor
In the lithium carbonate purity that obtains of lithium reach more than 99.5% battery-level lithium carbonate quality.
The technical solution adopted by the present invention is：
A kind of method that lithium is recycled into battery-level lithium carbonate in sinker mother liquor, comprises the following steps：
Step one：To being that the sinker mother liquor produced when raw material reacts production lithium carbonate with sodium carbonate first carries out freezing analysis with lithium sulfate
Salt refined filtration process step：The sinker mother liquor produced when reacting production lithium carbonate with lithium sulfate and sodium carbonate is first carried out frozen cooling
To -5 DEG C~5 DEG C, the mixed solution that sal glauberi solid obtains analysing the lithium carbonate after salt and sodium sulphate is then demultiplex out, then it is right
The mixed solution obtains refined filtration liquid after carrying out secondary filter；
Step 2：Concentration sinker step：Lithium carbonate crystal seed is added in the refined filtration liquid that step one is obtained, concentration is then evaporated
Precipitation lithium carbonate, subsequently carries out separation of solid and liquid, obtains lithium carbonate crude product and concentrated mother liquor；
Step 3：Washing and drying step：The lithium carbonate crude product that step 2 is obtained first is washed simultaneously with the refined filtration liquid of step one
Separation of solid and liquid, is then carried out with pure water washing and separation of solid and liquid again, and the lithium carbonate after washing is dried just obtains high-purity
Battery-level lithium carbonate product, in the refined filtration liquid of washing lotion return to step one.
Refined filtration liquid concentration described in preferred step 2,120~270g/ is reached when sulfate concentration therein is concentrated into
Stop concentration during L.
Freezing analysis salt refined filtration treatment is carried out in the concentrated mother liquor return to step one that preferred step 2 is obtained.
Compared with prior art, it is an advantage of the invention that：The present invention reclaims the electricity that the lithium carbonate purity for obtaining reaches more than 99.5%
Pond level lithium carbonate quality, and sinker mother liquor be not required to sulfuric acid neutralize, be also not required to carry out sinker again with sodium carbonate again, improving back
Cost is also reduced while the lithium carbonate quality of receipts.
Specific embodiment：
Embodiment 1
Step one：The sinker mother liquor 4000L produced when taking lithium sulfate with sodium carbonate reaction production lithium carbonate is placed in the cold of 5000L
Freeze in kettle first carries out frozen cooling to -5 DEG C under stirring, after being then demultiplex out sal glauberi solid so as to obtain analysis salt
Lithium carbonate and the mixed solution of sodium sulphate, refined filtration liquid is obtained after then carrying out secondary filter to the mixed solution；
Step 2：The refined filtration liquid that step one is obtained is placed in the evaporator with stirring and adds lithium carbonate crystal seed, then in stirring
Mix and be evaporated concentrating and precipitating lithium carbonate under state, concentration is stopped when sulfate concentration reaches 120g/L in being concentrated to refined filtration liquid
And separation of solid and liquid is carried out, obtain lithium carbonate crude product and concentrated mother liquor；
Step 3：The lithium carbonate crude product that step 2 is obtained first with the refined filtration liquid of step one wash and separation of solid and liquid, then
Carried out washing with pure water again and separation of solid and liquid, the lithium carbonate after washing is dried just obtain battery-level lithium carbonate product.
Embodiment 2
Step one：The sinker mother liquor 4000L produced when taking lithium sulfate with sodium carbonate reaction production lithium carbonate is placed in the cold of 5000L
Freeze in kettle first carries out frozen cooling to 5 DEG C under stirring, after being then demultiplex out sal glauberi solid so as to obtain analysis salt
Lithium carbonate and the mixed solution of low-concentration sulfuric acid sodium, refined filtration liquid is obtained after then carrying out secondary filter to the mixed solution；
Step 2：The refined filtration liquid that step one is obtained is placed in the evaporator with stirring and adds lithium carbonate crystal seed, then in stirring
Mix and be evaporated concentrating and precipitating lithium carbonate under state, concentration is stopped when sulfate concentration reaches 270g/L in being concentrated to refined filtration liquid
And separation of solid and liquid is carried out, obtain lithium carbonate crude product and concentrated mother liquor；
Step 3：The lithium carbonate crude product that step 2 is obtained first with the refined filtration liquid of step one wash and separation of solid and liquid, then
Carried out washing with pure water again and separation of solid and liquid, the lithium carbonate after washing is dried just obtain battery-level lithium carbonate product.
Embodiment 3
Step one：The sinker mother liquor 4000L produced when taking lithium sulfate with sodium carbonate reaction production lithium carbonate is placed in the cold of 5000L
Freeze in kettle first carries out frozen cooling to 0 DEG C under stirring, after being then demultiplex out sal glauberi solid so as to obtain analysis salt
Lithium carbonate and the mixed solution of low-concentration sulfuric acid sodium, refined filtration liquid is obtained after then carrying out secondary filter to the mixed solution；
Step 2：The refined filtration liquid that step one is obtained is placed in the evaporator with stirring and adds lithium carbonate crystal seed, then in stirring
Mix and be evaporated concentrating and precipitating lithium carbonate under state, concentration is stopped when sulfate concentration reaches 180g/L in being concentrated to refined filtration liquid
And separation of solid and liquid is carried out, obtain lithium carbonate crude product and concentrated mother liquor；
Step 3：The lithium carbonate crude product that step 2 is obtained first with the refined filtration liquid of step one wash and separation of solid and liquid, then
Carried out washing with pure water again and separation of solid and liquid, the lithium carbonate after washing is dried just obtain battery-level lithium carbonate product
The pure Lithium Carbonate product sampling analysis detection for being obtained to embodiment 1-3 respectively, each component content is as follows in sample：
As seen from the above table, sinker mother liquor is not required to be neutralized with sulfuric acid in preparation method of the invention, is also not required to be carried out with sodium carbonate again
Sinker, cost is also reduced while the lithium carbonate quality for reclaiming is improved again.
The preferred embodiments of the present invention are the foregoing is only, is not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.It is all within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (3)
1. a kind of method that lithium is recycled into battery-level lithium carbonate in sinker mother liquor, it is characterised in that：Step one：To being with lithium sulfate
The sinker mother liquor produced when raw material is with sodium carbonate reaction production lithium carbonate first carries out freezing analysis salt refined filtration process step：Using sulfuric acid
The sinker mother liquor produced when lithium is with sodium carbonate reaction production lithium carbonate first carries out frozen cooling to -5 DEG C~5 DEG C, is then demultiplex out
Sal glauberi solid just obtains analysing the mixed solution of the lithium carbonate after salt and sodium sulphate, then carries out accurate mistake to the mixed solution
Refined filtration liquid is obtained after filter；
Step 2：Concentration sinker step：Lithium carbonate crystal seed is added in the refined filtration liquid that step one is obtained, concentration is then evaporated
Precipitation lithium carbonate, subsequently carries out separation of solid and liquid, obtains lithium carbonate crude product and concentrated mother liquor；
Step 3：Washing and drying step：The lithium carbonate crude product that step 2 is obtained first is washed simultaneously with the refined filtration liquid of step one
Separation of solid and liquid, is then carried out with pure water washing and separation of solid and liquid again, and the lithium carbonate after washing is dried just obtains high-purity
Battery-level lithium carbonate product, in the refined filtration liquid of washing lotion return to step one.
2. the method that lithium is recycled into battery-level lithium carbonate in sinker mother liquor according to claim 1, it is characterised in that：Step
Refined filtration liquid concentration described in two, concentration is stopped when being concentrated into sulfate concentration therein and reaching 120~270g/L.
3. the method that lithium is recycled into battery-level lithium carbonate in sinker mother liquor according to claim 1, it is characterised in that：Step
Freezing analysis salt refined filtration treatment is carried out in the two concentrated mother liquor return to step one for obtaining.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710152049.2A CN106882822A (en) | 2017-03-15 | 2017-03-15 | A kind of method that lithium is recycled into battery-level lithium carbonate in sinker mother liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710152049.2A CN106882822A (en) | 2017-03-15 | 2017-03-15 | A kind of method that lithium is recycled into battery-level lithium carbonate in sinker mother liquor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106882822A true CN106882822A (en) | 2017-06-23 |
Family
ID=59180831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710152049.2A Pending CN106882822A (en) | 2017-03-15 | 2017-03-15 | A kind of method that lithium is recycled into battery-level lithium carbonate in sinker mother liquor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106882822A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108439439A (en) * | 2018-06-12 | 2018-08-24 | 佛山市灏金赢科技有限公司 | A kind of preparation method of battery-level lithium carbonate |
| CN110040750A (en) * | 2019-04-26 | 2019-07-23 | 核工业北京化工冶金研究院 | A kind of processing method of lithium carbonate mother liquor of precipitation of ammonium |
| CN110194492A (en) * | 2018-02-27 | 2019-09-03 | 荆门市格林美新材料有限公司 | A kind of preparation method of basic nickel carbonate |
| CN110451536A (en) * | 2019-08-26 | 2019-11-15 | 新中天环保股份有限公司 | A method of recycling lithium from battery-level lithium carbonate mother liquor |
| CN111333089A (en) * | 2020-03-05 | 2020-06-26 | 赣州龙凯科技有限公司 | Complete equipment and method for recycling lithium carbonate from waste lithium iron phosphate batteries |
| CN111533146A (en) * | 2020-05-07 | 2020-08-14 | 四川泛宇锂能新材料科技有限公司 | Method for recovering lithium in lithium carbonate lithium precipitation mother liquor |
| CN112142080A (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 freezing, circulating and recycling lithium precipitation concentrated mother solution |
| CN113800541A (en) * | 2021-11-08 | 2021-12-17 | 江苏瑞达环保科技有限公司 | Processing technology for refining lithium chloride by lithium carbonate precipitation and conversion |
| CN113896212A (en) * | 2021-11-15 | 2022-01-07 | 福州大学 | Method for recovering lithium carbonate by carbonizing and freezing lithium precipitation mother liquor to remove mirabilite |
| CN113912090A (en) * | 2021-11-15 | 2022-01-11 | 福州大学 | Method for recovering high-purity lithium carbonate by causticizing, freezing and removing mirabilite from lithium precipitation mother liquor |
| CN114014342A (en) * | 2021-12-22 | 2022-02-08 | 长沙道尚循环科技有限公司 | Method for purifying battery-grade lithium carbonate from crude lithium carbonate |
| WO2022121989A1 (en) | 2020-12-09 | 2022-06-16 | 西安蓝晓科技新材料股份有限公司 | Method for recovering lithium from lithium precipitation mother liquor |
| CN115849408A (en) * | 2022-12-23 | 2023-03-28 | 杭州水处理技术研究开发中心有限公司 | Method for recovering lithium resources in waste lithium batteries |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481125A (en) * | 2009-02-13 | 2009-07-15 | 海门容汇通用锂业有限公司 | Method for cyclically using lithium deposition for preparing sodium carbonate solution to produce lithium carbonate |
| CN103833053A (en) * | 2014-01-21 | 2014-06-04 | 四川天齐锂业股份有限公司 | Method of preparing high-purity lithium carbonate of the 5 N grade |
| CN104338441A (en) * | 2014-10-17 | 2015-02-11 | 南京格洛特环境工程股份有限公司 | Treatment process of lithium precipitation mother solution |
| CN106276988A (en) * | 2016-08-12 | 2017-01-04 | 青海大学 | A kind of method preparing battery-level lithium carbonate for precipitant with potassium carbonate |
-
2017
- 2017-03-15 CN CN201710152049.2A patent/CN106882822A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481125A (en) * | 2009-02-13 | 2009-07-15 | 海门容汇通用锂业有限公司 | Method for cyclically using lithium deposition for preparing sodium carbonate solution to produce lithium carbonate |
| CN103833053A (en) * | 2014-01-21 | 2014-06-04 | 四川天齐锂业股份有限公司 | Method of preparing high-purity lithium carbonate of the 5 N grade |
| CN104338441A (en) * | 2014-10-17 | 2015-02-11 | 南京格洛特环境工程股份有限公司 | Treatment process of lithium precipitation mother solution |
| CN106276988A (en) * | 2016-08-12 | 2017-01-04 | 青海大学 | A kind of method preparing battery-level lithium carbonate for precipitant with potassium carbonate |
Non-Patent Citations (2)
| Title |
|---|
| 侯文贵: "沉锂母液冷冻析钠工艺探讨", 《新疆有色金属》 * |
| 石颖: "沉锂母液自循环工艺的理论与方法", 《新疆有色金属》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110194492A (en) * | 2018-02-27 | 2019-09-03 | 荆门市格林美新材料有限公司 | A kind of preparation method of basic nickel carbonate |
| CN108439439A (en) * | 2018-06-12 | 2018-08-24 | 佛山市灏金赢科技有限公司 | A kind of preparation method of battery-level lithium carbonate |
| CN110040750B (en) * | 2019-04-26 | 2021-10-22 | 核工业北京化工冶金研究院 | Method for treating lithium carbonate precipitation mother liquor |
| CN110040750A (en) * | 2019-04-26 | 2019-07-23 | 核工业北京化工冶金研究院 | A kind of processing method of lithium carbonate mother liquor of precipitation of ammonium |
| CN110451536A (en) * | 2019-08-26 | 2019-11-15 | 新中天环保股份有限公司 | A method of recycling lithium from battery-level lithium carbonate mother liquor |
| CN111333089A (en) * | 2020-03-05 | 2020-06-26 | 赣州龙凯科技有限公司 | Complete equipment and method for recycling lithium carbonate from waste lithium iron phosphate batteries |
| CN111533146A (en) * | 2020-05-07 | 2020-08-14 | 四川泛宇锂能新材料科技有限公司 | Method for recovering lithium in lithium carbonate lithium precipitation mother liquor |
| CN112142080A (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 freezing, circulating and recycling lithium precipitation concentrated mother solution |
| WO2022121989A1 (en) | 2020-12-09 | 2022-06-16 | 西安蓝晓科技新材料股份有限公司 | Method for recovering lithium from lithium precipitation mother liquor |
| CN113800541A (en) * | 2021-11-08 | 2021-12-17 | 江苏瑞达环保科技有限公司 | Processing technology for refining lithium chloride by lithium carbonate precipitation and conversion |
| CN113896212A (en) * | 2021-11-15 | 2022-01-07 | 福州大学 | Method for recovering lithium carbonate by carbonizing and freezing lithium precipitation mother liquor to remove mirabilite |
| CN113912090A (en) * | 2021-11-15 | 2022-01-11 | 福州大学 | Method for recovering high-purity lithium carbonate by causticizing, freezing and removing mirabilite from lithium precipitation mother liquor |
| CN113896212B (en) * | 2021-11-15 | 2023-08-08 | 福州大学 | Method for recovering lithium carbonate by carbonizing and freezing lithium precipitation mother liquor and removing mirabilite |
| CN114014342A (en) * | 2021-12-22 | 2022-02-08 | 长沙道尚循环科技有限公司 | Method for purifying battery-grade lithium carbonate from crude lithium carbonate |
| CN115849408A (en) * | 2022-12-23 | 2023-03-28 | 杭州水处理技术研究开发中心有限公司 | Method for recovering lithium resources in waste lithium batteries |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106882822A (en) | A kind of method that lithium is recycled into battery-level lithium carbonate in sinker mother liquor | |
| CN106542512A (en) | Using the high-purity phosphoric acid lithium preparation method of the lithium waste liquid of old and useless battery | |
| CN103382170A (en) | Preparation method for taurine | |
| WO2018076994A1 (en) | Method for recovering lithium from low content extraction tailwater, and method for recycling extraction tailwater | |
| CN104945289A (en) | Method for preparing taurine through solid isethionic acid sodium salt | |
| CN110040750B (en) | Method for treating lithium carbonate precipitation mother liquor | |
| CN102531222B (en) | Treatment method for vanadium precipitating waste water | |
| CN104495927B (en) | Prepare the method for Vanadium Pentoxide in FLAKES | |
| CN108517403A (en) | A kind of method of metallic cobalt battery grade cobalt sulfate | |
| CN108439438A (en) | The method that nickel cobalt mn sulphate and lithium carbonate are prepared by waste and old ternary battery material | |
| WO2017121280A1 (en) | Method for continuously producing battery-grade lithium carbonate | |
| CN105819472A (en) | Method for producing highly-pure battery grade lithium carbonate by using lithium sulfate solution | |
| CN110451536A (en) | A method of recycling lithium from battery-level lithium carbonate mother liquor | |
| CN103849902A (en) | Recovery process of stibium and bismuth in copper electrolyte | |
| CN103408046B (en) | Method for separating sodium and magnesium from laterite-nickel ore smelting primary wastewater | |
| CN106744694B (en) | The recovery method of potassium hyperchlorate production method and chlorination mother liquid of sodium | |
| CN109336141B (en) | Method for improving recovery rate of lithium in wastewater | |
| CN112359224B (en) | Method for purifying cadmium-containing nickel-cobalt solution to remove cadmium | |
| CN106830104B (en) | A method of producing cobalt sulfate | |
| CN104628609A (en) | Separation and extraction method of taurine | |
| CN104150519B (en) | A kind of method utilizing sodium sulfate waste liquid to prepare barium sulfate and sodium carbonate | |
| CN116212765A (en) | Waste lithium material recovery method and system based on ammonium chloride circulation | |
| CN110078097A (en) | A kind of technique of instant solution process for preparing potassium nitrate by double decomposition | |
| CN104447529B (en) | Method for extracting and purifying 3,6-matrigon | |
| CN113387338A (en) | Method for producing lithium ion battery raw material based on lithium sulfate and lithium sulfate resource utilization process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170623 |