CN102030319A - Lithium dihydrogen phosphate preparation method - Google Patents
Lithium dihydrogen phosphate preparation method Download PDFInfo
- Publication number
- CN102030319A CN102030319A CN2009101964380A CN200910196438A CN102030319A CN 102030319 A CN102030319 A CN 102030319A CN 2009101964380 A CN2009101964380 A CN 2009101964380A CN 200910196438 A CN200910196438 A CN 200910196438A CN 102030319 A CN102030319 A CN 102030319A
- Authority
- CN
- China
- Prior art keywords
- phosphate
- lithium
- monometallic
- weight
- raw material
- 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
Abstract
The invention provides a lithium dihydrogen phosphate preparation method, comprising the following steps: (1) raw material-lithium carbonate is added in a phosphoric acid aqueous solution, the mixture is stirred for 15-45 minutes, and then a lithium hydroxide solution is added to adjust the pH value to be 8-9, wherein the raw material-lithium carbonate is in technical grade; (2) solid-liquid separation is carried out at 85-95 DEG C, so as to obtain wet lithium phosphate; (3) the wet lithium phosphate obtained in the step (2) is added in the phosphoric acid aqueous solution, after the wet lithium phosphate is dissolved, phosphoric acid or lithium phosphate is added, the pH of the solution is adjusted to be 2-3, and a filtrate containing the lithium dihydrogen phosphate is collected; and (4) the filtrate containing the lithium dihydrogen phosphate in the step (3) is evaporated and concentrated, and then is cooled and crystallized, the lithium dihydrogen phosphate is collected, and then the product is obtained after being dried. In the method, crystallized products can be obtained, the product cost is reduced, and the yield and quality of the products are improved. The lithium dihydrogen phosphate preparation method has the advantages that the battery grade lithium dihydrogen phosphate with high efficiency, high purity and low cost can be produced.
Description
Technical field
The present invention relates to the preparation technology of monometallic.
Background technology
Lithium ion battery, it mainly is made up of positive pole, negative pole, barrier film, electrolytic solution etc.Wherein mainly contain cobalt acid lithium, cobalt acid nickel, lithium manganate, ferrous acid lithium, LiFePO 4 etc. as the positive electrode material positive active material.
Cobalt acid lithium is always as the first-selection of Postive electrode material of li-ion accumulator since the nearly more than ten years, though excellent property, but cost an arm and a leg, develop rapidly along with mobile communication electronics and electromobile, lithium-ions battery is being proposed new requirement aspect high cycle performance, the high-energy-density, therefore with new forms of energy and new material technology be the research of Postive electrode material of li-ion accumulator of background also in the continuous new direction of developing, seek to substitute low cost, high-energy-density, environmental friendliness, long-life novel anode material of cobalt acid lithium.
LiFePO 4 becomes the emphasis of research with its good thermostability and good cycle characteristics.This material has the characteristic of high life, high safety, high environmental protection, and the discovery of this material property has brought life for the further popularization of power truck, and domestic numerous scientific research institution's prophesies " it " will become the substitute of following lead-acid cell the time.In addition, monometallic is one of critical materials of producing LiFePO 4.
Usually, monometallic prepares with the following method:
Use technical grade Quilonum Retard or lithium hydroxide and phosphoric acid to carry out neutralization reaction, evaporate then, crystallization, drying or directly carry out spraying drying and obtain product.Because the reaction end pH value of solution is acid, impurity can't be removed with this understanding, will all enter product and mother liquor, just must use purified Quilonum Retard or lithium hydroxide if will obtain highly purified product.The major defect of this method is: if use technical grade Quilonum Retard or lithium hydroxide to be raw material, under the prerequisite that guarantees product quality, product yield will be very low.Need regularly the monometallic mother liquor to be handled, if deal with improperly, the mother liquor that gives off will pollute environment.If technical grade Quilonum Retard or the lithium hydroxide back of purifying is used,, product cost is increased owing to limit by the purification process yield.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing monometallic, to overcome the above-mentioned defective that prior art exists.
Method of the present invention comprises the steps:
(1) the raw material Quilonum Retard being added weight concentration is 30～40% phosphate aqueous solution, stirs 15～45 minutes down at 85～95 ℃, and adding weight concentration then and be 12～15% lithium hydroxide solution, to regulate pH be 8～9;
Described raw material Quilonum Retard is a technical grade, and wherein, the weight content of Quilonum Retard is 99.0～99.5, sodium (Na), potassium (K), chlorine root (Cl
-), sulfate radical (SO
4 2-) to wait foreign matter content be 20～1000PPm;
The weight ratio of phosphoric acid and raw material Quilonum Retard is: phosphoric acid: raw material Quilonum Retard=1～1.5: 1;
(2) 85～95 ℃ of following solid-liquid separation, obtain wet Trilithium phosphate, wherein, the weight content of moisture content is 2～10%;
(3) the wet Trilithium phosphate adding weight concentration that step (2) is obtained is 38～42% phosphate aqueous solution, after the dissolving, adds phosphoric acid or Trilithium phosphate again, and transferring pH value of solution is 2～3, filters, and collects the filtrate of containing monometallic;
The weight consumption of described wet Trilithium phosphate be weight concentration be 38～42% phosphate aqueous solution weight 20～25%;
(4) filtrate of containing monometallic with step (3) is heated to 130～135 ℃, evaporation concentration to the weight content of water is 18～20%, be cooled to 30～35 ℃ then, crystallisation by cooling is collected monometallic then, dry, drying temperature is 130～135 ℃, and drying obtains product, and total recovery reaches more than 95%, purity is up to more than 99.9%, sodium in the product (Na), potassium (K), chlorine root (Cl
-), sulfate radical (SO
4 2-) wait foreign matter content to be low to moderate below the 10PPm.
Further, the mother liquor that step obtains can be recycled, and is about to it and returns the initial period of step (4).
Method of the present invention can obtain crystalline product, and reduces product cost, improves product yield, quality.Advantage of the present invention is to produce high yield, high purity, the battery-grade lithium dihydrogen phosphate of lower cost.
Embodiment
The following example is only illustrating the present invention, and does not limit the scope of the invention.
Embodiment 1
Described raw material Quilonum Retard is a technical grade, and wherein, the weight content of Quilonum Retard is 99.0～99.5%, sodium (Na), potassium (K), chlorine root (Cl
-), sulfate radical (SO
4 2-) to wait foreign matter content be 20～1000PPm;
(1) 5M
3Add pure water 3400Kg in the stainless steel cauldron, add food grade phosphoric acid 2000Kg, stir adding technical grade Quilonum Retard 1845Kg down, be heated to 95 ℃ and stirred 30 minutes, with weight concentration is that 15%% lithium hydroxide in industrial grade solution is transferred about pH=8, needs lithium hydroxide 110Kg approximately.
(2) synthetic good Trilithium phosphate carries out solid-liquid separation at 95 ℃, and disengaging time was not less than 30 minutes, obtains Trilithium phosphate wet feed 2095Kg, and moisture is 5.3%, and yield is more than 99%;
When (3) the monometallic mother liquor does not return
3M
3Add pure water 1000L in the reactor of lining teflon material, add phosphatase 11 382Kg, stir adding Trilithium phosphate 692Kg down, treat that Trilithium phosphate dissolves the back fully and transfers pH value of solution=2.53 with phosphoric acid;
Synthetic good monometallic solution filters stand-by with polypropylene sheet frame pressure filter.
When the monometallic mother liquor returns
3M
3Add pure water 750L in the reactor of lining teflon material, add phosphoric acid 675Kg, add monometallic mother liquor 900Kg, stir and add Trilithium phosphate 385Kg down, treat that Trilithium phosphate dissolves the back fully and transfers solution PH=2.56 with phosphoric acid or Trilithium phosphate, synthetic good monometallic solution filters stand-by with polypropylene sheet frame pressure filter.
(4) 3M
3Add in the enamel reaction still and filter good monometallic solution 3565Kg, stir down and boil with being steam heated to, open induced draft fan, vapor pressure is controlled at 0.3Mpa, and the centre is added and filtered good monometallic solution, controls liquid level well, finally being evaporated to solution temperature is 133 ℃, evaporation concentration to the weight content of water is 19.5%, and the monometallic solution that evaporation is good is cooled to below 35 ℃ with recirculated cooling water, separates out monometallic.The good monometallic solution of crystallisation by cooling carries out solid-liquid separation not being higher than under 35 ℃, obtain monometallic wet feed 1346Kg, and output mother liquor 1950Kg, moisture weight content are 1.7%;
At 3M
3Add monometallic wet feed 1363Kg in the enamel Vacuumdrier, open revolution, open vacuum system, open the steam heating material, final drying temperature is 135 ℃, and dryer inner pressure is-0.092Mpa.The monometallic that oven dry is good is cooled under 35 ℃ with recirculated cooling water, obtains the 1340Kg product.
Total recovery reaches more than 95%, adopts the Shanghai City company standard to detect, and monometallic purity is up to more than 99.9%, sodium in the product (Na), potassium (K), chlorine root (Cl
-), sulfate radical (SO
4 2-) wait foreign matter content to be low to moderate below the 10PPm.
Embodiment 2
Adopt the method identical, wherein, in the step (3), transfer pH value of solution=2.57 with Trilithium phosphate with embodiment 1;
Finally obtain the 1360Kg product.
Total recovery reaches more than 95%%, adopts the Shanghai City company standard to detect, and monometallic purity is up to more than 99.9%, sodium in the product (Na), potassium (K), chlorine root (Cl
-), sulfate radical (SO
4 2-) wait foreign matter content to be low to moderate below the 10PPm.
Embodiment 3
Described raw material Quilonum Retard is a technical grade, and wherein, the weight content of Quilonum Retard is 99.0～99.5%, sodium (Na), potassium (K), chlorine root (Cl
-), sulfate radical (SO
4 2-) to wait foreign matter content be 20～1000PPm;
(1) 5M
3Add pure water 3400Kg in the stainless steel cauldron, add food grade phosphoric acid 2020Kg, stir adding technical grade Quilonum Retard 1850Kg down, be heated to 95 ℃ and stirred 30 minutes, with weight concentration is that 15% lithium hydroxide in industrial grade solution is transferred about pH=8, needs lithium hydroxide 111Kg approximately.
(2) synthetic good Trilithium phosphate carries out solid-liquid separation at 95 ℃, and disengaging time was not less than 30 minutes, obtains Trilithium phosphate wet feed 2116Kg, and moisture is 5.25%, weight, and yield is more than 99%;
When (3) the monometallic mother liquor does not return
3M
3Add pure water 1000L in the reactor of lining teflon material, add phosphatase 11 380Kg, stir adding Trilithium phosphate 690Kg down, treat that Trilithium phosphate dissolves the back fully and transfers pH value of solution=2.58 with phosphoric acid;
Synthetic good monometallic solution filters stand-by with polypropylene sheet frame pressure filter.
When the monometallic mother liquor returns
3M
3Add pure water 750L in the reactor of lining teflon material, add phosphoric acid 670Kg, add monometallic mother liquor 900Kg, stir and add Trilithium phosphate 380Kg down, treat that Trilithium phosphate dissolves the back fully and transfers pH value of solution=2.64 with phosphoric acid or Trilithium phosphate, synthetic good monometallic solution filters stand-by with polypropylene sheet frame pressure filter.
(4) 3M
3Add in the enamel reaction still and filter good monometallic solution 3565Kg, stir down and boil with being steam heated to, open induced draft fan, vapor pressure is controlled at 0.3Mpa, and the centre is added and filtered good monometallic solution, controls liquid level well, finally being evaporated to solution temperature is 133 ℃, evaporation concentration to the weight content of water is 18.02%, and the monometallic solution that evaporation is good is cooled to below 35 ℃ with recirculated cooling water, separates out monometallic.The good monometallic solution of crystallisation by cooling carries out solid-liquid separation not being higher than under 35 ℃, obtain monometallic wet feed 1544Kg, and output mother liquor 1875Kg, moisture weight content are 1.74%;
At 3M
3Add monometallic wet feed 1370Kg in the enamel Vacuumdrier, open revolution, open vacuum system, open the steam heating material, final drying temperature is 135 ℃, and dryer inner pressure is-0.092Mpa.The monometallic that oven dry is good is cooled under 35 ℃ with recirculated cooling water, obtains the 1346Kg product.
Total recovery reaches more than 95%, adopts the Shanghai City company standard to detect, and monometallic purity is up to more than 99.9%, sodium in the product (Na), potassium (K), chlorine root (Cl
-), sulfate radical (SO
4 2-) wait foreign matter content to be low to moderate below the 10PPm.
Claims (7)
1. the monometallic preparation method is characterized in that, comprises the steps:
(1) the raw material Quilonum Retard is added phosphate aqueous solution, stirred 15～45 minutes, adding lithium hydroxide solution adjusting pH then is pH=8～9; Described raw material Quilonum Retard is a technical grade;
(2), obtain wet Trilithium phosphate 85～95 ℃ of following solid-liquid separation;
(3) the wet Trilithium phosphate that step (2) is obtained adds phosphate aqueous solution, after the dissolving, adds phosphoric acid or Trilithium phosphate again, and transferring pH value of solution is 2～3, collects the filtrate of containing monometallic;
(4) with the filtrate evaporation concentration that contains monometallic of step (3), crystallisation by cooling is collected monometallic then, and drying obtains product.
2. method according to claim 1, it is characterized in that in the step (1), it is 30～40% phosphate aqueous solution that the raw material Quilonum Retard is added weight concentration, stirred 15～45 minutes down at 85～95 ℃, adding weight concentration then and be 12～15% lithium hydroxide solution, to regulate pH be 8～9.
3. method according to claim 1 is characterized in that, in the described raw material Quilonum Retard, the weight content of Quilonum Retard is 99.0～99.5%, sodium (Na), potassium (K) chlorine root (Cl
-) and sulfate radical (SO
4 2-) foreign matter content is 20～1000PPm.
4. method according to claim 1 is characterized in that, the weight ratio of phosphoric acid and raw material Quilonum Retard is: phosphoric acid: raw material Quilonum Retard=1～1.5: 1.
5. method according to claim 1 is characterized in that, step (2) obtains in the wet Trilithium phosphate, and the weight content of moisture content is 2～10%.
6. method according to claim 1, it is characterized in that, in the step (3), it is 38～42% phosphate aqueous solution that the wet Trilithium phosphate that step (2) is obtained adds weight concentration, the weight consumption of described wet Trilithium phosphate be weight concentration be 38～42% phosphate aqueous solution weight 20～25%.
7. method according to claim 1 is characterized in that, the filtrate of containing monometallic of step (3) is heated to 130～135 ℃, and evaporation concentration to the weight content of water is 18～20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101964380A CN102030319A (en) | 2009-09-25 | 2009-09-25 | Lithium dihydrogen phosphate preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101964380A CN102030319A (en) | 2009-09-25 | 2009-09-25 | Lithium dihydrogen phosphate preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102030319A true CN102030319A (en) | 2011-04-27 |
Family
ID=43883844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101964380A Pending CN102030319A (en) | 2009-09-25 | 2009-09-25 | Lithium dihydrogen phosphate preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102030319A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351160A (en) * | 2011-05-06 | 2012-02-15 | 江西赣锋锂业股份有限公司 | Method for preparing battery grade lithium dihydrogen phosphate with high-purity lithium carbonate lithium depositing mother solution |
| CN104445128A (en) * | 2014-12-23 | 2015-03-25 | 中国地质科学院郑州矿产综合利用研究所 | Preparation method of battery-grade lithium dihydrogen phosphate |
| CN112703260A (en) * | 2018-05-30 | 2021-04-23 | 澳大利亚锂公司 | Method for recovering lithium values |
| CN113044820A (en) * | 2021-04-28 | 2021-06-29 | 四川思特瑞锂业有限公司 | Method for producing battery-grade lithium dihydrogen phosphate from crude lithium salt |
| CN114906828A (en) * | 2022-06-28 | 2022-08-16 | 四川思特瑞锂业有限公司 | Method for treating lithium dihydrogen phosphate mother liquor |
| CN116143091A (en) * | 2022-12-06 | 2023-05-23 | 四川思特瑞锂业有限公司 | Method for producing battery grade lithium dihydrogen phosphate from brine lithium chloride |
-
2009
- 2009-09-25 CN CN2009101964380A patent/CN102030319A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351160A (en) * | 2011-05-06 | 2012-02-15 | 江西赣锋锂业股份有限公司 | Method for preparing battery grade lithium dihydrogen phosphate with high-purity lithium carbonate lithium depositing mother solution |
| CN102351160B (en) * | 2011-05-06 | 2013-10-30 | 江西赣锋锂业股份有限公司 | Method for preparing battery grade lithium dihydrogen phosphate with high-purity lithium carbonate lithium depositing mother solution |
| CN104445128A (en) * | 2014-12-23 | 2015-03-25 | 中国地质科学院郑州矿产综合利用研究所 | Preparation method of battery-grade lithium dihydrogen phosphate |
| CN104445128B (en) * | 2014-12-23 | 2016-08-24 | 中国地质科学院郑州矿产综合利用研究所 | Preparation method of battery-grade lithium dihydrogen phosphate |
| CN112703260A (en) * | 2018-05-30 | 2021-04-23 | 澳大利亚锂公司 | Method for recovering lithium values |
| CN113044820A (en) * | 2021-04-28 | 2021-06-29 | 四川思特瑞锂业有限公司 | Method for producing battery-grade lithium dihydrogen phosphate from crude lithium salt |
| CN114906828A (en) * | 2022-06-28 | 2022-08-16 | 四川思特瑞锂业有限公司 | Method for treating lithium dihydrogen phosphate mother liquor |
| CN116143091A (en) * | 2022-12-06 | 2023-05-23 | 四川思特瑞锂业有限公司 | Method for producing battery grade lithium dihydrogen phosphate from brine lithium chloride |
| CN116143091B (en) * | 2022-12-06 | 2023-09-12 | 四川思特瑞锂业有限公司 | Method for producing battery grade lithium dihydrogen phosphate from brine lithium chloride |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102030319A (en) | Lithium dihydrogen phosphate preparation method | |
| CN109941982B (en) | Purification method of lithium difluorophosphate | |
| CN103400983B (en) | Method for synthesizing nano lithium iron phosphate without water of crystallization through atmospheric water phase | |
| CN113061723A (en) | Method for recovering lithium from waste lithium iron phosphate batteries and preparing iron phosphate | |
| CN109775678A (en) | The method that battery-grade iron phosphate and PHOSPHORIC ACID TECH.GRADE lithium are prepared in waste lithium iron phosphate battery | |
| CN104447564A (en) | Preparation method of high-purity 4,5-dicyano-2-trifluoromethylimidazole and salts thereof | |
| CN111924819A (en) | Method for recycling waste disassembled lithium iron phosphate cathode material | |
| US20240063451A1 (en) | Method for recycling and preparing positive electrode material from waste lithium iron phosphate batteries | |
| WO2013056541A1 (en) | Method for producing lithium iron phosphate by using lithium ore as lithium source | |
| CN100482577C (en) | Preparation for battery level lithium dihydrogen phosphate | |
| CN115304039B (en) | Purification device and method for bis (chlorosulfonyl) imide | |
| CN111268700A (en) | Efficient lithium hexafluorophosphate production method | |
| CN104119243B (en) | A kind of energy-saving clean production method of iminodiethanoic acid | |
| CN113651360A (en) | Synthesis method and application of vanadium oxide | |
| CN109504861B (en) | Method for recycling residual lithium in electrode material reaction mother liquor prepared by hydrothermal method | |
| CN109110774B (en) | Preparation method of lithium tetrafluoroborate | |
| CN216737932U (en) | Electrolytic waste residue and fluorine-containing wastewater treatment device for electrolytic fluorine production process | |
| CN114573006B (en) | Method for purifying and recovering lithium by-product lithium-containing crude sodium sulfate in lithium extraction process of nickel cobalt lithium manganate anode material recovery | |
| CN101830484A (en) | Method for recovering lithium hydroxide from waste filtrate generated in preparation of LiFePO4 material by liquid-phase method | |
| CN102502565B (en) | Preparation method of lithium hexafluorophate | |
| WO2023010973A1 (en) | Method for recovering lithium from waste lithium iron phosphate material | |
| CN112331847B (en) | Method for preparing high-electrochemical-activity lithium iron phosphate positive electrode material by using unqualified lithium iron phosphate positive electrode material | |
| CN108046233A (en) | A kind of preparation method of LiBF4 | |
| CN105859542A (en) | Preparing method for high-purity lithium oxalate | |
| CN110950752A (en) | Preparation method of lithium formate solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110427 |