CN108862335A - A method of lithium carbonate is prepared with lithium phosphate - Google Patents
A method of lithium carbonate is prepared with lithium phosphate Download PDFInfo
- Publication number
- CN108862335A CN108862335A CN201810804655.2A CN201810804655A CN108862335A CN 108862335 A CN108862335 A CN 108862335A CN 201810804655 A CN201810804655 A CN 201810804655A CN 108862335 A CN108862335 A CN 108862335A
- Authority
- CN
- China
- Prior art keywords
- lithium
- phosphate
- acid
- carbonate
- salts
- 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.)
- Granted
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a kind of methods for preparing lithium carbonate with lithium phosphate, include the following steps：Lithium phosphate is dissolved in acid, lithium dihydrogen phosphate and lithium salts are generated；Evaporate, isolate the lithium salts of crystallization；Adjust pH value to alkalescent after the lithium salts is dissolved in water, filtering and impurity removing obtains high-purity lithium salt solution；Soda ash is added in high-purity lithium salt solution, lithium carbonate is obtained after filtration washing.The present invention utilizes lithium dihydrogen phosphate and other soluble lithium salt dissolubility differences, dexterously realize the separation of lithium salts and phosphate radical, high added value raw material are not used in process, and the lithium rate of recovery reaches 98.5% or more, and producer's use of production lithium phosphate waste material can be provided by abandoning the sodium phosphate that liquid processing generates.Present invention process is practical, and the rate of recovery is high, and processing cost is low, and process is substantially totally-enclosed, the lithium carbonate product of available high-quality.
Description
Technical field
The present invention relates to lithium carbonate preparation fields, and in particular to a method of lithium carbonate is prepared with lithium phosphate.
Background technique
The lithium salts that concentration for the treatment of is lower at present or soluble impurity is more, what is most frequently used is exactly that sodium phosphate production is added
The method of the extremely low lithium phosphate of solubility, the lithium phosphate obtained in this way can not be used directly as raw material or product, can not
It is purified by simple method, along with the use scope of lithium phosphate is extremely narrow, therefore research converts it to common carbon
The technique of sour lithium provides more cost-effective method for lithium salts recycling and has a very important significance.
After prior art report dissolves lithium phosphate, phosphate radical is removed with calcium, but lithium phosphate solubility is smaller than calcium phosphate,
It can not be achieved at all；There are also after dissolving lithium phosphate, it directly is settled out lithium carbonate with sodium carbonate, but the solubility of lithium carbonate is remote
Much larger than lithium phosphate, lithium phosphate will be settled out again in this way.Therefore carbon is converted by lithium phosphate there is presently no effective
The method of sour lithium.
Summary of the invention
The object of the present invention is to provide a kind of methods for preparing lithium carbonate with lithium phosphate, to solve on existing for background technique
State defect.
The present invention realizes by the following technical solutions：
A method of lithium carbonate being prepared with lithium phosphate, is included the following steps：
Lithium phosphate is dissolved in acid by step 1, generates lithium dihydrogen phosphate and lithium salts；
The lithium salts of crystallization is evaporated, isolated to step 2；
Step 3 adjusts pH value to alkalescent after the lithium salts is dissolved in water, and filtering and impurity removing obtains high-purity lithium salt solution；
Step 4 is added soda ash in high-purity lithium salt solution, lithium carbonate is obtained after filtration washing.
In step 1, the acid can be inorganic acid, be also possible to organic acid, and sulfuric acid, hydrochloric acid, nitric acid may be selected in inorganic acid
Deng organic acid can be acetic acid etc., preferably inorganic acid, more preferably sulfuric acid.Furthermore, it should be ensured that lithium phosphate is completely dissolved
Afterwards, pH value of solution is acidity.
Preferably, evaporation, separation temperature are -20 DEG C~30 DEG C in step 2.
Preferably, with sodium hydroxide tune pH value to 7.5-9 after lithium salts being dissolved in step 3.
The washing lotion that filtration washing step described in step 4 generates as a preferred technical solution, is circularly used for step 1
In the dilution of middle acid, step 3 in the dissolution or step 4 of lithium salts soda ash dissolution.
As further preferred technical solution, produced after the crystalline mother solution and step 4 precipitation reaction after step 2 is separated
Raw mother liquor mixing, adjusts pH to 7.5-9 with sodium hydroxide, converts lithium phosphate for lithium dihydrogen phosphate and is recycled.
Lithium phosphate does not almost dissolve in water, and solubility is only more slightly larger than barium phosphate in all common phosphate, and barium
With very big toxicity, a large amount of use is economically also uneconomical, therefore technological difficulties are how to remove phosphate radical.
The principle of the invention is that lithium phosphate is dissolved in diluted acid (below by taking sulfuric acid as an example), generates lithium dihydrogen phosphate and sulfuric acid
The mixture (reaction process is as shown in formula one) of lithium, since lithium dihydrogen phosphate solubility is higher, and lithium sulfate solubility is lower, and
And lithium sulfate solubility with temperature increases the characteristics of decline, and utilizes the concentration and poor solubility of lithium dihydrogen phosphate and lithium sulfate
It is different, evaporate, isolate crystallization single water lithium sulfate (other lithium salts, as lithium chloride, lithium nitrate, lithium acetate at the same temperature
Solubility is below lithium dihydrogen phosphate, is separated based on identical principle)；With sodium hydroxide tune pH after the lithium sulfate is dissolved
To alkalescence, the phosphate impurities of generation are filtered to remove, lithium sulfate solution are precipitated by common soda ash, washing methods obtains carbon
Sour lithium (reaction process is as shown in formula two)；After the mother liquor hybrid reaction generated after mother liquor and precipitation reaction after evaporation, hydrogen-oxygen is used
Change sodium tune pH to alkalescence, converts lithium phosphate for lithium and come back to above-mentioned removal process (four institute of reaction process such as formula three and formula
Show).
Fundamental reaction formula is as follows：
Li3PO4+H2SO4+H2O→LiH2PO4+Li2SO4(formula one)
Li2SO4+Na2CO3→Li2CO3↓+Na2SO4(formula two)
3LiH2PO4+6NaOH→Li3PO4↓+Na3PO4+6H2O (formula three)
Li2SO4+LiH2PO4+NaOH→Li3PO4↓+Na2SO4+H2O (formula four)
Present invention utilizes lithium dihydrogen phosphate dissolubilities, and concentration and dissolubility difference with other lithium salts, dexterously
The separation of other soluble lithium salts and phosphate radical is realized, high added value raw material are not used in process, and the lithium rate of recovery reaches
98.5% or more, abandoning the sodium phosphate that liquid processing generates can be used for precipitate phosphoric acid lithium, and the producer for providing production lithium phosphate waste material makes
With, since the lithium sulfate solution that processing obtains is much purer than the lithium sulfate that usual ore treatment obtains, the carbon that the later period obtains
Sour lithium quality is just corresponding preferable.Present invention process is practical, and the rate of recovery is high, and processing cost is low, and process is substantially totally-enclosed, can be with
Obtain lithium carbonate product more better than quality in the market.
Detailed description of the invention
Fig. 1 is the process flow chart of one embodiment of the invention.
Specific embodiment
The present invention is illustrated below by specific embodiment, but is not intended to limit the present invention.
Embodiment 1：
Entire technical process is as shown in Figure 1, include the following steps：
1, washing raw phosphoric acid lithium is stand-by, liquid-solid ratio 3：1；
2, sulfuric acid is added in acid-resistant reacting kettle, is diluted to 20% concentration with the washing lotion of step 6；
3, the lithium phosphate after washing is added, it is ensured that after being completely dissolved, solution PH is acidity；
4, it is concentrated by evaporation the solution, crystallization obtains single water lithium sulfate, and solid-liquor separation temperature is -20 DEG C~30 DEG C, lithium sulfate
It is smaller in high-temperature digestion degree, and lithium dihydrogen phosphate high-temperature digestion degree is big, therefore selects higher temperature separation；
5, after the lithium sulfate dissolution isolated, with sodium hydroxide tune PH to alkalescence (7.5-9), with lithium sulfate coprecipitation
Lithium dihydrogen phosphate out will precipitate into lithium phosphate, the impurity such as calcium and magnesium also can coprecipitation remove, just obtained after filtering pure
Lithium sulfate solution；
6, lithium sulfate solution is precipitated as lithium carbonate with sodium carbonate, and lithium carbonate product is obtained after washing, and (washing lotion is in step 2
Complex acid and dissolution sodium carbonate).
7, the mother liquor generated in step 6 sodium carbonate depositing technology and the crystalline mother solution hybrid reaction generated in step 4 are necessary
When be added sodium hydroxide adjust PH to alkalescence (7.5-9), lithium dihydrogen phosphate is precipitated as again lithium phosphate be recycled, process
Only produce abandoning liquid when crystalline mother solution recycling, in the solution, since lithium phosphate solubility is extremely low, the loss of total lithium less than
1%.
Embodiment 2：
Entire technical process includes the following steps：
1, washing raw phosphoric acid lithium is stand-by, liquid-solid ratio 10：1；
2, hydrochloric acid is added in acid-resistant reacting kettle, is diluted to 30% concentration with the washing lotion of step 6；
3, the lithium phosphate after washing is added, it is ensured that after being completely dissolved, solution PH is acidity；
4, it is concentrated by evaporation the solution, crystallization obtains lithium chloride, and solid-liquor separation temperature is -20 DEG C~30 DEG C；
5, after the lithium chloride dissolution isolated, with sodium hydroxide tune PH to alkalescence (7.5-9), with lithium chloride coprecipitation
Lithium dihydrogen phosphate out will precipitate into lithium phosphate, the impurity such as calcium and magnesium also can coprecipitation remove, just obtained after filtering pure
Lithium chloride solution；
6, lithium chloride solution is precipitated as lithium carbonate with sodium carbonate, and lithium carbonate product is obtained after washing, and (washing lotion is in step 2
Complex acid and dissolution sodium carbonate).
7, the mother liquor generated in step 6 sodium carbonate depositing technology and the crystalline mother solution hybrid reaction generated in step 4 are necessary
When be added sodium hydroxide adjust PH to alkalescence (7.5-9), lithium dihydrogen phosphate is precipitated as again lithium phosphate be recycled, process
Only produce abandoning liquid when crystalline mother solution recycling, in the solution, since lithium phosphate solubility is extremely low, the loss of total lithium less than
1%.
Embodiment 3：
Entire technical process includes the following steps：
1, washing raw phosphoric acid lithium is stand-by, liquid-solid ratio 15：1；
2, nitric acid is added in acid-resistant reacting kettle, is diluted to 40% concentration with the washing lotion of step 6；
3, the lithium phosphate after washing is added, it is ensured that after being completely dissolved, solution PH is acidity；
4, it is concentrated by evaporation the solution, crystallization obtains lithium nitrate, and solid-liquor separation temperature is -20 DEG C~30 DEG C；
5, after the lithium nitrate dissolution isolated, with sodium hydroxide tune PH to alkalescence (7.5-9), with lithium nitrate coprecipitation
Lithium dihydrogen phosphate out will precipitate into lithium phosphate, the impurity such as calcium and magnesium also can coprecipitation remove, just obtained after filtering pure
Lithium nitrate solution；
6, lithium nitrate solution is precipitated as lithium carbonate with sodium carbonate, and lithium carbonate product is obtained after washing, and (washing lotion is in step 2
Complex acid and dissolution sodium carbonate).
7, the mother liquor generated in step 6 sodium carbonate depositing technology and the crystalline mother solution hybrid reaction generated in step 4 are necessary
When be added sodium hydroxide adjust PH to alkalescence (7.5-9), lithium dihydrogen phosphate is precipitated as again lithium phosphate be recycled, process
Only produce abandoning liquid when crystalline mother solution recycling, in the solution, since lithium phosphate solubility is extremely low, the loss of total lithium less than
1%.
Embodiment 4：
Entire technical process includes the following steps：
1, washing raw phosphoric acid lithium is stand-by, liquid-solid ratio 20：1；
2, acetic acid is added in acid-resistant reacting kettle, is diluted to 50% concentration with the washing lotion of step 6；
3, the lithium phosphate after washing is added, it is ensured that after being completely dissolved, solution PH is acidity；
4, it is concentrated by evaporation the solution, crystallization obtains lithium acetate, and solid-liquor separation temperature is 0 DEG C~30 DEG C；
5, after the lithium acetate dissolution isolated, with sodium hydroxide tune PH to alkalescence (7.5-9), with lithium acetate coprecipitation
Lithium dihydrogen phosphate out will precipitate into lithium phosphate, the impurity such as calcium and magnesium also can coprecipitation remove, just obtained after filtering pure
Lithium acetate solution；
6, lithium acetate solution is precipitated as lithium carbonate with sodium carbonate, and lithium carbonate product is obtained after washing, and (washing lotion is in step 2
Complex acid and dissolution sodium carbonate).
7, the mother liquor generated in step 6 sodium carbonate depositing technology and the crystalline mother solution hybrid reaction generated in step 4 are necessary
When be added sodium hydroxide adjust PH to alkalescence (7.5-9), lithium dihydrogen phosphate is precipitated as again lithium phosphate be recycled, process
Only produce abandoning liquid when crystalline mother solution recycling, in the solution, since lithium phosphate solubility is extremely low, the loss of total lithium less than
1%.
High added value raw material are not used during present invention process, the lithium rate of recovery reaches 98.5% or more, abandons liquid processing
The sodium phosphate of generation can be used for precipitate phosphoric acid lithium, and the producer for providing production lithium phosphate waste material uses.
The above shows and describes the basic principle, main features and advantages of the invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (9)
1. a kind of method for preparing lithium carbonate with lithium phosphate, which is characterized in that include the following steps：
Lithium phosphate is dissolved in acid by step 1, generates lithium dihydrogen phosphate and lithium salts；
The lithium salts of crystallization is evaporated, isolated to step 2；
Step 3 adjusts pH value to alkalescent after the lithium salts is dissolved in water, and filtering and impurity removing obtains high-purity lithium salt solution；
Step 4 is added soda ash in high-purity lithium salt solution, lithium carbonate is obtained after filtration washing.
2. the method as described in claim 1, which is characterized in that in step 1, the acid is selected from inorganic acid or organic acid.
3. method according to claim 2, which is characterized in that the inorganic acid is selected from sulfuric acid, hydrochloric acid or nitric acid.
4. method according to claim 2, which is characterized in that the organic acid is acetic acid.
5. the method as described in claim 1, which is characterized in that in step 1, the acid is sulfuric acid.
6. the method as described in claim 1, which is characterized in that evaporation, separation temperature are -20 DEG C~30 DEG C in step 2.
7. the method as described in claim 1, which is characterized in that after dissolving lithium salts in step 3 extremely with sodium hydroxide tune pH value
7.5-9。
8. the method as described in claim 1, which is characterized in that the washing lotion that filtration washing step described in step 4 generates can be followed
Dissolution of the ring for soda ash in the dissolution or step 4 of lithium salts in dilution sour in step 1, step 3.
9. the method as described in claim 1, which is characterized in that the crystalline mother solution and step 4 precipitating after separating step 2 are anti-
The mother liquor mixing that should be generated afterwards, adjusts pH to 7.5-9 with sodium hydroxide, converts lithium phosphate for lithium dihydrogen phosphate and is recycled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810804655.2A CN108862335B (en) | 2018-07-20 | 2018-07-20 | Method for preparing lithium carbonate from lithium phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810804655.2A CN108862335B (en) | 2018-07-20 | 2018-07-20 | Method for preparing lithium carbonate from lithium phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108862335A true CN108862335A (en) | 2018-11-23 |
| CN108862335B CN108862335B (en) | 2021-04-23 |
Family
ID=64303751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810804655.2A Active CN108862335B (en) | 2018-07-20 | 2018-07-20 | Method for preparing lithium carbonate from lithium phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108862335B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110127731A (en) * | 2019-05-15 | 2019-08-16 | 上海中锂实业有限公司 | A method of battery-level lithium carbonate is directly prepared by lithium phosphate |
| CN110316747A (en) * | 2019-07-25 | 2019-10-11 | 湖南邦普循环科技有限公司 | A method of synthetical recovery lithium and phosphorus from lithium phosphate |
| CN110759364A (en) * | 2019-11-13 | 2020-02-07 | 江西金辉锂业有限公司 | Method for preparing high-purity lithium carbonate by using crude lithium phosphate |
| 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 |
| CN114751432A (en) * | 2022-03-18 | 2022-07-15 | 瑜华科技(上海)有限公司 | Process method for preparing lithium hydroxide by using lithium phosphate |
| 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 |
| US11973225B2 (en) * | 2022-10-04 | 2024-04-30 | Rivian Ip Holdings, Llc | Lithium metal phosphate electrode manufacturing |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106241838A (en) * | 2016-08-15 | 2016-12-21 | 孙东江 | Lithium carbonate technique produced by lithium phosphate |
-
2018
- 2018-07-20 CN CN201810804655.2A patent/CN108862335B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106241838A (en) * | 2016-08-15 | 2016-12-21 | 孙东江 | Lithium carbonate technique produced by lithium phosphate |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110127731A (en) * | 2019-05-15 | 2019-08-16 | 上海中锂实业有限公司 | A method of battery-level lithium carbonate is directly prepared by lithium phosphate |
| CN110316747A (en) * | 2019-07-25 | 2019-10-11 | 湖南邦普循环科技有限公司 | A method of synthetical recovery lithium and phosphorus from lithium phosphate |
| CN110316747B (en) * | 2019-07-25 | 2022-03-11 | 湖南邦普循环科技有限公司 | Method for comprehensively recovering lithium and phosphorus from lithium phosphate |
| CN110759364A (en) * | 2019-11-13 | 2020-02-07 | 江西金辉锂业有限公司 | Method for preparing high-purity lithium carbonate by using crude lithium phosphate |
| 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 |
| CN114751432A (en) * | 2022-03-18 | 2022-07-15 | 瑜华科技(上海)有限公司 | Process method for preparing lithium hydroxide by using lithium phosphate |
| 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 |
| US11973225B2 (en) * | 2022-10-04 | 2024-04-30 | Rivian Ip Holdings, Llc | Lithium metal phosphate electrode manufacturing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108862335B (en) | 2021-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108862335A (en) | A method of lithium carbonate is prepared with lithium phosphate | |
| CN111057848A (en) | Method for extracting lithium from lithium-containing solution by solvent extraction | |
| CN103979590B (en) | A kind of method preparing high purity crystalline aluminum chloride | |
| US2608465A (en) | Process of producing lithium sulfate from lithium phosphates | |
| CN109516479B (en) | Preparation method of battery-grade lithium hydroxide | |
| KR102085016B1 (en) | Purification of lithium carbonate by removing sulfate ion impurities | |
| CN111960445A (en) | Method for preparing battery-grade lithium carbonate by using lithium sulfate coarse ore and recycling by-products | |
| WO2022094696A1 (en) | Process for the production of lithium hydroxide | |
| JP6926010B2 (en) | Method for producing lithium hydroxide | |
| WO2023169432A1 (en) | Method and system for preparing battery-grade lithium hydroxide and lithium carbonate | |
| CN111235591B (en) | Method for preparing lithium hydroxide monohydrate from spodumene sulfuric acid leaching solution | |
| JP2022186836A (en) | Production method of high-purity lithium salt aqueous solution | |
| CN102167369B (en) | Method for reducing content of NaCl in LiCl | |
| CN109022784B (en) | Method for removing bismuth, arsenic and antimony from copper electrolyte | |
| CN111908510B (en) | Preparation method of high-purity manganese sulfate | |
| KR101973475B1 (en) | Manufacturing Method of Controlling Size and High Purity Lithium Carbonate Using Lithium Sulfate and Low Purity Barium Hydroxide | |
| CN115010176B (en) | Preparation method of high-purity vanadium pentoxide | |
| 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 | |
| CN109534369A (en) | A kind of film is integrated to prepare lithium chloride device and method thereof | |
| CN101746782A (en) | Method for removing SO4<-2> in brine | |
| US3172830A (en) | Koh ore | |
| JP7385976B1 (en) | Method for recovering lithium from aqueous liquids containing lithium salts | |
| CN114959306B (en) | Method for recycling lithium from lithium precipitation mother liquor by closed cycle method | |
| US20240092654A1 (en) | Process for the purification of manganese sulfate solutions and subsequent crystallization of high purity manganese sulfate monohydrate | |
| CN115818605A (en) | Iron phosphate dihydrate, preparation method thereof and preparation method of lithium iron phosphate cathode material |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |