CN110040750A - A kind of processing method of lithium carbonate mother liquor of precipitation of ammonium - Google Patents
A kind of processing method of lithium carbonate mother liquor of precipitation of ammonium Download PDFInfo
- Publication number
- CN110040750A CN110040750A CN201910341935.9A CN201910341935A CN110040750A CN 110040750 A CN110040750 A CN 110040750A CN 201910341935 A CN201910341935 A CN 201910341935A CN 110040750 A CN110040750 A CN 110040750A
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- mother liquor
- precipitation
- ammonium
- lithium
- lithium carbonate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/06—Sulfates; Sulfites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
Abstract
The present invention provides a kind of processing methods of lithium carbonate mother liquor of precipitation of ammonium, comprising the following steps: 1) sulfuric acid is added and destroys remaining CO in lithium carbonate mother liquor of precipitation of ammonium3 2‑；2) mother liquor of precipitation of ammonium is freezed and sodium sulphate is precipitated and is separated by filtration；3) the mother liquid evaporation concentration after freezing analysis sodium；4) concentrate spray dryer is pumped into be dried and dehydrated；5) sodium sulphate for adding partial freeze to be precipitated in sodium sulphate, potassium sulfate and lithium sulfate that spray dryer obtains, back to adding salt calcining process to carry out potassium, the reuse of sodium and the recycling of lithium.The present invention can all recycle the lithium in mother liquor of precipitation of ammonium, and concentration lithium concentration is high, the rate of recovery nearly 100%.Meanwhile potassium sulfate is recycled with sodium sulphate, is significantly reduced and is added salt calcination process cost.In addition, the terminal being concentrated by evaporation by control, and spray drying is combined, concentration energy consumption is reduced, fouling and the analysis salt stopping state of evaporation and concentration, production run continuous and stable are substantially alleviated.
Description
Technical field
The invention belongs to ores to mention lithium technology field, and in particular to a kind of carbonic acid for lepidolite sulfating roasting technique
The processing method of lithium mother liquor of precipitation of ammonium.
Background technique
Due to the development of electric car, demand of the lithium battery in world market is constantly soaring, also fast to the demand of lithium
Speed is soaring, how to develop and use various lithium resources and prepares lithium carbonate, meets the needs of market is to lithium carbonate, is pendulum in face of us
Urgent task.
Lithium mainly exists in the form of solid mineral resource and two kinds of liquid Mineral resource in nature, solid mineral resource
It is divided into spodumene mineral and lepidolite mineral again.Chinese spodumene mineral resources compare shortage, and lepidolite is but very abundant, Jiangxi Province
Yichun Prefecture's lepidolite reserves are huge, and the reserves (in terms of lithia) of lithium are 257.8 ten thousand tons.
The step for no matter being prepared lithium carbonate using which kind of lithium resource, all can't do without sodium carbonate sinker, there is sinker mother liquor
It needs to handle.The current lithium carbonate production in China is mainly spodumene production technology, and the conventional method of lithium is recycled from sinker mother liquor
It is that removing carbonate first is neutralized to sinker mother liquor with sulfuric acid, concentration analysis then is evaporated to the mother liquor after neutralization again
Anhydrous sodium sulfate solid out, is then isolated removing and obtains the mixed liquor of lithium sulfate and sodium sulphate, and it is molten that sodium carbonate is then added
Lithium carbonate is made in liquid sinker.
Patent CN106882822A " in a kind of sinker mother liquor lithium recycling at battery-level lithium carbonate method ", disclose one kind
The method of sinker disposing mother liquor lithium, first sodium sulphate is precipitated in freezing, is then concentrated by evaporation the mixture that lithium carbonate and sodium sulphate is precipitated,
Then the mixture is carried out washing obtained battery-level lithium carbonate repeatedly, advantage is not have to that sulfuric acid is added to destroy carbonate, does not have to add
Sodium carbonate sinker saves reagent, but that there are the lithium rate of recovery is low, still has part sinker mother liquor to need to recycle, be concentrated by evaporation
Journey is precipitated with lithium carbonate, causes evaporation equipment fouling serious, it is difficult to continuous and steady operation.
Yang Huachun is selected in " research of the comprehensive utilization process of mother liquor containing lithium " text and phosphoric acid is added in lithium carbonate mother liquor, is made
Lithium is precipitated out in the form of lithium phosphate, and gained lithium phosphate product meets YS/T637-2007 " color phosphor lithium phosphate "
Index request.
But lepidolite be raw material prepare lithium carbonate mother liquor of precipitation of ammonium and spodumene mother liquor it is different, containing potassium it is higher,
The potassium content of the especially lithium carbonate mother liquor of precipitation of ammonium of lepidolite sulfating roasting technique is very high, after taking traditional destruction carbonate
The method of concentration will lead to lithium and enter potassium sulfate lithium double salt precipitation and be unable to get enrichment method.
It would therefore be highly desirable to which solving the lithium as caused by potassium content is high in mother liquor of precipitation of ammonium in traditional treatment method loses big, concentration
A large amount of sodium sulphate and potassium sulfate can be precipitated in the not high disadvantage of lithium concentration and concentration process, lead to evaporation concentration equipment knot
The problems such as dirt blocking.
Summary of the invention
The main object of the present invention is to provide a kind of processing method for being concisely and efficiently lepidolite lithium carbonate mother liquor of precipitation of ammonium, especially
It is the processing for the lithium carbonate mother liquor of precipitation of ammonium of lepidolite sulfating roasting technique, and effect is more preferable.
The technical solution used in the present invention are as follows:
A kind of processing method of lithium carbonate mother liquor of precipitation of ammonium, comprising the following steps:
1) sulfuric acid is added and destroys remaining CO in lithium carbonate mother liquor of precipitation of ammonium3 2-；
2) mother liquor of precipitation of ammonium is freezed and sodium sulphate is precipitated and is separated by filtration；
3) the mother liquid evaporation concentration after freezing analysis sodium；
4) concentrate is dried and dehydrated；
5) sodium sulphate that sodium sulphate, potassium sulfate and the lithium sulfate and partial freeze obtained drying and dehydrating is precipitated returns
Potassium, the reuse of sodium and the recycling of lithium are carried out to lepidolite plus salt calcining process.
Wherein, step 1) control endpoint pH is 7.5~8.0.
The cryogenic temperature of step 2) is 0 DEG C~5 DEG C.
The terminal point control of the evaporation and concentration of step 3) has just been precipitated there is sodium sulphate with potassium sulfate.
Step 4) is dehydrated by the way of spray drying, and drying temperature is 100 DEG C~150 DEG C.
It is obtained by the present invention to have the beneficial effect that
1) lithium in mother liquor of precipitation of ammonium is all recycled, and concentration lithium concentration is high, the rate of recovery nearly 100%.
2) potassium sulfate is recycled with sodium sulphate, is significantly reduced and is added salt calcination process cost.
3) terminal being concentrated by evaporation by control, and spray drying is combined, concentration energy consumption is reduced, evaporation is substantially alleviated
The fouling of concentration and analysis salt stopping state, production run continuous and stable.
Detailed description of the invention
Fig. 1 is the processing method process flow chart of lithium carbonate mother liquor of precipitation of ammonium.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
As shown in Figure 1, being especially suitable for the present invention provides a kind of processing method for being concisely and efficiently lithium carbonate mother liquor of precipitation of ammonium
The processing of the lithium carbonate mother liquor of precipitation of ammonium of lepidolite sulfating roasting technique.
Technical scheme is as follows:
A kind of processing method of lithium carbonate mother liquor of precipitation of ammonium, comprising the following steps:
1) sulfuric acid is added and destroys remaining CO in lithium carbonate mother liquor of precipitation of ammonium3 2-；
2) mother liquor of precipitation of ammonium is freezed and sodium sulphate is precipitated and is separated by filtration；
3) the mother liquid evaporation concentration after freezing analysis sodium；
4) concentrate is dried and dehydrated；
5) sodium sulphate that sodium sulphate, potassium sulfate and the lithium sulfate and partial freeze obtained drying and dehydrating is precipitated returns
Potassium, the reuse of sodium and the recycling of lithium are carried out to lepidolite plus salt calcining process.
Wherein, step 1) control endpoint pH is 7.5~8.0.
The cryogenic temperature of step 2) is 0 DEG C~5 DEG C.
The terminal point control of the evaporation and concentration of step 3) has just been precipitated there is sodium sulphate with potassium sulfate.
Step 4) is dehydrated by the way of spray drying, and drying temperature is 100 DEG C~150 DEG C.
It is illustrated below by two embodiments.
Certain lepidolite sulfating roasting technique lithium carbonate mother liquor of precipitation of ammonium composition is as shown in table 1:
1 lithium carbonate mother liquor of precipitation of ammonium ingredient of table
| Ingredient | Li | Na2SO4 | K2SO4 | pH |
| Content g/L | 2.6 | 182.5 | 65.4 | 9.6 |
Embodiment one
The lithium carbonate mother liquor of precipitation of ammonium in 1000ml table 1 is measured, is operated as follows:
1. the concentrated sulfuric acid, which is added, destroys remaining CO in lithium carbonate mother liquor of precipitation of ammonium3 2-, endpoint pH 8.0；
Sodium sulphate and be separated by filtration 2. mother liquor of precipitation of ammonium is freezed to be precipitated, cryogenic temperature is 5 DEG C, obtain 855ml mother liquor and
232.4g Na2SO4·10H2O；
3. in beaker to freezing analyse sodium after mother liquid evaporation be concentrated, be concentrated to volume be 300ml when, have a small amount of sulfate
Crystal is precipitated；
Be dried and dehydrated 4. the beaker for filling concentrate is put into baking oven, 105 DEG C of drying temperature, obtain potassium sulfate,
The salt-mixture of sodium sulphate and lithium sulfate, wherein sulfur acid potassium 65g, sodium sulphate 82g, lithium sulfate 13g；
5. the sodium sulphate that the whole sodium sulphate being finally dried to obtain, potassium sulfate and lithium sulfate salt-mixture and freezing are precipitated,
And part of sulfuric acid potassium is supplemented, add salt to roast back to lepidolite, lithium is recycled from the leachate of roasting material.
Embodiment two
Take 10m in table 13Lithium carbonate mother liquor of precipitation of ammonium, operated as follows:
1. the concentrated sulfuric acid, which is added, destroys remaining CO in lithium carbonate mother liquor of precipitation of ammonium3 2-, endpoint pH 7.5；
Sodium sulphate is precipitated and is separated by filtration 2. mother liquor of precipitation of ammonium is freezed, cryogenic temperature is 0 DEG C, obtains 8.4m3Mother liquor and
2534kg Na2SO4·10H2O；
3. analysing the mother liquid evaporation after sodium to freezing in MVR to be concentrated, being concentrated to volume is 2.7m3When, there is a small amount of sulfate
Crystal is precipitated；
It is dried and dehydrated 4. concentrate is pumped into spray dryer, 150 DEG C of drying temperature, obtains potassium sulfate, sulfuric acid
The salt-mixture of sodium and lithium sulfate, wherein sulfur acid potassium 646kg, sodium sulphate 785kg, lithium sulfate 131kg；
5. the sodium sulphate that whole sodium sulphate, potassium sulfate and lithium sulfate salt-mixture and freezing that spray drying is obtained are precipitated,
And part of sulfuric acid potassium is supplemented, add salt to roast back to lepidolite, lithium is recycled from the leachate of roasting material.
Claims (6)
1. a kind of processing method of lithium carbonate mother liquor of precipitation of ammonium, it is characterised in that: the following steps are included:
1) sulfuric acid is added and destroys remaining CO in lithium carbonate mother liquor of precipitation of ammonium3 2-；
2) mother liquor of precipitation of ammonium is freezed and sodium sulphate is precipitated and is separated by filtration；
3) the mother liquid evaporation concentration after freezing analysis sodium；
4) concentrate is dried and dehydrated；
5) sodium sulphate that sodium sulphate, potassium sulfate and the lithium sulfate and partial freeze obtained drying and dehydrating is precipitated returns to lithium
Mica adds salt calcining process to carry out potassium, the reuse of sodium and the recycling of lithium.
2. the processing method of lithium carbonate mother liquor of precipitation of ammonium as described in claim 1, it is characterised in that: the step 1) controls terminal
PH value is 7.5~8.0.
3. the processing method of lithium carbonate mother liquor of precipitation of ammonium as described in claim 1, it is characterised in that: the freezing temperature of the step 2)
Degree is 0 DEG C~5 DEG C.
4. the processing method of lithium carbonate mother liquor of precipitation of ammonium as described in claim 1, it is characterised in that: the evaporation of the step 3) is dense
The terminal point control of contracting has just been precipitated there is sodium sulphate with potassium sulfate.
5. the processing method of lithium carbonate mother liquor of precipitation of ammonium as described in claim 1, it is characterised in that: the step 4) is using spraying
Dry mode is dehydrated.
6. the processing method of lithium carbonate mother liquor of precipitation of ammonium as claimed in claim 1 or 5, it is characterised in that: the step 4) is done
Dry temperature is 100 DEG C~150 DEG C.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110923452A (en) * | 2019-11-11 | 2020-03-27 | 中南大学 | Process for recovering potassium and sodium salts from lithium-precipitated liquid of lepidolite by using ethanol |
| CN112978769A (en) * | 2021-05-08 | 2021-06-18 | 雅化锂业(雅安)有限公司 | Method for removing potassium from anhydrous sodium sulfate in lithium hydroxide production |
| CN113636578A (en) * | 2021-09-10 | 2021-11-12 | 宜春银锂新能源有限责任公司 | Process for preparing lithium carbonate from lepidolite to improve quality |
| CN114655970A (en) * | 2022-03-31 | 2022-06-24 | 神华准能资源综合开发有限公司 | Method for preparing lithium carbonate from scale evaporation mother liquor |
| CN115536046A (en) * | 2022-11-07 | 2022-12-30 | 广东邦普循环科技有限公司 | Method for co-producing lithium carbonate and lithium hydroxide by lithium-containing solution |
| GB2608460A (en) * | 2021-07-02 | 2023-01-04 | British Lithium Ltd | Process for the recovery and reuse of sulphate reagents from brines derived from lithium micas |
| CN117303415A (en) * | 2023-11-30 | 2023-12-29 | 常州中源工程技术有限公司 | Technology for preparing lithium carbonate from water leaching solution after lepidolite roasting |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110923452A (en) * | 2019-11-11 | 2020-03-27 | 中南大学 | Process for recovering potassium and sodium salts from lithium-precipitated liquid of lepidolite by using ethanol |
| CN112978769A (en) * | 2021-05-08 | 2021-06-18 | 雅化锂业(雅安)有限公司 | Method for removing potassium from anhydrous sodium sulfate in lithium hydroxide production |
| GB2608460A (en) * | 2021-07-02 | 2023-01-04 | British Lithium Ltd | Process for the recovery and reuse of sulphate reagents from brines derived from lithium micas |
| CN113636578A (en) * | 2021-09-10 | 2021-11-12 | 宜春银锂新能源有限责任公司 | Process for preparing lithium carbonate from lepidolite to improve quality |
| CN114655970A (en) * | 2022-03-31 | 2022-06-24 | 神华准能资源综合开发有限公司 | Method for preparing lithium carbonate from scale evaporation mother liquor |
| CN114655970B (en) * | 2022-03-31 | 2023-11-24 | 神华准能资源综合开发有限公司 | Method for preparing lithium carbonate from scale steaming mother liquor |
| CN115536046A (en) * | 2022-11-07 | 2022-12-30 | 广东邦普循环科技有限公司 | Method for co-producing lithium carbonate and lithium hydroxide by lithium-containing solution |
| CN117303415A (en) * | 2023-11-30 | 2023-12-29 | 常州中源工程技术有限公司 | Technology for preparing lithium carbonate from water leaching solution after lepidolite roasting |
| CN117303415B (en) * | 2023-11-30 | 2024-03-12 | 常州中源工程技术有限公司 | Technology for preparing lithium carbonate from water leaching solution after lepidolite roasting |
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