CN115536047A - Method for preparing lithium carbonate by using lithium-containing wastewater - Google Patents
Method for preparing lithium carbonate by using lithium-containing wastewater Download PDFInfo
- Publication number
- CN115536047A CN115536047A CN202211415618.5A CN202211415618A CN115536047A CN 115536047 A CN115536047 A CN 115536047A CN 202211415618 A CN202211415618 A CN 202211415618A CN 115536047 A CN115536047 A CN 115536047A
- Authority
- CN
- China
- Prior art keywords
- lithium
- carbonate
- roasting
- reaction
- filtering
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for preparing lithium carbonate by using lithium-containing wastewater. The method comprises the following steps: s1, a step: spray roasting, namely spray roasting the lithium-containing wastewater to obtain a lithium-containing precipitate, wherein the roasting temperature is 450-900 ℃; and S2, a step: a water leaching step, mixing water with the lithium-containing precipitate, and filtering to obtain a first lithium-enriched solution; and S3, a step: a deep impurity removal step, namely adding phosphate into the first lithium enrichment solution for reaction, and filtering to obtain a second lithium enrichment solution; and S4, a step: and adding carbonate into the second lithium enrichment solution for reaction, and filtering to obtain lithium carbonate. By adopting the method provided by the application to extract the lithium carbonate from the lithium-containing wastewater, higher extraction rate and purity can be obtained. In addition, the method extracts valuable element lithium in the industrial wastewater, has the effect of waste resource utilization, and plays a good demonstration role in improving the value of bulk solid waste of the fly ash and resource utilization.
Description
Technical Field
The invention relates to the technical field of trace metal lithium recovery, in particular to a method for preparing lithium carbonate by using waste water from the production of alumina by fly ash, and more particularly relates to a method for preparing lithium carbonate by using waste water from the production of alumina by a fly ash acid method.
Background
The valuable element content in the inorganic components of the quasi-Gelle area coal is high, wherein the alumina content is more than 50 percent, and the lithium content is more than 300mg/Kg, which exceeds the utilization grade (120.00 mg/Kg) of associated lithium ores in coal in China, and the quasi-Gelle area coal has great development and utilization values. In the process of producing alumina by an acid method, lithium element is enriched in aluminum extraction wastewater. The main element content in the wastewater is 1.2g/L of aluminum ions, 7.7g/L of calcium ions, 0.48g/L of magnesium ions, 1.30g/L of potassium ions, 0.8g/L of sodium ions and 0.01g/L, pH of lithium ions, the value is 5, the concentration of chloride ions is 0.4mol/L, wherein the molar ratio of Mg/Li is about 5, and the wastewater belongs to a high-quality resource with low magnesium-lithium ratio. In conclusion, the aluminum and lithium are extracted from the fly ash in a grading manner, so that the gap of the market with large demand on aluminum and lithium resources is hopeful to be filled, and the method has important significance on the resource utilization and the environmental protection of the fly ash.
Lithium metal and related compounds are widely applied to the aspects of metallurgy, fuel, nuclear device coolant, lithium battery, lubricant, aviation material, semiconductor, glass and the like, and are important metal elements for the scientific and technological development of the new century. The traditional extraction of lithium products mainly focuses on pegmatite salt mine and salt lake extraction of lithium. The global lithium mine is mainly concentrated in the countries of intelligence, argentina and the like, while the resources of salt lakes and lithium mines in China are limited and mainly distributed in northwest, wherein the molar ratio of Mg/Li in the salt lakes is between 60 and 90, and the extraction difficulty is high. The global lithium demand reaches 6000 tons every year, and the production capacity of the metallic lithium only accounts for about one half of the global demand. Therefore, developing a new lithium extraction technology and searching a new mineral source have great economic value, and are problems to be solved urgently in China.
Disclosure of Invention
The invention mainly aims to provide a method for preparing lithium carbonate by using lithium-containing wastewater so as to solve the problems of lithium resource shortage and high lithium extraction difficulty in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing lithium carbonate using lithium-containing wastewater, comprising the steps of: s1, a step: spray roasting, namely spray roasting the lithium-containing wastewater to obtain a lithium-containing precipitate, wherein the roasting temperature is 450-900 ℃; s2, a step: a water leaching step, mixing water with the lithium-containing precipitate, and filtering to obtain a first lithium-enriched solution; and S3, a step: a deep impurity removal step, namely adding phosphate into the first lithium enrichment solution for reaction, and filtering to obtain a second lithium enrichment solution; and S4, a step: and adding carbonate into the second lithium enrichment solution for reaction, and filtering to obtain lithium carbonate.
Further, in the method, the lithium-containing wastewater is wastewater from the production of alumina from fly ash.
Further, in the method, in the step S1, the roasting temperature is 600-850 ℃, and the roasting time is 1-5 h.
Further, in the above method, before the spray roasting step, the method further comprises an evaporation concentration step of evaporating and concentrating the lithium containing waste water.
Further, in the above method, in the S2 step, the weight ratio of the lithium-containing precipitate to water is 1.
Further, in the above method, the temperature in the water leaching step is 80 to 160 ℃.
Further, in the above method, in the S3 step, the phosphate is sodium phosphate or potassium phosphate.
Further, in the above method, in the step S3, the reaction temperature is 60 to 120 ℃.
Further, in the above method, in the step S4, the carbonate is added in an amount of 1 to 2 times the theoretical value of the reaction with lithium chloride in the second lithium-rich liquid.
Further, in the above method, in the step S4, the reaction temperature is 60 to 120 ℃.
In the technical scheme of the invention, the method for preparing lithium carbonate by using lithium-containing wastewater is firstly provided, in particular to the method for preparing lithium carbonate by using industrial wastewater generated in the process of producing alumina by using a fly ash acid method; in addition, the method provided by the application is adopted to extract the lithium carbonate from the lithium-containing wastewater, so that higher extraction rate and purity can be obtained. In addition, the method extracts valuable element lithium in the industrial wastewater, has the effect of waste resource utilization, and plays a good demonstration role in improving the value of bulk solid waste of the fly ash and resource utilization.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to the following examples, which are not intended to limit the scope of the claims of the present application.
In view of the above-mentioned deficiencies in the prior art, one embodiment of the present invention provides a method for preparing lithium carbonate from lithium-containing wastewater, comprising the steps of: spray roasting, namely spray roasting the lithium-containing wastewater to obtain a lithium-containing precipitate, wherein the roasting temperature is 450-900 ℃; a water leaching step, mixing water with the lithium-containing precipitate, and filtering to obtain a first lithium-enriched solution; a deep impurity removal step, namely adding phosphate into the first lithium enrichment solution for reaction, and filtering to obtain a second lithium enrichment solution; and adding carbonate into the second lithium enrichment solution for reaction, and filtering to obtain lithium carbonate.
In the method for preparing lithium carbonate by using lithium-containing wastewater, high extraction rate and purity can be obtained by using the lithium-containing wastewater as a raw material through the steps of spray roasting, water leaching, deep impurity removal and precipitation, and specifically, the extraction rate of lithium element is more than 85% and the purity of the obtained lithium carbonate is more than 97%. In addition, the method extracts valuable element lithium in the industrial wastewater, has the effect of waste resource utilization, and plays a good demonstration role in improving the value of bulk solid waste of the fly ash and resource utilization.
In the spray roasting step, most of aluminum impurities in the lithium-containing wastewater are converted into an alumina form by setting the roasting temperature to be 450-900 ℃, and other metal impurities are all in a chloride form. In the deep impurity removal step, phosphate is added to enable aluminum ions, calcium ions and magnesium ions remaining in the first lithium-enriched liquid to react with the phosphate to generate water-insoluble precipitate, and the precipitate is removed through filtration to obtain a second lithium-enriched liquid; the impurity content in the second lithium enrichment solution is obviously reduced, the second lithium enrichment solution mainly contains lithium chloride, and the lithium chloride is converted into lithium carbonate precipitate by adding carbonate into the second lithium enrichment solution. The pH value of the solution is controlled between 9 and 10.5 by phosphate, lithium phosphate is dissolved in water, and other phosphate is precipitated.
In a preferred embodiment of the method for preparing lithium carbonate by using lithium-containing wastewater according to the invention, the lithium-containing wastewater is wastewater from the production of alumina by fly ash, in particular industrial wastewater from the production of alumina by fly ash acid method. The method provided by the invention provides a new lithium resource by using the wastewater from the production of alumina by fly ash as a raw material, can recover valuable element lithium in industrial wastewater, has the effect of waste resource utilization, and has good demonstration effects on value improvement and resource utilization of bulk solid waste of fly ash.
Preferably, in step S1, the calcination temperature is 600 to 850 ℃, e.g., 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃ or 850 ℃, and the calcination time is 1 to 5 hours, preferably 2 to 3 hours, e.g., 1 hour, 2 hours, 3 hours, 4 hours or 5 hours. The spray roasting is carried out by using a roasting furnace, and the roasting temperature is controlled to be lower than the melting point of the obtained substance. The spray roasting of the lithium-containing wastewater in the temperature range and the time range can better convert impurity aluminum ions in the lithium-containing wastewater into aluminum oxide, can better prevent the lithium-containing precipitate obtained in the roasting process from melting, and can ensure that the roasting is fully carried out, and simultaneously, the economic consumption is minimized.
In another preferred embodiment of the method for preparing lithium carbonate using lithium-containing wastewater according to the present invention, the method further includes an evaporation concentration step of evaporating and concentrating the lithium-containing wastewater before the spray roasting step. Preferably, lithium-containing wastewater is evaporated to the concentration of lithium ions of about 0.1g/L to 0.3g/L, filtered (wherein salt precipitated in the evaporation concentration process, crystals such as calcium chloride and magnesium chloride are filtered out), washed and precipitated by deionized water, and the filtrate and filtrate are combined for spray roasting; more preferably, the evaporation temperature is 80-160 ℃, preferably 90-140 ℃, for example, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or 160 ℃; the evaporation time is from 1 to 12 hours, preferably from 1 to 5 hours, more preferably from 2 to 3 hours, for example 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours. Before the spray roasting step, the lithium waste water is firstly evaporated and concentrated to the lithium ion concentration in a specific range, so that the spray roasting step is more facilitated while part of impurities are removed. The evaporation temperature and evaporation time are not limited to the above specific ranges, and can be adjusted as necessary by those skilled in the art to obtain the concentrated lithium-containing wastewater required for spray roasting.
In still another preferred embodiment of the method for preparing lithium carbonate using lithium-containing wastewater according to the present invention, in the S2 step, the weight ratio of the lithium-containing precipitate to water is 1. Water leaching refers to a unit process that uses water as a solvent to extract soluble components from a solid material, the material undergoing leaching being a mixture of a solute, which is the soluble component, and an insoluble solid. In the process of the present invention, water is mixed with the lithium-containing precipitate, wherein the alumina in the lithium-containing precipitate is dissolved as an insoluble solid and the other substance comprising lithium chloride is dissolved as a solute in the solvent water. In the water leaching step, by controlling the weight ratio of the lithium-containing precipitate to water within the above range, it is possible to not only remove the solid precipitate alumina better but also perform the water leaching step in a more economical manner.
In still another preferred embodiment of the method for preparing lithium carbonate using lithium-containing wastewater according to the present invention, the temperature of the water leaching step is 80 to 160 ℃, preferably 100 to 140 ℃, for example, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or 160 ℃; and preferably the time of the water extraction step is from 1 to 4 hours, preferably from 1.5 to 3 hours, for example 1 hour, 2 hours, 3 hours or 4 hours.
Preferably, in the method for preparing lithium carbonate using lithium-containing wastewater according to the present invention, in the S3 step, the phosphate is sodium phosphate or potassium phosphate, preferably sodium phosphate. In the deep impurity removal step, impurities of aluminum, calcium, and magnesium may be converted into aluminum phosphate, calcium phosphate, and magnesium phosphate precipitates, respectively, by adding a phosphate such as sodium phosphate or potassium phosphate, and these impurity precipitates are removed by filtration to obtain a second lithium-enriched liquor containing lithium chloride and sodium chloride. The phosphate is not limited to sodium or potassium phosphate, but both are used for economic and ready availability, and one skilled in the art can select a suitable phosphate as desired.
Preferably, in the S3 step, the phosphate is added in an amount of 0.8 to 1.5 times, for example, 0.8 times, 0.9 times, 1.0 times, 1.1 times, 1.2 times, 1.3 times, 1.4 times, or 1.5 times, the theoretical value of reaction with impurities of aluminum, calcium, and magnesium in the first lithium-rich liquid. By controlling the amount of phosphate added within this range, impurities can be removed better while cost can be effectively controlled.
Preferably, in the method for preparing lithium carbonate using lithium-containing wastewater according to the present invention, in the S3 step, the reaction temperature is 60 to 120 ℃, preferably 80 to 100 ℃, for example, 60 ℃, 70 ℃,80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃; the reaction time is from 1 to 4 hours, preferably from 2 to 4 hours, for example 1 hour, 2 hours, 3 hours or 4 hours. At this reaction temperature and reaction time, it can be ensured that the impurities aluminum, calcium and magnesium in the first lithium-rich liquid can be converted more quickly and sufficiently into the corresponding phosphate precipitates.
Preferably, in the method for preparing lithium carbonate using lithium-containing wastewater according to the present invention, the carbonate is added in excess, preferably in an amount of 1 to 2 times, for example, 1 time, 1.1 times, 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times, 1.8 times, 1.9 times or 2 times, the theoretical value of the reaction with lithium chloride in the second lithium-rich liquid in the S4 step. In this step, the carbonate reacts with lithium chloride in the second lithium-enriched liquid to generate lithium carbonate, which is slightly soluble in water to precipitate from the solution, and is then filtered, washed, and dried to prepare lithium carbonate. In order to completely convert lithium chloride into lithium carbonate, carbonate may be optionally added in an excess amount, and it is preferable to add carbonate in an amount of 1 to 2 times the theoretical value for reaction with lithium chloride in the second lithium-enriched liquid, taking into consideration economic aspects. The carbonate may be selected from potassium carbonate or sodium carbonate, which are readily available on the market.
Preferably, in the method for preparing lithium carbonate using lithium-containing wastewater according to the present invention, the post-filtration drying temperature is 150 to 250 ℃, preferably 180 to 230 ℃ in the S4 step. The melting point of lithium carbonate is 720 ℃, and the above drying temperature range can better ensure that lithium carbonate exists in a solid form and can well remove moisture. Those skilled in the art can select a suitable drying temperature and drying time as needed, which is not limited to the above specific ranges.
Preferably, in the method for preparing lithium carbonate using lithium-containing wastewater according to the present invention, in the S4 step, the reaction temperature is 60 to 120 ℃, preferably 80 to 90 ℃, for example, 60 ℃, 70 ℃,80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃, and the reaction time is 1 to 4 hours, preferably 1 to 2 hours, for example, 1 hour, 2 hours, 3 hours or 4 hours. By selecting the reaction temperature within this temperature range, the reaction of the carbonate with lithium chloride can be made to proceed faster and more fully, and the resulting precipitated lithium carbonate has a lower solubility at this temperature. However, in the S4 step, the reaction temperature and the reaction time are not limited thereto, and those skilled in the art can select an appropriate reaction temperature and reaction time as needed.
Examples
In the following examples, all the raw materials used were industrial wastewater from the production of alumina by fly ash acid process.
Example 1
And (3) evaporation concentration step: evaporating and concentrating 1000L of lithium-containing wastewater until the concentration of lithium ions is about 0.2g/L, filtering, washing and precipitating by using deionized water, and combining filtrate and washing liquid to obtain about 100L of feed liquid; the evaporation temperature is 90 ℃, and the evaporation time is 12h;
spray roasting: roasting the combined solution obtained in the evaporation concentration step by adopting a spray roasting process to obtain a lithium-containing precipitate, wherein the roasting temperature is 800 ℃, and the roasting time is 1h;
water leaching step: mixing 1L of water with 250g of lithium-containing precipitate obtained in the spray roasting step, wherein the solid-to-liquid ratio is 1:4 by weight, reacting the mixture at 100 ℃ for 2h, and filtering to obtain 0.8L of first lithium-enriched liquid;
deeply removing impurities: adding sodium phosphate into the first lithium-enriched liquid obtained in the water leaching step, reacting for 2 hours at a reaction temperature of 80 ℃, and filtering to obtain a second lithium-enriched liquid, wherein the addition amount of the sodium phosphate is 400g, which is 1.5 times of the theoretical value of reaction with impurities aluminum, calcium and magnesium in the first lithium-enriched liquid;
preparing lithium carbonate: and adding 10.2g of sodium carbonate into the second lithium enrichment solution obtained in the deep impurity removal step, reacting for 2 hours at the reaction temperature of 90 ℃, filtering the obtained precipitate, washing with distilled water, and drying at 180 ℃ to obtain 3.6g of lithium carbonate. In this example, the extraction rate of lithium element was 86.8%, and the purity of lithium carbonate measured by ICP-OES was 97.8%.
Example 2
And (3) evaporation concentration step: evaporating and concentrating 1000L of lithium-containing wastewater until the concentration of lithium ions is about 0.2g/L, filtering, washing and precipitating by using deionized water, and combining filtrate and washing liquid to obtain about 100L of feed liquid; the evaporation temperature is 90 ℃, and the evaporation time is 12h;
spray roasting: roasting the combined solution obtained in the evaporation concentration step by adopting a spray roasting process to obtain a lithium-containing precipitate, wherein the roasting temperature is 450 ℃, and the roasting time is 2 hours;
water leaching step: mixing 1L of water with 250g of lithium-containing precipitate obtained in the spray roasting step, wherein the solid-to-liquid ratio is 1:4 by weight, reacting the mixture at 120 ℃ for 2h, and filtering to obtain 0.8L of first lithium-enriched liquid;
deeply removing impurities: adding sodium phosphate into the first lithium-enriched liquid obtained in the water leaching step, reacting for 2 hours at a reaction temperature of 80 ℃, and filtering to obtain a second lithium-enriched liquid, wherein the addition amount of the sodium phosphate is 450g and is 1.5 times of the theoretical value of the reaction with impurities aluminum, calcium and magnesium in the first lithium-enriched liquid;
preparing lithium carbonate: adding 9.5g of sodium carbonate into the second lithium enrichment solution obtained in the deep impurity removal step, reacting for 2h at the reaction temperature of 90 ℃, filtering the obtained precipitate, washing with distilled water, and drying at 180 ℃ to obtain 3.2g of lithium carbonate. In this example, the extraction rate of lithium element was 91.8%, and the purity of lithium carbonate measured by ICP-OES was 98.2%.
Example 3
And (3) evaporation concentration step: evaporating and concentrating 1000L of lithium-containing wastewater until the concentration of lithium ions is about 0.2g/L, filtering, washing and precipitating by using deionized water, and combining filtrate and washing liquid to obtain about 100L of feed liquid; the evaporation temperature is 90 ℃, and the evaporation time is 12h;
spray roasting: roasting the combined solution obtained in the evaporation concentration step by adopting a spray roasting process to obtain a lithium-containing precipitate, wherein the roasting temperature is 800 ℃, and the roasting time is 1h;
water leaching step: mixing 0.5L of water with 250g of the lithium-containing precipitate obtained in the spray roasting step, wherein the solid-to-liquid ratio by weight is 1;
deeply removing impurities: adding sodium phosphate into the first lithium-enriched liquid obtained in the water leaching step, reacting for 2 hours at a reaction temperature of 80 ℃, and filtering to obtain a second lithium-enriched liquid, wherein the addition amount of the sodium phosphate is 400g, which is 1.5 times of the theoretical value of reaction with impurities aluminum, calcium and magnesium in the first lithium-enriched liquid;
preparing lithium carbonate: and adding 10.8g of sodium carbonate into the second lithium enrichment solution obtained in the deep impurity removal step, reacting for 2 hours at the reaction temperature of 90 ℃, filtering the obtained precipitate, washing with distilled water, and drying at 180 ℃ to obtain 3.9g of lithium carbonate. In this example, the extraction rate of lithium element was 85.8%, and the purity of lithium carbonate measured by ICP-OES was 97.9%.
Example 4
And (3) evaporation concentration step: evaporating and concentrating 1000L of lithium-containing wastewater until the concentration of lithium ions is about 0.2g/L, filtering, washing and precipitating by using deionized water, and combining filtrate and washing liquid to obtain about 100L of feed liquid; the evaporation temperature is 90 ℃, and the evaporation time is 12h;
spray roasting: roasting the combined solution obtained in the evaporation concentration step by adopting a spray roasting process to obtain a lithium-containing precipitate, wherein the roasting temperature is 800 ℃, and the roasting time is 1h;
water leaching step: mixing 2.5L of water with 250g of lithium-containing precipitate obtained in the spray roasting step, wherein the solid-to-liquid ratio is 1;
a deep impurity removal step: adding sodium phosphate into the first lithium-enriched liquid obtained in the water leaching step, reacting for 2 hours at a reaction temperature of 80 ℃, and filtering to obtain a second lithium-enriched liquid, wherein the addition amount of the sodium phosphate is 400g, which is 1.5 times of the theoretical value of reaction with impurities aluminum, calcium and magnesium in the first lithium-enriched liquid;
preparing lithium carbonate: and adding 10.2g of sodium carbonate into the second lithium enrichment solution obtained in the deep impurity removal step, reacting for 2 hours at the reaction temperature of 90 ℃, filtering the obtained precipitate, washing with distilled water, and drying at 180 ℃ to obtain 3.6g of lithium carbonate. In this example, the extraction rate of lithium element was 88.9%, and the purity of lithium carbonate measured by ICP-OES was 96.9%.
In the technical scheme, the method for preparing the lithium carbonate by utilizing the lithium-containing wastewater is firstly provided, in particular to the method for preparing the lithium carbonate by utilizing the industrial wastewater generated in the process of producing the alumina by the acid method of the fly ash; in addition, the method provided by the application is adopted to extract the lithium carbonate from the lithium-containing wastewater, so that higher extraction rate and purity can be obtained. In addition, the method extracts valuable element lithium in the industrial wastewater, has the effect of waste resource utilization, and plays a good demonstration role in improving the value of bulk solid waste of the fly ash and resource utilization.
While the present application has been particularly shown and described with reference to preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing and other changes in forms and details may be made without departing from the spirit and scope of the present application. Thus, variations that are consistent with the principles of the invention of this application should be considered as within the scope of the invention.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing lithium carbonate by using lithium-containing wastewater is characterized by comprising the following steps:
s1, a step: spray roasting step, spray roasting lithium-containing waste water to obtain lithium-containing precipitate, wherein the roasting temperature is 450-900 ℃;
and S2, a step: a water leaching step, mixing water with the lithium-containing precipitate, and filtering to obtain a first lithium-enriched solution;
and S3, a step: a deep impurity removal step, namely adding phosphate into the first lithium enrichment solution for reaction, and filtering to obtain a second lithium enrichment solution;
and S4, a step: and adding carbonate into the second lithium enrichment solution for reaction, and filtering to obtain lithium carbonate.
2. The method of claim 1, wherein the lithium-containing wastewater is wastewater from the production of alumina from fly ash.
3. The method according to claim 1, wherein in the step S1, the roasting temperature is 600-850 ℃ and the roasting time is 1-5 h.
4. The method according to any one of claims 1 to 3, wherein the method further comprises an evaporative concentration step of evaporative concentration of the lithium-containing wastewater before the spray roasting step.
5. The method according to any one of claims 1 to 3, wherein in the S2 step, the weight ratio of the lithium-containing precipitate to water is 1.
6. A method according to any one of claims 1 to 3, wherein the temperature of the water extraction step is 80 to 160 ℃.
7. The method according to any one of claims 1 to 3, wherein in the S3 step, the phosphate is sodium phosphate or potassium phosphate.
8. The method according to any one of claims 1 to 3, wherein, in the S3 step, the reaction temperature is 60 to 120 ℃.
9. The method according to any one of claims 1 to 3, wherein the carbonate is added in an amount of 1 to 2 times the theoretical value of the reaction with lithium chloride in the second lithium-rich liquid in the S4 step.
10. The method according to any one of claims 1 to 3, wherein the reaction temperature in the S4 step is 60 to 120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211415618.5A CN115536047A (en) | 2022-11-11 | 2022-11-11 | Method for preparing lithium carbonate by using lithium-containing wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211415618.5A CN115536047A (en) | 2022-11-11 | 2022-11-11 | Method for preparing lithium carbonate by using lithium-containing wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115536047A true CN115536047A (en) | 2022-12-30 |
Family
ID=84719832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211415618.5A Pending CN115536047A (en) | 2022-11-11 | 2022-11-11 | Method for preparing lithium carbonate by using lithium-containing wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115536047A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103069022A (en) * | 2010-07-09 | 2013-04-24 | 浦项产业科学研究院 | Method for economical extraction of lithium from solution including lithium |
| KR101384803B1 (en) * | 2012-12-21 | 2014-04-21 | 재단법인 포항산업과학연구원 | Method for extraction of lithium from solution including lithium |
| CN108193054A (en) * | 2018-03-12 | 2018-06-22 | 中国科学院过程工程研究所 | A kind of method that lithium is extracted from waste water containing lithium |
| CN108946772A (en) * | 2018-09-27 | 2018-12-07 | 山东泰和水处理科技股份有限公司 | A method of pure Lithium Carbonate is prepared by lithium ore |
| CN109336141A (en) * | 2018-11-30 | 2019-02-15 | 浙江三晟化工有限公司 | A kind of method of the lithium rate of recovery in raising waste water |
| CN109354046A (en) * | 2018-11-08 | 2019-02-19 | 中国神华能源股份有限公司 | A method of lithium carbonate is prepared using dirty mother liquor is steamed |
| CN109354045A (en) * | 2018-11-08 | 2019-02-19 | 中国神华能源股份有限公司 | A method of lithium carbonate is prepared using dirty mother liquor is steamed |
| JP2020045576A (en) * | 2017-03-31 | 2020-03-26 | Ｊｘ金属株式会社 | Method for recovering lithium |
| KR20200078393A (en) * | 2018-12-21 | 2020-07-01 | 동우 화인켐 주식회사 | Manufacturing method of lithium carbonate from waste solution containing lithium-ion |
| 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 |
-
2022
- 2022-11-11 CN CN202211415618.5A patent/CN115536047A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103069022A (en) * | 2010-07-09 | 2013-04-24 | 浦项产业科学研究院 | Method for economical extraction of lithium from solution including lithium |
| KR101384803B1 (en) * | 2012-12-21 | 2014-04-21 | 재단법인 포항산업과학연구원 | Method for extraction of lithium from solution including lithium |
| JP2020045576A (en) * | 2017-03-31 | 2020-03-26 | Ｊｘ金属株式会社 | Method for recovering lithium |
| CN108193054A (en) * | 2018-03-12 | 2018-06-22 | 中国科学院过程工程研究所 | A kind of method that lithium is extracted from waste water containing lithium |
| CN108946772A (en) * | 2018-09-27 | 2018-12-07 | 山东泰和水处理科技股份有限公司 | A method of pure Lithium Carbonate is prepared by lithium ore |
| CN109354046A (en) * | 2018-11-08 | 2019-02-19 | 中国神华能源股份有限公司 | A method of lithium carbonate is prepared using dirty mother liquor is steamed |
| CN109354045A (en) * | 2018-11-08 | 2019-02-19 | 中国神华能源股份有限公司 | A method of lithium carbonate is prepared using dirty mother liquor is steamed |
| CN109336141A (en) * | 2018-11-30 | 2019-02-15 | 浙江三晟化工有限公司 | A kind of method of the lithium rate of recovery in raising waste water |
| KR20200078393A (en) * | 2018-12-21 | 2020-07-01 | 동우 화인켐 주식회사 | Manufacturing method of lithium carbonate from waste solution containing lithium-ion |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 程芳琴,李华,田园春: "盐湖卤水净化除杂的试验研究", 山西大学学报(自然科学版), no. 04, pages 387 - 391 * |
| 陈东 等: "氯化铝溶液中分离、制取碳酸锂新技术研究", 轻金属, no. 2, pages 14 - 17 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110040748B (en) | Method for producing potassium salt and sodium salt by utilizing waste incineration fly ash | |
| CN103086405B (en) | Clean production method of battery level lithium carbonate | |
| CN110885090A (en) | Method for preparing battery-grade lithium carbonate by using lepidolite as raw material through one-step method | |
| CN104745823B (en) | Method for recycling lithium from waste lithium ion battery | |
| US9169125B2 (en) | Method for producing high-purity lithium carbonate | |
| CN114105171B (en) | Method for comprehensively utilizing lepidolite resources and lithium hydroxide prepared by method | |
| CN102244309B (en) | Method for recovering lithium from lithium power battery of electric automobile | |
| CN102020294B (en) | Lithium hydroxide monohydrate and preparation method thereof | |
| CN111960445B (en) | Method for preparing battery-grade lithium carbonate by using lithium sulfate coarse ore and recycling by-products | |
| CN104271781A (en) | Processing of lithium containing material | |
| CN115323196A (en) | Processing of lithium-containing materials including HCl blasting | |
| CN101234766B (en) | Method for producing potassium chloride by steel enterprise sintering electro-precipitating dust | |
| CN108910851B (en) | Method for preparing lithium-containing compound from lithium-phosphorus-aluminum | |
| CN108330298B (en) | Method for extracting rubidium, cesium, lithium and potassium from polymetallic mica ore | |
| CN110004294B (en) | Method for treating scheelite alkali decomposition slag | |
| CN102502720A (en) | Process for producing battery-grade lithium carbonate through processing carbonate type lithium concentrate by deep carbonation method | |
| CN107055575B (en) | A kind of production technology of LITHIUM BATTERY lithium hydroxide | |
| CN101451200A (en) | Rare-earth enrichment recovery method from phosphorite | |
| JP2019099901A (en) | Method for recovering lithium from lithium-containing solution | |
| CN103274470B (en) | Method for preparing electronic-grade manganese sulfate by utilizing tungsten ore alkaline leaching slag | |
| CN104884648B (en) | The method of lithium is extracted from lithium-containing solution | |
| CN112624161B (en) | Method for preparing lithium carbonate by extracting lithium from mechanically activated lepidolite | |
| CN115140777B (en) | Method for producing ferromanganese composite material for soft magnetic by utilizing ocean manganese nodule | |
| CN102101699A (en) | Method for extracting pyrolusite and producing manganese sulfate by utilizing by-product in production of titanium white | |
| CN113651342A (en) | Method for producing lithium product by processing lepidolite through nitric acid atmospheric pressure method |
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 |