CN110817907B - Treatment system and method for purifying high-purity lithium carbonate - Google Patents
Treatment system and method for purifying high-purity lithium carbonate Download PDFInfo
- Publication number
- CN110817907B CN110817907B CN201810915675.7A CN201810915675A CN110817907B CN 110817907 B CN110817907 B CN 110817907B CN 201810915675 A CN201810915675 A CN 201810915675A CN 110817907 B CN110817907 B CN 110817907B
- Authority
- CN
- China
- Prior art keywords
- lithium
- solution
- lithium carbonate
- ions
- carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
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
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the field of oil field exploration, and improves the comprehensive resource utilization of high added value in the oil field exploitation process. The method comprises the steps of precipitation impurity removal, falling film evaporation concentration, ion exchange treatment, ultrafiltration membrane refining, pulse lithium precipitation reaction, and the like, wherein a series of technologies such as a falling film evaporator technology, an ultrafiltration membrane technology, an ion exchange technology, a supergravity machine technology, a pulse control technology, a lithium precipitation crystallization control technology and the like are adopted for lithium-rich eluent, so that high-purity lithium carbonate is obtained.
Description
Technical Field
The invention relates to a treatment system and a treatment method for purifying high-purity lithium carbonate, which are mainly applied to comprehensive utilization of lithium resources in oil field water, coal bed gas field produced water, salt lake brine, salt lake intercrystalline brine, geothermal water, underground brine, seawater and hot spring water in an oil field exploration process.
Background
Lithium carbonate is used as a strategic resource and has a wide application range. Is an indispensable raw material in important industrial fields such as glass, energy, metallurgy, batteries, medicine and the like. With the temperature rise of global new energy development and the high-speed development of lithium ion batteries for power and energy storage, lithium carbonate serving as a core raw material has a very wide market prospect. NewThe rapid development of the energy automobile industry continuously drives the demand of lithium to rise, and the demand of global lithium carbonate in 2018 and 2019 is predicted to be 28.07 ten thousand tons and 34.74 ten thousand tons respectively according to the prediction of relevant mechanisms. In 2018, the price of lithium carbonate slightly falls back, but still maintains the high level of more than 15 ten thousand yuan/ton. The current domestic lithium carbonate standards comprise GB/T11075-2013 lithium carbonate, YS/T582-2013 battery grade lithium carbonate, YS/T546-2008 high-purity lithium carbonate and GB/T23853-2009 lithium brine carbonate, and the lithium carbonate is divided into industrial grade lithium carbonate [ w (Li (lithium carbonate)) 2 CO 3 )<99.50%]99.50% or less of battery grade lithium carbonate (Li) 2 CO 3 )<99.99%]And high-purity lithium carbonate [ w (Li) ] 2 CO 3 )≥99.99%]And 3, types.
The oilfield brine is oilfield water containing a large amount of salt minerals in an underground oil well in oil exploitation, and is rich in K + 、B 2 O 3 、Li + 、Br - 、I - And the content of the useful components reaches and exceeds the industrial production index, so that the brine mine becomes the brine mine of the oil field. It features wide distribution and large storage. With the maturity of the lithium extraction technology from brine, the international market supply and demand of industrial lithium carbonate tends to be saturated, the industry competition is intense, and the product profit is reduced. The development of battery-grade or above lithium carbonate can increase the added value of products, and is beneficial to the serial development of salt lake lithium products and the extension of a lithium industry chain; on the other hand, with the continuous expansion of the application of the current lithium products in the fields of high technology and the like, the demand of lithium salts is increased rapidly at home and abroad, and the requirement on the purity of the products is higher and higher.
The main process routes of the methods include brine impurity removal, carbonate precipitation to obtain industrial-grade lithium carbonate, conversion of lithium carbonate into lithium bicarbonate by using carbon dioxide, filtration, resin impurity removal to obtain a refined lithium bicarbonate solution, heating of the lithium bicarbonate solution to decompose carbon dioxide, precipitation of lithium carbonate, solid-liquid separation, washing and drying to obtain a battery-grade lithium carbonate product. However, the technology has long process flow, large treatment capacity of intermediate wastewater, strict requirements on pressure, reaction temperature, pH value, concentration control and the like, and severe fouling of a reactor, and is not beneficial to large-scale production. Patent CN103958412a mentions that while there are many ways to extract lithium carbonate from lithium-containing brines, there is no simplified process to prepare high purity (cell grade) lithium carbonate from lithium-concentrated brines containing significant amounts of, for example, boron, magnesium, calcium, sodium, potassium, chloride and sulfate. Patent CN102432044a discloses a method for extracting ultra-pure lithium carbonate from salt lake brine with high magnesium-lithium ratio, which comprises preparing lithium chloride concentrated solution by adsorption-desorption and evaporation concentration processes, precipitating lithium carbonate by using ammonium bicarbonate water slurry after purification, then converting into lithium bicarbonate solution, filtering and decarbonizing. The invention has high energy consumption for directly evaporating and concentrating the desorption solution, which leads to high extraction cost. The equipment such as the rotary packed bed and the spray dryer adopted in CN104386715B, CN102408120B, CN105399115B further pay attention to the refinement of the particle size of lithium carbonate and the removal of magnetic substances.
The present purification technology of high-purity lithium carbonate mainly includes causticizing method, recrystallization method, electrolysis method, hydrogenation precipitation method and hydrogenation decomposition method, etc. its key technology is to reduce the mass fraction of metal impurity ions to 1X 10 -5 The method is even lower, but the existing purification technology still has the problems of unstable product quality, low lithium resource recovery rate and the like. Therefore, the development of a green and energy-saving purification technology of high-purity lithium salt products with high added values is imperative.
Disclosure of Invention
Aiming at the problems of high purification cost, longer process flow, large wastewater treatment capacity, unstable product quality, low lithium resource recovery rate and the like in the prior art, the invention aims to provide a novel method for comprehensively utilizing lithium resources.
Therefore, the following technical scheme is adopted: processing system of high-purity lithium carbonate purification, its characterized in that it includes:
a precipitation impurity removal unit, which is used for reacting the lithium-rich eluent with a precipitation impurity removal agent to precipitate impurity ions of magnesium, manganese and calcium in the lithium-rich eluent;
the evaporation concentration unit is used for carrying out vacuum concentration on the filtrate from the precipitation and impurity removal unit;
the ion exchange unit is used for carrying out ion exchange on the concentrated solution from the evaporation concentration unit to realize the advanced treatment of anions and cations;
a purification and refining unit, which is used for refining the purified solution by adding a complexing agent and a membrane separation technology into the solution from the ion exchange unit;
and a lithium precipitation reaction unit, wherein the adding speed of sodium carbonate is controlled by the purified liquid from the purification and refining unit, crystal seeds are added, the generation of lithium carbonate precipitation is accelerated, lithium carbonate slurry is obtained, and high-purity lithium carbonate is prepared after filtering, washing and drying.
The lithium-rich eluent is prepared by extracting and treating oil field water, coal bed gas field produced water, salt lake brine, salt lake intercrystalline brine, geothermal water, underground brine, seawater and thermal spring water in the oil field exploration process.
Further, the precipitation and impurity removal unit comprises a supergravity machine; the evaporation concentration unit comprises a falling film evaporator; the ion exchange unit comprises one or more stages of ion exchange columns; the refining unit comprises an ultrafiltration membrane separator.
The invention realizes the high-efficiency and energy-saving concentration of the eluent by the falling film evaporator, strengthens the mass transfer, impurity removal and precipitation reaction by the hypergravity machine, realizes the advanced treatment of anions and cations by the ion exchange resin, removes impurities by the complexing agent, refines the purified solution by the ultrafiltration membrane, and adds the pulse automatic control sodium carbonate solution, and accelerates the lithium precipitation reaction by the seed crystal.
The invention also provides a high-purity lithium carbonate purification treatment method adopting the treatment system, which comprises the following steps:
step I, conveying the lithium-rich eluent into a supergravity machine through a liquid conveying pump, adding an impurity removing agent, heating to 40-60 ℃, keeping the temperature, stirring and reacting for 0.5-2 h, controlling the pH value of the reaction end point to be 12 +/-0.5, and filtering to remove precipitates after the reaction is finished to obtain a filtrate;
step II, concentrating the filtrate obtained in the step I through a falling film steam generator, and controlling the evaporation temperature to be 90 ℃, the temperature difference to be 3 to 10 ℃ and the vacuum degree to be-0.3 to-0.6 MPa; evaporating and concentrating to obtain a concentrated solution, and reserving evaporated condensed water for later use;
step III, enabling the concentrated solution in the step II to pass through one-stage or multi-stage ion exchange columns loaded with cation exchange resin, anion exchange resin and/or chelating resin at a certain flow rate, and respectively removing impurities such as calcium and magnesium divalent ions, boron and other trivalent ions in the solution;
step IV, adding a complexing agent into the solution obtained in the step III, complexing trace calcium, magnesium and iron ions in the filtrate into complex ions with larger volume, and separating lithium ions with smaller volume through an ultrafiltration membrane to obtain a refined lithium-rich solution;
and V, adding the refined lithium-rich solution in the step IV into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse form, keeping the temperature, stirring uniformly, reacting for 0.5-2 h, adding seed crystals to promote crystallization of lithium carbonate to form lithium carbonate slurry, and carrying out solid-liquid separation, washing with evaporated and concentrated water, and drying to obtain the high-purity lithium carbonate.
Further, in the step I, the impurity removing agent is one or more of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium oxalate, potassium oxalate and oxalic acid.
Further, in the step III, the cation exchange resin is selected from one or more of styrene, acrylic acid and phenolic aldehyde; the anion exchange resin is selected from one or more of styrene, acrylic acid and epoxy; the chelating resin is selected from one or more of D110, D113, D152, D401, D403, D418 and D564.
Further, in step III, the flow rate of the concentrate through the ion exchange column is 5 to 50BV/h, preferably 8 to 20BV/h.
Further, in the step IV, the complexing agent is one or more of EDTA, crown ether, nitrilotriacetic acid, citric acid, tartaric acid, oleic acid, gluconic acid and diethylenetriamine pentaacetic acid.
Further, in the step IV, the ultrafiltration membrane is made of ceramics, polysulfone, polyetheretherketone, polyvinylidene fluoride or polytetrafluoroethylene, the filtration precision of the ultrafiltration membrane is 10-100nm, the component mode of the ultrafiltration membrane is hollow fiber, roll type, plate type or tube type, and the filtration mode of the ultrafiltration membrane is cross-flow or counter-flow filtration.
Furthermore, in the step V, the pulse frequency of the saturated sodium carbonate solution is added to the solution at 10 to 100KHz, preferably 20 to 30KHz.
Further, in the step V, the seed crystal is lithium carbonate, the particle size can be various particle sizes of nanometer grade and hundreds of micrometers, and the shape can be one or more of spherical shape, rod shape, flower shape, sheet shape and hollow sphere.
Compared with the existing method for utilizing the lithium resource with high added value, the invention initiates a lithium resource comprehensive utilization process of precipitation and impurity removal, falling film evaporation and concentration, ion exchange treatment, ultrafiltration membrane refining and pulse lithium precipitation reaction of the hypergravity machine, organically combines the hypergravity machine, the falling film evaporation and concentration method, the ion exchange method and the membrane method together, greatly reduces the energy consumption and the cost, effectively removes calcium ions and magnesium ions in the mother liquor, ensures that the finally prepared lithium carbonate has the advantages of high purity, stable quality, high utilization rate of the original mother liquor, simple and convenient operation, low energy consumption, stable effect, high yield, low cost, comprehensive utilization of water resources, continuous and controllable process, low investment, high efficiency and the like, and the whole processing process is very clean and does not generate intermediate pollution.
Drawings
FIG. 1 is a schematic process flow diagram of a treatment method according to an embodiment of the present invention.
In the figure, 1-a solution pump, 2-a super gravity machine, 3-a trash removal conveying pump, 4-a plate and frame filter press, 5-a falling film evaporator, 6-a solution pump, 7-a first-stage ion exchange column, 8-a second-stage ion exchange column, 9-a solution pump, 10-a reaction kettle, 11-a solution pump, 12-an ultrafiltration membrane, 13-a purification liquid pump, 14-a reaction kettle, 15-a solution pump and 16-a plate and frame filter press.
Detailed Description
The invention is further described in detail with reference to the following drawings and specific examples.
Example (b): as shown in the attached figure 1, the implementation of the invention is realized by a processing system for purifying high-purity lithium carbonate, and the processing system mainly comprises a solution pump (1), a supergravity machine (2), an impurity removal conveying pump (3), a plate-and-frame filter press (4), a falling film evaporator (5), a solution pump (6), a primary ion exchange column (7), a secondary ion exchange column (8), a solution pump (9), a reaction kettle (10), a solution pump (11), an ultrafiltration membrane (12), a purification liquid pump (13), a reaction kettle (14), a solution pump (15), a plate-and-frame filter press (16) and other dynamic and static equipment.
The operation process of the system is as follows: when the system is started, conveying the lithium-rich eluent subjected to lithium extraction into a hypergravity machine through a liquid conveying pump, adding an impurity removing agent, heating to 40-60 ℃, keeping the temperature, stirring and reacting for 0.5-2 hours to precipitate 90-99% of impurities such as magnesium, manganese, calcium and the like, controlling the pH value of a reaction end point to be 12 +/-0.5, and filtering through a filter press after the reaction is finished to obtain a filtrate; carrying out recompression concentration on the filtrate by utilizing falling film steam, controlling the evaporation temperature of an evaporation concentration part to be 90 ℃, controlling the effective temperature difference to be 3-10 ℃ and controlling the vacuum degree to be-0.3-0.6 MPa; salt is crystallized and separated out in the evaporation concentration process to obtain a concentrated solution, and evaporated water is condensed for later use; passing the concentrated solution through two stages of ion exchange columns loaded with cation exchange resin and anion exchange resin at proper flow rate to remove impurities such as divalent ions such as calcium and magnesium and trivalent ions such as boron in the solution; adding a complexing agent, complexing trace calcium, magnesium, iron and other ions in the filtrate to form complex ions with larger volume, and separating lithium ions with smaller volume by using a membrane separation technology to obtain a refined lithium-rich solution; adding the refined lithium-rich solution into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse manner, keeping the temperature, stirring uniformly, reacting for 0.5-2 h, and adding seed crystals to promote precipitation of lithium carbonate; and carrying out solid-liquid precipitation separation on the lithium carbonate slurry, washing with evaporated and concentrated water, and drying to obtain high-purity lithium carbonate.
Example 1
The water to be treated is a selective eluent of certain oil field water through a lithium ion sieve, and the scale of the eluent is 80m 3 H, eluent composition:
| composition (I) | Li + | Ca 2+ | Mg 2+ | Mn 2+ | B 2 O 3 | Na + | K+ | Cl - | SO 4 2- |
| Content (g/L) | 3 | 0.15 | 0.3 | 0.9 | 0.3 | 0.4 | 0.15 | 2.2 | 1.5 |
At the start, the lithium-rich eluent after the lithium extraction treatment is 80m 3 Feeding the mixture into a supergravity machine through a liquid delivery pump, adding an impurity removing agent, heating to 45 ℃, keeping the temperature, stirring and reacting for 0.5 hour to precipitate 96% of impurities such as magnesium, manganese, calcium and the like, controlling the pH value of the reaction end point to be 12, and filtering through a filter press after the reaction is finished to obtain a filtrate; carrying out recompression and concentration on the filtrate by utilizing falling film steam, controlling the evaporation temperature of an evaporation and concentration part to be 90 ℃, controlling the effective temperature difference to be 5.6 ℃ and controlling the vacuum degree to be-0.35 MPa; salt is crystallized and separated out in the evaporation concentration process to obtain a concentrated solution, and evaporated water is condensed for later use; passing the concentrated solution through two stages of ion exchange columns loaded with cation exchange resin and anion exchange resin at the flow rate of 12BV/h, and respectively removing impurities such as divalent ions such as calcium and magnesium and trivalent ions such as boron in the solution; adding EDTA, complexing trace calcium, magnesium, iron and other ions in the filtrate to form complex ions with larger volume, and separating lithium ions with smaller volume by using an ultrafiltration membrane made of ceramic to obtain a refined lithium-rich solution; adding the refined lithium-rich solution into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse mode, wherein the pulse frequency is 18KHz, keeping the temperature, stirring uniformly, reacting for 1.5h, and adding rod-shaped lithium carbonate crystal seeds to promote the precipitation of lithium carbonate; and (3) carrying out solid-liquid precipitation separation on the lithium carbonate slurry, washing with evaporated and concentrated water, and drying to obtain high-purity lithium carbonate, weighing 9640 tons, wherein the purity of the high-purity lithium carbonate is 99.993 percent, and the product meets the quality standard of YS/T546-2008 & lthigh-purity lithium carbonate & gt.
Comparative example 1
The water to be treated is a selective eluent of certain oil field water through a lithium ion sieve, and the scale of the eluent is 80m 3 H, eluent composition:
| composition (I) | Li + | Ca 2+ | Mg 2+ | Mn 2+ | B 2 O 3 | Na + | K+ | Cl - | SO 4 2- |
| Content (g/L) | 3 | 0.15 | 0.3 | 0.9 | 0.3 | 0.4 | 0.15 | 2.2 | 1.5 |
At the start, the eluent rich in lithium after the lithium extraction treatment is 80m 3 H is fed into the supergravity machine through a liquid delivery pumpAdding an impurity removing agent, heating to 30 ℃, keeping the temperature, stirring and reacting for 0.5 hour to precipitate 96% of impurities such as magnesium, manganese, calcium and the like, controlling the pH value of a reaction end point to be 13, and filtering through a filter press after the reaction is finished to obtain a filtrate; carrying out recompression and concentration on the filtrate by utilizing falling film steam, controlling the evaporation temperature of an evaporation and concentration part to be 90 ℃, controlling the effective temperature difference to be 5.6 ℃ and controlling the vacuum degree to be-0.35 MPa; salt is crystallized and separated out in the evaporation concentration process to obtain a concentrated solution, and evaporated water is condensed for later use; enabling the concentrated solution to pass through two stages of ion exchange columns loaded with cation exchange resin and anion exchange resin at the flow rate of 5BV/h, and respectively removing impurities such as divalent ions such as calcium, magnesium and the like and trivalent ions such as boron and the like in the solution; directly separating out lithium ions with small volume by using an ultrafiltration membrane made of ceramics without adding a complexing agent to obtain a refined lithium-rich solution; adding the refined lithium-rich solution into a reaction kettle, heating to 90-95 ℃, directly adding a saturated sodium carbonate solution without adopting a pulse mode, and directly and naturally precipitating lithium carbonate without adding seed crystals; and carrying out solid-liquid precipitation separation on the lithium carbonate slurry, washing with evaporated and concentrated water, and drying to obtain high-purity lithium carbonate, weighing 9120 tons, wherein the purity of the high-purity lithium carbonate is 98.5%, and the product meets the quality standard of YS/T546-2008 high-purity lithium carbonate.
Example 2
The scale of the eluent to be treated is 50m after the coal bed water is treated 3 H, eluent composition:
| composition (A) | Li + | Ca 2+ | Mg 2+ | Mn 2+ | B 2 O 3 | Na + | K+ | Cl - | SO 4 2- |
| Content (g/L) | 2.5 | 0.2 | 0.27 | 0.4 | 0.2 | 0.6 | 0.2 | 0.4 | 2.8 |
At the start, the lithium-rich eluent after the lithium extraction treatment is 50m 3 Feeding the mixture into a supergravity machine through a liquid delivery pump, adding an impurity removing agent, heating to 50 ℃, keeping the temperature, stirring and reacting for 1.5 hours to precipitate 98% of impurities such as magnesium, manganese, calcium and the like, controlling the pH value of the reaction end point to be 12.2, and filtering through a filter press after the reaction is finished to obtain filtrate; carrying out recompression and concentration on the filtrate by utilizing falling film steam, controlling the evaporation temperature of an evaporation and concentration part to be 90 ℃, controlling the effective temperature difference to be 3.5 ℃ and controlling the vacuum degree to be-0.50 MPa; salt is crystallized and separated out in the evaporation concentration process to obtain a concentrated solution, and evaporated water is condensed for later use; the concentrated solution was passed through two stages loaded with cation exchange resin at a flow rate of 10BV/h, and then, anion-exchangedIon exchange column of the sub-exchange resin, remove divalent ion such as calcium and magnesium and trivalent ion such as boron in solution separately; adding nitrilotriacetic acid, complexing trace calcium, magnesium, iron and other ions in the filtrate to form complex ions with larger volume, and separating lithium ions with smaller volume by using an ultrafiltration membrane made of polyether-ether-ketone to obtain a refined lithium-rich solution; adding the refined lithium-rich solution into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse mode, wherein the pulse frequency is 21KHz, keeping the temperature, stirring uniformly, reacting for 1h, and adding a hollow lithium carbonate crystal seed to promote the precipitation of lithium carbonate; and carrying out solid-liquid precipitation separation on the lithium carbonate slurry, washing with evaporated and concentrated water, and drying to obtain high-purity lithium carbonate, weighing 5020 tons of the high-purity lithium carbonate, wherein the purity of the high-purity lithium carbonate is 99.992%, and the product meets the quality standard of YS/T546-2008 high-purity lithium carbonate.
Example 3
The lithium-rich solution to be treated is a lithium-rich solution obtained by electrodialysis treatment of salt lake brine of certain Qinghai, and the scale of the lithium-rich solution is 120m 3 H, eluent composition:
| composition (I) | Li + | Ca 2+ | Mg 2+ | Mn 2+ | B 2 O 3 | Na + | K+ | Cl - | SO 4 2- |
| Content (g/L) | 4.3 | 0.4 | 0.8 | 0.3 | 0.25 | 0.9 | 1.1 | 0.6 | 1.7 |
At the start, the lithium-rich eluent after the lithium extraction treatment is 120m 3 Feeding the mixture into a supergravity machine through a liquid delivery pump, adding an impurity removing agent, heating to 55 ℃, keeping the temperature, stirring and reacting for 2 hours to precipitate 96% of impurities such as magnesium, manganese, calcium and the like, controlling the pH value of the reaction end point to be 12.5, and filtering through a filter press after the reaction is finished to obtain filtrate; carrying out recompression and concentration on the filtrate by utilizing falling film steam, controlling the evaporation temperature of an evaporation and concentration part to be 90 ℃, controlling the effective temperature difference to be 8.6 ℃ and controlling the vacuum degree to be-0.60 MPa; salt is crystallized and separated out in the evaporation concentration process to obtain a concentrated solution, and evaporated water is condensed for later use; passing the concentrated solution through two stages of ion exchange columns loaded with cation exchange resin and anion exchange resin at the flow rate of 12BV/h, and respectively removing impurities such as divalent ions such as calcium and magnesium and trivalent ions such as boron in the solution; adding citric acid, complexing trace calcium, magnesium, iron and other ions in the filtrate to form complex ions with larger volume, and separating lithium ions with smaller volume by using an ultrafiltration membrane made of polytetrafluoroethylene to obtain a refined lithium-rich solution; adding the refined lithium-rich solution into a reaction kettleHeating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse mode, wherein the pulse frequency is 24KHz, keeping the temperature, stirring uniformly, reacting for 1.5h, and adding micron-sized lithium carbonate seed crystals to promote the precipitation of lithium carbonate; and carrying out solid-liquid precipitation separation on the lithium carbonate slurry, washing with evaporated and concentrated water, and drying to obtain high-purity lithium carbonate, weighing 20700 tons, wherein the purity of the high-purity lithium carbonate is 99.991 percent, and the product meets the quality standard of YS/T546-2008 high-purity lithium carbonate.
Example 4
The lithium-rich eluent after adsorption of certain seawater is treated, and the scale of the eluent is 60m 3 H, eluent composition:
| composition (I) | Li + | Ca 2+ | Mg 2+ | Mn 2+ | B 2 O 3 | Na + | K+ | Cl - | SO 4 2- |
| Content (g/L) | 0.5 | 0.3 | 0.5 | 0.2 | 0.15 | 1.1 | 0.8 | 1.2 | 0.7 |
At the start, the lithium-rich eluent after the lithium extraction treatment is 60m 3 Feeding the mixture into a supergravity machine through a liquid delivery pump, adding an impurity removing agent, heating to 43 ℃, keeping the temperature, stirring and reacting for 1.3 hours to precipitate 99% of impurities such as magnesium, manganese, calcium and the like, controlling the pH value of the reaction end point to be 11.8, and filtering through a filter press after the reaction is finished to obtain filtrate; carrying out recompression and concentration on the filtrate by utilizing falling film steam, controlling the evaporation temperature of an evaporation and concentration part to be 90 ℃, controlling the effective temperature difference to be 3.2 ℃ and controlling the vacuum degree to be-0.47 MPa; salt is crystallized and separated out in the evaporation concentration process to obtain a concentrated solution, and evaporated water is condensed for later use; passing the concentrated solution through two stages of ion exchange columns loaded with cation exchange resin and anion exchange resin at a flow rate of 16BV/h to respectively remove impurities such as divalent ions such as calcium and magnesium and trivalent ions such as boron in the solution; adding diethylenetriaminepentaacetic acid, complexing trace ions such as calcium, magnesium and iron in the filtrate to form complex ions with larger volume, and separating lithium ions with smaller volume by using an ultrafiltration membrane made of polysulfone to obtain a refined lithium-rich solution; adding the refined lithium-rich solution into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse mode, keeping the pulse frequency at 20KHz, uniformly stirring for reacting for 1.2h, and adding seed crystals to promote precipitation of lithium carbonate; and carrying out solid-liquid precipitation separation on the lithium carbonate slurry, washing with evaporated and concentrated water, and drying to obtain high-purity lithium carbonate, weighing 1200 tons of the high-purity lithium carbonate, wherein the purity of the high-purity lithium carbonate is 99.995%, and the product meets the quality standard of YS/T546-2008 'high-purity lithium carbonate'.
Example 5
The lithium-rich eluent is lithium-rich eluent after electrodialysis treatment of underground brine in a certain area of Bohai Bay in eastern mountain, and the scale of the lithium-rich eluent is 70m 3 H, eluent composition:
| composition (I) | Li + | Ca 2+ | Mg 2+ | Mn 2+ | B 2 O 3 | Na + | K+ | Cl - | SO 4 2- |
| Content (g/L) | 2.8 | 0.32 | 0.75 | 0.26 | 0.24 | 0.8 | 0.9 | 1.5 | 0.6 |
At the start, the lithium-rich eluent after the lithium extraction treatment is 70m 3 Feeding the mixture into a supergravity machine through a liquid delivery pump, adding an impurity removing agent, heating to 56 ℃, keeping the temperature, stirring and reacting for 1.8 hours to precipitate 99% of impurities such as magnesium, manganese, calcium and the like, controlling the pH value of the reaction end point to be 12, and filtering through a filter press after the reaction is finished to obtain filtrate; carrying out recompression and concentration on the filtrate by utilizing falling film steam, controlling the evaporation temperature of an evaporation and concentration part to be 90 ℃, controlling the effective temperature difference to be 4.3 ℃ and controlling the vacuum degree to be-0.58 MPa; salt is crystallized and separated out in the evaporation concentration process to obtain a concentrated solution, and evaporated water is condensed for later use; enabling the concentrated solution to pass through two stages of ion exchange columns loaded with cation exchange resin and anion exchange resin at the flow rate of 8BV/h, and respectively removing impurities such as divalent ions such as calcium, magnesium and the like and trivalent ions such as boron and the like in the solution; adding EDTA, complexing trace calcium, magnesium, iron and other ions in the filtrate to form complex ions with larger volume, and separating lithium ions with smaller volume by using an ultrafiltration membrane made of polyvinylidene fluoride to obtain a refined lithium-rich solution; adding the refined lithium-rich solution into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse mode, wherein the pulse frequency is 28KHz, keeping the temperature, stirring uniformly, reacting for 1.5h, and adding a hollow lithium carbonate crystal seed to promote the precipitation of lithium carbonate; and (3) carrying out solid-liquid precipitation separation on the lithium carbonate slurry, washing with evaporated and concentrated water, and drying to obtain high-purity lithium carbonate, weighing 7870 tons, wherein the purity of the high-purity lithium carbonate is 99.992%, and the product meets the quality standard of YS/T546-2008 high-purity lithium carbonate.
Example 6
The lithium-rich eluent after the hot spring water in a certain region of Jiangsu is adsorbed is treated, and the scale of the lithium-rich eluent is 30m 3 H, eluent composition:
| composition (I) | Li + | Ca 2+ | Mg 2+ | Mn 2+ | B 2 O 3 | Na + | K+ | Cl - | SO 4 2- |
| Content (g/L) | 0.8 | 0.4 | 0.68 | 0.35 | 0.2 | 1.0 | 1.2 | 1.4 | 0.5 |
At the start, the lithium-rich eluent after the lithium extraction treatment is 30m 3 [ h ] transport via liquidPumping into a supergravity machine, adding an impurity removing agent, heating to 52 ℃, keeping the temperature, stirring and reacting for 0.8h to precipitate 99% of impurities such as magnesium, manganese, calcium and the like, controlling the pH value of the reaction end point to be 11.6, and filtering through a filter press after the reaction is finished to obtain filtrate; carrying out recompression and concentration on the filtrate by utilizing falling film steam, controlling the evaporation temperature of an evaporation and concentration part to be 90 ℃, controlling the effective temperature difference to be 7.8 ℃ and controlling the vacuum degree to be-0.50 MPa; salt is crystallized and separated out in the evaporation concentration process to obtain a concentrated solution, and evaporated water is condensed for later use; passing the concentrated solution through two stages of ion exchange columns loaded with cation exchange resin and anion exchange resin at the flow rate of 10BV/h, and respectively removing impurities such as divalent ions such as calcium and magnesium and trivalent ions such as boron in the solution; adding tartaric acid, complexing trace calcium, magnesium, iron and other ions in the filtrate to form complex ions with larger volume, and separating lithium ions with smaller volume by using an ultrafiltration membrane made of polyether ketone to obtain a refined lithium-rich solution; adding the refined lithium-rich solution into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse mode, wherein the pulse frequency is 25KHz, keeping the temperature, stirring uniformly, reacting for 1.6h, and adding nano-scale lithium carbonate crystal seeds to promote the precipitation of lithium carbonate; and (3) carrying out solid-liquid precipitation separation on the lithium carbonate slurry, washing with evaporated and concentrated water, and drying to obtain high-purity lithium carbonate, weighing 960 tons of the lithium carbonate, wherein the purity of the high-purity lithium carbonate is 99.994%, and the product meets the quality standard of YS/T546-2008 & lthigh-purity lithium carbonate & gt.
Example 7
The lithium-rich eluent after the electrodialysis treatment of geothermal water in a certain area of Jiangsu is treated, and the scale of the lithium-rich eluent is 40m 3 H, eluent composition:
| composition (A) | Li + | Ca 2+ | Mg 2+ | Mn 2+ | B 2 O 3 | Na + | K+ | Cl - | SO 4 2- |
| Content (g/L) | 2.6 | 0.5 | 0.9 | 0.1 | 0.13 | 1.4 | 0.9 | 1.5 | 0.3 |
At the start, the lithium-rich eluent after the lithium extraction treatment is 40m 3 Feeding the mixture into a supergravity machine through a liquid conveying pump, adding an impurity removing agent, heating to 40 ℃, keeping the temperature, stirring and reacting for 1.3 hours to precipitate 98% of impurities such as magnesium, manganese, calcium and the like, controlling the pH value of a reaction end point to be 12.1, and filtering through a filter press after the reaction is finished to obtain filtrate; the filtrate is recompressed and concentrated by falling film steam, the evaporation temperature of the evaporation concentration part is controlled to be 90 ℃, the effective temperature difference is controlled to be 5.6 ℃, and the vacuum degree is controlled to be-0.44MPa; salt is crystallized and separated out in the evaporation concentration process to obtain a concentrated solution, and evaporated water is condensed for later use; enabling the concentrated solution to pass through two stages of ion exchange columns loaded with cation exchange resin and anion exchange resin at the flow rate of 13BV/h, and respectively removing impurities such as divalent ions including calcium, magnesium and the like and trivalent ions including boron and the like in the solution; adding gluconic acid, complexing trace calcium, magnesium, iron and other ions in the filtrate to form complex ions with larger volume, and separating lithium ions with smaller volume by using an ultrafiltration membrane made of ceramic to obtain a refined lithium-rich solution; adding the refined lithium-rich solution into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse mode, wherein the pulse frequency is 30KHz, keeping the temperature, stirring uniformly, reacting for 1.8h, and adding flower-shaped lithium carbonate crystal seeds to promote the precipitation of lithium carbonate; and carrying out solid-liquid precipitation separation on the lithium carbonate slurry, washing with evaporated and concentrated water, and drying to obtain high-purity lithium carbonate, weighing 4170 tons of the high-purity lithium carbonate, wherein the purity of the high-purity lithium carbonate is 99.992%, and the product meets the quality standard of YS/T546-2008 high-purity lithium carbonate.
Example 8
The lithium-rich eluent after being treated in a certain salt lake of Tibet is treated, and the scale of the lithium-rich eluent is 60m 3 H, eluent composition:
| composition (I) | Li + | Ca 2+ | Mg 2+ | Mn 2+ | B 2 O 3 | Na + | K+ | Cl - | CO 3 2- |
| Content (g/L) | 4.5 | 0.1 | 0.1 | 0.1 | 0.2 | 1.0 | 1.2 | 0.3 | 1.2 |
At the start, the lithium-rich eluent after the lithium extraction treatment is 60m 3 Feeding the mixture into a supergravity machine through a liquid delivery pump, adding an impurity removing agent, heating to 53 ℃, keeping the temperature, stirring and reacting for 1.6 hours to precipitate 99% of impurities such as magnesium, manganese, calcium and the like, controlling the pH value of the reaction end point to be 12, and filtering through a filter press after the reaction is finished to obtain filtrate; carrying out recompression and concentration on the filtrate by utilizing falling film steam, controlling the evaporation temperature of an evaporation and concentration part to be 90 ℃, controlling the effective temperature difference to be 6.2 ℃ and controlling the vacuum degree to be-0.51 MPa; salt is crystallized and separated out in the evaporation concentration process to obtain a concentrated solution, and evaporated water is condensed for later use; enabling the concentrated solution to pass through two stages of ion exchange columns loaded with cation exchange resin and anion exchange resin at the flow rate of 9BV/h, and respectively removing impurities such as divalent ions including calcium, magnesium and the like and trivalent ions including boron and the like in the solution; adding citric acid, and complexing trace calcium, magnesium, iron, etc. ions in the filtrate to form larger volumeComplexing ions, namely separating lithium ions with small volume by using an ultrafiltration membrane made of polysulfone to obtain a refined lithium-rich solution; adding the refined lithium-rich solution into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse mode, wherein the pulse frequency is 22KHz, keeping the temperature, stirring uniformly, reacting for 0.9h, adding spherical lithium carbonate seed crystals to promote precipitation, and precipitating a large amount of lithium carbonate; and carrying out solid-liquid precipitation separation on the lithium carbonate slurry, washing with evaporated and concentrated water, and drying to obtain high-purity lithium carbonate, weighing 10800 tons of the lithium carbonate, wherein the purity of the high-purity lithium carbonate is 99.99%, and the product meets the quality standard of YS/T546-2008 high-purity lithium carbonate.
The novel method for comprehensively utilizing the lithium resources provided by the invention organically combines an ion exchange method, a membrane method and an evaporation method together through a lithium resource comprehensive utilization process of precipitation impurity removal, falling film evaporation concentration, ion exchange treatment, ultrafiltration membrane refining and pulse lithium deposition reaction, greatly reduces the energy consumption, reduces the cost, effectively removes calcium ions and magnesium ions in a mother solution, ensures that the finally prepared lithium carbonate has the advantages of high purity and stable quality, and the original mother solution has high utilization rate, is simple and convenient to operate, low in energy consumption, stable in effect, high in yield, low in cost, comprehensive utilization of water resources, continuous and controllable in process, low in investment, high in efficiency and the like, is very clean in the whole processing process, does not generate intermediate pollution, meets the current national requirements on environmental protection and benefit, and is worthy of great advocation and wide popularization.
Claims (9)
1. A processing method for purifying high-purity lithium carbonate is characterized by comprising the following steps:
step I, conveying the lithium-rich eluent into a supergravity machine through a liquid conveying pump, adding an impurity removing agent, heating to 40-60 ℃, keeping the temperature, stirring and reacting for 0.5-2 h, controlling the pH value of the reaction end point to be 12 +/-0.5, and filtering to remove precipitates after the reaction is finished to obtain a filtrate;
step II, concentrating the filtrate obtained in the step I by a falling film steam device, controlling the evaporation temperature to be 90 ℃, the temperature difference to be 3-10 ℃ and the vacuum degree to be-0.3-0.6 MPa; evaporating and concentrating to obtain a concentrated solution, and reserving evaporated condensed water for later use;
step III, passing the concentrated solution in the step II through one-stage or multi-stage ion exchange columns loaded with cation exchange resin, anion exchange resin and/or chelating resin to respectively remove impurities of calcium and magnesium divalent ions and boron trivalent ions in the solution;
step IV, adding a complexing agent into the solution obtained in the step III, complexing trace calcium, magnesium and iron ions in the filtrate into complex ions with larger volume, and separating lithium ions with smaller volume through an ultrafiltration membrane to obtain a refined lithium-rich solution;
step V, adding the refined lithium-rich solution in the step IV into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse form, keeping the temperature, stirring uniformly, reacting for 0.5-2 h, adding seed crystals to promote crystallization of lithium carbonate to form lithium carbonate slurry, and carrying out solid-liquid separation, washing with evaporated and concentrated water, and drying to obtain high-purity lithium carbonate;
wherein, in the step I, the lithium ion concentration in the lithium-rich eluent is more than or equal to the magnesium ion concentration;
wherein the impurity removing agent is one or more of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium oxalate, potassium oxalate and oxalic acid.
2. The treatment method according to claim 1, wherein the lithium-rich eluent is a lithium-rich eluent obtained by extracting oil field water, coal bed gas field produced water, salt lake brine, salt lake intercrystalline brine, geothermal water, underground brine, seawater and thermal spring water in an oil field exploration process.
3. The treatment method according to claim 1, wherein in the step III, the cation exchange resin is selected from one or more of styrene, acrylic acid and phenolic aldehyde; the anion exchange resin is selected from one or more of styrene, acrylic acid and epoxy; the chelating resin is selected from one or more of D110, D113, D152, D401, D403, D418 and D564.
4. The process of claim 1, wherein in step III, the flow rate of the concentrate through the ion exchange column is 5 to 50BV/h.
5. The processing method according to claim 1, characterized in that: in the step IV, the complexing agent is one or more of EDTA, crown ether, nitrilotriacetic acid, citric acid, tartaric acid, oleic acid, gluconic acid and diethylenetriaminepentaacetic acid.
6. The processing method according to claim 1, characterized in that: in the step IV, the ultrafiltration membrane is made of ceramics, polysulfone, polyether ether ketone, polyvinylidene fluoride or polytetrafluoroethylene, the filtration precision of the ultrafiltration membrane is 10-100nm, the component mode of the ultrafiltration membrane is hollow fiber, roll type, plate type or tube type, and the filtration mode of the ultrafiltration membrane is cross flow or counter flow filtration.
7. The processing method according to claim 1, characterized in that: in the step V, the pulse frequency of the saturated sodium carbonate solution is 10-100 KHz.
8. The processing method according to claim 7, characterized in that: and in the step V, the pulse frequency of the saturated sodium carbonate solution is 20-30 KHz.
9. The processing method according to claim 1, characterized in that: in the step V, the seed crystal is lithium carbonate with the particle size of nano-scale and various particle sizes of hundreds of microns, and the shape of the seed crystal is one or more of spherical, rod-shaped, flower-shaped, sheet-shaped and hollow spheres.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810915675.7A CN110817907B (en) | 2018-08-13 | 2018-08-13 | Treatment system and method for purifying high-purity lithium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810915675.7A CN110817907B (en) | 2018-08-13 | 2018-08-13 | Treatment system and method for purifying high-purity lithium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110817907A CN110817907A (en) | 2020-02-21 |
| CN110817907B true CN110817907B (en) | 2022-12-27 |
Family
ID=69546764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810915675.7A Active CN110817907B (en) | 2018-08-13 | 2018-08-13 | Treatment system and method for purifying high-purity lithium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110817907B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111960444A (en) * | 2020-08-28 | 2020-11-20 | 贵州大龙汇成新材料有限公司 | Method for preparing lithium carbonate by utilizing manganese-containing wastewater and waste lithium battery lithium-rich solution |
| CN112875731B (en) * | 2021-04-19 | 2023-12-08 | 青海盐湖工业股份有限公司 | Preparation method of lithium carbonate |
| CN114361431B (en) * | 2021-08-20 | 2024-07-02 | 山东瑞福锂业有限公司 | Process and method for regulating and controlling structure of regular micron-sized lithium carbonate material for ternary positive electrode material in lithium ion battery |
| CN114042352A (en) * | 2021-11-12 | 2022-02-15 | 荆门市格林美新材料有限公司 | A kind of ammonium bicarbonate solution oil removing device and method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538057A (en) * | 2009-04-24 | 2009-09-23 | 钟辉 | Method for separating magnesium from lithium and extracting lithium from brine |
| CN103539142A (en) * | 2013-10-24 | 2014-01-29 | 中国地质科学院郑州矿产综合利用研究所 | Method for combined extraction of potassium-magnesium fertilizer, boric acid and lithium carbonate from sodium sulfate subtype salt lake |
| CN105399115A (en) * | 2015-12-31 | 2016-03-16 | 中国科学院青海盐湖研究所 | Preparation method for high-purity submicron lithium carbonate |
| CN105540619A (en) * | 2015-08-17 | 2016-05-04 | 马培华 | Method for directly preparing battery grade lithium carbonate from salt lake brine with high magnesium-to-lithium ratio |
| CN107739040A (en) * | 2017-11-15 | 2018-02-27 | 韶关中弘金属实业有限公司 | Waste material containing lithium produces the production technology of high-purity lithium carbonate |
-
2018
- 2018-08-13 CN CN201810915675.7A patent/CN110817907B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538057A (en) * | 2009-04-24 | 2009-09-23 | 钟辉 | Method for separating magnesium from lithium and extracting lithium from brine |
| CN103539142A (en) * | 2013-10-24 | 2014-01-29 | 中国地质科学院郑州矿产综合利用研究所 | Method for combined extraction of potassium-magnesium fertilizer, boric acid and lithium carbonate from sodium sulfate subtype salt lake |
| CN105540619A (en) * | 2015-08-17 | 2016-05-04 | 马培华 | Method for directly preparing battery grade lithium carbonate from salt lake brine with high magnesium-to-lithium ratio |
| CN105399115A (en) * | 2015-12-31 | 2016-03-16 | 中国科学院青海盐湖研究所 | Preparation method for high-purity submicron lithium carbonate |
| CN107739040A (en) * | 2017-11-15 | 2018-02-27 | 韶关中弘金属实业有限公司 | Waste material containing lithium produces the production technology of high-purity lithium carbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110817907A (en) | 2020-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11097954B2 (en) | Method and system for preparing battery grade and high purity grade lithium hydroxide and lithium carbonate from high-impurity lithium sources | |
| CN110817907B (en) | Treatment system and method for purifying high-purity lithium carbonate | |
| CN102531002B (en) | Method for purifying lithium carbonate | |
| CN102145905B (en) | Method for preparing metallurgy-level aluminum oxide by using fluidized bed pulverized fuel ash | |
| CN100469697C (en) | Method for producing low-magnesium battery-stage lithium carbonate from lithium sulfate solution | |
| CN103958412A (en) | Process for producing lithium carbonate from concentrated lithium brine | |
| CN102602966B (en) | A method for separating magnesium and lithium from salt lake brine and preparing lithium carbonate | |
| CN105540619A (en) | Method for directly preparing battery grade lithium carbonate from salt lake brine with high magnesium-to-lithium ratio | |
| CN104261607A (en) | Processing method of complex raffinate | |
| CN113511663A (en) | Process for preparing lithium carbonate by extracting lithium from oil field underground brine | |
| CN109678196B (en) | Method for fully recycling anions and cations in microetching waste liquid | |
| CN113336260B (en) | Method for recovering copper sulfate in acidic copper sulfate waste liquid | |
| CN111960445A (en) | Method for preparing battery-grade lithium carbonate by using lithium sulfate coarse ore and recycling by-products | |
| CN110817908A (en) | System and method for preparing high-purity lithium carbonate by using lithium-containing waste material | |
| CN110106356B (en) | Method for separating lithium from salt lake brine by using powder type titanium ion exchanger | |
| CN106006681A (en) | Method for resourceful treatment of high-salt wastewater | |
| CN109851084B (en) | Resourceful treatment method for reducing content of ammonia nitrogen, calcium and magnesium ions in manganese-containing wastewater | |
| CN109264751B (en) | Method for extracting lithium carbonate and ammonium metavanadate from lepidolite and vanadium-containing shale | |
| CN111592017A (en) | Method for preparing battery-grade lithium chloride by pressing and soaking spodumene | |
| CN109534369B (en) | Membrane integrated lithium chloride preparation equipment and method thereof | |
| KR101158828B1 (en) | Method for economical extraction of magnesium, boron and calcium from brine | |
| CN103172122A (en) | Method for purifying high purity ammonium rhenate from liquid containing ammonium rhenate | |
| CN110563009A (en) | A kind of carbonization decomposition method prepares the method for battery grade lithium carbonate from fly ash | |
| CN102319592B (en) | Method for preparing inorganic potassium salt based on sugar making diethyl ether and dilute juice desalination | |
| CN102120592B (en) | Method for extracting lithium carbonate by flotation of mixed salt of NaCl and lithium carbonate |
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 |