CN110711551A - Lithium adsorbent and preparation method thereof - Google Patents
Lithium adsorbent and preparation method thereof Download PDFInfo
- Publication number
- CN110711551A CN110711551A CN201911029579.3A CN201911029579A CN110711551A CN 110711551 A CN110711551 A CN 110711551A CN 201911029579 A CN201911029579 A CN 201911029579A CN 110711551 A CN110711551 A CN 110711551A
- Authority
- CN
- China
- Prior art keywords
- lithium
- adsorbent
- salt
- aluminum
- chloride
- 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
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0211—Compounds of Ti, Zr, Hf
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a lithium adsorbent and a manufacturing method thereof. The lithium salt adsorbent which has lattice defects and a stable structure is prepared by taking aluminum-zirconium salt and lithium salt as raw materials through the steps of high-speed shearing and mixing, pH adjustment, lithium salt adding again, separation, washing, drying and the like. The adsorbent has good lithium selectivity, can reduce the magnesium-lithium ratio of brine higher than 500:1 to below 10:1, has the characteristics of large adsorption capacity, low dissolution loss rate and long service life, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of lithium extraction adsorption, in particular to a lithium adsorbent and a manufacturing method thereof.
Background
Lithium is currently known as the lightest metal and the smallest radius alkali metal. The method is widely applied to many fields of new energy, medicines, chemical industry, new materials and the like. With the popularization of electronic products and the rise of new energy vehicles, the demand of the society for lithium batteries is increasing day by day, which directly leads to the rapid rise of the demand for lithium, and the lithium becomes an important strategic resource. Lithium resources in nature mainly exist in liquid resources such as lithium ores, salt lakes, seawater and the like. Lithium resources are limited and distributed intensively around the world. Since the concentration of lithium in seawater is too low, this fraction of lithium is not currently available. The cost of extracting lithium from ore is high and limited by the mining scale, and the requirement of low cost and rapid increase of lithium batteries is difficult to meet, so that the lithium extraction from salt lakes is more and more emphasized by people, and the method has a wide development prospect. Most of the lithium resources in China are salt lake lithium, which accounts for more than 80% of the total amount, but the salt lake brine in China has low grade, particularly the Qinghai salt lake has high magnesium-lithium ratio, magnesium and lithium are positioned at adjacent diagonal positions in the periodic table of elements, the magnesium and the lithium have extremely similar chemical properties, and the common physical and chemical methods are difficult to effectively separate, so that the difficulty is brought to the exploitation of the lithium resources.
The method widely used for extracting lithium from salt lake or brine at present mainly comprises the following steps: calcining, extracting, membrane separating and adsorbing (Li Zeng, Liu Guo Wang, Tang Fang Man. Qinghai salt lake lithium resource and lithium extraction technical overview. resource information and engineering, 2017,5: 94-97).
The calcining method is that the dry powder after the old brine is evaporated and dried is calcined at high temperature, bischofite is decomposed into magnesium oxide and hydrogen chloride gas at the temperature higher than 550 ℃, the calcined sinter is soaked in water to obtain lithium chloride solution containing a small amount of impurities, and then the lithium carbonate product is obtained after filtering, evaporation, alkaline precipitation and drying. The calcining method has high energy consumption, a large amount of hydrogen chloride gas is generated in the calcining process, the equipment is seriously corroded and polluted, lithium is carried in the low-grade magnesium oxide of the product, the lithium yield is low, the cost is high, and therefore the calcining method is gradually eliminated.
The extraction method can extract lithium from low-grade brine. Organic matters such as TBP (tributyl phosphate) and the like are usually used as an extracting agent, ferric chloride is used as a complexing agent, hydrochloric acid is used as a back-extracting agent, organic phases are recovered through the procedures of multi-stage countercurrent extraction washing, back-extraction, acid washing and the like, and back-extracting solution is subjected to evaporation concentration, impurity removal, alkali addition for lithium carbonate preparation or drying for lithium chloride preparation. The method has good magnesium-lithium separation effect and high lithium yield, but has the disadvantages of large water consumption in the extraction process, high energy consumption of back extraction solution evaporation and concentration, corrosion of equipment by dilute acid and serious environmental pollution caused by used organic matters.
The membrane separation method (electrodialysis method) is to make lithium-containing brine pass through a multi-stage ion selective electrodialyzer, and realize magnesium-lithium separation and lithium concentration by utilizing the selectivity of the membrane. The membrane method has good separation effect, is green and environment-friendly, but has high requirements on the membrane, high price and high energy consumption when electricity is used as external force for separation.
The adsorption method is to use a lithium ion selective adsorbent to adsorb and extract lithium ions in the brine, and then use water or dilute acid to elute the lithium ions, so as to achieve the purpose of separating the lithium ions from other ions. Is a preferred method for brine with low lithium content. The adsorption method has simple process, is green and environment-friendly, but has higher requirement on the adsorbent.
Compared comprehensively, the adsorption method is a simple, convenient and efficient method, has wide prospect in extracting lithium from salt lakes, and has the key of extracting lithium by the method, namely a high-performance adsorbent. Currently, adsorbents are mainly classified into organic ion exchange adsorbents and inorganic ion exchange adsorbents. The organic ion exchange adsorbent has low selectivity to lithium ions, and the selectivity is difficult to control, while the inorganic ion adsorbent has high selectivity to lithium, so the organic ion exchange adsorbent is widely applied. Currently, the commonly used inorganic ion exchange adsorbents mainly include: amorphous hydroxide adsorbent, ion sieve type oxide adsorbent, layered adsorbent, composite antimonate adsorbent and aluminum salt adsorbent. Wherein the aluminum salt adsorbent has high selectivity, good stability and wider application prospect.
In the presently disclosed technology, the adsorbent for lithium adsorption tends to be subjected to a high-energy milling mixing reaction with aluminum hydroxide and lithium chloride, and the method may have the defects of uneven reaction, low aluminum-lithium ratio and deviation of lithium intercalation lattice parameters. Finally, the defects of low lithium adsorption amount, poor lithium selectivity, high magnesium-lithium ratio of the reverse adsorption liquid and difficult separation are caused. Meanwhile, the deviation of the lattice parameter can cause the collapse of the structure in the circulation process, and finally the adsorbent fails. Therefore, the lithium salt adsorbent is expected to be recycled from the aspects of material forming and modification.
Chinese patent application No. 201810593699.5 discloses an aluminum salt adsorbent and its use in extracting lithium from salt lake brine. The invention adopts modified macroporous resin as a carrier, and aluminum hydroxide which is surface modified by a coupling agent is loaded on the resin. The method has good dispersion and effectively reduces the dissolution loss rate, but introduces a plurality of organic matters in the process to increase the environmental protection pressure, has complex manufacturing process and higher cost, and is not beneficial to industrial production. Chinese patent application No. 201710009167.8 discloses a method for making a particulate sorbent for use in extracting lithium from lithium-containing brines. The invention adds alkaline reagent into aluminum chloride solution with lithium ion, adjusts pH value to 6-7, Al: li in an atomic ratio of 3.0 to 3.5 to produce LiCl.3Al (OH)3•nH2The O lithium aluminum double hydroxide improves the utilization rate of single lithium ions. Due to the fact that the content of Al is increased, after repeated cyclic adsorption is carried out, the crystal structure is easily damaged, and the service life of the adsorbent is affected.
Disclosure of Invention
The present invention is directed to a method for preparing a novel lithium adsorbent, which addresses the problems of the background art.
The two most critical steps in the present invention are, first, the formation of metastable crystalline material with sufficient crystal defects to produce as many surface defects as possible; secondly, the crystal containing a large number of defects is mineralized, and the stability of the main skeleton of the crystal is ensured. Lithium salt and aluminum zirconium salt are used to generate aluminum zirconium lithium hydrated crystal with defects (lithium intercalation lattice) after high-speed shearing dispersion, the aluminum zirconium lithium ratio is ensured, the condition is controlled to carry out lithium salt soaking mineralization after mixed metastable state slurry is formed, the completeness and stability of the crystal structure are ensured, and finally the adsorbent with high adsorption capacity, stability and pollution resistance is obtained.
The technical scheme of the invention is as follows:
mixing aluminum zirconium salt and lithium salt according to the molar ratio of aluminum zirconium lithium atoms of 1:0.3-0.8, feeding water serving as a medium into a high-speed shearing mixer, ensuring that the hourly circulation volume of a shearing machine is more than 10 times of the volume of the treated mixed slurry, adjusting the pH value to 7.6-10.5 by using acid or alkali after mixing is finished, adding lithium chloride with 0.5-3 times of the molar amount of the lithium salt, standing and mineralizing for 1-200 hours, performing filter pressing separation, and washing by using water with 3 times of the volume of the slurry. And drying to obtain the lithium adsorbent with a stable crystal structure. The molecular formula of the lithium adsorbent is aLiCl3•cLiOH•nH2O
The invention has the beneficial effects that: 1. the adsorbent of the invention has lithium intercalation lattice defect, larger adsorption capacity and higher lithium selectivity, and can ensure that the initial magnesium-lithium ratio is 500:1 to below 10: 1. 2. The adsorbent of the invention has reasonable aluminum-zirconium-lithium ratio, stable crystal structure, pollution resistance and longer service life. 3. The invention has simple process and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a microscopic view of a crystal prepared by the method of the present invention.
Fig. 2 is an XRD pattern before mineralization of the prepared lithium adsorbent.
Fig. 3 is an XRD pattern after mineralization of the prepared lithium adsorbent.
Detailed Description
Example 1
The lithium adsorbent is prepared by the method, and the specific method comprises the following steps:
(1) weighing 10mol of aluminum zirconium chloride, and dissolving the aluminum zirconium chloride in 4L of water to obtain 2.5mol/L solution;
(2) weighing 3mol of lithium chloride, and dissolving in 1L of water;
(3) adding 1L of deionized water into a high-speed shearing and stirring kettle, increasing the shearing and stirring speed to 450 revolutions per minute, adding the aluminum zirconium chloride solution and lithium chloride into the kettle in a parallel flow manner, and continuing stirring after the addition is finished;
(4) the pH of the slurry was adjusted to 7.6 with 5mol/L NaOH solution, the pH varied during the addition of alkali, and when the pH exceeded 7.6, the pH was lowered to 7.6 by adding an appropriate amount of 5mol/L sulfuric acid. Adding 1.5mol of lithium chloride, stirring for 30 minutes, separating by using a filter press, washing by using 20L of deionized water, and finally, enabling the content of chloride ions in the washing liquid to be lower than 0.1%;
(5) and drying the filter cake to obtain the adsorbent with 10% of water.
Example 2
(1) Weighing 10mol of aluminum zirconium chloride, and dissolving in 4L of water;
(2) weighing 8mol of lithium nitrate, and dissolving in 1.6L of water;
(3) adding 1L of deionized water into a high-speed shearing and stirring kettle, increasing the shearing and stirring speed to 450 revolutions per minute, adding the aluminum zirconium chloride solution and the lithium nitrate solution into the kettle in a parallel flow manner, and continuing stirring after the addition is finished;
(4) adjusting the pH value of the slurry to 10.5 by using 10mol/L sodium hydroxide solution, adding 24mol of lithium chloride, stirring for 30 minutes, separating by using a filter press, washing by using 20L of deionized water, and finally, ensuring that the nitrate content in the washing liquid is lower than 0.05 percent;
(5) the filter cake was dried to give an adsorbent containing 10% water.
Example 3
(1) Weighing 10mol of aluminum zirconium chloride, and dissolving in 4L of water;
(2) weighing 1.5mol of lithium sulfate monohydrate, and dissolving in 1.5mol of water;
(3) adding 1L of deionized water into a high-speed shearing and stirring kettle, increasing the shearing and stirring speed to 450 revolutions per minute, adding the aluminum zirconium chloride solution and the lithium sulfate solution into the kettle in a parallel flow manner, and continuing stirring after the addition is finished;
(4) adjusting the pH value of the slurry to 6 by using 10mol/L sodium hydroxide, adding 9mol of lithium chloride, stirring for 30 minutes, separating by using a filter press, washing by using 20L of deionized water, and finally, enabling the sulfate radical content in the washing liquid to be lower than 0.05%;
(5) and adding deionized water into the obtained filter cake to prepare slurry with the solid content of 20%, and drying to obtain the adsorbent with the water content of 10%.
Example 4
(1) Weighing 5mol of aluminum zirconium sulfate, and dissolving in 4L of water;
(2) weighing 8mol of lithium chloride, and dissolving in 1L of water;
(3) adding 1L of deionized water into a high-speed shearing and stirring kettle, increasing the shearing and stirring speed to 450 rpm, adding the aluminum zirconium sulfate solution and the lithium chloride solution into the kettle in a concurrent flow manner, and continuing stirring for 30 minutes after the addition is finished;
(4) adjusting the pH value of the slurry to 9 by using 10mol/L sodium hydroxide, stirring for 30 minutes, separating by using a filter press, and washing by using 20L deionized water, wherein the sulfate radical content in the washing liquid is lower than 0.05 percent finally;
(5) the filter cake was dried to give an adsorbent containing 10% water.
Sorbent performance testing
The lithium adsorbents prepared in the examples and the comparative examples are respectively subjected to adsorption performance tests by adopting salt lake brine, wherein the adsorption performance tests comprise adsorption capacity, magnesium-lithium ratio after adsorption, and Li+The elution rate. The composition of the salt lake brine is shown in Table 1
TABLE 1 chemical composition of salt lake brines used
| Element(s) | Mg | Na | K | Ca | Li | Mg/Li |
| Content (mg/L) | 77062 | 3514 | 1032 | 165 | 218 | 353.5 |
The test procedure was as follows:
accurately weighing 30g of adsorbent, adding the adsorbent into simulated brine according to the proportion of m/V =1:10, stirring for 4h at a constant temperature of 25 ℃, and measuring the content of metal ions in the solution by using ICP (inductively coupled plasma); accurately weighing the adsorbed and dried adsorbent powder, adding the adsorbent powder into deionized water according to the proportion of m/V =1:10, stirring for 4 hours at a constant temperature of 25 ℃ for desorption, filtering, and testing the content of each metal ion in the filtrate. And drying the filtered adsorbent, weighing, and calculating the dissolution loss rate of the adsorbent.
Wherein the calculation formula of the adsorption capacity is as follows:
adsorption capacity = (lithium content in brine before adsorption-lithium content in brine after adsorption) × column-passing brine quality/adsorbent powder quality
The test results are shown in Table 2
| Sample (I) | Li adsorption amount (mg/g) | Mg/Li ratio after adsorption | Dissolution rate (500 cycles) |
| Example 1 | 12 | 5.1:1 | 0.05% |
| Example 2 | 11.5 | 5.4:1 | 0.06% |
| Example 3 | 9 | 7.9:1 | 0.05% |
| Example 4 | 15 | 5.6:1 | 0.07% |
The experimental result shows that the adsorbent prepared by mixing the aluminum zirconium salt and the lithium salt is used for Li+High selectivity, higher adsorption capacity than common aluminum salt adsorbent, more stable structure and longer service life.
The above examples are only for better illustration of the technical process involved in the invention, and any extension based on the principle of the invention is included in the scope of the present patent protection.
Claims (8)
1. A lithium adsorbent and a method for producing the same, characterized in that: mixing aluminum zirconium salt and lithium salt according to a proportion, taking water as a medium, feeding the mixture into a high-speed shearing mixer, adjusting the pH value after the mixing is finished, adding lithium chloride, standing for 1-6 hours, performing filter pressing separation, washing with deionized water, and drying to obtain an adsorbent product.
2. The lithium adsorbent and the production method thereof according to claim 1, wherein the content of zirconium in the aluminum zirconium salt is 0.5%, and the aluminum zirconium salt and the lithium salt are in an aluminum zirconium lithium atomic molar ratio of 1:0.3 to 1: 0.8.
3. The lithium adsorbent and the method for producing the same according to claim 1, wherein the aluminum zirconium salt and the lithium salt are both water-soluble salts, the aluminum zirconium salt is aluminum chloride doped zirconium chloride, aluminum nitrate doped zirconium nitrate, aluminum sulfate doped zirconium sulfate, and the lithium salt is lithium chloride, lithium sulfate, lithium nitrate.
4. The lithium adsorbent and the method for producing the same according to claim 1, wherein the lithium salt and the aluminum zirconium salt are mixed in the high speed shear mixer in such a manner that the volume of the mixture is 10 times or more the volume of the slurry to be treated per hour.
5. The lithium adsorbent and the method for producing the same as claimed in claim 1, wherein the pH of the slurry after shear mixing is adjusted to 7.6 to 10.5 by using 5 to 10mol/L sodium hydroxide solution and 5 to 20mol/L sulfuric acid.
6. The lithium adsorbent and the method for producing the same according to claim 1, wherein the molar amount of lithium chloride added after the pH adjustment and the ratio of the lithium salt added in claim 2 are 0.5 to 3 times.
7. The lithium adsorbent and the production method thereof according to claim 1, wherein the index of the water washing acceptability is that the contents of sulfate, nitrate and chloride ions in the washing liquid are < 1%.
8. The lithium adsorbent and the method for producing the same according to claim 1, wherein water is added to reduce the solid content of the slurry to 20% or less during the drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911029579.3A CN110711551A (en) | 2019-10-28 | 2019-10-28 | Lithium adsorbent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911029579.3A CN110711551A (en) | 2019-10-28 | 2019-10-28 | Lithium adsorbent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110711551A true CN110711551A (en) | 2020-01-21 |
Family
ID=69213350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911029579.3A Pending CN110711551A (en) | 2019-10-28 | 2019-10-28 | Lithium adsorbent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110711551A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618440A (en) * | 2020-12-14 | 2022-06-14 | 中蓝长化工程科技有限公司 | Synthesis process of lithium salt adsorbent precursor |
-
2019
- 2019-10-28 CN CN201911029579.3A patent/CN110711551A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618440A (en) * | 2020-12-14 | 2022-06-14 | 中蓝长化工程科技有限公司 | Synthesis process of lithium salt adsorbent precursor |
| CN114618440B (en) * | 2020-12-14 | 2023-07-11 | 中蓝长化工程科技有限公司 | Synthesis process of lithium salt adsorbent precursor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Orooji et al. | Recent advances in nanomaterial development for lithium ion-sieving technologies | |
| US11524901B2 (en) | Method for efficiently separating magnesium and lithium from salt lake brine and simultaneously preparing high-purity magnesium oxide and battery-grade lithium carbonate | |
| Chitrakar et al. | Synthesis of iron-doped manganese oxides with an ion-sieve property: lithium adsorption from Bolivian brine | |
| CN110639467A (en) | Preparation method of magnetic aluminum salt lithium adsorbent | |
| CN107376827A (en) | A kind of zirconia-coated manganese systems lithium ion sieve and its preparation method and application | |
| CN204162442U (en) | A kind of device being extracted battery grade lithium by bittern | |
| Wang et al. | Application of citric acid as eluting medium for titanium type lithium ion sieve | |
| CN113926419A (en) | Preparation method of Keggin chain structure aluminum lithium adsorbent | |
| CN113511663A (en) | Process for preparing lithium carbonate by extracting lithium from oil field underground brine | |
| Liu et al. | Alkaline resins enhancing Li+/H+ Ion exchange for lithium recovery from brines using granular titanium-type lithium ion-sieves | |
| CN102502722A (en) | Preparation method of high-purity magnesium oxide | |
| Gao et al. | Enhanced Li+ adsorption by magnetically recyclable iron-doped lithium manganese oxide ion-sieve: Synthesis, characterization, adsorption kinetics and isotherm | |
| CN110180489B (en) | Sulfur-doped lithium-rich manganese lithium adsorbent and preparation method and application thereof | |
| Özmal et al. | Li+ adsorption/desorption properties of lithium ion-sieves in aqueous solution and recovery of lithium from borogypsum | |
| CN109504857B (en) | Method for extracting soluble potassium ions from biotite by magnesium ion exchange method | |
| CN110711551A (en) | Lithium adsorbent and preparation method thereof | |
| CN115739004B (en) | Lithium-aluminum adsorption material prepared from salt lake brine with high magnesium-lithium ratio and method thereof | |
| CN116440873A (en) | Adsorbent for adsorbing lithium from refined liquid of alumina produced by Bayer process and use method thereof | |
| KR100850009B1 (en) | A manufacturing method of high degree of purity indium oxide from ito target | |
| CN115646474A (en) | Manganese titanium-based composite lithium ion sieve and preparation method and application thereof | |
| CN114618440B (en) | Synthesis process of lithium salt adsorbent precursor | |
| CN116159531A (en) | Preparation method of hollow fiber membrane lithium ion adsorbent | |
| CN115448282A (en) | Method for preparing lithium iron phosphate from nickel-iron alloy and application of lithium iron phosphate | |
| GB2622157A (en) | Wastewater adsorbent, and preparation method therefor and use thereof | |
| CN111250034B (en) | Modification method and application of desulfurization slag |
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 |