KR20160134085A - Magnetic lithium adsorbent, method for preparing the same, and method of recovering lithium by using the same - Google Patents
Magnetic lithium adsorbent, method for preparing the same, and method of recovering lithium by using the same Download PDFInfo
- Publication number
- KR20160134085A KR20160134085A KR1020150067520A KR20150067520A KR20160134085A KR 20160134085 A KR20160134085 A KR 20160134085A KR 1020150067520 A KR1020150067520 A KR 1020150067520A KR 20150067520 A KR20150067520 A KR 20150067520A KR 20160134085 A KR20160134085 A KR 20160134085A
- Authority
- KR
- South Korea
- Prior art keywords
- lithium
- manganese oxide
- magnetic
- precursor
- oxide particles
- Prior art date
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
- B01J20/0222—Compounds of Mn, Re
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
- B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
- B01J20/3219—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond involving a particular spacer or linking group, e.g. for attaching an active group
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Substituted lithium manganese oxide particles and magnetic particles, wherein the magnetic particles are located on the surface of the lithium manganese oxide particles substituted with the hydrogen ion, or the lithium manganese oxide particles are hybridized with each other Wherein the hydrogen ion-substituted lithium manganese oxide particles are all or part of lithium ions present in the lithium manganese oxide particles are substituted with hydrogen ions, a process for producing the same, and a process for recovering lithium using the same.
Description
The present invention relates to a magnetic lithium adsorbent, a method for producing the same, and a method for recovering lithium using the same. More particularly, the present invention relates to a magnetic lithium adsorbent capable of selectively adsorbing lithium and capable of easily separating in water, a method for producing the same, and a method for recovering lithium using the same.
Recently, as the demand for secondary batteries for smart phones and electric vehicles has increased sharply internationally, the usage of lithium-based secondary batteries has been greatly increasing. This disparity in supply due to the increased demand of lithium will cause various international resource policies and export restrictions due to the increase of lithium resource prices and resource depletion, which is expected to have a great impact on the international economy.
Accordingly, attention is focused on new lithium resources to meet the demand for lithium.
Pegmatite, a kind of ore, and Brine in salt lake, which has a high lithium ion concentration, account for 26% and 66% of international lithium supply, respectively. (J.Ind.Ecol. 2011, 15, 760-775.) However, both of these resources have disadvantages that are distributed locally in Bolivia, Chile, Argentina, China, and the United States. Seawater, which is expected to be a new resource, is a semi-permanent resource estimated at a total of 230 billion tons. However, it has about 0.17 mg / L lithium ion concentration compared with other ions dissolved together. Therefore, the evaporation method used for lithium extraction in conventional salt is not suitable for application. For this purpose, methods such as adsorption method, solvent extraction method and coprecipitation method have been studied. However, it is known that the adsorption method using a lithium adsorbent based on manganese oxide which has a high selectivity to lithium and is inexpensive and environmentally harmless is known as the most preferable method. In addition, the manganese oxide-based adsorbent selectively adsorbs lithium ions in water due to ion exchange and oxidation-reduction reactions, and removes lithium adsorbed through hydrogen ions in a dilute acid solution, thereby recovering lithium. Therefore, the process can be repeated to realize a process that can be reused.
In order to realize the reuse process, it is necessary to pass a large number of processes for separating the adsorbent in water, but in the case of a powdery lithium adsorbent, it is not suitable for underwater separation. For this purpose, research groups have been conducting studies to realize a lithium adsorbent in granular form or in the form of a separator using polyvinyl chloride (PVC) using a binder of various materials. However, these methods require complicated processes or high operating costs, or require the use of dimethyl formates (see, for example, < RTI ID = 0.0 > Amide (DMF), a large amount of harmful wastewater can be discharged.
SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a process for separating a powdery material from water using an external magnetic field as a method for replacing existing methods having the above problems, It is an object of the present invention to provide a magnetic lithium adsorbent having magnetic properties and capable of reacting immediately to an external magnetic field and easily separating from water and having a lithium adsorption function of manganese oxide, a method for producing the same, and a method for recovering lithium using the same.
In order to solve the above problems, according to one aspect of the present invention,
Wherein the lithium manganese oxide particles are hydrogen ion-substituted, and the magnetic particles are located on the surface of the lithium manganese oxide particles that are hydrogen-ion-substituted, or the lithium manganese oxide particles are hydrogen-ion- And the hydrogen ion-substituted lithium manganese oxide particles are replaced with hydrogen ions in whole or in part of lithium ions present in lithium manganese oxide particles.
According to another aspect of the present invention,
Mixing an aqueous solution of a lithium precursor with an aqueous solution of a manganese precursor to prepare a mixture;
Subjecting the mixture to hydrothermal reaction to produce lithium manganese oxide particles;
Adding the lithium manganese oxide particles to an aqueous solution of iron hydroxide (Fe (OH) 2 ) to form a magnetic lithium adsorbent precursor complexed with magnetic particles and lithium manganese oxide particles; And
And subjecting the magnetic lithium adsorbent precursor to an acid treatment to impart a lithium ion exchange adsorption capability to the magnetic lithium adsorbent precursor.
According to another aspect of the present invention,
Adding the above magnetic lithium adsorbent to a lithium-dissolved solution to adsorb lithium; And
And separating the magnetic lithium adsorbent from the solution by using a magnet after completion of the adsorption step.
The present invention can be expected to reduce costs for practical industrial applications by introducing magnetic particles using relatively inexpensive reactants to a conventional selective lithium ion exchange functional manganese oxide and simplifying a lithium recovery apparatus using a magnetic lithium adsorbent, Solvents and reactants are not used, which has a more environment-friendly advantage. Further, lithium can be recovered by the ion exchange method, and the lithium adsorbent can be easily separated at low cost under an external magnetic field, which is advantageous for repeated use. Therefore, it is expected that it can be usefully used as a material for continuous lithium recovery process.
Fig. 1 shows XRD analysis results of the magnetic lithium adsorbent precursor prepared in Example 1. Fig.
FIG. 2 shows the result of surface analysis using the TEM of the magnetic lithium adsorbent precursor prepared in Example 1 and HR-TEM analysis using the FFT.
FIG. 3 shows the results of magnetic characteristic analysis using a vibrating sample magnetometer (VSM) of the magnetic lithium adsorbent precursor prepared in Example 1. FIG.
4 is a result of underwater separation test using the magnetic lithium adsorbent prepared in Example 1. Fig.
Fig. 5 shows the result of underwater separation test using the lithium adsorbent prepared in Comparative Example 1. Fig.
Hereinafter, the present invention will be described in detail. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It should be construed in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined. Therefore, the constitution described in the drawings described in the present specification is merely the most preferred embodiment of the present invention, and does not represent all the technical ideas of the present invention, so that various equivalents and variations Examples should be understood.
The magnetic lithium adsorbent according to one aspect of the present invention comprises hydrogen ion-substituted lithium manganese oxide particles and magnetic particles, wherein the magnetic particles are positioned on the surface of the lithium ion-substituted lithium manganese oxide particles, The lithium manganese oxide particles are combined with each other to form lithium manganese oxide particles, and all or part of lithium ions present in the lithium manganese oxide particles are replaced with hydrogen ions.
The hydrogen ion-substituted lithium manganese oxide particle is a precursor of a manganese oxide-based lithium adsorbent having an adsorption ability by lithium ion exchange, and is a kind of a structure to which magnetic particles are introduced and a material responsible for the lithium adsorption function of the magnetic lithium adsorbent.
In order to realize a lithium adsorbent having a capability of adsorbing through a stable lithium ion exchange, it is most preferable to form a composite material by introducing magnetic particles into the synthesized lithium manganese oxide particles, but the present invention is not limited thereto. A composite material obtained by introducing lithium manganese oxide particles into magnetic particles may also be applied to the present invention.
The lithium manganese oxide particles may be made of lithium manganese oxide having a spinel crystal structure and having a tunnel structure capable of moving lithium ions.
The lithium manganese oxide having such a spinel crystal structure may have the formula Li 1 + x Mn 2-x O 4 (0? X? 0.33), or Li 1.6 Mn 1.6 O 4 . Such lithium manganese oxide has high chemical stability and can be selectively used as a precursor of a lithium adsorbent because it can exhibit selective adsorption performance against lithium ions when formed with an ionic sieve.
The lithium manganese oxide may have a manganese oxidation number of 3.5 to 4. In the case of Li 1.33 Mn 1.67 O 4 having an average manganese oxidation number (ZMn to 4.00) of 4.00, the lithium manganese oxide can maximize the lithium absorption efficiency And it is easy to handle, and a desorption process for recovery of lithium ions after adsorption is also easy, and is most preferable, but is not limited thereto. Lithium manganese oxide having a spinel crystal structure having similar average manganese oxidation number is also applicable to the present invention.
The magnetic particles may be composed of at least one selected from the group consisting of magnetite (Fe 3 O 4 ), maghemite (γ-Fe 2 O 3 ) and ferrite, and among them, magnetite is preferable.
The content of the hydrogen-ion-substituted lithium manganese oxide particles is 50 to 150 parts by weight, preferably 70 to 120 parts by weight, more preferably 90 to 100 parts by weight based on 100 parts by weight of the magnetic particles. When the content of the hydrogen ion-substituted lithium manganese oxide particles satisfies the above range, the recovery rate of lithium by the ion exchange method is improved, and the lithium adsorbent can be separated from the lithium ion adsorbent easily and at low cost under external magnetic field.
All or a part of the lithium ions present in the lithium manganese oxide particles are replaced with hydrogen ions in the hydrogen ion-substituted lithium manganese oxide particles.
According to one embodiment of the present invention, all of the lithium ions present in the lithium manganese oxide particles are converted into lithium manganese oxide particles before being subjected to hydrogen ion replacement, that is, before the acid treatment, Li 1 + x Mn 2-x O 4 (0 ≤ x ≤ 0.33), or Li 1.6 Mn 1.6 O in 4 cases, the proton-substituted lithium manganese oxide particles H 1 + x Mn 2-x O 4 (0 ≤ x ≤ 0.33), or H 1.6 Mn 1.6 O 4 .
When only a part of the lithium ions is replaced with hydrogen ions, the degree of substitution is not particularly limited as long as it has the ability to adsorb lithium ions by an ion exchange reaction. For example, at least 20%, preferably at least 50%, of the lithium ions present in the lithium manganese oxide particles may be substituted.
The average particle diameters of the lithium manganese oxide particles and the magnetic particles may independently be 10 nm to 500 m, preferably 20 nm to 100 m, and more preferably 30 nm to 10 m.
According to an embodiment of the present invention, in the magnetic lithium adsorbent, the magnetic particles may be formed as a coating layer by being positioned on a part or all of the surface of the hydrogen ion-substituted lithium manganese oxide particles. In addition, the magnetic particles may be formed as a composite with each other by being positioned between a plurality of hydrogen ion-substituted lithium manganese oxide particles and connecting them to each other.
According to an embodiment of the present invention, in the magnetic lithium adsorbent, the magnetic particles and the hydrogen-ion-substituted lithium manganese oxide particles may be physically aggregated into one another or may be chemically bonded to each other have.
According to another aspect of the present invention, there is provided a method of preparing a magnetic lithium adsorbent, comprising: preparing lithium manganese oxide particles by mixing an aqueous solution of a lithium precursor with an aqueous solution of a manganese precursor; Adding the lithium manganese oxide particles to an aqueous solution of iron hydroxide (Fe (OH) 2 ) to form a magnetic lithium adsorbent precursor complexed with magnetic particles and lithium manganese oxide particles; And subjecting the magnetic lithium adsorbent precursor to acid treatment to impart lithium ion exchange adsorption capability.
First, an aqueous solution of a lithium precursor is mixed with an aqueous solution of a manganese precursor to prepare lithium manganese oxide particles.
The manganese precursor may be at least one selected from manganese sulfate, manganese nitrate, and manganese chloride. The lithium precursor may be lithium hydroxide alone or a mixture of lithium chloride and lithium hydroxide. At this time, manganese sulfate (MnSO 4 ) and lithium hydroxide (LiOH) are preferably used as the manganese precursor and the lithium precursor, but the present invention is not limited thereto.
At this time, the aqueous solution of the lithium precursor may further include hydrogen peroxide selectively. The hydrogen peroxide serves as an oxidizing agent for oxidizing manganese when synthesizing lithium manganese oxide.
The lithium manganese oxide particles may be prepared by various processes such as solid-phase reaction, gel reaction, hydrothermal reaction, etc. under various lithium and manganese compositions, but are not limited thereto, and double hydrothermal reaction is preferred. The lithium manganese oxide particles thus prepared can be further washed.
Next, the lithium manganese oxide particles are added to an aqueous solution of iron hydroxide (Fe (OH) 2 ) to form a magnetic lithium adsorbent precursor in which magnetic particles and lithium manganese oxide particles are complexed.
The magnetic lithium adsorbent according to one embodiment of the present invention is a composite material of the lithium manganese oxide particles and magnetic particles and includes a process of introducing magnetic particles into lithium manganese oxide particles and a process of introducing lithium manganese oxide particles into magnetic particles In this case, various manufacturing methods such as a heat treatment or a method using a gel state can be applied.
The aqueous solution of iron hydroxide can be obtained by mixing an aqueous solution of an iron precursor and an aqueous solution of a hydroxide ion precursor. As the iron precursor, at least one selected from the group consisting of iron chloride, iron sulfate, and iron nitrate, which is an iron precursor having a divalent oxidation number (Fe 2+ ), may be used, and iron sulfate (FeSO 4 ) But is not limited thereto. As the hydroxide ion precursor, at least one selected from the group consisting of sodium hydroxide, lithium hydroxide, potassium hydroxide and ammonia can be used.
As the solvent used in the above step, water is preferably distilled water in which other metal ions and oxygen are removed. In order to minimize oxygen inflow from the outside, it is necessary to proceed in an inert gas environment. Among them, an inert gas such as nitrogen and argon Environment is preferable.
According to an embodiment of the present invention, an iron precursor such as iron sulfate is added to the distilled water from which oxygen has been removed in an inert environment during the production of the aqueous solution of iron hydroxide, and then the uniformity of the magnetic particles introduced into the lithium manganese oxide particles And to further improve the degree of dispersion of the finally obtained magnetic lithium adsorbent in water, a dispersant may be further added.
The dispersant can be used without limitation as long as it has chelating ability with metal ions and a dispersing ability capable of increasing the degree of dispersion of the formed particles. Examples of the dispersant include at least one selected from the group consisting of glutamate, glutamic acid, acetate, and acetic acid. Examples of the glutamate include potassium glutamate, sodium glutamate, and potassium glutamate. As the acetate, potassium acetate, sodium acetate, Potassium acetate and the like can be used.
According to an embodiment of the present invention, an iron precursor such as iron sulfate and a dispersing agent such as sodium acetate are added to distilled water deoxygenated and then stirred for a sufficient time. Thereafter, an aqueous solution of a hydroxide ion precursor To prepare an aqueous solution of iron hydroxide.
Thereafter, an aqueous dispersion of the lithium manganese oxide particles sufficiently dispersed in the oxygen-depleted distilled water is added to the aqueous solution of iron hydroxide. Then stirring is performed for about 30 minutes to 2 hours, but it is not limited thereto. The sufficiently stirred mixture is transferred to a reaction vessel made of, for example, Teflon (polytetrafluoroethylene, PTFE) or the like, and the reaction proceeds at a high temperature of 433 K or more.
After a long period of time, for example, for 8 to 40 hours, the magnetic lithium adsorbent precursor can be formed through thorough washing with distilled water.
Next, an acid treatment is performed to impart the lithium ion-exchange adsorption capability to the magnetic lithium adsorbent precursor.
Through the acid treatment, all or a part of the lithium ions present in the lithium manganese oxide particles are replaced with hydrogen ions, and as a result, only the lithium ions dissolved in the target solution are selectively adsorbed and desorbed to easily recover lithium do.
According to one embodiment of the present invention, the following formula Li 1 + x Mn 2-x O 4 (0? X? 0.33) and Li 1.6 Mn 1.6 O 4, which are examples of lithium manganese oxide, All can be exchanged for hydrogen ions.
[Reaction Scheme]
(Li) [Li x Mn (IV) 2-x ] O 4 ↔ (H) [H x Mn (IV) 2-x ] O 4 (0 ≤ x ≤ 0.33)
(Li) [Li 0.6 Mn (IV) 1.6 ] O 4 ↔ (H) [H 0.6 Mn (IV) 1.6 ] O 4
The acid aqueous solution used in the acid treatment may be various acid aqueous solutions, but an aqueous hydrochloric acid solution is preferred, and the aqueous acid solution preferably has a concentration of 0.1 to 0.5 M, but is not limited thereto. The precursor of the magnetic lithium adsorbent added to the aqueous acid solution is dispersed through a stirrer and a shaker. The dispersion time is not limited so long as it is sufficient for hydrogen and lithium ion exchange to take place, for example, 18 to 30 hours, preferably 20 to 28 hours.
After the acid treatment, the magnetic lithium adsorbent can be sufficiently washed with distilled water.
According to another aspect of the present invention, there is provided a method of recovering lithium comprising the steps of: adding a magnetic lithium adsorbent according to an embodiment of the present invention to a lithium-dissolved solution to adsorb lithium; And separating the magnetic lithium adsorbent from the solution using a magnet after completion of the adsorption step.
It is preferable that the magnetic lithium adsorbent is sufficiently dispersed by using a stirrer and a shaker after charging the lithium-dissolved lithium solution to be recovered. It is preferable that the ion exchange between the hydrogen ion contained in the magnetic lithium adsorbent and the lithium ion to be recovered sufficiently After a period of time has passed, the magnetic lithium adsorbent is removed in water.
As the recovered lithium-dissolved lithium solution, seawater, wastewater, lithium battery waste solution and the like can be applied.
At this time, it is possible to implement a repetitive lithium recovery process of the magnetic lithium adsorbent by repeating the acid treatment process and the lithium solution input process.
A separation method using a magnet may be applied to a method of separating the magnetic lithium adsorbent in water. The magnet is preferably a neodymium magnet and an electromagnet, but is not limited thereto.
BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to the following examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the following embodiments. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art.
Example
Example 1
(Preparation of Lithium Manganese Oxide Particles)
The manganese precursor, MnSO 4 , was dissolved in distilled water to a concentration of 0.4 M, and an aqueous solution having a lithium precursor, lithium hydroxide (LiOH) concentration of 2.5 M and hydrogen peroxide (H 2 O 2 ) concentration of 1.2 M, Add to the prepared manganese solution.
Using a magnetic stirrer, sufficiently stirred mixture is transferred to a Teflon container and the reaction proceeds at 110 ° C. The reaction product was separated, dried, and then heat-treated at 400 ° C to prepare lithium manganese oxide particles having a spinel structure. As a result of component analysis using Inductively Coupled Plasma (ICP), it was confirmed that the manganese oxide had a manganese oxidation number of 4.00 and Li 1.33 Mn 1.67 O 4 .
(Preparation of magnetic lithium adsorbent precursor)
1.6 g of iron sulfate (FeSO 4 ) as an iron precursor and 3.0 g of sodium acetate (CH 3 COONa) were added to distilled water deoxygenated and then an aqueous solution of sodium hydroxide (NaOH) of 40% as a precursor of hydroxide ion was added in a nitrogen atmosphere An Fe (OH) 2 aqueous solution was prepared. An aqueous dispersion obtained by sufficiently dispersing the lithium manganese oxide particles prepared above was added to the Fe (OH) 2 aqueous solution prepared above to obtain a mixture, and the mixture was sufficiently stirred. The stirred mixture was transferred to a Teflon container and reacted at 200 ° C for 10 hours to prepare a composite material which is a precursor of magnetic lithium adsorbent. As a result of crystal analysis using X-ray diffraction (XRD) and high-resolution transmission electron microscope (HR-TEM), as shown in FIGS. 1 and 2, the magnetite particles and the lithium manganese oxide particles It was confirmed that two crystal patterns appeared together.
FIG. 3 is a graph showing the results of magnetic characteristic analysis using a vibrating sample magnetometer (VSM) of the magnetic lithium adsorbent precursor prepared as described above, wherein the magnetic lithium adsorbent precursor is a composite of magnetite particles and lithium manganese oxide particles Were formed and successfully magnetized
(Production of magnetic lithium adsorbent)
The precursor of the magnetic lithium adsorbent was added to an aqueous hydrochloric acid solution having a concentration of 0.5 M to disperse the precursor of the magnetic lithium adsorbent for 24 hours in order to impart lithium adsorption function to the precursor of the magnetic lithium adsorbent, Was separated in aqueous solution. The separated product was sufficiently washed with distilled water to finally produce a magnetic lithium adsorbent.
Evaluation of Lithium Adsorption Characteristics of Magnetic Lithium Adsorbent
The magnetic lithium adsorbent prepared in Example 1 was added to a lithium aqueous solution having a lithium concentration of 70 ppm (mg / L) at a concentration of 1.0 g / L to evaluate lithium adsorption characteristics.
The adsorption experiments were carried out for about 3 days in order to cause the exchange reaction of the hydrogen ions in the lithium manganese oxide crystals in the crystals constituting the magnetic lithium adsorbent to the solution lithium ions sufficiently.
The magnetic lithium adsorbent was separated by using a magnet, and the lithium solution was analyzed before and after the adsorption experiment using inductively coupled plasma (ICP).
As a result, it was confirmed that the magnetite magnetic particles were introduced after complexing, but had a lithium ion exchange adsorption capacity.
Evaluation of the possibility of repeated use of magnetic lithium adsorbent
The above lithium-adsorbed magnetic lithium adsorbent was added to an aqueous hydrochloric acid solution having a concentration of 0.5 M and the acid treatment was conducted again in the same manner as in Example 1 above. Thereafter, the lithium adsorption test was carried out in the same manner and under the same conditions as in Example 3, and the lithium adsorbent was separated in water using a magnet. This method was repeated to evaluate the lithium adsorption characteristics three times in total. The results are shown in Table 1.
As a result of the above repeated experiment, it was confirmed that the adsorption characteristics of the total of three times are similar to those of repeated use by maintaining the adsorption capacity of 89.3% of the initial adsorption test results as in Table 1.
Repetition efficiency (%) = (Lithium adsorption performance per cycle / Lithium adsorption performance per cycle) X 100
Comparative Example 1
A lithium adsorbent was prepared in the same manner as in Example 1, except that the lithium manganese oxide particles were subjected to an acid treatment in an aqueous 0.5M hydrochloric acid solution.
At this time, the lithium adsorbent was thoroughly washed with distilled water by the acid treatment using a screening apparatus.
In addition, a method of separating the magnetic lithium adsorbent prepared in Example 1 in water using a magnet was attempted, but the magnet was not reacted as shown in FIG.
Comparative Example 2
The magnetite prepared by reacting iron oxide (Fe (OH) 2 ) at 200 占 폚 was subjected to evaluation of adsorption characteristics in the same manner as in the evaluation of the lithium adsorption characteristics. Each material was added at a concentration of 1.0 g / L to a lithium aqueous solution having a lithium concentration of 70 ppm (mg / L), and the adsorption experiment was conducted for 3 days.
As a result of the adsorption experiment, it was confirmed that the magnetite does not show the lithium adsorption ability and does not have the ability as the lithium adsorbent.
Claims (17)
Wherein the lithium manganese oxide particles comprise lithium manganese oxide having a spinel crystal structure.
Wherein the lithium manganese oxide has the formula Li 1 + x Mn 2 -x O 4 (0? X? 0.33) or Li 1.6 Mn 1.6 O 4 .
Wherein the lithium manganese oxide has a manganese oxidation number of 3.5 to 4. [
Wherein the magnetic particles are at least one selected from the group consisting of magnetite (Fe 3 O 4 ), maghemite (? -Fe 2 O 3 ), and ferrite.
Wherein the content of the hydrogen ion-substituted lithium manganese oxide particles is 50 to 150 parts by weight based on 100 parts by weight of the magnetic particles.
Adding the lithium manganese oxide particles to an aqueous solution of iron hydroxide (Fe (OH) 2 ) to form a magnetic lithium adsorbent precursor complexed with magnetic particles and lithium manganese oxide particles; And
Subjecting the magnetic lithium adsorbent precursor to an acid treatment to impart a lithium ion exchange adsorption capability to the magnetic lithium adsorbent precursor.
Wherein the manganese precursor is at least one selected from the group consisting of manganese sulfate, manganese nitrate and manganese chloride, and the lithium precursor is a mixture of lithium hydroxide or lithium chloride and lithium hydroxide.
Wherein the lithium manganese oxide is prepared by solid phase reaction, gel reaction, or hydrothermal reaction method.
Wherein the aqueous solution of iron hydroxide is obtained by mixing an aqueous solution of an iron precursor and an aqueous solution of a hydroxide ion precursor.
Wherein the iron precursor is at least one selected from the group consisting of iron chloride, iron sulfate and iron nitrate, and the hydroxide ion precursor is at least one selected from the group consisting of sodium hydroxide, lithium hydroxide, potassium hydroxide and ammonia. Way.
Wherein the step of forming the magnetic particles is carried out using a hydrothermal reaction.
Wherein the magnetic lithium adsorbent precursor further comprises a dispersant in the step of forming the magnetic lithium adsorbent precursor.
Wherein the dispersant is at least one selected from the group consisting of glutamate, glutamic acid, acetate, and acetic acid.
Wherein an acid aqueous solution having a concentration of 0.1 to 0.5 M is used in the step of performing the acid treatment.
And separating the magnetic lithium adsorbent from the solution using a magnet after completion of the adsorption step.
Wherein the magnet is at least one of neodymium magnet and electromagnet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150067520A KR101735814B1 (en) | 2015-05-14 | 2015-05-14 | Magnetic lithium adsorbent, method for preparing the same, and method of recovering lithium by using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150067520A KR101735814B1 (en) | 2015-05-14 | 2015-05-14 | Magnetic lithium adsorbent, method for preparing the same, and method of recovering lithium by using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20160134085A true KR20160134085A (en) | 2016-11-23 |
| KR101735814B1 KR101735814B1 (en) | 2017-05-15 |
Family
ID=57541366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150067520A KR101735814B1 (en) | 2015-05-14 | 2015-05-14 | Magnetic lithium adsorbent, method for preparing the same, and method of recovering lithium by using the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101735814B1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109012567A (en) * | 2017-11-10 | 2018-12-18 | 江苏旌凯中科超导高技术有限公司 | Magnetic aluminium base lithium adsorbent and preparation method thereof |
| CN109266851A (en) * | 2018-09-07 | 2019-01-25 | 中国科学院青海盐湖研究所 | A method of lithium is extracted by magnetic micropore lithium adsorbent |
| WO2019209011A1 (en) * | 2018-04-23 | 2019-10-31 | 주식회사 포스코 | Lithium-adsorptive molded object and manufacturing method therefor |
| WO2023116570A1 (en) * | 2021-12-20 | 2023-06-29 | 比亚迪股份有限公司 | Magnetic titanium-based lithium adsorbent and preparation method therefor |
| EP4076728A4 (en) * | 2019-12-20 | 2024-06-19 | E3 Lithium Ltd. | Sorbent compositions and methods of manufacture for use in concentrating lithium from brines |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100670872B1 (en) * | 2005-07-05 | 2007-01-19 | 한국과학기술연구원 | Zeolite Combined Magnetic Beads for Removal of Ammonium Ion from Water and Preparation Method Thereof |
-
2015
- 2015-05-14 KR KR1020150067520A patent/KR101735814B1/en active IP Right Grant
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109012567A (en) * | 2017-11-10 | 2018-12-18 | 江苏旌凯中科超导高技术有限公司 | Magnetic aluminium base lithium adsorbent and preparation method thereof |
| CN109012567B (en) * | 2017-11-10 | 2022-03-29 | 西宁永正锂业有限公司 | Magnetic aluminum-based lithium adsorbent and preparation method thereof |
| WO2019209011A1 (en) * | 2018-04-23 | 2019-10-31 | 주식회사 포스코 | Lithium-adsorptive molded object and manufacturing method therefor |
| KR20190123164A (en) * | 2018-04-23 | 2019-10-31 | 주식회사 포스코 | Adsorbent molded body for lithium and manufacturing method for the same |
| CN112313006A (en) * | 2018-04-23 | 2021-02-02 | 株式会社Posco | Lithium-adsorbing molded article and method for producing same |
| CN112313006B (en) * | 2018-04-23 | 2023-10-13 | 浦项股份有限公司 | Lithium-adsorbing molded article and method for producing same |
| US12048912B2 (en) | 2018-04-23 | 2024-07-30 | Posco Co., Ltd | Lithium-adsorptive molded object |
| CN109266851A (en) * | 2018-09-07 | 2019-01-25 | 中国科学院青海盐湖研究所 | A method of lithium is extracted by magnetic micropore lithium adsorbent |
| EP4076728A4 (en) * | 2019-12-20 | 2024-06-19 | E3 Lithium Ltd. | Sorbent compositions and methods of manufacture for use in concentrating lithium from brines |
| WO2023116570A1 (en) * | 2021-12-20 | 2023-06-29 | 比亚迪股份有限公司 | Magnetic titanium-based lithium adsorbent and preparation method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101735814B1 (en) | 2017-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101735814B1 (en) | Magnetic lithium adsorbent, method for preparing the same, and method of recovering lithium by using the same | |
| Cui et al. | Synthesis of a novel magnetic Caragana korshinskii biochar/Mg–Al layered double hydroxide composite and its strong adsorption of phosphate in aqueous solutions | |
| CN102049238B (en) | Ion sieve for selectively extracting lithium and application thereof | |
| KR101182271B1 (en) | Porous manganese oxide absorbent for Lithium having spinel type structure and a method of manufacturing the same | |
| CN103191699B (en) | Ferrite/graphene composite adsorbent and preparation and using methods thereof | |
| Qi et al. | Enhanced oxidative and adsorptive capability towards antimony by copper-doping into magnetite magnetic particles | |
| WO2019237619A1 (en) | Magnetic ferromanganese oxide-loaded mesoporous cellulose biochar composite material, preparation method therefor and use thereof | |
| CN108704610B (en) | Magnetic carbon modified magnesium-iron hydrotalcite composite material and preparation method and application thereof | |
| KR101325176B1 (en) | Method of manufacturing chemical manganese dioxide from trivalent cathode active material, the chemical manganese dioxide manufactured by the method and secondary battery including the chemical manganese dioxide | |
| Zhang et al. | Polyacrylic acid-functionalized graphene oxide for high-performance adsorption of gallium from aqueous solution | |
| CN106984272A (en) | A kind of preparation method of magnetic active carbon adsorbent for water process | |
| CN112934164A (en) | Magnetic phosphorus removal adsorbent and preparation method and application thereof | |
| CN107970898B (en) | Method for preparing in-situ synthesis sponge iron oxide-loaded nanoparticle composite material | |
| WO2024114262A1 (en) | Three-way catalyst and preparation method therefor and use thereof | |
| CN112216894B (en) | Preparation method and recovery method of lithium ion sieve composite material | |
| KR102521570B1 (en) | Lithium ion adsorbent and a method for recovering lithium ion using the same | |
| CN113145062A (en) | Preparation method of magnetic adsorption material based on Prussian blue and hydrotalcite | |
| Miyamoto et al. | Synthesis of ultrasmall Li–Mn spinel oxides exhibiting unusual ion exchange, electrochemical and catalytic properties | |
| Dong et al. | Synthesis of Fe–Mn-based materials and their applications in advanced oxidation processes for wastewater decontamination: a review | |
| US10233099B2 (en) | Radioactive cesium decontaminator and method of producing the same, and method of removing the radioactive cesium | |
| CN109046357A (en) | A kind of preparation method of metal oxide-LDH loaded catalyst | |
| US10273560B2 (en) | Recovery method of useful resources in seawater and brine | |
| Recepoğlu et al. | Granulation of hydrometallurgically synthesized spinel lithium manganese oxide using cross-linked chitosan for lithium adsorption from water | |
| Pittman et al. | Ionic double-shell magnetic covalent organic framework for sharp and fast adsorption of critical metals | |
| JP2014115135A (en) | RADIOACTIVE Cs ADSORBENT AND METHOD OF MANUFACTURING THE SAME |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| AMND | Amendment | ||
| E601 | Decision to refuse application | ||
| AMND | Amendment | ||
| X701 | Decision to grant (after re-examination) | ||
| GRNT | Written decision to grant |