CN109012567B - Magnetic aluminum-based lithium adsorbent and preparation method thereof - Google Patents
Magnetic aluminum-based lithium adsorbent and preparation method thereof Download PDFInfo
- Publication number
- CN109012567B CN109012567B CN201811072622.XA CN201811072622A CN109012567B CN 109012567 B CN109012567 B CN 109012567B CN 201811072622 A CN201811072622 A CN 201811072622A CN 109012567 B CN109012567 B CN 109012567B
- Authority
- CN
- China
- Prior art keywords
- magnetic
- aluminum
- lithium
- adsorbent
- magnetic core
- 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
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
- B01J20/06—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
-
- 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
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- 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
Abstract
The invention discloses a magnetic aluminum-based lithium adsorbent and a preparation method thereof, wherein a micro-nano magnetic nucleus is taken as a crystal nucleus, aluminum hydroxide crystals are generated on the surface of the crystal nucleus, and then a magnetic nucleus @ LiX.2Al (OH) is generated3·nH2And O, wherein X is inorganic acid radical ions, and finally the magnetic aluminum lithium adsorbent is generated, wherein the mass ratio of magnetic cores to aluminum hydroxide is 3:1-1:20, the ratio of median particle size to magnetic core particle size of the adsorbent is 3:1-30:1, and if X is multivalent, Li is increased correspondingly. The magnetic aluminum-based lithium adsorbent can separate the magnetic aluminum-based lithium adsorbent from water through magnetic separation, retains the high adsorption capacity of the magnetic aluminum-based lithium adsorbent, avoids the complex process of granulation or film formation, greatly reduces the adsorbent loss caused by crushing of granular materials, greatly improves the current situation of the lithium extraction technology by an adsorption method, and the magnetic core is made of Al (OH)3The uniform coating can prevent the magnetic core from being oxidized and demagnetized in the long-term use process, and simultaneously prevent the active ingredients of the adsorbent and the magnetic core from being stripped in the long-term use process.
Description
Technical Field
The invention belongs to the field of extracting lithium from salt lakes, seawater and the like, and particularly relates to a magnetic aluminum-based lithium adsorbent and a preparation method thereof.
Background
There are many methods for extracting lithium from brine and seawater, and the general methods can be divided into adsorption method, membrane separation method, extraction method, calcination method, etc. The adsorption method has remarkable advantages of extracting lithium from low-content brine or seawater, such as environmental friendliness, low production cost, no need of pretreatment and the like. The lithium adsorbent is a key material for extracting lithium by a salt lake and seawater adsorption method. The lithium adsorbent can be generally divided into a manganese system, an aluminum base, a titanium system and the like, while the aluminum-based lithium adsorbent has many advantages, particularly, the aluminum-based lithium adsorbent is desorbed by water, acid and alkali are not needed to be added in the whole process, and the adsorbent is not chemically dissolved and damaged in the adsorption and desorption process. At present, the aluminum-based lithium adsorbent is only successfully applied in the process of extracting lithium from seawater and brine by an adsorption method.
There are many production processes for aluminum-based adsorbents, and after 1990s, there are a large number of foreign patents reporting the production processes of adsorbents, but the aluminum-based adsorbents prepared by any process are all powder with the particle size of micron. The traditional powder aluminum-based adsorbent cannot be used in production, and the main reasons include: 1. the powdery aluminum-based adsorbent cannot be filled in the adsorption bed, the permeability is extremely poor, and brine and water cannot naturally pass through the adsorption bed; 2. the traditional solid-liquid separation modes such as plate-and-frame filter pressing, membrane separation, centrifugation and the like cannot be applied to brine with high salinity and high viscosity characteristics; 3. when the traditional solid-liquid separation mode is applied to lithium extraction from brine or seawater, the separation equipment and the operation cost are too high, and the equipment is very easy to block and cannot be continuously produced.
In order to overcome the defects of the traditional powder aluminum-based lithium adsorbent in the application link and enable the powder aluminum-based lithium adsorbent to be used for continuous industrial production, the powder aluminum-based lithium adsorbent is considered to be made into particles with the particle size of more than 0.2mm in the existing documents, patents and industrial implementation processes. After the powder is granulated, the permeability after accumulation can be greatly improved, and then the adsorption bed is filled for use. There are many documents and patents detailing the granulation process of the powdery aluminum-based lithium adsorbent and the loading of the aluminum-based lithium adsorbent. Of course, there is also a few studies to fill the powdered aluminum-based lithium adsorbent into a membrane or other fixable substrate to simulate the operation of the adsorbent bed, and the technical principle is consistent with granulation.
In the process of granulating or preparing the membrane by the powder adsorbent, as the components such as adhesive, pore-forming agent and the like need to be added, the effective specific surface area of the active components is greatly reduced. Generally accepted by the industry, the adsorption activity of the powder adsorbent can be reduced by more than 50% after the powder adsorbent is granulated or made into a film. In addition, the particle adsorbent is of a porous structure, and the structure is easy to break in the long-term use process, so that the adsorbent is lost, and the production cost is greatly increased. The work adsorption activity of the currently realized industrially applied particle aluminum-based lithium adsorbent is 2-3mg/g, the annual loss is about 10-20%, and the work adsorption activity of the powdery aluminum-based lithium adsorbent can generally reach 5-7 mg/g.
Disclosure of Invention
Based on the problems, the invention creatively provides a magnetic aluminum-based lithium adsorbent and a preparation method thereof, and the magnetic aluminum-based lithium adsorbent provided by the invention is a powder material, so that on one hand, the damage of a granulation process to the activity of the adsorbent is avoided; on the other hand, the magnetic aluminum-based lithium adsorbent can realize the efficient and thorough separation of the adsorbent from high-viscosity and high-salinity brine or seawater by a magnetic separation method. Considering the wide application of the magnetic separator in the mineral processing industry, the separation equipment of the adsorbent and the brine or the seawater has stable operation and low price. Therefore, the successful implementation of the method can greatly improve the industrial current situation of lithium extraction by a brine or seawater adsorption method, and on one hand, the lithium recovery rate of brine or seawater can be greatly improved because the adsorption activity is far higher than that of the traditional granular adsorbent; on the other hand, the production cost of extracting lithium by the adsorption method is greatly reduced due to the high reliability and low cost of magnetic separation.
The preparation of the magnetic aluminum-based lithium adsorbent has two key problems, namely how to protect the magnetic core and avoid the magnetic core from being oxidized and demagnetized in the long-term use process, and how to avoid the active ingredients of the aluminum adsorbent and the magnetic core from being stripped in the long-term use process, thereby causing the loss of functional materials. In order to achieve the purpose, the invention creatively provides a method for preparing the micro-nano magnetic aluminum-based lithium adsorbent by in-situ deposition and synchronous crystallization of a magnetic nuclear interface.
The invention is realized by the following technical scheme:
the magnetic aluminum-based lithium adsorbent takes micro-nano magnetic nuclei as crystal nuclei, aluminum hydroxide crystals are generated on the surfaces of the crystal nuclei, and then the magnetic nuclei @ LiX.2Al (OH) are generated3·nH2And O, wherein X is inorganic acid radical ions, and finally the magnetic aluminum lithium adsorbent is generated, wherein the mass ratio of magnetic cores to aluminum hydroxide is 3:1-1:20, the ratio of median particle size to magnetic core particle size of the adsorbent is 3:1-30:1, and if X is multivalent, Li is increased correspondingly.
The mass ratio of the magnetic core to the aluminum hydroxide is selected to be 3:1-1:20, because the inventor finds that if the ratio of the magnetic core to the aluminum hydroxide is higher than 3:1 through a large amount of experiments, the activity of the adsorbent is remarkably reduced, and the working adsorption capacity is reduced to be less than 3 mg/g. The electron microscope and energy spectrum data show that when the ratio of the magnetic core to the aluminum hydroxide is higher than 3:1, the aluminum hydroxide crystal cannot completely cover the magnetic core interface, and the magnetic core is exposed, so that the magnetic core is easily oxidized and demagnetized after long-term use. On the other hand, if the ratio of the magnetic core to the aluminum hydroxide is lower than 1:20, on one hand, the saturation magnetization of the magnetic functional material is lower than 5emu/g, and the loss of the adsorbent is easily caused when the magnetic separator is used for realizing solid-liquid separation, and on the other hand, the aluminum hydroxide crystal layer is too thick, so that the aluminum hydroxide crystal layer is easily stripped from the magnetic core in the long-term use process, and the loss of the adsorbent is greatly improved.
Preferably, the mass ratio of the magnetic core to the aluminum hydroxide is 3:1-1: 5.
Preferably, the mass ratio of the magnetic core to the aluminum hydroxide is 1:1-1: 5. The inventor finds that when the mass ratio of the magnetic core to the aluminum hydroxide is 1:1-1:5, the work adsorption activity of the magnetic aluminum-based lithium adsorbent can reach 5-6mg/g, the saturation magnetization can reach 8-20emu/g, and the loss of 200 circulating adsorbents is less than five ten-thousandths.
Preferably, the magnetic core is a ferromagnetic mineral, the ferromagnetic mineral comprises ferroferric oxide, iron, cobalt, a nickel simple substance and ferrite, and the median particle size of the ferromagnetic mineral is 5nm-50 μm. The inventor finds out through a large number of experiments that if the median particle size of the ferromagnetic mineral is less than 5nm, effective dispersion cannot be realized, so that a large number of magnetic cores are agglomerated, and further the effective surface area of the magnetic cores is wasted greatly. If the median diameter of the magnetic core is larger than 50 μm, the specific surface area of the magnetic core is greatly reduced, and the aluminum hydroxide crystals which can be effectively deposited are greatly reduced.
In order to ensure the structural stability of the magnetic adsorbent, the median particle size of the adsorbent after molding and the median particle size of the selected magnetic core need to be kept between 3:1 and 30:1, and if the ratio is lower than 3:1, the amount of aluminum hydroxide deposited on the interface is too low, so that the magnetic core is exposed and the adsorption activity is too low; if the ratio is greater than 30:1, the amount of aluminum hydroxide deposited on the interface is too high, and the aluminum hydroxide is easy to fall off from the magnetic core.
The upper limit median particle size of the magnetic core is 50 μm, the lower limit is 5nm, and the median particle size of the finally synthesized adsorbent and the median particle size of the selected magnetic core are controlled to be between 3:1 and 30:1, so that the adsorption activity, stability, magnetic induction intensity and adsorbent manufacturing cost of the magnetic aluminum-based lithium adsorbent are balanced.
Further, the ratio of the median particle size of the adsorbent to the magnetic core particle size is 3:1 to 10: 1.
Preferably, the X is one or more of chloride, sulfate, nitrate and carbonate.
Preferably, the crystalline lattice structure mineral phase formed by the aluminum hydroxide crystals comprises one or more of amorphous aluminum hydroxide, gibbsite, bayerite and noralite.
The invention also provides a preparation method of the magnetic aluminum-based lithium adsorbent, which comprises the following steps:
(1) using micro-nano magnetic nucleus as crystal nucleus in the crystallization process of aluminium hydroxide to make aluminium hydroxide deposit and crystallize on the surface of magnetic nucleus to prepare magnetic nucleus @ Al (OH)3A composite crystal;
(2) mixing the magnetic core @ Al (OH)3The composite crystal reacts with lithium salt or lithium hydroxide to prepare magnetic nucleus @ LiX.2Al (OH)3·nH2A lithium O sorbent precursor, where X is an inorganic acid ion, and if X is multivalent, then Li is increased by a corresponding amount;
(3) the magnetic core @ LiX.2Al (OH)3·nH2And (4) washing out lithium salt in the O lithium adsorbent precursor to prepare the magnetic aluminum lithium adsorbent.
The step (2) is matched with the step (3), the step (2) is to allow lithium salt to enter the crystal lattice of the aluminum hydroxide, and then the lithium salt is washed out in the step (3), so that a space for allowing the lithium salt to enter or exit is left in the crystal lattice of the aluminum hydroxide, and the lithium salt trapping mechanism is also a mechanism for trapping the lithium salt in the brine when the material is placed in the brine or seawater. The finished product magnetic aluminum adsorbent after the delithiation treatment is put into brine containing lithium salt, the lithium salt can enter vacancies of aluminum hydroxide crystal lattices, then the material and the brine are separated by magnetic separation, and finally the lithium is washed out by water, so that the lithium in the brine is extracted.
Preferably, in the step (1), the magnetic core is a ferromagnetic mineral, the ferromagnetic mineral comprises ferroferric oxide, iron, cobalt, a nickel simple substance and ferrite, and the particle size of the ferromagnetic mineral is 5nm-50 μm.
Preferably, the ratio of the median particle diameter of the adsorbent to the magnetic core particle diameter is from 3:1 to 30: 1. If the particle size of the formed adsorbent is too small, the formed adsorbent is not beneficial to aluminum hydroxide to wrap magnetic cores, the magnetic cores can be oxidized and demagnetized, and if the particle size of the adsorbent is too large, the specific surface area of the adsorbing material is influenced, and the adsorption activity is further reduced.
More preferably, the ratio of the median particle size of the adsorbent to the magnetic core particle size is from 3:1 to 10: 1.
Preferably, the magnetic core @ Al (OH) in the step (1)3The preparation process of the composite crystal comprises the following steps: the micro-nano magnetic core is completely dispersed in the crystallization process of the aluminum hydroxide by adopting a dispersion mode; aluminum chloride or sodium metaaluminate is used as a raw material, so that aluminum hydroxide is gradually deposited and crystallized on a magnetic core interface, and the crystallization process of the aluminum hydroxide lasts for 0.5-72 h; then carrying out filter pressing, centrifugation or magnetic separation solid-liquid separation, washing for a plurality of times, removing redundant salt, and obtaining magnetic core @ Al (OH)3And (4) compounding crystals.
More preferably, the dispersing means comprises one or more of strong high speed stirring, ultrasound, addition of a dispersing agent.
Preferably, Al (OH) in the step (1)3The crystalline formed lattice structure mineral phase comprises one or more of amorphous aluminum hydroxide, gibbsite, bayerite and noralite.
The crystallization process of aluminium hydroxide is chosen to last for 0.5-72 hours because different aluminium hydroxide ore phases require different crystallization times. There may be various crystallization routes for aluminum hydroxide, which may lead to one or more of amorphous aluminum hydroxide, gibbsite, bayerite or noralite.
Preferably, the mass ratio of the micro-nano magnetic cores to the aluminum hydroxide in the step (1) is 3:1-1: 20. The aluminum hydroxide with too high proportion is easy to strip from magnetic cores to cause material loss on one hand, and the material with too low magnetism cannot be separated from brine through magnetic separation on the other hand; too high a magnetic core occupancy ratio lowers the adsorption activity of the functional material.
Preferably, the mass ratio of the magnetic core to the aluminum hydroxide is 3:1-1:5,
furthermore, the mass ratio of the magnetic core to the aluminum hydroxide is 1:1-1: 5. The inventor finds that when the mass ratio of the magnetic core to the aluminum hydroxide is 1:1-1:5, the work adsorption activity of the magnetic aluminum-based lithium adsorbent can reach 5-6mg/g, the saturation magnetization can reach 8-20emu/g, and the loss of 200 circulating adsorbents is less than five ten-thousandths.
Preferably, when solid-liquid separation is required in the synthesis process of the magnetic aluminum-based lithium adsorbent, one or more separation modes of pressure filtration, permanent magnet, electromagnetism, superconducting magnetic separation and centrifugation are used.
Preferably, in the step (2), the magnetic core @ Al (OH)3The temperature of the reaction of the composite crystal and lithium salt or lithium hydroxide is 20-150 ℃, the reaction time is 0.5-48h, the ratio of aluminum to lithium is 5:1 to 1:10, and the lithium hydroxide or lithium salt enters the lattice of the aluminum hydroxide to prepare a magnetic core @ LiX.2Al (OH)3·nH2O; if lithium hydroxide is added, the magnetic core @ LiOH 2Al (OH) is prepared under the same reaction conditions3·nH2O, then slowly adding HX, wherein X is inorganic acid radical ions, controlling the pH value of the reaction system to be between 3 and 6, and preferably stabilizing the pH value to be between 4 and 6, converting lithium hydroxide into lithium salt to obtain a magnetic core @ LiX.2Al (OH)3·nH2O。
So that the magnetic core @ Al (OH) is controlled3The temperature of the reaction between the composite crystal and lithium salt or lithium hydroxide is 20-150 ℃, because experiments show that the reaction speed of the lithium salt entering the aluminum hydroxide crystal lattice is too slow and is close to the reaction, the reaction cannot be carried out, the crystal lattice structure of the aluminum hydroxide with the temperature higher than 150 ℃ is changed, and Al can be produced by dehydration2O3。
So that the magnetic core @ Al (OH) is controlled3Composite crystal and lithiumThe time for the salt or lithium hydroxide to react is 0.5 to 48 hours because different crystalline forms of aluminum hydroxide react with lithium salts in different times, resulting in shorter crystallization times for amorphous aluminum hydroxide crystals and longer crystallization times for bayer formation.
The reason why the ratio of aluminum to lithium is controlled to be 5:1 to 1:10 is because experimental data show that the adsorption activity is remarkably reduced when the ratio of aluminum to lithium is too high or too low, no lithium salt is inserted into a large amount of aluminum hydroxide crystals when the ratio of aluminum to lithium is too high, and the lattice structure of aluminum hydroxide can be remarkably damaged by lithium salt when the ratio of aluminum to lithium is too low.
Preferably, the lithium salt is washed out by using water in the step (3), wherein the water is one or more of tap water, deionized water and distilled water.
The invention has the beneficial effects that:
the adsorbent prepared by the invention is a magnetic aluminum-based lithium adsorbent, and can separate a lithium ion sieve from water through magnetic separation, so that on one hand, the high adsorption capacity of a powder material is kept, on the other hand, the high cost and material loss of granulation or film forming are avoided, the adsorbent can be widely applied to separation production operation of lithium, and the current situation of the lithium extraction technology by an adsorption method is greatly improved. In addition, the magnetic core in the magnetic aluminum-based lithium adsorbent can be well protected, the magnetic core is prevented from being oxidized and demagnetized in the long-term use process, and meanwhile, the active ingredients of the adsorbent and the magnetic core are prevented from being stripped in the long-term use process, so that the loss of functional materials is avoided.
The preparation process of the magnetic aluminum-based lithium adsorbent is reasonable and simple, the process parameters are accurately controlled, the product quality is stable, the method is environment-friendly, and the method is worthy of popularization.
Detailed Description
The magnetic aluminum-based lithium adsorbent is characterized in that a micro-nano magnetic nucleus is taken as a crystal nucleus, aluminum hydroxide crystals are generated on the surface of the crystal nucleus, and then the magnetic nucleus @ LiX.2Al (OH) is generated3·nH2And O, wherein X is inorganic acid radical ions, and finally the magnetic aluminum lithium adsorbent is generated, wherein the mass ratio of magnetic cores to aluminum hydroxide is 3:1-1:20, the ratio of median particle size to magnetic core particle size of the adsorbent is 3:1-30:1, and if X is multivalent, Li is increased correspondingly.
The mass ratio of the magnetic core to the aluminum hydroxide is 3:1-1: 20.
The ratio of the median particle size of the adsorbent to the magnetic core particle size is 3:1-30: 1.
The magnetic core is a ferromagnetic mineral which comprises ferroferric oxide, iron, cobalt, a nickel simple substance and ferrite, and the particle size range of the ferromagnetic mineral is 5nm-50 mu m.
And X is one or more of chloride, sulfate, nitrate and carbonate.
The mineral phase of the aluminum hydroxide crystals comprises one or more of amorphous aluminum hydroxide, gibbsite, bayerite, and noralite.
The preparation method of the magnetic aluminum-based lithium adsorbent comprises the following steps:
(1) using micro-nano magnetic nucleus as crystal nucleus in the crystallization process of aluminium hydroxide to make aluminium hydroxide deposit and crystallize on the surface of magnetic nucleus to prepare magnetic nucleus @ Al (OH)3A composite crystal;
(2) mixing the magnetic core @ Al (OH)3The composite crystal reacts with lithium salt or lithium hydroxide to prepare magnetic nucleus @ LiX.2Al (OH)3·nH2A lithium O sorbent precursor, where X is an inorganic acid ion, and if X is multivalent, then Li is increased by a corresponding amount;
(3) the magnetic core @ LiX.2Al (OH)3·nH2And (4) washing out lithium salt in the O lithium adsorbent precursor to prepare the magnetic aluminum lithium adsorbent.
The magnetic core @ Al (OH) in the step (1)3The preparation process of the composite crystal comprises the following steps: the micro-nano magnetic core is completely dispersed in the crystallization process of the aluminum hydroxide by adopting a dispersion mode; aluminum chloride or sodium metaaluminate is used as a raw material, so that aluminum hydroxide is gradually deposited and crystallized on a magnetic core interface, and the crystallization process of the aluminum hydroxide lasts for 0.5-72 h; then carrying out filter pressing, centrifugation or magnetic separation solid-liquid separation, washing for a plurality of times, removing redundant salt, and obtaining magnetic core @ Al (OH)3And (4) compounding crystals.
The dispersing mode comprises one or more of strong high-speed stirring, ultrasonic treatment and addition of a dispersing agent.
The magnetic core @ Al (OH)3The temperature of the reaction of the composite crystal and lithium salt or lithium hydroxide is 20-150 ℃, the reaction time is 0.5-48h, the ratio of aluminum to lithium is 5:1 to 1:10, and the lithium hydroxide or lithium salt enters the lattice of the aluminum hydroxide to prepare a magnetic core @ LiX.2Al (OH)3·nH2O; if lithium hydroxide is added, the magnetic core @ LiOH 2Al (OH) is prepared under the same reaction conditions3·nH2O, then slowly adding HX, wherein X is inorganic acid radical ions, controlling the pH of the reaction system to be 3-6, converting lithium hydroxide into lithium salt, and preparing magnetic core @ LiX.2Al (OH)3·nH2O。
Example 1:
adding 100g of ferroferric oxide powder with the median particle size of 70nm into 1L of deionized water, adding 0.3g of sodium hexametaphosphate as a dispersing agent, carrying out auxiliary ultrasonic treatment, stirring with a stirrer at 1000rpm, and adding 100g of AlCl into the ferroferric oxide dispersion liquid3Pulverizing, dispersing, and stirring for 30min to make AlCl3Fully dissolving. Then 30g of sodium hydroxide powder is added into the system within 30min to ensure that the aluminum hydroxide is gradually deposited on a ferroferric oxide interface to prepare a magnetic core @ Al (OH)3·nH2O，Al(OH)3Is amorphous aluminum hydroxide. Then 42g LiCl powder is added into the system, and the magnetic core @ LiX.2Al (OH) is prepared after dispersion and reaction for 10min3·nH2And O. The mixed liquid is subjected to solid-liquid separation by a magnetic separator, a filter press or a centrifuge to obtain dehydrated magnetic nuclei @ LiX.2Al (OH)3·nH2And O, adding 1L of deionized water into the material for washing, and washing for three times to obtain the magnetic aluminum-based lithium adsorbent. The average particle size of the magnetic aluminum-based lithium adsorbent prepared by the method is about 150nm, the adsorption capacity of working lithium can reach 5-6mg/g, and the saturation magnetization can reach 20 emu/g. Because the aluminum hydroxide is generated gradually by taking ferroferric oxide as a crystal nucleus, and the mixture ratio of the aluminum hydroxide layer and the ferroferric oxide is strictly controlled, the two crystal lattices are combined tightly, so that the structural stability of the magnetic aluminum-based lithium adsorbent is ensured. After the adsorbent prepared by the method is subjected to adsorption and desorption processes for 100 times, the falling amount of aluminum hydroxide is less than five ten-thousandths.
Example 2:
200g NaAlO was added to 500mL of deionized water2Powder, stirring and heating the system to 90 degrees, adding 0.6g of sodium silicate as a dispersant, assisting with ultrasound, stirring vigorously with a 1000rpm stirrer, and thereafter adding 100g of zinc ferrite powder having a median particle size of 100nm to the above system. Then reducing the temperature of the system to 30 ℃, reacting for 24-48h, and gradually crystallizing and crystallizing aluminum hydroxide by taking zinc ferrite powder as a crystal nucleus to obtain a magnetic nucleus @ Al (OH)3·nH2O，Al(OH)3The crystalline form of (a) is bayer stone. Then 30g of LiOH powder is added into the system, and the magnetic core @ LiOH 2Al (OH) is prepared after dispersion and reaction for 1h3·nH2And O. The mixed liquid is subjected to solid-liquid separation by a magnetic separator, a filter press or a centrifuge to obtain dehydrated magnetic nuclei @ LiOH 2Al (OH)3·nH2O, adding 1L of deionized water into the materials, adjusting the pH to 4-5 by using HCl, and preparing magnetic nuclei @ LiCl.2Al (OH)3·nH2And O, washing the solution for two to three times by using deionized water to prepare the magnetic aluminum-based lithium adsorbent. The average grain diameter of the magnetic aluminum-based lithium adsorbent prepared by the method is about 200nm, the adsorption capacity of working lithium can reach 4-5mg/g, and the saturation magnetization can reach 25 emu/g. Because the aluminum hydroxide is generated gradually by taking ferroferric oxide as a crystal nucleus, and the mixture ratio of the aluminum hydroxide layer and the ferroferric oxide is strictly controlled, the two crystal lattices are combined tightly, so that the structural stability of the magnetic aluminum-based lithium adsorbent is ensured. After the adsorbent prepared by the method is subjected to adsorption and desorption processes for 100 times, the falling amount of aluminum hydroxide is less than five ten-thousandths.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that are not thought of through the inventive work should be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
Claims (11)
1. The magnetic aluminum-based lithium adsorbent is characterized in that a micro-nano magnetic nucleus is taken as a crystal nucleus, aluminum hydroxide crystals are generated on the surface of the crystal nucleus, and then the magnetic nucleus @ LiX.2Al (OH) is generated3•nH2O, wherein X is inorganic acid radical ions, and finally the magnetic aluminum lithium adsorbent is generated, wherein the mass ratio of magnetic nuclei to aluminum hydroxide is 3:1-1:20, the ratio of median particle size to magnetic nuclei particle size of the adsorbent is 3:1-30:1, and if X is multivalent, Li is increased correspondingly; the preparation method of the magnetic aluminum-based lithium adsorbent comprises the following steps: (1) using micro-nano magnetic nucleus as crystal nucleus in the crystallization process of aluminium hydroxide to make aluminium hydroxide deposit and crystallize on the surface of magnetic nucleus to prepare magnetic nucleus @ Al (OH)3A composite crystal; (2) mixing the magnetic core @ Al (OH)3The composite crystal reacts with lithium salt or lithium hydroxide to prepare magnetic nucleus @ LiX.2Al (OH)3•nH2A lithium O sorbent precursor, where X is an inorganic acid ion, and if X is multivalent, then Li is increased by a corresponding amount; (3) mixing the magnetic core @ LiX.2Al (OH)3•nH2And (4) washing out lithium salt in the O lithium adsorbent precursor to prepare the magnetic aluminum lithium adsorbent.
2. The magnetic aluminum-based lithium adsorbent according to claim 1, wherein the mass ratio of the magnetic core to the aluminum hydroxide is 3:1 to 1: 5.
3. The magnetic aluminum-based lithium adsorbent according to claim 1, wherein the magnetic core is a ferromagnetic mineral containing ferriferrous oxide, iron, cobalt, a simple substance of nickel, and ferrite, and the particle size of the ferromagnetic mineral is in a range of 5nm to 50 μm.
4. The magnetic aluminum-based lithium adsorbent of claim 1, wherein X is one or more of chloride, sulfate, nitrate, carbonate.
5. The magnetic aluminum-based lithium adsorbent of claim 1, wherein the mineral phase of aluminum hydroxide crystals comprises one or more of amorphous aluminum hydroxide, gibbsite, bayerite, and noralite.
6. The preparation method of the magnetic aluminum-based lithium adsorbent is characterized by comprising the following steps:
(1) using micro-nano magnetic nucleus as crystal nucleus in the crystallization process of aluminium hydroxide to make aluminium hydroxide deposit and crystallize on the surface of magnetic nucleus to prepare magnetic nucleus @ Al (OH)3A composite crystal;
(2) mixing the magnetic core @ Al (OH)3The composite crystal reacts with lithium salt or lithium hydroxide to prepare magnetic nucleus @ LiX.2Al (OH)3•nH2A lithium O sorbent precursor, where X is an inorganic acid ion, and if X is multivalent, then Li is increased by a corresponding amount;
(3) mixing the magnetic core @ LiX.2Al (OH)3•nH2And (3) washing lithium salt in the O lithium adsorbent precursor to prepare the magnetic aluminum lithium adsorbent, wherein the mass ratio of the magnetic core to the aluminum hydroxide is 3:1-1:20, and the ratio of the median particle size of the adsorbent to the magnetic core particle size is 3:1-30: 1.
7. The preparation method of the magnetic aluminum-based lithium adsorbent according to claim 6, wherein the magnetic core in the step (1) is a ferromagnetic mineral, the ferromagnetic mineral comprises ferroferric oxide, iron, cobalt, a nickel simple substance and ferrite, and the particle size of the ferromagnetic mineral is in the range of 5nm to 50 μm.
8. The method for preparing a magnetic aluminum-based lithium adsorbent according to claim 6, wherein the magnetic core @ Al (OH) in the step (1)3The preparation process of the composite crystal comprises the following steps: the micro-nano magnetic core is completely dispersed in the crystallization process of the aluminum hydroxide by adopting a dispersion mode; aluminum chloride or sodium metaaluminate is used as a raw material, so that aluminum hydroxide is gradually deposited and crystallized on a magnetic core interface, and the crystallization process of the aluminum hydroxide lasts for 0.5-72 h; then carrying out filter pressing, centrifugation or magnetic separation solid-liquid separation, washing for a plurality of times, removing redundant salt, and obtaining magnetic core @ Al (OH)3And (4) compounding crystals.
9. The method of claim 8, wherein the dispersing means comprises one or more of vigorous high-speed stirring, sonication, and addition of dispersants.
10. The method for preparing a magnetic aluminum-based lithium adsorbent according to claim 6, wherein Al (OH) in the step (1)3The crystalline formed lattice structure mineral phase comprises one or more of amorphous aluminum hydroxide, gibbsite, bayerite and noralite.
11. The method for preparing a magnetic aluminum-based lithium adsorbent according to claim 6, wherein in the step (2), the magnetic core @ Al (OH)3The temperature of the reaction of the composite crystal and lithium salt or lithium hydroxide is 20-150 ℃, the reaction time is 0.5-48h, the aluminum-lithium ratio is 5:1 to 1:10, and the lithium hydroxide or lithium salt enters the aluminum hydroxide lattice to prepare a magnetic core @ LiX.2Al (OH)3•nH2O; if lithium hydroxide is added, the magnetic core @ LiOH.2Al (OH) is prepared under the same reaction conditions3•nH2O, then HX is slowly added, wherein X is inorganic acid radical ions, the pH of the reaction system is controlled to be 3-6, lithium hydroxide is converted into lithium salt, and the magnetic core @ LiX.2Al (OH) is prepared3•nH2O。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711104186.5A CN107930575A (en) | 2017-11-10 | 2017-11-10 | Magnetic aluminium base lithium adsorbent and preparation method thereof |
| CN2017111041865 | 2017-11-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109012567A CN109012567A (en) | 2018-12-18 |
| CN109012567B true CN109012567B (en) | 2022-03-29 |
Family
ID=61933784
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711104186.5A Pending CN107930575A (en) | 2017-11-10 | 2017-11-10 | Magnetic aluminium base lithium adsorbent and preparation method thereof |
| CN201811072622.XA Active CN109012567B (en) | 2017-11-10 | 2018-09-14 | Magnetic aluminum-based lithium adsorbent and preparation method thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711104186.5A Pending CN107930575A (en) | 2017-11-10 | 2017-11-10 | Magnetic aluminium base lithium adsorbent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN107930575A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107930575A (en) * | 2017-11-10 | 2018-04-20 | 江苏旌凯中科超导高技术有限公司 | Magnetic aluminium base lithium adsorbent and preparation method thereof |
| CN109266851B (en) * | 2018-09-07 | 2020-06-09 | 中国科学院青海盐湖研究所 | Method for extracting lithium through magnetic microporous lithium adsorbent |
| CN109078602B (en) * | 2018-09-07 | 2021-02-23 | 中国科学院青海盐湖研究所 | Magnetic microporous lithium adsorbent and preparation method and application thereof |
| CN110639467A (en) * | 2019-10-18 | 2020-01-03 | 华东理工大学 | Preparation method of magnetic aluminum salt lithium adsorbent |
| CN111644145A (en) * | 2020-06-08 | 2020-09-11 | 杭州海虹精细化工有限公司 | Preparation method of magnetic lithium adsorbent |
| CN111804270B (en) * | 2020-06-28 | 2022-11-15 | 湖南邦普循环科技有限公司 | Aluminum-based lithium adsorbent and preparation method thereof |
| CN115837266A (en) * | 2021-09-18 | 2023-03-24 | 比亚迪股份有限公司 | Liquid-phase precipitation synthesis method of aluminum salt type lithium ion adsorbent |
| CN115872421A (en) * | 2021-09-30 | 2023-03-31 | 比亚迪股份有限公司 | Method for recovering lithium from lithium-containing solution |
| CN116272846A (en) * | 2021-12-20 | 2023-06-23 | 比亚迪股份有限公司 | Magnetic titanium-based lithium adsorbent and preparation method thereof |
| CN114558557B (en) * | 2022-03-22 | 2022-09-09 | 北京中科顺谷科技发展有限公司 | Molecular sieve adsorbent-based natural brine lithium extraction adsorption particles and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928828A (en) * | 2010-09-25 | 2010-12-29 | 西安蓝晓科技有限公司 | Method for extracting lithium from salt lake brine by adsorption method |
| CN104014308A (en) * | 2014-02-25 | 2014-09-03 | 江苏海普功能材料有限公司 | Method for preparing high-performance brine lithium-extraction adsorption agent and adsorption agent prepared by method |
| CN104711436A (en) * | 2015-03-27 | 2015-06-17 | 中南大学 | Method for extracting lithium from lithium-containing solution |
| KR20160134085A (en) * | 2015-05-14 | 2016-11-23 | 서울대학교산학협력단 | Magnetic lithium adsorbent, method for preparing the same, and method of recovering lithium by using the same |
| CN106345394A (en) * | 2016-11-02 | 2017-01-25 | 江苏旌凯中科超导高技术有限公司 | Method for extracting lithium from bittern and preparing high-purity lithium concentrate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101829538B (en) * | 2010-05-19 | 2013-06-26 | 浙江海虹控股集团有限公司 | Preparation method of high-performance lithium adsorbent |
| CN107930575A (en) * | 2017-11-10 | 2018-04-20 | 江苏旌凯中科超导高技术有限公司 | Magnetic aluminium base lithium adsorbent and preparation method thereof |
-
2017
- 2017-11-10 CN CN201711104186.5A patent/CN107930575A/en active Pending
-
2018
- 2018-09-14 CN CN201811072622.XA patent/CN109012567B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928828A (en) * | 2010-09-25 | 2010-12-29 | 西安蓝晓科技有限公司 | Method for extracting lithium from salt lake brine by adsorption method |
| CN104014308A (en) * | 2014-02-25 | 2014-09-03 | 江苏海普功能材料有限公司 | Method for preparing high-performance brine lithium-extraction adsorption agent and adsorption agent prepared by method |
| CN104711436A (en) * | 2015-03-27 | 2015-06-17 | 中南大学 | Method for extracting lithium from lithium-containing solution |
| KR20160134085A (en) * | 2015-05-14 | 2016-11-23 | 서울대학교산학협력단 | Magnetic lithium adsorbent, method for preparing the same, and method of recovering lithium by using the same |
| CN106345394A (en) * | 2016-11-02 | 2017-01-25 | 江苏旌凯中科超导高技术有限公司 | Method for extracting lithium from bittern and preparing high-purity lithium concentrate |
Non-Patent Citations (2)
| Title |
|---|
| 磁性锂离子筛的制备及提锂性能研究;李志勇等;《有色金属（冶炼部分）》;20170930(第8期);摘要 * |
| 铝盐吸附剂从盐湖卤水中吸附锂的研究;董茜等;《稀有金属》;20070630;第31卷(第3期);摘要、第357页1.2吸附剂的制备 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109012567A (en) | 2018-12-18 |
| CN107930575A (en) | 2018-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109012567B (en) | Magnetic aluminum-based lithium adsorbent and preparation method thereof | |
| Gu et al. | Lithium ion sieve synthesized via an improved solid state method and adsorption performance for West Taijinar Salt Lake brine | |
| Marthi et al. | Application and limitations of a H2TiO3–Diatomaceous earth composite synthesized from titania slag as a selective lithium adsorbent | |
| CN110639467A (en) | Preparation method of magnetic aluminum salt lithium adsorbent | |
| CN108083301A (en) | The method that lithium is extracted from bittern using magnetic powder aluminium system lithium adsorbent | |
| Wang et al. | Application of citric acid as eluting medium for titanium type lithium ion sieve | |
| Liu et al. | Effect of Fe (II) on the formation of iron oxide synthesized from pyrite cinders by hydrothermal process | |
| US20230027987A1 (en) | Orthosilicate-based adsorbent and selective metal adsorption from brines using orthosilicate-based adsorbent | |
| CN101239733A (en) | Method for preparing calcium aluminum hydrotalcite used as concrete additive | |
| CN109692648B (en) | Adsorbent for efficiently adsorbing sulfate ions in water and preparation method thereof | |
| CN102139926A (en) | Method for preparing nano oxide with high purity, high specific surface area and fine grains | |
| CN102942202A (en) | Method for synthesizing ultrathin rare earth lamellar Ln2(OH)5NO3.nH2O nanosheets through low temperature coprecipitation method | |
| CN111804270B (en) | Aluminum-based lithium adsorbent and preparation method thereof | |
| Sulistiyono et al. | Study of lithium extraction from brine water, Bledug Kuwu, Indonesia by the precipitation series of oxalic acid and carbonate sodium | |
| US20240010514A1 (en) | Nanomaterial Composites Useful for the Extraction and Recovery of Lithium from Aqueous Solutions | |
| KR20200041816A (en) | Lithium Ion Sieve and Lithium Ion Extraction Method Using the Same | |
| CN115646474A (en) | Manganese titanium-based composite lithium ion sieve and preparation method and application thereof | |
| JP2015051416A (en) | Manufacturing method of adsorbent, and the adsorbent manufactured by the method | |
| You et al. | Synthesis of Lithium Manganese Oxide by Wet Mixing and its Removal Characteristic of Lithium Ion | |
| CN116354409A (en) | Ultrahigh BET high-nickel ternary precursor and continuous preparation method thereof | |
| CN110711551A (en) | Lithium adsorbent and preparation method thereof | |
| CN115779851B (en) | Synthesis method of lithium manganate ion sieve adsorbent with coating structure | |
| TWI414483B (en) | Method for preparing layered double hydroxides | |
| US20230278024A1 (en) | Method of manufacturing inorganic ion exchanger for the selective extraction of lithium from lithium-containing natural and technological brines | |
| Noerochim et al. | Adsorption Performance of Li1. 6Mn1. 67O4 for Lithium Extraction from Geothermal Fluid of Lumpur Sidoarjo |
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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200810 Address after: Room 1013, building 1, No. 457, Qiyi Road, Chengzhong District, Xining City, Qinghai Province 810000 Applicant after: Xining Yongzheng Lithium Industry Co.,Ltd. Address before: 214400 Xicheng Road 1027, Yuecheng Town, Jiangyin City, Wuxi City, Jiangsu Province Applicant before: JIANGSU JINGKAI ZHONGKE SUPERCONDUCTION HIGH TECHNOLOGY Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: Room 101, No. 15 Chuncheng Road, Quzhou City, Zhejiang Province, 324012 Patentee after: Quzhou Yongzheng Lithium Industry Technology Co.,Ltd. Address before: 810000 room 1013, building 1, No. 457, Qiyi Road, Chengzhong District, Xining City, Qinghai Province Patentee before: Xining Yongzheng Lithium Industry Co.,Ltd. |