CN110639467A - Preparation method of magnetic aluminum salt lithium adsorbent - Google Patents

Preparation method of magnetic aluminum salt lithium adsorbent Download PDF

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CN110639467A
CN110639467A CN201910995832.4A CN201910995832A CN110639467A CN 110639467 A CN110639467 A CN 110639467A CN 201910995832 A CN201910995832 A CN 201910995832A CN 110639467 A CN110639467 A CN 110639467A
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lithium
aluminum
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solution
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林森
陈君
宋兴福
于建国
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East China University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J20/046—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 containing halogens, e.g. halides
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    • 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
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    • 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
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • 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
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    • B01J2220/42—Materials comprising a mixture of inorganic materials

Abstract

The invention discloses a preparation method of a magnetic aluminum salt lithium adsorbent, which comprises the following steps: preparing a lithium-aluminum mixed solution; preparing magnetic core suspension; adding an alkali solution and a lithium-aluminum mixed solution into the magnetic core suspension to obtain a precursor solution; and sequentially carrying out organic solvent washing, drying, grinding, deionized water washing and drying treatment on the solid product in the precursor solution to finally obtain the magnetic aluminum-salt lithium adsorbent. The preparation method of the magnetic aluminum salt lithium adsorbent is simple, short in time consumption and low in cost, the obtained magnetic aluminum salt lithium adsorbent reserves the adsorption capacity of lithium aluminum layered double hydroxide, namely the aluminum salt lithium adsorbent, can be applied to extracting lithium resources from lithium-containing solution with high magnesium-lithium ratio and low lithium concentration, has good magnetism, can be quickly separated from the solution under the action of an external magnetic field, is convenient to recover and recycle, and avoids the problems that the powder adsorbent is difficult to separate and recover in the application process, and the adsorption performance is sharply reduced due to molding granulation.

Description

Preparation method of magnetic aluminum salt lithium adsorbent
Technical Field
The invention relates to a preparation method of an adsorbent, in particular to a preparation method of a magnetic aluminum salt lithium adsorbent, belonging to the technical field of preparation of inorganic adsorbents.
Background
Lithium is one of important rare metal elements, and has been widely applied to a plurality of industries and fields such as batteries, ceramics, glass, lubricating grease, metallurgy, atomic thermonuclear fusion and the like.
In nature, lithium resources are mainly assigned to granite pegmatite type lithium ore deposits and salt lake brine. At present, only a few countries of solid lithium ores have commercial development value, and the extraction of lithium from ores in China is limited by the aspects of low average grade of the ores, less resource reserves, high mining cost, relatively backward mining and selecting technology, serious environmental pollution and the like, and the production and processing of lithium products by only mining the ores cannot meet the requirements of modern production development. In contrast, the lithium resource content in the salt lake brine accounts for more than 80% of the globally proven reserves, the mining cost is low, the lithium extraction technology is gradually developed along with the continuous exploration and development of the salt lake resources at home and abroad, and the global salt lake lithium yield is increased year by year. The salt lake brine in China contains a large amount of lithium resources, but generally contains a large amount of alkali metal and alkaline earth metal ions with chemical properties similar to those of Li < + >, compared with the salt lake brine in China, particularly the existence of Mg2 < + > brings great difficulty to extraction of Li < + >, and meanwhile, the starting of lithium extraction from the salt lake brine in China is late, so that how to separate magnesium and lithium economically and efficiently and develop and perfect corresponding process technologies are problems to be solved urgently in the research field.
At present, common process methods for extracting lithium from salt lake brine with high magnesium-lithium ratio comprise a solvent extraction method, a membrane separation method, an adsorption method and the like. The adsorption method has the advantages of simple process operation, short time consumption, environmental friendliness and the like, and the adsorbent with excellent preparation performance is the key of the lithium extraction effect of the adsorption method, so that the adsorption material is required to have high lithium selectivity, large adsorption capacity, stable performance and convenience in recovery. In recent years, research on lithium adsorbents has been focused on several inorganic adsorbents, including manganese-based, titanium-based ion sieves, and aluminum salt adsorbents. Generally, the manganese ion sieve has high selectivity and large adsorption capacity to lithium ions, but the desorption process is too dependent on acid washing, so that the loss rate of the adsorbent is high; compared with manganese ion sieves, the titanium ion sieves have improved stability, and have the problems that the synthesis process has strict requirements on temperature, and the desorption has serious trailing phenomenon; the aluminum lithium adsorbent is used for extracting lithium from salt lake brine and developed from an aluminum salt precipitation method, is a layered double hydroxide and can be generally expressed as LiCl & 2Al (OH)3 & nH2O, achieves the aim of selectively adsorbing lithium based on the memory effect of Li < + > and the steric hindrance effect on metal ions with larger radius, and has the advantages of simple preparation process, no need of acid washing, low dissolution loss rate, good stability, economy and environmental protection, and the adsorption capacity is generally about 6-8mg/g, so that the aluminum lithium adsorbent has good industrial application prospect. However, if the powdery aluminum salt lithium adsorbent is filled in the adsorption bed without treatment, the phenomena of poor liquid fluidity and permeability, difficult solid-liquid separation and the like occur, so that the powdery adsorbent cannot be directly applied to large-scale continuous industrial production. In order to solve the problem, organic binders are generally used for forming and granulating the powder, but a large number of experimental results show that the adsorption capacity of the adsorbent after granulation is sharply reduced to only 2-3mg/g, the forming technology is not mature, and slight loss still exists in the adsorption and desorption process.
Disclosure of Invention
The invention aims to: provided is a method for preparing a magnetic aluminum salt lithium adsorbent, which can extract lithium from a lithium-containing solution (salt lake brine, geothermal brine, seawater and the like) with low lithium concentration and multiple impurities and can be rapidly separated from the solution through an external magnetic field.
In order to achieve the above object, the present invention provides a method for preparing a magnetic aluminum-salt lithium adsorbent, comprising the following steps:
step 1, dissolving soluble lithium salt and aluminum salt in deionized water to prepare a lithium-aluminum mixed solution;
step 2, adding the magnetic nano particles into deionized water to obtain magnetic core suspension;
step 3, adding an alkali solution and a lithium-aluminum mixed solution into the magnetic core suspension under the condition of stirring, and controlling the pH value of the end point to be 3-12;
step 4, stopping stirring, and then sequentially performing aging and hydrothermal reaction to obtain a precursor solution;
and 5, separating a solid product from the precursor solution, and sequentially performing organic solvent washing, drying, grinding, deionized water washing and drying treatment on the solid product to finally obtain the magnetic aluminum-salt-lithium adsorbent.
Further, in the step 1, the soluble lithium salt is at least one of lithium chloride, lithium nitrate, lithium sulfate and lithium hydroxide; the soluble aluminum salt is at least one of aluminum chloride, aluminum nitrate and aluminum sulfate.
Further, in step 1, after the soluble lithium salt and the aluminum salt are dissolved in deionized water, performing ultrasonic treatment at a temperature of 20-70 ℃ for 5-180min to prepare a lithium-aluminum mixed solution, wherein the molar ratio of lithium to aluminum in the lithium-aluminum mixed solution is 0.2: 2 to 2: 2, the concentration of lithium ions is 0.01-10mol/L, and the concentration of aluminum ions is 0.1-10 mol/L.
Further, in the step 2, the magnetic nanoparticles are at least one of ferroferric oxide, iron, cobalt and nickel elementary substances.
Further, in the step 2, after the magnetic nanoparticles are added into deionized water, ultrasonic dispersion is carried out for 3-300min at the temperature of 20-70 ℃ to obtain the magnetic core suspension.
Further, in step 3, the alkali solution is prepared by dissolving alkali in water, wherein the alkali is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium metaaluminate and ammonia water.
Further, in step 3, the addition mode of the alkali solution and the lithium aluminum mixed solution is as follows: firstly, pouring 1-20mol/L alkali solution into the magnetic core suspension, and then dropwise adding the lithium-aluminum mixed solution at the speed of 1-30 mL/min; or firstly pouring the lithium-aluminum mixed solution into the magnetic core suspension, and then dropwise adding 1-20mol/L alkali solution at the speed of 1-30 mL/min; or dropping the lithium-aluminum mixed solution and the alkali solution with the concentration of 1-20mol/L into the magnetic nucleus suspension in a concurrent flow manner at the speed of 1-30 mL/min.
Further, in step 3, in the adding process of the alkali solution and the lithium aluminum mixed solution, the reaction temperature is controlled within 25-100 ℃, and the stirring speed is controlled within 100-800 rpm.
Further, in the step 4, the aging is carried out at the temperature of 25-100 ℃, and the aging time is controlled within 0.5-48 h; the temperature of the hydrothermal reaction is controlled within 100 ℃ and 300 ℃, and the reaction time is controlled within 8-48 h.
Further, in step 5, the organic solvent is at least one of acetone, ethanol, chloroform and methanol; the solid-liquid separation mode after the deionized water washing is at least one of vacuum filtration, magnetic separation and centrifugation; the temperature of the two drying treatments is controlled to be 40-150 ℃, and the time duration of the two drying treatments is controlled to be 4-24 h; the temperature of the deionized water is controlled between 25 and 150 ℃ when the deionized water is washed.
The invention has the beneficial effects that: the magnetic aluminum-salt-lithium adsorbent prepared by the preparation method of the invention comprises magnetic cores and effective adsorption components LiCl. mAl (OH)3·nH2O is stably combined, so that the adsorption capacity and high selectivity of the aluminum salt adsorbent to lithium are reserved, the aluminum salt adsorbent is suitable for extracting lithium from lithium-containing solution with high magnesium-lithium ratio and low lithium concentration, and magnetic nuclei are doped to make the powder magnetic, solid-liquid separation in the adsorption and desorption process can be realized by applying an external magnetic field, the operability is strong, and the problems caused by bonded granulation are effectively avoided; in addition, the preparation method of the magnetic aluminum salt lithium adsorbent is simple and reasonable, the overall conditions are mild, the control is easy, the product composition can be flexibly adjusted according to actual needs, the cost and the energy consumption are low, and no environmental pollution is caused.
Drawings
FIG. 1 is a flow chart of a preparation method of the present invention;
FIG. 2 is an XRD pattern of magnetic lithium aluminum salt adsorbents prepared in examples 1-4 of the present invention;
fig. 3 is an SEM photograph of the magnetic aluminum-salt lithium adsorbent prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the embodiments.
As shown in fig. 1, the invention discloses a preparation method of a magnetic aluminum salt lithium adsorbent, which comprises the following steps:
step 1, dissolving soluble lithium salt and aluminum salt in deionized water to prepare a lithium-aluminum mixed solution;
step 2, adding the magnetic nano particles into deionized water to obtain magnetic core suspension;
step 3, adding an alkali solution and a lithium-aluminum mixed solution into the magnetic core suspension under the condition of stirring, and controlling the end point pH value to be 3-12, preferably 4.5;
step 4, stopping stirring, and then sequentially performing aging and hydrothermal reaction to obtain a precursor solution;
and 5, separating a solid product from the precursor solution, and sequentially performing organic solvent washing, drying, grinding, deionized water washing and drying treatment on the solid product to finally obtain the magnetic aluminum-salt-lithium adsorbent.
The magnetic aluminum salt lithium adsorbent is represented as: magnetic core @ LiCl. mAl (OH)3·nH2And O, wherein m is 2-5, n is 1-10, and in order to ensure that the magnetic aluminum lithium salt adsorbent has enough adsorption capacity for lithium and can realize high-efficiency separation and recovery by utilizing magnetism, the mass of the added magnetic core accounts for 2-70% of the total mass of the adsorbent.
The preparation method of the magnetic aluminum lithium adsorbent disclosed by the invention is simple, short in time consumption and low in cost, the obtained magnetic aluminum lithium adsorbent retains the adsorption capacity of lithium aluminum layered double hydroxide, namely the aluminum lithium adsorbent, has the advantages of high lithium selectivity and good repeatability, can be applied to extracting lithium resources from lithium-containing solution with high magnesium-lithium ratio and low lithium concentration, has good magnetism, can be quickly separated from the solution under the action of an external magnetic field, is convenient to recover and recycle, avoids the problems that the separation and recovery difficulty of a powder adsorbent in the application process is large, the adsorption performance is sharply reduced due to molding granulation and the like, and has important significance for the development of an adsorption lithium extraction technology.
Further, in the step 1, the soluble lithium salt is at least one of lithium chloride, lithium nitrate, lithium sulfate and lithium hydroxide; the soluble aluminum salt is at least one of aluminum chloride, aluminum nitrate and aluminum sulfate.
Further, in step 1, after the soluble lithium salt and the aluminum salt are dissolved in the deionized water, the solution is subjected to ultrasonic treatment at a temperature of 20-70 ℃ for 5-180min to prepare a lithium-aluminum mixed solution, preferably at a temperature of 60 ℃, preferably for a time of 60min, and the molar ratio of lithium to aluminum in the lithium-aluminum mixed solution is 0.2: 2 to 2: 2, preferably in a molar ratio of 0.8: 2, the lithium ion concentration is 0.01-10mol/L, preferably 0.4mol/L, and the aluminum ion concentration is 0.1-10mol/L, preferably 1.0 mol/L.
Further, in step 2, the magnetic nanoparticles are at least one of ferroferric oxide, iron, cobalt and nickel simple substance, for example, Fe prepared by coprecipitation method3O4And (3) solid powder.
Further, in step 2, after the magnetic nanoparticles are added into deionized water, ultrasonic dispersion is carried out for 3-300min at the temperature of 20-70 ℃ to obtain a magnetic core suspension, preferably at the temperature of 50 ℃ for 60 min.
Further, in step 3, the alkali solution is prepared by dissolving alkali in water, wherein the alkali is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium metaaluminate and ammonia water, for example, NaOH is used.
Further, in step 3, the addition mode of the alkali solution and the lithium aluminum mixed solution is as follows: firstly, pouring 1-20mol/L alkali solution into the magnetic core suspension, wherein the preferable concentration of NaOH solution is 8mol/L, and then dropwise adding the lithium-aluminum mixed solution at the speed of 1-30mL/min, wherein the preferable dropwise adding speed is 5 mL/min; or firstly pouring the lithium-aluminum mixed solution into the magnetic core suspension, and then dripping 1-20mol/L alkali solution at the speed of 1-30mL/min, wherein the preferable concentration of the NaOH solution is 8mol/L, and the preferable dripping speed is 5 mL/min; or dropping the lithium-aluminum mixed solution and the alkali solution with the concentration of 1-20mol/L into the magnetic nucleus suspension in a concurrent flow manner at the speed of 1-30mL/min, wherein the dropping speed is preferably 5mL/min, and the preferable concentration of the NaOH solution is 8 mol/L.
Further, in step 3, during the addition of the alkali solution and the lithium aluminum mixed solution, the reaction temperature is controlled within 25-100 ℃, preferably 45 ℃ constant temperature water bath, and the stirring speed is controlled within 100-800rpm, preferably 300 rpm.
Further, in the step 4, the aging is carried out at the temperature of 25-100 ℃, preferably at the temperature of 45 ℃, and the aging time is controlled within 0.5-48h, preferably 2 h; the temperature of the hydrothermal reaction is controlled within 100-300 ℃, the preferred temperature is 160 ℃, and the reaction time is within 8-48h, the preferred time is 24 h.
Further, in step 5, the organic solvent is at least one of acetone, ethanol, chloroform and methanol, preferably acetone; the solid-liquid separation mode after the deionized water washing is at least one of vacuum filtration, magnetic separation and centrifugation; the temperature of the two drying treatments is controlled to be 40-150 ℃, the preferred temperature is 60 ℃, the time duration of the two drying treatments is controlled to be 4-24h, and the preferred time duration is 12 h; the temperature of the deionized water is controlled between 25 and 150 ℃ during the deionized water washing, and is preferably 40 ℃.
The salt lake brine used in the following examples is sodium potassium depleted old brine from the khaki salt lake of the Qinghai province, and the main cations and the concentrations thereof in the old brine are shown in Table 1:
TABLE 1 Primary cation and concentration in the Carlo old brine
Cation(s) Li+ Mg2+ Na+ K+ Ca2+
Concentration (mg/L) 397.14 112800 1428.7 486.825 50.35
Example 1
19.57g AlCl was weighed out separately3·6H2O and 1.86g LiCl. H2Dissolving O in 80mL of deionized water, carrying out ultrasonic treatment at the temperature of 60 ℃ for 60min, and uniformly mixing to prepare a lithium-aluminum mixed solution with Li/Al of 0.8/2, wherein the concentration of lithium ions is 0.4mol/L, and the concentration of aluminum ions is 1.0 mol/L. 1.20g of Fe prepared by coprecipitation3O4The solid powder was added to 100mL of deionized water and ultrasonically dispersed at 50 ℃ for 60 min. To Fe3O4And adding 20mL of 8mol/L NaOH solution into the suspension, dropwise adding the lithium-aluminum mixed solution into the reaction kettle at a dropwise adding speed of 5mL/min, carrying out the whole process under the condition of 45 ℃ constant-temperature water bath, wherein the stirring speed is 300rpm, and controlling the pH value at the dropwise adding end point to be 4.5. And after the reaction is finished, aging at 45 ℃ for 2h, transferring the reaction system to a polytetrafluoroethylene hydrothermal kettle after the aging is finished, carrying out hydrothermal reaction at 160 ℃ for 24h to obtain a precursor of the magnetic aluminum-salt-lithium adsorbent, filtering, washing with acetone, and drying at 60 ℃ for 12 h. Grinding the dried solid into powder, washing with deionized water at 40 deg.C, and drying at 60 deg.C for 12 hr to obtain Fe3O4@LiCl·mAl(OH)3·nH2A magnetic aluminum salt lithium adsorbent for O, wherein the Fe/Al molar ratio is 0.23, m is 3.3, and n is 5.0. The average particle diameter of the adsorbent is 9.62 μm, and the solid-liquid ratio is 30 mL: adding 1g of the mixture into salt lake brine, statically adsorbing for 24 hours at the temperature of 25 ℃ and the oscillation frequency of 150rpm, and measuring that the equilibrium lithium adsorption capacity is 5.90Mg/g and the Mg adsorption of an adsorbent is2+Selectivity coefficient of (a) LMigThe saturation magnetization is 15.17emu/g, the magnetic recovery rate can reach 95.15% when the magnetic material is only stood for 10min in the magnetic field of a 0.6T permanent magnet. As shown in fig. 3, is an SEM photograph of the magnetic aluminum salt lithium adsorbent prepared in example 1.
Example 2
19.57g AlCl was weighed out separately3·6H2O and 1.86g LiCl. H2Dissolving O in 80mL deionized water, carrying out ultrasonic treatment at 60 ℃ for 60min, uniformly mixing, preparing a lithium-aluminum mixed solution with Li/Al being 0.8/2,wherein the concentration of lithium ions is 0.4mol/L, and the concentration of aluminum ions is 1.0 mol/L. 2.40g of Fe prepared by a coprecipitation method3O4The solid powder was added to 100mL of deionized water and ultrasonically dispersed at 50 ℃ for 60 min. To Fe3O4And adding 20mL of 8mol/L NaOH solution into the suspension, dropwise adding the lithium-aluminum mixed solution into the reaction kettle at a dropwise adding speed of 5mL/min, carrying out the whole process under the condition of 45 ℃ constant-temperature water bath, wherein the stirring speed is 300rpm, and controlling the pH value at the dropwise adding end point to be 4.5. And after the reaction is finished, aging at 45 ℃ for 2h, transferring the reaction system to a polytetrafluoroethylene hydrothermal kettle after the aging is finished, carrying out hydrothermal reaction at 160 ℃ for 24h to obtain a precursor of the magnetic aluminum-salt-lithium adsorbent, filtering, washing with acetone, and drying at 60 ℃ for 12 h. Grinding the dried solid into powder, washing with deionized water at 40 deg.C, and drying at 60 deg.C for 12 hr to obtain Fe3O4@LiCl·mAl(OH)3·nH2A magnetic aluminum salt lithium adsorbent for O, wherein the Fe/Al molar ratio is 0.40, m is 3.5, and n is 5.7. The average particle diameter of the adsorbent is 12.0 μm, and the solid-liquid ratio is 30 mL: adding 1g of the mixture into salt lake brine, statically adsorbing for 24 hours at the temperature of 25 ℃ and the oscillation frequency of 150rpm, and measuring that the equilibrium lithium adsorption capacity is 4.71Mg/g and the Mg pair is adsorbed by an adsorbent2+Selectivity coefficient of (a) LMigThe saturation magnetization reaches 242.48, the saturation magnetization is 17.30emu/g, the magnetic recovery rate can reach 98.20 percent after only standing for 10min in the magnetic field of a 0.6T permanent magnet.
Example 3
19.57g AlCl was weighed out separately3·6H2O and 1.86g LiCl. H2Dissolving O in 80mL of deionized water, carrying out ultrasonic treatment at the temperature of 60 ℃ for 60min, and uniformly mixing to prepare a lithium-aluminum mixed solution with Li/Al of 0.8/2, wherein the concentration of lithium ions is 0.4mol/L, and the concentration of aluminum ions is 1.0 mol/L. 3.60g of Fe prepared by a coprecipitation method3O4The solid powder was added to 100mL of deionized water and ultrasonically dispersed at 50 ℃ for 60 min. To Fe3O4Adding 20mL of 8mol/L NaOH solution into the suspension, dropwise adding the lithium-aluminum mixed solution into the reaction kettle at a dropwise adding speed of 5mL/min, carrying out the whole process under the condition of 45 ℃ constant-temperature water bath, stirring at a speed of 300rpm, and controllingThe pH at the end of the addition was 4.5. And after the reaction is finished, aging at 45 ℃ for 2h, transferring the reaction system to a polytetrafluoroethylene hydrothermal kettle after the aging is finished, carrying out hydrothermal reaction at 160 ℃ for 24h to obtain a precursor of the magnetic aluminum-salt-lithium adsorbent, filtering, washing with acetone, and drying at 60 ℃ for 12 h. Grinding the dried solid into powder, washing with deionized water at 40 deg.C, and drying at 60 deg.C for 12 hr to obtain Fe3O4@LiCl·mAl(OH)3·nH2A magnetic aluminum salt lithium adsorbent for O, wherein the Fe/Al molar ratio is 0.63, m is 3.2, and n is 6.3. The average particle diameter of the adsorbent is 18.4 μm, and the solid-liquid ratio is 30 mL: adding 1g of the mixture into salt lake brine, statically adsorbing for 24 hours at the temperature of 25 ℃ and the oscillation frequency of 150rpm, and measuring that the equilibrium lithium adsorption capacity is 3.95Mg/g and the Mg adsorption of an adsorbent is2+Selectivity coefficient of (a) LMigThe saturation magnetization reaches 298.02, the saturation magnetization is 20.75emu/g, the magnetic recovery rate can reach 99.57 percent after the magnetic material is only stood for 10min in the magnetic field of a 0.6T permanent magnet.
Example 4
19.57g AlCl was weighed out separately3·6H2O and 1.86g LiCl. H2Dissolving O in 80mL of deionized water, carrying out ultrasonic treatment at the temperature of 60 ℃ for 60min, and uniformly mixing to prepare a lithium-aluminum mixed solution with Li/Al of 0.8/2, wherein the concentration of lithium ions is 0.4mol/L, and the concentration of aluminum ions is 1.0 mol/L. 4.80g of Fe prepared by a coprecipitation method3O4The solid powder was added to 100mL of deionized water and ultrasonically dispersed at 50 ℃ for 60 min. To Fe3O4And adding 20mL of 8mol/L NaOH solution into the suspension, dropwise adding the lithium-aluminum mixed solution into the reaction kettle at a dropwise adding speed of 5mL/min, carrying out the whole process under the condition of 45 ℃ constant-temperature water bath, wherein the stirring speed is 300rpm, and controlling the pH value at the dropwise adding end point to be 4.5. And after the reaction is finished, aging at 45 ℃ for 2h, transferring the reaction system to a polytetrafluoroethylene hydrothermal kettle after the aging is finished, carrying out hydrothermal reaction at 160 ℃ for 24h to obtain a precursor of the magnetic aluminum-salt-lithium adsorbent, filtering, washing with acetone, and drying at 60 ℃ for 12 h. Grinding the dried solid into powder, washing with deionized water at 40 deg.C, and drying at 60 deg.C for 12 hr to obtain Fe3O4@LiCl·mAl(OH)3·nH2A magnetic aluminum salt lithium adsorbent for O, wherein the Fe/Al molar ratio is 0.74, m is 3.5, and n is 7.2. The average particle diameter of the adsorbent is 21.1 μm, and the solid-liquid ratio is 30 mL: adding 1g of the mixture into salt lake brine, statically adsorbing for 24 hours at the temperature of 25 ℃ and the oscillation frequency of 150rpm, measuring that the equilibrium lithium adsorption capacity is 3.56Mg/g, and adsorbing Mg by an adsorbent2+Selectivity coefficient of (a) LMigThe saturation magnetization reaches 362.68, the saturation magnetization is 21.62emu/g, the magnetic recovery rate can reach 99.60 percent after only standing for 10min in the magnetic field of a 0.6T permanent magnet.
As shown in FIG. 2, XRD patterns of the magnetic aluminum-salt lithium adsorbents prepared in examples 1 to 4, except for magnetic nuclei and LDH (LiCl. mAl (OH))3·nH2O) two phases, no diffraction peak of other substances.
The above examples show that the magnetic aluminum salt lithium adsorbent prepared by the method of the present invention still has the adsorption capacity of the aluminum salt adsorbent, is suitable for extracting lithium from lithium-containing solution with high magnesium-lithium ratio, and is easy to magnetically separate and recover in a short time.
The foregoing is considered as illustrative only of the principles, general features, advantages and embodiments of this invention, and it is to be understood that the invention is not limited thereto, but is intended to cover modifications within the spirit and scope of the invention.

Claims (10)

1. A preparation method of a magnetic aluminum salt lithium adsorbent is characterized by comprising the following steps:
step 1, dissolving soluble lithium salt and aluminum salt in deionized water to prepare a lithium-aluminum mixed solution;
step 2, adding the magnetic nano particles into deionized water to obtain magnetic core suspension;
step 3, adding an alkali solution and a lithium-aluminum mixed solution into the magnetic core suspension under the condition of stirring, and controlling the pH value of the end point to be 3-12;
step 4, stopping stirring, and then sequentially performing aging and hydrothermal reaction to obtain a precursor solution;
and 5, separating a solid product from the precursor solution, and sequentially performing organic solvent washing, drying, grinding, deionized water washing and drying treatment on the solid product to finally obtain the magnetic aluminum-salt-lithium adsorbent.
2. The method for preparing a magnetic aluminum-salt lithium adsorbent according to claim 1, wherein in step 1, the soluble lithium salt is at least one of lithium chloride, lithium nitrate, lithium sulfate and lithium hydroxide; the soluble aluminum salt is at least one of aluminum chloride, aluminum nitrate and aluminum sulfate.
3. The method for preparing a magnetic aluminum-salt lithium adsorbent according to claim 1, wherein in step 1, after the soluble lithium salt and the aluminum salt are dissolved in deionized water, the solution is mixed by ultrasonic treatment at 20-70 ℃ for 5-180min to prepare a lithium-aluminum mixed solution, and the molar ratio of lithium to aluminum in the lithium-aluminum mixed solution is 0.2: 2 to 2: 2, the concentration of lithium ions is 0.01-10mol/L, and the concentration of aluminum ions is 0.1-10 mol/L.
4. The method for preparing the magnetic aluminum-salt lithium adsorbent according to claim 1, wherein in the step 2, the magnetic nanoparticles are at least one of ferroferric oxide, iron, cobalt and nickel.
5. The method for preparing a magnetic aluminum-salt lithium adsorbent according to claim 1, wherein in the step 2, after the magnetic nanoparticles are added into deionized water, the magnetic nanoparticles are ultrasonically dispersed at a temperature of 20-70 ℃ for 3-300min to obtain a magnetic core suspension.
6. The method of claim 1, wherein the alkali solution is prepared by dissolving an alkali in water in step 3, wherein the alkali is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium metaaluminate and ammonia water.
7. The method for preparing a magnetic aluminum-salt lithium adsorbent according to claim 1, wherein in the step 3, the alkali solution and the lithium-aluminum mixed solution are added in a manner that: firstly, pouring 1-20mol/L alkali solution into the magnetic core suspension, and then dropwise adding the lithium-aluminum mixed solution at the speed of 1-30 mL/min; or firstly pouring the lithium-aluminum mixed solution into the magnetic core suspension, and then dropwise adding 1-20mol/L alkali solution at the speed of 1-30 mL/min; or dropping the lithium-aluminum mixed solution and the alkali solution with the concentration of 1-20mol/L into the magnetic nucleus suspension in a concurrent flow manner at the speed of 1-30 mL/min.
8. The method for preparing a magnetic aluminum-salt lithium adsorbent as claimed in claim 1, wherein in the step 3, the reaction temperature is controlled within 25-100 ℃ and the stirring speed is controlled within 100-800rpm during the addition of the alkali solution and the lithium-aluminum mixed solution.
9. The method for preparing a magnetic aluminum-salt lithium adsorbent according to claim 1, wherein in the step 4, the aging is performed at a temperature of 25 to 100 ℃ and the aging time is controlled within 0.5 to 48 hours; the temperature of the hydrothermal reaction is controlled within 100 ℃ and 300 ℃, and the reaction time is controlled within 8-48 h.
10. The method for preparing a magnetic aluminum-salt lithium adsorbent according to claim 1, wherein in the step 5, the organic solvent is at least one of acetone, ethanol, chloroform, and methanol; the solid-liquid separation mode after the deionized water washing is at least one of vacuum filtration, magnetic separation and centrifugation; the temperature of the two drying treatments is controlled to be 40-150 ℃, and the time duration of the two drying treatments is controlled to be 4-24 h; the temperature of the deionized water is controlled between 25 and 150 ℃ when the deionized water is washed.
CN201910995832.4A 2019-10-18 2019-10-18 Preparation method of magnetic aluminum salt lithium adsorbent Pending CN110639467A (en)

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