CN112342378A - Lithium ion adsorbent and preparation method thereof - Google Patents
Lithium ion adsorbent and preparation method thereof Download PDFInfo
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- 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
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- 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
Abstract
The invention relates to a lithium ion adsorbent and a preparation method thereof, and belongs to the technical field of adsorption and lithium extraction. The main technical idea is that in the preparation process of a sol-gel method, gel is simultaneously loaded on a carbon nitride carrier with a catalytic degradation effect, the degradation effect of the carbon nitride is utilized to relieve the problems of the reduction of the adsorption capacity and the service life of a lithium ion adsorbent in the cyclic adsorption process, and the adsorbent is simultaneously doped with Ni for delaying the loss of Mn; meanwhile, the invention also provides a method and a device for extracting lithium from brine based on the lithium ion selective adsorbent.
Description
Technical Field
The invention relates to a lithium ion adsorbent and a preparation method thereof, and belongs to the technical field of adsorption and lithium extraction.
Background
Lithium is present in nature mainly as solid hectorite in pegmatite such as spodumene and lepidolite, and as lithium ions in salt lake brine, underground brine and seawater. According to statistics, brine lithium resources in lithium resources found and newly found in the world have absolute advantages and approximately occupy the earth lithium resources. In recent years, lithium extraction from brine has the advantages of low cost and simple process, and solid lithium ore resources are increasingly exhausted, so lithium carbonate and lithium chloride produced from solid minerals in the marketAnd after a large amount of lithium products are reduced, the proportion of the lithium products from the brine is greatly improved, and the development and application directions of lithium resources are greatly turned. The inorganic ion adsorption method is to use inorganic ion adsorbent to adsorb Li+Has the characteristics of higher selectivity and specific memory effect, realizes the method for selectively extracting lithium from dilute solution, particularly the inorganic ion exchange adsorbent with the ion sieve effect, and the method can be used for extracting Li in salt lake brine with high magnesium-lithium ratio+Has good competitive selective adsorption. Currently, inorganic ion exchange adsorbents mainly include: amorphous hydroxide adsorbents, layered adsorbents, composite antimonate adsorbents, aluminum salt adsorbents, ion sieve type oxide adsorbents, and the like.
For example: CN1702043A discloses a method for preparing a lithium manganese oxide lithium ion sieve material by a hydrothermal method, which comprises the steps of mixing a lithium source substance and a manganese source substance according to the lithium manganese molar ratio of 0.5-3.0: 1, fully mixing and grinding the mixture, transferring the mixture into a high-pressure hydrothermal reaction kettle, adding distilled water, fully stirring, carrying out hydrothermal treatment for 4-96 h at 100-240 ℃, filtering and washing the obtained product until the pH value of the filtrate is 7-8, drying at 40-120 ℃, pre-roasting at 300 ℃ for 2h, roasting at 300-800 ℃ in an air atmosphere for 1-24 h to obtain the lithium manganese oxide lithium ion sieve, and applying the lithium manganese oxide lithium ion sieve to adsorption and separation of lithium. CN103121724A discloses a method for preparing lithium ion sieve adsorbent MnO2·0.5H2O and its precursor Li1.6Mn1.6O4The method of (1). The invention adopts inorganic manganese salt and lithium salt as raw materials, obtains the needed precursor Li by one-step hydro-thermal synthesis of an intermediate and then roasting at low temperature1.6Mn1.6O4(ii) a Then the precursor is treated by acid to extract Li therein, which is changed into H-And (4) washing, filtering and drying the molded ion sieve to obtain the ion sieve adsorbent with the lithium ion sieving effect.
However, since brine generally contains some organic pollutants, which tend to cause adsorption pollution on the adsorbent, and the service life of the adsorbent is reduced, it is necessary to develop a lithium ion sieve adsorbent used in an organic pollution environment.
Disclosure of Invention
The purpose of the invention is: the main technical idea is that gel is simultaneously loaded on a carbon nitride carrier with catalytic degradation effect in the preparation process of a sol-gel method, the degradation of the carbon nitride is utilized to slow down the problems of absorption capacity and service life reduction of the lithium ion adsorbent in the cyclic absorption process, and the adsorbent is simultaneously doped with Ni for delaying the loss of Mn; meanwhile, the invention also provides a method and a device for extracting lithium from brine based on the lithium ion selective adsorbent.
The technical scheme is as follows:
in a first aspect of the present invention, there is provided:
a selective lithium ion adsorbent is LiNi loaded on carbon nitride carriernMn2-nO4(ii) a Wherein n is more than 0 and less than 0.3.
In one embodiment, n = 0.2.
In a second aspect of the present invention, there is provided:
the preparation method of the lithium ion selective adsorbent comprises the following steps:
step 1, preparing carbon nitride nano particles: melamine, sodium citrate and deionized water are mixed according to the weight ratio of 2-3: 1-1.5: 100-150, performing hydrothermal reaction to synthesize carbon nitride, centrifuging to remove large particles after the reaction is finished, dialyzing the supernatant by using a dialysis bag to remove inorganic salts which are not completely reacted, and performing reduced pressure evaporation to dryness treatment on the purified reaction solution to obtain carbon nitride nanoparticles;
step 3, preparing lithium manganese oxide sol: mixing citric acid and ethylene glycol uniformly to obtain a solution, and adding LiNO into the solution3And Mn (NO)3)2Then ammonia water is dripped to adjust the pH value to 7.5-8 for hydrolysis reaction, and Ni (NO) is added into the reaction liquid after the reaction is finished3)2Stirring to obtain sol; wherein, citric acid, ethylene glycol, LiNO3、Mn(NO3)2And Ni (NO)3)2The molar ratio is 1: 150-200: 0.8-1.2: 1.6-2.0: 0.1 to 0.3;
and 5, sintering the adsorbent: and (4) roasting the gel obtained in the step (4) to obtain the adsorbent.
In one embodiment, in step 1, the hydrothermal reaction parameters are: reacting for 3-5 h at 180-200 ℃; the parameters of the centrifugation process are: centrifuging at a rotating speed of 8000-10000 r/min for 20-50 min, wherein the cut-off molecular weight of the dialysis bag is 200-800 Da.
In one embodiment, in the step 2, the concentration of the hydrochloric acid aqueous solution is 2-4 mol/L, and the soaking time is 4-6 h; the grafting reaction conditions of the silane coupling agent are as follows: reacting for 4-6 h at 40-50 ℃; the conditions of the crosslinking reaction of the ionic liquid are: reacting for 20-30 h at 70-75 ℃.
In one embodiment, in the step 3, the concentration of the ammonia water is 5 to 10wt%, and the hydrolysis reaction condition is 70 to 75 ℃ for 8 to 10 hours.
In one embodiment, the temperature of the vacuum drying in the 4 th step is 70 to 80 ℃.
In one embodiment, in the step 5, the roasting condition is that the roasting is carried out for 4-6 hours at the temperature of 750-780 ℃.
In a third aspect of the present invention, there is provided:
the application of the lithium ion selective adsorbent in the adsorption and separation of lithium in liquid.
In a fourth aspect of the present invention, there is provided:
a process for extracting lithium from brine comprises the following steps:
the lithium ion selective adsorbent is used for selectively adsorbing and desorbing lithium ions in the brine.
In a fifth aspect of the present invention, there is provided:
a device for extracting lithium from brine comprises an adsorption device, wherein the adsorption device is added with the lithium ion selective adsorbent.
Advantageous effects
The lithium ion selective adsorbent provided by the invention utilizes carbon nitride with a photocatalytic effect as a carrier, on one hand, the lithium ion selective adsorbent has a higher specific surface area, so that the adsorption capacity of lithium is larger, and simultaneously, the influence of COD (chemical oxygen demand) substances contained in brine on the recycling frequency of the adsorbent can be reduced. The adsorbent can be used for extracting lithium from brine.
Drawings
FIG. 1 is an SEM image of a lithium ion selective adsorbent provided by the present invention;
FIG. 2 is an XRD pattern of a lithium ion selective adsorbent provided by the present invention;
FIG. 3 is a graph comparing Li dissolution rates in acid leaching experiments;
FIG. 4 is a graph comparing the adsorption amounts in Li adsorption experiments;
fig. 5 is a graph showing changes in the adsorption amount in the cyclic adsorption experiment.
Detailed Description
Example 1 preparation of lithium ion Selective adsorbent
Step 1, preparing carbon nitride nano particles: 2g of melamine, 1g of sodium citrate and 100g of deionized water are uniformly mixed under the action of ultrasound, and the mixture is subjected to hydrothermal reaction to synthesize carbon nitride, wherein the reaction parameters are as follows: reacting at 180 ℃ for 3 hours, after the reaction is finished, centrifuging at a rotating speed of 8000 r/min to remove large particles, dialyzing the supernatant by using a dialysis bag, removing inorganic salts which are not completely reacted with the dialysis bag with a molecular weight cutoff of 200Da, and then carrying out reduced pressure evaporation to dryness treatment on the purified reaction solution to obtain 1.02g of carbon nitride nanoparticles;
step 3, preparing lithium manganese oxide sol: mixing citric acid with ethylene glycolMixing to obtain solution, adding LiNO into the solution3And Mn (NO)3)2Dropwise adding 5wt% ammonia water to adjust the pH value to 7.5-8, carrying out hydrolysis reaction for 8 hours at 70 ℃, and after the reaction is finished, adding Ni (NO) into the reaction solution3)2Stirring to obtain sol; wherein, citric acid, ethylene glycol, LiNO3、Mn(NO3)2And Ni (NO)3)2The molar ratio is 1: 150: 0.8: 1.6: 0.1;
and 5, sintering the adsorbent: and (4) roasting the gel obtained in the step (4) for 4 hours at the temperature of 750 ℃ to obtain the adsorbent.
Example 2 preparation of lithium ion Selective adsorbent
Step 1, preparing carbon nitride nano particles: 2g of melamine, 1g of sodium citrate and 100g of deionized water are uniformly mixed under the action of ultrasound, and the mixture is subjected to hydrothermal reaction to synthesize carbon nitride, wherein the reaction parameters are as follows: reacting at 180 ℃ for 3 hours, after the reaction is finished, centrifuging at a rotating speed of 8000 r/min to remove large particles, dialyzing the supernatant by using a dialysis bag, removing inorganic salts which are not completely reacted with the dialysis bag with a molecular weight cutoff of 200Da, and then carrying out reduced pressure evaporation to dryness treatment on the purified reaction solution to obtain 1.02g of carbon nitride nanoparticles;
step 3, preparing lithium manganese oxide sol: mixing citric acid and ethylene glycol uniformly to obtain a solution, and adding LiNO into the solution3And Mn (NO)3)2Then, 10wt% of ammonia water is dripped to adjust the pH value to 7.5-8, hydrolysis reaction is carried out, the hydrolysis reaction condition is that the reaction is carried out for 10 hours at 75 ℃, and Ni (NO) is added into the reaction liquid after the reaction is finished3)2Stirring to obtain sol; wherein, citric acid, ethylene glycol, LiNO3、Mn(NO3)2And Ni (NO)3)2The molar ratio is 1: 200: 1.2: 2.0: 0.3;
and 5, sintering the adsorbent: and (4) roasting the gel obtained in the step (4) for 6 hours at the temperature of 780 ℃ to obtain the adsorbent.
Example 3 preparation of lithium ion Selective adsorbent
Step 1, preparing carbon nitride nano particles: 2g of melamine, 1.2g of sodium citrate and 130g of deionized water are uniformly mixed under the action of ultrasound, and the mixture is subjected to hydrothermal reaction to synthesize carbon nitride, wherein the reaction parameters are as follows: reacting at 190 ℃ for 4 hours, centrifuging at a rotating speed of 9000 r/min to remove large particles after the reaction is finished, dialyzing the supernatant by using a dialysis bag, removing inorganic salts which are not completely reacted with the dialysis bag with a molecular weight cutoff of 400Da, and performing reduced pressure evaporation to dryness treatment on the purified reaction solution to obtain 1.15g of carbon nitride nanoparticles;
step 3, preparing lithium manganese oxide sol: mixing citric acid and ethylene glycol uniformly to obtain a solution, and adding LiNO into the solution3And Mn (NO)3)2Then, 10wt% of ammonia water is dripped to adjust the pH value to 7.5-8, hydrolysis reaction is carried out, the hydrolysis reaction condition is that the reaction is carried out for 10 hours at 75 ℃, and Ni (NO) is added into the reaction liquid after the reaction is finished3)2Stirring to obtain sol; wherein, citric acid, ethylene glycol, LiNO3、Mn(NO3)2And Ni (NO)3)2The molar ratio is 1: 180: 1.0: 1.8: 0.2;
and 5, sintering the adsorbent: and (4) roasting the gel obtained in the step (4) for 5 hours at the temperature of 770 ℃ to obtain the adsorbent.
Comparative example 1
The differences from example 3 are: ni (NO)3)2When added with LiNO3And Mn (NO)3)2And simultaneously adding.
Step 1, preparing carbon nitride nano particles: 2g of melamine, 1.2g of sodium citrate and 130g of deionized water are uniformly mixed under the action of ultrasound, and the mixture is subjected to hydrothermal reaction to synthesize carbon nitride, wherein the reaction parameters are as follows: reacting at 190 ℃ for 4 hours, centrifuging at a rotating speed of 9000 r/min to remove large particles after the reaction is finished, dialyzing the supernatant by using a dialysis bag, removing inorganic salts which are not completely reacted with the dialysis bag with a molecular weight cutoff of 400Da, and performing reduced pressure evaporation to dryness treatment on the purified reaction solution to obtain 1.15g of carbon nitride nanoparticles;
step 3, preparing lithium manganese oxide sol: mixing citric acid and ethylene glycol uniformly to obtain a solution, and adding LiNO into the solution3、Mn(NO3)2And Ni (NO)3)2Then, dropwise adding 10wt% ammonia water to adjust the pH value to 7.5-8, and carrying out hydrolysis reaction under the condition of reaction at 75 ℃ for 10 hours to obtain sol after the reaction is finished; wherein, citric acid, ethylene glycol, LiNO3、Mn(NO3)2And Ni (NO)3)2The molar ratio is 1: 180: 1.0: 1.8: 0.2;
and 5, sintering the adsorbent: and (4) roasting the gel obtained in the step (4) for 5 hours at the temperature of 770 ℃ to obtain the adsorbent.
Comparative example 2
The differences from example 3 are: the ionic liquid is not grafted on the surface of the carbon nitride nano particle.
Step 1, preparing carbon nitride nano particles: 2g of melamine, 1.2g of sodium citrate and 130g of deionized water are uniformly mixed under the action of ultrasound, and the mixture is subjected to hydrothermal reaction to synthesize carbon nitride, wherein the reaction parameters are as follows: reacting at 190 ℃ for 4 hours, centrifuging at a rotating speed of 9000 r/min to remove large particles after the reaction is finished, dialyzing the supernatant by using a dialysis bag, removing inorganic salts which are not completely reacted with the dialysis bag with a molecular weight cutoff of 400Da, and performing reduced pressure evaporation to dryness treatment on the purified reaction solution to obtain 1.15g of carbon nitride nanoparticles;
step 3, preparing lithium manganese oxide sol: mixing citric acid and ethylene glycol uniformly to obtain a solution, and adding LiNO into the solution3And Mn (NO)3)2Then, 10wt% of ammonia water is dripped to adjust the pH value to 7.5-8, hydrolysis reaction is carried out, the hydrolysis reaction condition is that the reaction is carried out for 10 hours at 75 ℃, and Ni (NO) is added into the reaction liquid after the reaction is finished3)2Stirring to obtain sol; wherein, citric acid, ethylene glycol, LiNO3、Mn(NO3)2And Ni (NO)3)2The molar ratio is 1: 180: 1.0: 1.8: 0.2;
and 5, sintering the adsorbent: and (4) roasting the gel obtained in the step (4) for 5 hours at the temperature of 770 ℃ to obtain the adsorbent.
Comparative example 3
The differences from example 3 are: the carbon nitride nanoparticles with surface ionic liquidization are added to be directly mixed with lithium manganese oxide instead of being used as a carrier.
Comparative example 4 preparation of conventional lithium manganese oxide adsorbent
Step 1, mixing citric acid and ethylene glycol uniformly to obtain a solution, and adding LiNO into the solution3And Mn (NO)3)2Then, 10wt% of ammonia water is dripped to adjust the pH value to 7.5-8, hydrolysis reaction is carried out, the hydrolysis reaction condition is that the reaction is carried out for 10 hours at 75 ℃, and Ni (NO) is added into the reaction liquid after the reaction is finished3)2Stirring to obtain sol; wherein, citric acid, ethylene glycol, LiNO3、Mn(NO3)2The molar ratio is 1: 180: 1.0: 1.8;
and 2, performing vacuum drying at 75 ℃ in 100g of the sol obtained in the step 1 to obtain gel, mixing the gel with 3g of carbon nitride nano particles subjected to surface ionic liquid, and roasting at 770 ℃ for 5 hours to obtain the adsorbent.
Characterization test of the adsorbent
SEM and XRD characterization
The lithium ion selective adsorbent prepared in example 3 was characterized by SEM and XRD, and XRD detection used cuK α (λ =0.154056nm) as a radiation source, a graphite monochromator, a tube pressure of 40kV, a tube current of 40mA, a scanning range of 10-80 °, and a SEM tube voltage of 20 kV.
Wherein the SEM photograph is shown in FIG. 1, it can be seen that the lithium manganese oxide particlesThe particles are uniformly distributed on the surface of the carbon nitride particles to form a porous structure. The XRD characterization pattern is shown in FIG. 2, where it can be seen that lithium manganese oxide is a pure spinel phase, and C3N4The characteristic peak at 27.1 ° is more pronounced, indicating that lithium manganese oxide has been supported on the carbon nitride support.
2. Acid leaching experiment
0.1g of each of the samples prepared in the above examples and comparative examples was weighed, and put in 100ml of 0.5mol/L hydrochloric acid, and after a certain period of time, the supernatant was taken and the concentration of Li was measured with an atomic absorption spectrophotometer, and the dissolution rate of Li was calculated from the following formula:
RLi=nLi/n0Li×100%
RLithe dissolution rate of a metal element Li; n isLiIs the mass of Li in solution; n is0LiThe mass of Li in the original samples was calculated by detection after dissolving all of each original sample in a strong acid.
The Li leaching rates under different time conditions are shown in FIG. 3, and it can be seen that the adsorbent prepared by the invention has a higher Li leaching speed in the initial stage of acid leaching, which indicates that after the silicon nitride carrier is adopted, more internal channels are formed, and the initial stage leaching rate of lithium is improved.
3.Mg2+/Li+Selective adsorption test
In practical industrial processes, it is necessary to extract Li from a large amount of mixed ion solution+. Thus, Li+The selective adsorption performance is also an important index for inspecting the performance of the lithium ion sieve.
Preparation of a lithium-containing alloy+And Mg2+Mixed solution of (2), Li+And Mg2+Was 20mg/L, pH =7, 10g of the adsorbent in each of the above examples and comparative examples was subjected to acid leaching and then placed in 1.0L of the above-mentioned mixed solution, stirred at room temperature for 24 hours and then filtered, and the content of each ion concentration was measured while retaining the filtrate. The distribution coefficient K is calculated bydAnd a separation factor alpha.
Kd=(C0-Ce)/Ce×(V/W)；
α=Kd(Li+)/Kd(Mg2+)；
C0Is the initial concentration of the ion, CeIs the equilibrium concentration of the ion, V is the volume of the solution, W is the weight of the lithium adsorbent; the distribution coefficient is an index for inspecting the preferential adsorption of the material to various ions, and the higher the distribution coefficient value of the ions is, the more preferential adsorption of the material to the ions is indicated; the separation factor is used to characterize various ions relative to Li+The higher the adsorption priority, the higher the ion separation factor value α, indicating a lower ion priority. As shown in the following table:
TABLE 1
As can be seen from the table, the present invention provides an adsorbent for Li+And Mg2+Has better selective adsorption and separation factor of more than 25.
4. Li extraction from brine containing COD+Cycle adsorption frequency experiment
Preparing LiCl solution containing 20ppm humic acid and 100mg/L, respectively placing 5.0g of the adsorbents prepared in the above examples and comparative examples into 1.0L of the above solution after acid leaching treatment at 25 ℃, adsorbing for 12h under the irradiation of a 500W xenon lamp, filtering out the adsorbent, dispersing the adsorbent into 1.0L0.2mol/L hydrochloric acid for desorption treatment, wherein the desorption time is 4h, filtering out the adsorbent after the desorption is finished, repeating the adsorption experiment, repeating the adsorption separation experiment for 8 times, and inspecting the adsorption quantity. The curve of the change of the adsorption amount in each cycle is shown in fig. 5, and it can be seen from the graph that the lithium adsorbent provided by the present invention is loaded on the carbon nitride carrier, so that the effect of the COD substance on the service life of the adsorbent can be effectively reduced by the photocatalytic degradation, and after 8 cycles, the adsorption amounts in the examples and the comparative examples are reduced as shown in the following table.
TABLE 2
As can be seen from the table, the reduction rate of the adsorption amount of the lithium adsorbent provided by the present invention can be maintained at about 10% after 8 times of use. It can be seen from the comparison between the example 3 and the comparative example that when carbon nitride is used as a carrier of the adsorbent through electrostatic coating, the COD substances adsorbed on the adsorbent can be effectively decomposed by utilizing the photocatalytic effect of the carbon nitride, and the adsorption amount of the carbon nitride in the process of multiple recycling is increased. By using Ni (NO) in the process of preparing lithium and manganese oxides by sol-gel3)2The added lithium manganese nano-particle can destroy the double electric layer structure of the formed sol to enable the nano-particle to have negative charges, and then after the carbon nitride particle modified by the positively charged ionic liquid group is added, the lithium manganese particle can be coated on the surface of the carbon nitride carrier through the electrostatic effect, so that the coating uniformity and the specific surface area of the obtained adsorbent are improved, and the adsorption capacity is improved. After the ionic liquid is adopted for grafting the surface of the carbon nitride, the loading effect of the lithium manganese oxide on the surface of the carrier can be effectively improved, the internal porosity is improved, and the lithium adsorption capacity is improved.
5. Experiment for extracting lithium from salt lake brine
Naturally evaporating and concentrating the brine, wherein Mg is contained in the brine2+The concentration is 132.1g/L, Li+The concentration is 2.3g/L, Na+The concentration is 2.2g/L, B+The concentration is 2.3g/L, SO4 2-Acidifying with sulfuric acid at concentration of 33.1g/L, COD of 190.9mg/L to extract boron to obtain boron-removed brine B+The concentration was 48 mg/L. 10g of the adsorbents prepared in the above examples and comparative examples are respectively taken, subjected to acid leaching treatment, placed in 2L of boron removal brine under the irradiation of a 500W xenon lamp for 10h of adsorption, filtered, adsorbed at 25 ℃, dispersed in 2.0L of 0.2mol/L hydrochloric acid for desorption treatment, the desorption time is 4h, the desorption temperature is 30 ℃, and after the desorption is finished, desorption solution is sent into a nanofiltration membrane for deep Mg removal2+Treating with nanofiltration pressure of 2.8Mpa and temperature of 35 deg.C, concentrating by 3.0 times, and desorbing and nanofiltration permeating liquid containing Mg2+And Li+The concentrations are as follows:
TABLE 3
The table shows that the lithium adsorbent provided by the invention can be effectively applied to the process of extracting lithium from brine containing COD (chemical oxygen demand) substances, can effectively reduce the magnesium-lithium ratio in brine, and can effectively realize the effect of enriching lithium from brine after being combined with a nanofiltration technology.
The above method was repeated 8 times in sequence to investigate the life of the adsorbent. After 8 times of adsorption and desorption experiments, the reduction ratio of the adsorption amount of the adsorbent is as follows:
TABLE 4
As can be seen from the table, the adsorbent provided by the invention has the effects of long service life and difficult influence of COD (chemical oxygen demand) substances in brine on the service life when being applied to the process of adsorbing and extracting lithium from real brine.
Claims (8)
1. A lithium ion selective adsorbent is characterized in that the lithium ion selective adsorbent is LiNi loaded on a carbon nitride carriernMn2-nO4(ii) a Wherein n is more than 0 and less than 0.3.
2. The lithium ion selective adsorbent of claim 1, wherein in one embodiment, n = 0.2.
3. The method for preparing a lithium ion selective adsorbent according to claim 1, comprising the steps of:
step 1, preparing carbon nitride nano particles: melamine, sodium citrate and deionized water are mixed according to the weight ratio of 2-3: 1-1.5: 100-150, performing hydrothermal reaction to synthesize carbon nitride, centrifuging to remove large particles after the reaction is finished, dialyzing the supernatant by using a dialysis bag to remove inorganic salts which are not completely reacted, and performing reduced pressure evaporation to dryness treatment on the purified reaction solution to obtain carbon nitride nanoparticles;
step 2, grafting ionic liquid on the surface of the carbon nitride nano particle: soaking the carbon nitride nanoparticles obtained in the step 1 in a hydrochloric acid aqueous solution, washing with deionized water, centrifuging to obtain activated nanoparticles, evaporating the nanoparticles to dryness under reduced pressure, and crushing, wherein the weight ratio of the nanoparticles to the hydrochloric acid aqueous solution is 5-6: 3-6: 100-110: 5-7, mixing carbon nitride nanoparticles, deionized water, toluene and a silane coupling agent, reacting, washing a solid product with ethanol and deionized water in sequence after the reaction is finished, drying, and grinding to obtain the carbon nitride nanoparticles with the surface grafted with the silane coupling agent; carbon nitride nano particles with the surface grafted with silane coupling agent, acetonitrile and [ BsAim][HSO4]The ionic liquid and the azobisisobutyronitrile are mixed according to the weight ratio of 4-6: 80-90: 1.5-2.0: 0.3-0.4, uniformly mixing in a nitrogen atmosphere, carrying out a crosslinking reaction of the ionic liquid, washing the solid product with ethanol and deionized water in sequence after the reaction is finished, drying, and grinding to obtain the carbon nitride nanoparticles with the ionic liquid on the surface;
step 3, preparing lithium manganese oxide sol: mixing citric acid and ethylene glycol uniformly to obtain a solution, and adding LiNO into the solution3And Mn (NO)3)2Then ammonia water is dripped to adjust the pH value to 7.5-8 for hydrolysis reaction, and Ni (NO) is added into the reaction liquid after the reaction is finished3)2Stirring to obtain sol; wherein, citric acid, ethylene glycol, LiNO3、Mn(NO3)2And Ni (NO)3)2The molar ratio is 1: 150-200: 0.8-1.2: 1.6-2.0: 0.1 to 0.3;
step 4, loading the sol on the surface of the carbon nitride particles: adding carbon nitride nano particles subjected to surface ionic liquid into the sol obtained in the step 3, and stirring, wherein the addition amount of the carbon nitride nano particles subjected to surface ionic liquid is 2-4% of the sol; evaporating out ethylene glycol under reduced pressure, and then carrying out vacuum drying to obtain gel;
and 5, sintering the adsorbent: and (4) roasting the gel obtained in the step (4) to obtain the adsorbent.
4. The method of claim 3, wherein in step 1, the hydrothermal reaction parameters are: reacting for 3-5 h at 180-200 ℃; the parameters of the centrifugation process are: centrifuging at a rotating speed of 8000-10000 r/min for 20-50 min, wherein the cut-off molecular weight of the dialysis bag is 200-800 Da.
5. The method for preparing a lithium ion selective adsorbent according to claim 3, wherein in one embodiment, in the step 2, the concentration of the hydrochloric acid aqueous solution is 2 to 4mol/L, and the soaking time is 4 to 6 hours; the grafting reaction conditions of the silane coupling agent are as follows: reacting for 4-6 h at 40-50 ℃; the conditions of the crosslinking reaction of the ionic liquid are: reacting for 20-30 h at 70-75 ℃.
6. The method for preparing a lithium ion selective adsorbent according to claim 3, wherein in the step 3, the concentration of ammonia water is 5 to 10wt%, and the hydrolysis reaction is performed at 70 to 75 ℃ for 8 to 10 hours.
7. The method for preparing the lithium ion selective adsorbent according to claim 3, wherein in the 4 th step, the temperature of vacuum drying is 70 to 80 ℃; in the step 5, roasting is carried out for 4-6 h under the condition of 750-780 ℃.
8. Use of the lithium ion selective adsorbent of any one of claims 1 or 2 in an adsorptive separation of lithium in a liquid.
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| CN110180489B (en) * | 2019-06-25 | 2021-12-07 | 四川泛宇锂能新材料科技有限公司 | Sulfur-doped lithium-rich manganese lithium adsorbent and preparation method and application thereof |
| CN112216894B (en) * | 2020-10-15 | 2021-11-19 | 天齐锂业（江苏）有限公司 | Preparation method and recovery method of lithium ion sieve composite material |
| DE102021114229A1 (en) * | 2021-06-01 | 2022-12-01 | EnBW Energie Baden-Württemberg AG | Method of clearing a well clogged by an adsorbent |
| CN113842877B (en) * | 2021-09-24 | 2023-09-22 | 中国科学院青海盐湖研究所 | Carbon-based adsorbent particles for liquid lithium resource extraction, preparation method and preparation device |
| CA3188018A1 (en) * | 2022-02-02 | 2023-08-02 | Conductive Energy Inc. | Lithium ion adsorbents |
| CN115212844B (en) * | 2022-08-09 | 2024-02-02 | 杭州电子科技大学 | Composite adsorbent for extracting lithium from salt lake brine and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803273A (en) * | 2005-12-15 | 2006-07-19 | 北京矿冶研究总院 | Preparation method of lithium adsorbent |
| CN101985098A (en) * | 2010-09-16 | 2011-03-16 | 中南大学 | Method for preparing manganese series lithium-ion sieve adsorbent H4Mn5O12 and precursor thereof |
| CN105664840A (en) * | 2016-01-12 | 2016-06-15 | 四川天齐锂业股份有限公司 | Modified aluminum salt adsorbent, preparation method and application thereof |
| CN106311190A (en) * | 2016-08-18 | 2017-01-11 | 佛山科学技术学院 | Preparation method of porous manganese-based lithium ion sieve adsorbent |
Family Cites Families (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330579C (en) * | 2005-04-12 | 2007-08-08 | 武汉理工大学 | Preparation of spinel type Li-Mn-oxide lithium ion screening materials by hydrothermal method |
| KR100939516B1 (en) * | 2007-11-29 | 2010-02-03 | 한국지질자원연구원 | Lithium-manganese oxides and method for preparing the same, and lithium adsorbent using the same |
| CN101928042A (en) * | 2010-09-16 | 2010-12-29 | 中南大学 | Spinel-type lithium-ion sieve and method for preparing precursor LiMn2O4 thereof |
| CN102000611B (en) * | 2010-11-08 | 2012-09-26 | 江苏强林生物能源有限公司 | Catalyst for synthesizing tirbutyl citrate and preparation method thereof |
| CN102513063B (en) * | 2011-12-16 | 2013-06-05 | 福建农林大学 | Active carbon immobilized imidazole ionic liquid, preparation method thereof and application thereof |
| CN102512983B (en) * | 2011-12-28 | 2014-01-15 | 河北工业大学 | Lithium ion sieve membrane and preparation method thereof |
| CN102872792A (en) * | 2012-08-28 | 2013-01-16 | 常州大学 | Composite adsorbing material for removing lithium ions in natural water and preparation method thereof |
| KR101536054B1 (en) * | 2012-09-24 | 2015-07-13 | 이상로 | Method of recovering lithium from bittern by using electrochemisty process |
| CN103121724B (en) * | 2012-12-24 | 2014-12-24 | 华东理工大学 | Method for preparing lithium ion sieve MnO2.0.5H2O and precursor thereof Li1.6Mn1.6O4 |
| CN103316623B (en) * | 2013-07-10 | 2015-04-15 | 华东理工大学 | Method for preparing spherical lithium ion sieve adsorbent |
| CN103991908B (en) * | 2014-05-08 | 2016-04-20 | 华东理工大学 | By the method for cation doping regulation and control lithium ion sieve stability |
| EP3215465A4 (en) * | 2014-11-07 | 2018-08-01 | Simbol Inc. | Porous activated alumina based sorbent for lithium extraction |
| KR101529897B1 (en) * | 2015-01-28 | 2015-06-19 | 한국지질자원연구원 | The method manufacturing of lithium adsorbent with high surface area |
| CN104998623B (en) * | 2015-03-24 | 2018-05-29 | 浙江工商大学 | A kind of composite magnetic nano particle adsorbent and its preparation method and application |
| CN105289455A (en) * | 2015-11-27 | 2016-02-03 | 上海空间电源研究所 | Method for prolonging service life of lithium ion sieve adsorbent through limiting practical use capacity |
| CN106076244A (en) * | 2016-06-12 | 2016-11-09 | 上海空间电源研究所 | A kind of preparation method of the long-life lithium ion sieve adsorbant of nano-oxide cladding |
| KR20170142661A (en) * | 2016-06-20 | 2017-12-28 | 연세대학교 산학협력단 | Lithium absorbent and method of manufacturing the same |
| CN106221665A (en) * | 2016-07-28 | 2016-12-14 | 王烽 | A kind of LED organic silicon packaging glue of nano-cerium oxide nano aluminum nitride hybrid modification and preparation method thereof |
| CN106622116B (en) * | 2016-09-16 | 2019-06-28 | 北京工业大学 | A kind of preparation method of spinel-type lithium-ion sieve |
| CN106390951A (en) * | 2016-09-30 | 2017-02-15 | 上海空间电源研究所 | Lithium ionic sieve adsorbent with self-cleaning function and preparation method and application thereof |
| CN106902781B (en) * | 2017-03-08 | 2019-06-28 | 江苏大学 | The preparation method and applications of modified meso-porous hollow silicon ball adsorbent |
| CN107385253A (en) * | 2017-06-28 | 2017-11-24 | 山东正凯机械科技有限公司 | A kind of preparation method of the wear-resisting magnesium alloy brake disc of nanocrystalline enhancing |
| CN107359302A (en) * | 2017-07-14 | 2017-11-17 | 东莞理工学院 | Nitrogenize carbon composite and preparation method and application |
| CN107188137B (en) * | 2017-07-18 | 2019-03-22 | 佛山市华堃环保科技有限公司 | A kind of modified carbonitride and preparation method thereof and a kind of dyeing waste water remover and preparation method thereof |
| CN107376827B (en) * | 2017-09-08 | 2020-03-27 | 中南大学 | Zirconium dioxide coated manganese lithium ion sieve and preparation method and application thereof |
| CN107863493B (en) * | 2017-10-26 | 2020-05-08 | 广东羚光新材料股份有限公司 | Preparation method of lithium battery negative pole piece |
-
2018
- 2018-03-31 CN CN201810287638.6A patent/CN108543516B/en active Active
- 2018-03-31 CN CN202011146543.6A patent/CN112342378A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803273A (en) * | 2005-12-15 | 2006-07-19 | 北京矿冶研究总院 | Preparation method of lithium adsorbent |
| CN101985098A (en) * | 2010-09-16 | 2011-03-16 | 中南大学 | Method for preparing manganese series lithium-ion sieve adsorbent H4Mn5O12 and precursor thereof |
| CN105664840A (en) * | 2016-01-12 | 2016-06-15 | 四川天齐锂业股份有限公司 | Modified aluminum salt adsorbent, preparation method and application thereof |
| CN106311190A (en) * | 2016-08-18 | 2017-01-11 | 佛山科学技术学院 | Preparation method of porous manganese-based lithium ion sieve adsorbent |
Non-Patent Citations (4)
| Title |
|---|
| LIN JING: "Covalently functionalized TiO2 with ionic liquid: A high-performance catalyst for photoelectrochemical water oxidation", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| YUTONG GONG: "Graphitic carbon nitride polymers: promising catalysts or catalyst supports for heterogeneous oxidation and hydrogenation", 《GREEN CHEMISTRY》 * |
| 庄欠粉: "基于氮化碳纳米粒子荧光检测金离子", 《高等学校化学学报》 * |
| 董殿权等: "溶胶-凝胶法制备尖晶石结构镍锰氧化物型锂离子筛", 《青岛科技大学学报(自然科学版)》 * |
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