CN111905700B - Resin-based inorganic nanoparticle composite lithium extraction particle - Google Patents
Resin-based inorganic nanoparticle composite lithium extraction particle Download PDFInfo
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Abstract
A resin-based inorganic nanoparticle composite lithium extraction particle is prepared by the following method: adding inorganic nanoparticles and a coupling agent into an organic solvent, carrying out ultrasonic stirring to obtain a mixed solution, centrifuging the mixed solution, carrying out vacuum drying, and grinding to obtain modified nanoparticle powder A; adding a high molecular polymer into an organic solvent, heating, ultrasonically stirring until no precipitate exists, adding the modified nano particle powder A, and continuously ultrasonically stirring to obtain a viscous mixed solution B; uniformly mixing the adsorbent precursor and a pore-forming agent, adding the mixture into the mixed solution B, adding a coupling agent, and performing ultrasonic stirring to obtain a viscous mixture C; vacuumizing the mixture C to remove air bubbles in the mixture, and preparing cylindrical granules D by using a granulator; and (5) drying the cylindrical particles D in vacuum to obtain the finished product. The obtained resin-based inorganic nano particle composite lithium extraction particle has the advantages of stable structure, small solvent loss rate, long cycle life and large lithium adsorption capacity, and uses water as a solvent for desorption.
Description
Technical Field
The invention relates to a resin-based lithium extraction particle, in particular to a resin-based nano particle composite lithium extraction particle.
Background
Lithium resources in China are mainly distributed in salt lake brine, accounting for 80% of the total lithium reserves in China, and are mainly distributed in Qinghai and Tibet regions in geographical positions. Most of the salt lake brine in China has low lithium content and high Mg/Li ratio, and the extraction efficiency is low by adopting the traditional salt lake lithium extraction technology, so that the industrial application of the salt lake lithium extraction is limited.
The adsorption method has simple process and environmental protection, is an effective method for extracting lithium from low-concentration lithium-containing solution, and the main medium of the adsorption method is a lithium ion selective adsorbent. Currently, most studied lithium ion adsorbents mainly include: amorphous hydroxide adsorbent, ion sieve type oxide adsorbent, layered adsorbent, composite antimonate adsorbent and aluminum salt adsorbent.
The disadvantages of the direct application of the adsorbent at the present stage are mainly three: (1) The conventional lithium adsorbent is powdery, has poor fluidity and permeability, high dissolution loss rate and poor mechanical strength, and can not realize industrialization in the actual application process; (2) After the adsorbent is granulated, the specific surface area is reduced more, and the adsorption capacity is low; (3) Part of the adsorbents need to use acid solution to elute lithium ions during work, the dissolution loss is serious, and a large amount of waste liquid is generated to be harmful to the ecological environment of the salt lake.
CN103316623A discloses a method for preparing a spherical lithium ion sieve adsorbent, which comprises heating, dissolving and mixing polysaccharide and solvent, adding an ion sieve precursor into the solution, stirring to obtain a viscous solution, and dropping the viscous solution into an oil phase such as petroleum ether to obtain a solid spherical adsorbent with a particle size of 2-5 mm. According to the method, manganese oxides are used as an adsorbent precursor, and lithium ions need to be eluted by using an acid solution, so that the structure of the adsorbent is easily damaged in the using process, and the dissolving loss amount is large; the granulation mode has low production efficiency and is difficult to realize large-scale application.
CN106975436A discloses a preparation method of a lithium adsorbent, the used granulation binder is chlorine-containing high molecular polymer and liquid chlorine, the organic matter dosage of the method is very large, and reaches 28-50 wt% of powder, which causes the effective specific surface area of the granulated lithium adsorbent to be greatly reduced and the working adsorption capacity to be lower; and liquid chlorine is a highly dangerous chemical and, once leaked, can cause serious pollution to the environment.
CN101955210A discloses a granular lithium ion sieve, which is a rod-like granule, wherein an inert gas is used as a protective gas in the preparation process to protect the reaction process, the precursor is not subjected to hydrophilic treatment, and the obtained lithium ion sieve has an adsorption effect but does not meet the requirement of serving as an adsorption column material; the preparation process does not carry out crosslinking and curing, and the product has certain shrinkage and deformation after being dried; the adsorbent needs to use an acid solution to elute lithium ions, and a large amount of acidic waste liquid is generated.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing the resin-based inorganic nanoparticle composite lithium extraction particle which has high lithium extraction rate, stable structure and small solvent loss rate and is desorbed by using water as a solvent.
The technical scheme adopted by the invention for solving the technical problems is as follows, and the resin-based inorganic nanoparticle composite lithium extraction particle is prepared by the following method:
(1) Adding inorganic nanoparticles and a coupling agent into an organic solvent, carrying out ultrasonic oscillation and mechanical stirring to obtain a mixed solution, centrifuging the mixed solution, carrying out vacuum drying, and grinding to obtain modified nanoparticle powder A;
(2) Adding a high molecular polymer into an organic solvent, heating, carrying out ultrasonic oscillation and mechanical stirring until no precipitate exists, adding the modified nanoparticle powder A obtained in the step (1), and carrying out continuous ultrasonic oscillation and mechanical stirring to obtain a viscous mixed solution B;
(3) Uniformly mixing an adsorbent precursor and a pore-forming agent, adding the mixture into the mixed solution B obtained in the step (2), adding a coupling agent, and mechanically stirring while performing ultrasonic oscillation to obtain a viscous mixture C;
(4) Vacuumizing the mixture C obtained in the step (3) to remove air bubbles in the mixture, and preparing cylindrical granules D by using a granulator;
(5) And (4) drying the cylindrical particles D obtained in the step (4) in vacuum to obtain the cylindrical particles.
Preferably, in the step (1), the inorganic nanoparticles are aluminum oxide (Al) 2 O 3 ) Graphene Oxide (GO) and titanium dioxide (TiO) 2 ) Silicon dioxide (SiO) 2 ) Zirconium dioxide (ZrO) 2 ) One or more than two of them.
Preferably, in the step (1), the coupling agent is one or two of a silane coupling agent and a titanate coupling agent.
Preferably, in the step (1), the organic solvent is one or more of acetone, ethanol, dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and Tetrahydrofuran (THF).
Preferably, in the step (1), the coupling agent is used in an amount of 1 to 10wt%, more preferably 3 to 5wt% of the inorganic nanoparticles; .
Preferably, in the step (1), the ultrasonic oscillation and the mechanical stirring are carried out for 1 to 8 hours, and more preferably for 4 to 6 hours.
Preferably, in the step (2), the high molecular polymer is one or more of Ethyl Cellulose (EC), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), phenol resin (PF), epoxy resin (EP), and Polyurethane (PU). The high molecular polymer is an organic substance having viscosity.
Preferably, in the step (2), the organic solvent is one or more of acetone, ethanol, dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and Tetrahydrofuran (THF).
Preferably, in the step (2), the heating is carried out by raising the temperature to 50-80 ℃.
Preferably, in the step (2), the modified nanoparticle powder A is used in an amount of 1 to 10wt%, more preferably 2 to 6 wt% of the high molecular polymer.
Preferably, in the step (2), the continuous ultrasonic oscillation and the mechanical stirring are carried out for 1 to 8 hours, and more preferably for 2 to 5 hours.
Preferably, in the step (3), the adsorbent precursor is one or more of amorphous hydroxide, manganese-based or titanium-based lithium ion sieve oxide, and layered aluminum salt, and more preferably, the chemical formula is LiCl 2Al (OH) 3 ·nH 2 A layered aluminum salt of O; the particle size of the adsorbent precursor is 10nm to 200 mu m.
Preferably, in the step (3), the pore-forming agent is sodium chloride (NaCl), potassium chloride (KCl), sodium carbonate (Na) 2 CO 3 ) Sodium bicarbonate (NaHCO) 3 ) Ammonium hydrogen carbonate (NH) 4 HCO 3 ) Potassium nitrate (KNO) 3 ) Sodium sulfate (NaCO) 3 ) One or more of glucose and polyvinylpyrrolidone (PVP). The pore-foaming agent is inorganic salt or water-soluble organic matter.
Preferably, in the step (3), the coupling agent is one or two of a silane coupling agent and a titanate coupling agent.
Preferably, in the step (3), the amount of the pore-forming agent is 0.2 to 10wt%, and more preferably 0.5 to 2wt% of the adsorbent precursor.
Preferably, in the step (3), the amount of the high molecular polymer in the mixed solution B is 5 to 30wt%, more preferably 10 to 25wt% of the adsorbent precursor.
Preferably, in the step (3), the amount of the coupling agent is 1-10 wt% of the adsorbent precursor.
Preferably, in the step (3), the temperature of the ultrasonic vibration and the mechanical stirring is 50-80 ℃, and the time is 0.5-8 h, and more preferably 1-3 h.
Preferably, in the step (4), the vacuum drying oven is used for the vacuum treatment for 0.1 to 3 hours, and more preferably 0.5 to 2 hours.
Preferably, in step (4), the diameter of the cylindrical particles D is 0.5 to 5mm, more preferably 0.8 to 1.5mm.
Preferably, in step (5), the temperature of the vacuum drying is 40 to 200 ℃, more preferably 60 to 120 ℃.
The invention compounds the nano-scale dispersion phase (inorganic nano-particles) and the resin matrix, the nano-particles used as the doped phase (dispersion phase) have the unique properties of large specific surface area, strong surface activity and the like, and can generate strong interaction with the matrix on a micro scale through the nanometer effect after being dispersed in the resin matrix, thereby greatly improving the properties of the composite material, such as strength, heat resistance and the like, and endowing the matrix material with other new functions. The resin-based inorganic nano particle composite lithium extraction particle has the characteristics of high strength, high thermal stability, excellent functionality and the like.
The invention has the beneficial effects that: (1) According to the invention, inorganic nanoparticles are doped with a high-molecular polymer binder, so that the obtained lithium extraction particles have the advantages of stable structure, pressure resistance, impact resistance, small dissolution loss rate and long cycle life; (2) The inorganic nano particles can promote the formation of polymer micropores, and the obtained lithium extraction particles contain a large number of micropores, so that the lithium adsorption capacity is large, and the extraction rate is high; (3) The hydrophilicity of the material is increased by the inorganic nano particles, and the obtained lithium extraction particles have higher adsorption mass transfer efficiency; (4) The thermal conductivity is high, which is beneficial to improving the elution speed of lithium ions; (5) The obtained lithium extraction particles are desorbed by using water as a solvent, so that the method is energy-saving and environment-friendly, and is suitable for large-scale industrial production of lithium extraction in salt lakes.
Drawings
FIG. 1 is an optical photograph of resin-based inorganic nanoparticle composite lithium-extracting particles obtained in example 1 of the present invention;
FIG. 2 is an X-ray diffraction (XRD) pattern of the resin-based inorganic nanoparticle composite lithium-extracting particles obtained in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
Example 1
The adsorbent precursor used in this example was a self-made LiCl.2Al (OH) 3 ·nH 2 O (using LiCl and AlCl) 3 Prepared by a conventional coprecipitation method), and the particle size is 20 to 150 mu m; the rest raw materials and solvents are all commercial products. LiCl was obtained from certain Shanghai company, alCl 3 From Guangdong, nano-alumina from Shanghai, KH570 silane coupling agent from Guangdong, PVC from Shanghai, DMF from Shanghai, KCl from Shanghai.
This example lithium extraction particles were prepared as follows:
(1) Weighing commercial nano-alumina (particle size of 30nm, alpha-Al) 2 O 3 ) Adding 10g of silane coupling agent (grade KH 570) and 0.3g of silane coupling agent into 150g of DMF solvent in sequence, and mechanically stirring for 5 hours while carrying out ultrasonic oscillation to obtain a mixed solution; then the mixed solution is centrifuged and vacuum dried, and the modified nano-alumina powder A is obtained after grinding for standby;
(2) Weighing 30g of PVC, adding into 500g of DMF, heating to 70 ℃, carrying out ultrasonic oscillation while mechanically stirring until no precipitate exists, then adding 1.5g of modified nano-alumina A, and continuing ultrasonic stirring for 2 hours to obtain a viscous mixed solution B;
(3) Weighing 200g of adsorbent precursor and 2g of pore-foaming agent KCl, and uniformly mixing the adsorbent precursor and the pore-foaming agent KCl to obtain mixed powder; adding the mixed powder into the solution B prepared in the step (2), adding 6g of silane coupling agent (grade KH 570), and ultrasonically stirring for 1h at 70 ℃ to obtain a viscous mixture C;
(4) And (4) placing the C obtained in the step (3) in a vacuum drying oven for vacuumizing for 0.5h, and removing bubbles in the mixture. Making the C into cylindrical particles D with the diameter of 0.8-1.5 mm by a granulator;
(5) And (4) drying the D at 80 ℃ in vacuum to obtain the product.
FIG. 1 is an optical photograph of the resin-based inorganic nanoparticle composite lithium-extracted particles obtained in this example, which shows that the obtained lithium-extracted particles have uniform particle size and are in a regular cylindrical shape. Measured and counted, the granules with the grain diameter of between 0.8mm and 1.5mm account for 96 percent.
FIG. 2 is the XRD test result of the resin-based inorganic nanoparticle composite lithium-extracting particles obtained in this example, and it can be seen that the crystalline phase part of the obtained composite lithium-extracting particles is mainly chlorine-containing lithium aluminum hydroxide hydrate.
Adsorption cycle test:
taking composite lithium extraction particles with the particle size of 0.8mm to 1.5mm to carry out static adsorption experiments on magnesium sulfate subtype salt lake original brine containing lithium of 0.257 g/L. The adsorption is stopped after 1.5h, the solid-liquid separation is complete, the saturated adsorption capacity is 5.08mg/g, and the extraction rate of lithium is 99.2%. And (3) carrying out sectional desorption on the adsorbed composite lithium-extracted particles by using water, wherein the desorption is carried out for 1h, and the desorption rate of lithium is 88.1%. The composite lithium extracting particle after desorption can be continuously used for the adsorption-desorption process. The circulation is carried out for 10 times, and the dissolution loss rate of the adsorbent is 0.18 percent.
Example 2
The adsorbent precursor used in this example was LiCl.2Al (OH) 3 ·nH 2 O (using LiCl and AlCl) 3 Prepared by a conventional coprecipitation method), and the particle size is 20 to 150 mu m; the rest raw materials and solvents are all commercial products. LiCl was purchased from Shanghai, alCl 3 From Guangdong, nanoaluminum was from Shanghai, nanosilica was from Shanghai, KH570 silane coupling agent was from Guangdong, PVC was from Shanghai, DMAc was from Shanghai, NH 4 HCO 3 Purchased from shanghai, a company.
This example lithium-extracted particles were prepared as follows:
(1) Weighing commercial nano aluminum oxide (particle size 40nm, alpha-Al) 2 O 3 ) Adding 5g of nano silicon oxide, 5g of nano silicon oxide (the particle size is 40 nm) and 0.3g of silane coupling agent (the brand KH 570) into 150g of DMAc solvent in sequence, and mechanically stirring for 4.5 hours while carrying out ultrasonic oscillation to obtain a mixed solution; then the mixed solution is centrifuged and vacuum dried, and modified nano-alumina-silicon oxide mixed powder A is obtained after grinding for standby;
(2) Weighing 30g of PVC, adding the PVC into 500g of DMAc, heating to 70 ℃, carrying out ultrasonic oscillation and mechanical stirring until no precipitate exists, then adding 1.5g of modified nano-alumina-silica mixed powder A, and continuing ultrasonic stirring for 2 hours to prepare a viscous mixed solution B;
(3) 200g of adsorbent precursor and 2g of pore-forming agent NH are weighed 4 HCO 3 Mixing the two uniformly to obtain mixed powder; adding the mixed powder into the solution B prepared in the step (2), adding 7g of silane coupling agent (grade KH 570), and ultrasonically stirring for 1h at 70 ℃ to obtain a viscous mixture C;
(4) And (4) placing the C obtained in the step (3) in a vacuum drying oven for vacuumizing for 0.5h, and removing bubbles in the mixture. Making the C into cylindrical particles D with the diameter of 0.8-1.5 mm by a granulator;
(5) And (4) drying the D at 70 ℃ in vacuum to obtain the product.
The lithium extraction particles obtained in the example have uniform particle size and are in a regular cylindrical shape. Measured and counted, the particles with the particle diameter of 0.8mm to 1.5mm account for 95 percent.
Through detection, the crystalline phase part of the resin-based inorganic nanoparticle composite lithium extraction particles obtained in the embodiment is mainly chlorine-containing hydrated lithium aluminum hydroxide.
Adsorption cycle testing:
taking composite lithium extraction particles with the particle size of 0.8mm to 1.5mm to carry out static adsorption experiments on chloride type salt lake brine containing lithium by 0.220 g/L. The adsorption is stopped after 1.5h, the solid-liquid separation is complete, the saturated adsorption capacity is 4.99mg/g, and the extraction rate of lithium is 99.3%. And (3) carrying out sectional desorption on the absorbed composite lithium extraction particles by using water, wherein the desorption is carried out for 1h, and the desorption rate of lithium is 89.2%. The composite lithium extracting particles can be continuously used for the adsorption-desorption process after desorption. The process is circulated for 10 times, and the dissolution loss rate of the adsorbent is 0.15 percent.
Example 3
The adsorbent precursor used in this example was LiOH 2Al (OH) 3 ·nH 2 O and LiCl 2Al (OH) 3 ·nH 2 Mixture of O (4 by weight 3 Prepared by a conventional coprecipitation method), and the particle size is 20 to 150 mu m; the rest raw materials and solvents are commercially availableAnd (5) producing the product. LiCl was obtained from certain Shanghai company, alCl 3 From Guangdong, nano-alumina, nano-titania, KH550 silane coupling agent, PVC, NMP, KNO 3 NaHCO from Shanghai 3 Purchased from shanghai, a company.
This example lithium extraction particles were prepared as follows:
(1) Weighing commercial nano-alumina (particle size of 40nm, alpha-Al) 2 O 3 ) Adding 5g of nano titanium oxide, 5g of nano titanium oxide (with the particle size of 30 nm) and 0.3g of silane coupling agent (with the trade name of KH 550) into 150g of NMP solvent in sequence, and mechanically stirring for 4 hours while carrying out ultrasonic oscillation to obtain a mixed solution; then the mixed solution is centrifuged and vacuum-dried, and modified nano-alumina-silica mixed powder A is obtained after grinding for later use;
(2) Weighing 30g of PVC, adding the PVC into 500g of NMP, heating to 70 ℃, carrying out ultrasonic oscillation while mechanically stirring until no precipitate exists, then adding 1.5g of modified nano-alumina-titanium oxide mixed powder A, and continuing to carry out ultrasonic stirring for 3 hours to prepare a viscous mixed solution B;
(3) 200g of adsorbent precursor and 2g of pore-forming agent (KNO) are weighed 3 And NaHCO 3 1g of each) and uniformly mixing the two to obtain mixed powder; adding the mixed powder into the solution B prepared in the step (2), adding 6g of silane coupling agent (trade name KH 550) and ultrasonically stirring at 70 ℃ for 1.5h to obtain a viscous mixture C;
(4) And (4) placing the C obtained in the step (3) in a vacuum drying oven for vacuumizing for 1h, and removing bubbles in the mixture. C is made into cylindrical particles D with the diameter of 0.8 to 1.5mm through a granulator;
(5) And (4) drying the D at 70 ℃ in vacuum to obtain the product.
The lithium extraction particles obtained in the example have uniform particle size and are in a regular cylindrical shape. According to measurement and statistics, the particles with the particle size of 0.8mm to 1.5mm account for 95 percent.
Through detection, the crystalline phase part of the resin-based inorganic nanoparticle composite lithium extraction particles obtained in the embodiment is mainly hydrated lithium aluminum hydroxide and contains part of chlorinated lithium aluminum hydroxide hydrate.
Adsorption cycle test:
taking composite lithium extraction particles with the particle size of 0.8mm to 1.5mm to carry out static adsorption experiments on LiCl solution containing lithium and 0.2g/L of lithium. The adsorption is stopped after 1.5h, the solid-liquid separation is complete, the saturated adsorption capacity is 4.99mg/g, and the extraction rate of lithium is 99.3%. And (3) carrying out sectional desorption on the adsorbed composite lithium-extracted particles by using water, wherein the desorption is carried out for 1h, and the desorption rate of lithium is 86.5%. The composite lithium extracting particle after desorption can be continuously used for the adsorption-desorption process. The process is circulated for 10 times, and the dissolution loss rate of the adsorbent is 0.15 percent.
Comparative example
The adsorbent precursor used in this example was a homemade LiCl.2Al (OH) 3 ·nH 2 O (using LiCl and AlCl) 3 ·6H 2 O is prepared by a conventional coprecipitation method), and the particle size is 20 to 150 mu m; the rest raw materials and solvents are all commercial products. LiCl was obtained from certain Shanghai company, alCl 3 ·6H 2 O was purchased from Guangdong, KH570 silane coupling agent was purchased from Guangdong, PVC was purchased from Shanghai, DMF was purchased from Shanghai, and KCl was purchased from Shanghai.
The comparative example is similar to the preparation method of the lithium extraction particles in example 1, and the difference is that: modified nanoparticles a were not used; the preparation method comprises the following steps:
weighing 30g of PVC, adding into 500g of DMF, heating to 70 ℃, and mechanically stirring while ultrasonically shaking until no precipitate exists to prepare a viscous solution B;
weighing 200g of adsorbent precursor and 2g of pore-forming agent KCl, and uniformly mixing the adsorbent precursor and the pore-forming agent KCl to obtain mixed powder; adding the mixed powder into the solution B prepared in the step (2), adding 6g of silane coupling agent (trade name KH 570), and ultrasonically stirring at 70 ℃ for 1h to obtain a viscous mixture C;
and (4) placing the C obtained in the step (3) in a vacuum drying oven for vacuumizing for 0.5h, and removing bubbles in the mixture. C is made into cylindrical particles D with the diameter of 0.8 to 1.5mm through a granulator;
and (4) drying the D at 80 ℃ in vacuum to obtain the finished product.
The lithium extraction particles obtained in the comparative example have uniform particle size and are in a regular cylindrical shape. According to measurement and statistics, the particles with the particle size of 0.8mm to 1.5mm account for 95 percent.
Through detection, the crystalline phase part of the resin-based inorganic nanoparticle composite lithium extraction particle obtained in the comparative example is mainly chlorine-containing hydrated lithium aluminum hydroxide.
Adsorption cycle testing:
taking composite lithium extraction particles with the particle size of 0.8mm to 1.5mm to carry out static adsorption experiments on magnesium sulfate subtype salt lake original brine containing lithium of 0.257 g/L. The adsorption is stopped after 1.5h, the solid-liquid separation is complete, the saturated adsorption capacity is 3.46mg/g, and the extraction rate of lithium is 96.5%. And (3) carrying out sectional desorption on the adsorbed composite lithium-extracted particles by using water, wherein the desorption is carried out for 1h, and the desorption rate of lithium is 82.1%. The composite lithium extracting particles can be continuously used for the adsorption-desorption process after desorption. The circulation is carried out for 10 times, and the dissolution loss rate of the adsorbent is 0.32 percent.
Claims (11)
1. A resin-based inorganic nanoparticle composite lithium extraction particle is characterized by being prepared by the following method:
(1) Adding inorganic nanoparticles and a coupling agent into an organic solvent, performing ultrasonic oscillation and mechanical stirring to obtain a mixed solution, centrifuging the mixed solution, performing vacuum drying, and grinding to obtain modified nanoparticle powder A;
(2) Adding a high-molecular polymer into an organic solvent, heating, performing ultrasonic oscillation and mechanical stirring at the same time until no precipitate exists, adding the modified nanoparticle powder A obtained in the step (1), and continuing the ultrasonic oscillation and mechanical stirring at the same time to obtain a viscous mixed solution B;
(3) Uniformly mixing an adsorbent precursor and a pore-foaming agent, adding the mixture into the mixed liquid B obtained in the step (2), adding a coupling agent, and mechanically stirring while performing ultrasonic oscillation to obtain a viscous mixture C;
(4) Vacuumizing the mixture C obtained in the step (3) to remove air bubbles in the mixture, and preparing cylindrical granules D by using a granulator;
(5) Drying the cylindrical particles D obtained in the step (4) in vacuum to obtain the cylindrical particles D;
in the step (1), the inorganic nanoparticles are one or more than two of aluminum oxide, graphene oxide, titanium dioxide, silicon dioxide and zirconium dioxide;
in the step (2), the amount of the modified nanoparticle powder A is 1-10 wt% of the high molecular polymer.
2. The resin-based inorganic nanoparticle composite lithium extraction particle according to claim 1, wherein in the step (1), the coupling agent is one or two of a silane coupling agent and a titanate coupling agent; the organic solvent is one or more than two of acetone, ethanol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and tetrahydrofuran.
3. The resin-based inorganic nanoparticle composite lithium extraction particle according to claim 1, wherein in the step (1), the amount of the coupling agent is 1-10 wt% of the inorganic nanoparticles; and the ultrasonic vibration and the mechanical stirring are carried out for 1-8 hours.
4. The resin-based inorganic nanoparticle composite lithium extraction particle according to claim 1, wherein in the step (2), the high molecular polymer is one or more of ethyl cellulose, polyvinyl chloride, polyvinylidene fluoride, polyvinyl alcohol, phenolic resin, epoxy resin and polyurethane; the organic solvent is one or more than two of acetone, ethanol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and tetrahydrofuran.
5. The resin-based inorganic nanoparticle composite lithium extraction particle according to claim 1, wherein in the step (2), the heating is carried out by raising the temperature to 50-80 ℃; the dosage of the modified nano particle powder A is 2-6 wt% of the high molecular polymer; and continuing ultrasonic oscillation and simultaneously mechanically stirring for 1-8 hours.
6. The resin-based inorganic nanoparticle composite lithium extraction particle according to any one of claims 1 to 5, wherein in the step (3), the adsorbent precursor is one or more of amorphous hydroxide, manganese-based or titanium-based lithium ion sieve oxide, and layered aluminum salt; the particle size of the adsorbent precursor is 10nm to 200 mu m; the pore-forming agent is one or more than two of sodium chloride, potassium chloride, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, potassium nitrate, sodium sulfate, glucose and polyvinylpyrrolidone; the coupling agent is one or two of silane coupling agent and titanate coupling agent.
7. The resin-based inorganic nanoparticle composite lithium extraction particle according to any one of claims 1 to 5, wherein in the step (3), the amount of the pore-forming agent is 0.2 to 10wt% of the adsorbent precursor; the amount of the high molecular polymer in the mixed solution B is 5-30 wt% of the adsorbent precursor; the dosage of the coupling agent is 1-10 wt% of the adsorbent precursor; the temperature of the ultrasonic vibration and the mechanical stirring is 50-80 ℃, and the time is 0.5-8 h.
8. The resin-based inorganic nanoparticle composite lithium extraction particle according to claim 6, wherein in the step (3), the amount of the pore-forming agent is 0.2-10 wt% of the adsorbent precursor; the amount of the high molecular polymer in the mixed solution B is 5-30 wt% of the adsorbent precursor; the dosage of the coupling agent is 1-10 wt% of the adsorbent precursor; the temperature of the ultrasonic vibration and the mechanical stirring is 50-80 ℃, and the time is 0.5-8 h.
9. The resin-based inorganic nanoparticle composite lithium extraction particle according to any one of claims 1 to 5, wherein in the step (4), the vacuuming treatment is performed for 0.1 to 3 hours by using a vacuum drying oven.
10. The resin-based inorganic nanoparticle composite lithium extraction particle according to any one of claims 1 to 5, wherein in the step (4), the diameter of the cylindrical particle D is 0.5-5 mm.
11. The resin-based inorganic nanoparticle composite lithium extraction particle according to any one of claims 1 to 5, wherein in the step (5), the temperature for vacuum drying is 40-200 ℃.
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| 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 |
| CN115106013B (en) * | 2022-06-14 | 2024-01-12 | 华东理工大学 | Inverted extrusion type granulating and forming method |
| CN115957727A (en) * | 2022-11-25 | 2023-04-14 | 广东松泉环保设备有限公司 | Composite lithium adsorbent and preparation process thereof |
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