Resin-based aluminum-based particle adsorbent, preparation method and use thereof

Abstract

The present invention provides a method for preparing a resin-based aluminum-based granular adsorbent, belonging to the technical field of selective separation of inorganic metal ions. The present invention provides a method for preparing a resin-based aluminum-based granular adsorbent, comprising the following steps: preparing a base liquid; preparing liquid A; preparing liquid B; preparing liquid C; preparing the resin-based aluminum-based granular adsorbent: adding liquid C to the base liquid under a protective atmosphere and stirring and dispersing; then dripping liquid A and liquid B in parallel, controlling the solution pH to 3-7, and reacting for a period of time after the dripping is completed; adjusting the temperature to a hardening temperature, thereby obtaining the resin-based aluminum-based granular adsorbent. The method for preparing the resin-based aluminum-based granular adsorbent of the present invention utilizes a one-step in-situ synthesis of the aluminum-based adsorbent and the resin-based carrier, has simple process steps, is easy to mass-produce, and has good social and economic benefits.

Description

Technical Field

[0001] The invention relates to a resin-based aluminum-based particle adsorbent, a preparation method and application thereof, and belongs to the technical field of selective separation of inorganic metal ions. Background Art

[0002] Lithium, the lightest metallic element in nature, possesses the most negative standard electrode potential, and possesses the smallest electrochemical equivalent. It is a high-energy-density material, yet its reserves in the Earth's crust are only 0.0065%. It is known as "white oil." Lithium exists naturally as a compound. Lithium salts are extracted from minerals and salt lakes, enriched, and purified to produce lithium salts. Due to their unique physical and chemical properties, lithium salts are widely used in glass, lubricants, ceramics, nuclear energy, aerospace, medicine, and energy storage. The depletion of fossil energy and environmental pollution are hindering sustainable global development. The development and utilization of efficient renewable energy sources has become a global consensus. Lithium batteries, with their lightweight, long cycle life, low pollution, high energy density, and high recyclability, are gradually replacing gasoline as a power source for automobiles. The increasing popularity and upgrading of electronic devices are also accelerating the strong market demand for lithium salts. Therefore, improving the production and quality of lithium salts has become a development focus for relevant companies in recent years. Lithium extraction from ore has drawbacks such as high energy consumption, high tailings, high corrosiveness, and low resource reserves. Lithium reserves in salt lake brines account for approximately 70-80% of total lithium resources, but the level of mining and utilization is far lower than that of lithium extraction from ore. Aluminum salt lithium adsorbents, as key materials for lithium extraction from brine, offer advantages such as low cost, high universality, stable performance, environmental friendliness, and high selectivity for lithium ions. Traditional aluminum-based adsorbent preparation processes are long, multi-step, and complex, increasing water and energy consumption. Therefore, it is necessary to improve the process to reduce costs and increase efficiency.

[0003] Patent application US4221767A discloses a method for recovering Li from brine. + The method specifically involves treating a resin and an aluminum salt with an aqueous ammonia solution. Then, at a certain temperature, lithium hydroxide is added to react with the resulting aluminum hydroxide to produce a resin-type granular adsorbent with lithium adsorption properties. However, this method has the following drawbacks: The aluminum salt and the resin do not interact, and the aluminum salt precipitates from the resin during the lithium extraction process from brine. Furthermore, the synthesis process requires three reactions, making it uncontrollable. Furthermore, the efficiency of aluminum salt insertion into the resin is insufficient, resulting in poor adsorption performance.

[0004] Patent application CN112237905 discloses a lithium extraction adsorbent for raw halogen and a preparation method thereof. The method comprises the following steps: crushing a cross-linked polystyrene resin, soaking it in a sufficient amount of solvent, fully expanding it, and then filtering off the free solvent to obtain a white ball powder; kneading the active powder of the lithium extraction adsorbent, a binder, white ball powder, and a solvent in a mass ratio of 1:(0.1-0.5):(0-0.3):(0.5-2.5) to obtain a mixture; extruding, crushing, screening, and drying the obtained mixture to obtain a semi-finished product; washing the semi-finished product with dilute acid, then washing it with water until neutral, and filtering off the free water to obtain the lithium extraction adsorbent for raw halogen. This method has the following drawbacks: it involves multiple processes, is time-consuming and costly, is uncontrollable, and frequently uses organic solvents and acids.

[0005] Patent application CN111215040A discloses a method for preparing a lithium extraction adsorbent. The method comprises the following steps: preparing a mixed salt solution containing 1-2 mol / L aluminum salt, 2-4 mol / L lithium salt, and 0-2 mol / L of a third salt, MX; preparing an aqueous solution containing 1-3 mol / L of an alkali; adding the aqueous alkali solution to the mixed salt solution under stirring, stirring, and subjecting the reaction mixture to solid-liquid separation to obtain a reaction mother liquor and an active phase; drying and pulverizing the active phase into a powder; kneading the powder with a polymer and a solvent, and then extruding the mixture; drying, crushing, and sieving particles with a particle size of 0.6-2.0 mm as the finished adsorbent. This method has the following drawbacks: during the granulation process, the powder is mixed with a highly viscoelastic binder and solvent, and then formed by extrusion, resulting in insufficient dispersion uniformity of the powder in the binder and a reduced number of pores, increasing production complexity. The powder and binder lack interaction, resulting in product shedding and a limited service life. Summary of the Invention

[0006] The technical problem solved by the present invention is a method for preparing a resin-based aluminum-based particle adsorbent.

[0007] The method for preparing a resin-based aluminum-based particle adsorbent of the present invention comprises the following steps:

[0008] a. Prepare a base solution: add polyvinyl alcohol, tricalcium phosphate, and a porogen to deionized water and stir until uniformly dispersed to obtain a base solution; wherein, based on 100 ml of deionized water, add 1.8-2.2 g of polyvinyl alcohol and 1.8-2.2 g of tricalcium phosphate, the concentration of the porogen in the base solution is 0.068-0.17 mol / L, and the concentration of polyvinyl alcohol in the base solution is 1.6-1.9 wt%;

[0009] b. Prepare Solution A: Prepare a solution containing sodium metaaluminate, sodium hydroxide, alcohol, and a coupling agent. The concentration of sodium metaaluminate, sodium hydroxide, alcohol, and coupling agent in Solution A is 1.07-1.50 mol / L, 0.26-0.4 mol / L, 1.8-2.2 mol / L, and 0.35-0.45 mol / L, respectively.

[0010] c. Prepare Solution B: Prepare a solution containing aluminum chloride, lithium halide, and HCl as Solution B; wherein the concentration of aluminum chloride in Solution B is 0.54-0.90 mol / L, the concentration of lithium halide is 0.70-1.42 mol / L, and the concentration of HCl is 2.20-3.28 mol / L;

[0011] d. Prepare Liquid C: Mix the resin monomer, solvent, and initiator in a weight ratio of 30-36:18-22:0.8-1.2 to obtain Liquid C; the weight ratio of the resin monomer, solvent, and initiator is preferably 32-34:19-21:0.9-1.1; the weight ratio of the resin monomer, solvent, and initiator is more preferably 33:20:1;

[0012] e. Pour liquid C into a reaction vessel filled with a base liquid and stir evenly, then add liquid A and liquid B dropwise in parallel, maintaining the solution pH at 3-7 to form amorphous aluminum hydroxide intercalated with lithium halide, and fix the adsorbent on the resin-based carrier through the action of a coupling agent. After adding liquid A and liquid B, continue the reaction until the reaction is completed, lower the reaction temperature to harden it, and obtain a resin-based granular adsorbent; wherein, during the reaction, a protective gas is continuously introduced to discharge oxygen in the reaction vessel, and the protective gas is a gas that does not participate in the reaction. The volume ratio of the base liquid, liquid A, liquid B, and liquid C is 9-13:28-35:14-20:3-7.

[0013] The porogen described in step a above may be a conventional porogen, such as at least one of sodium chloride, potassium chloride, sodium bicarbonate, ammonium bicarbonate, and polyethylene glycol-6000.

[0014] Furthermore, in order to improve the dispersion effect, an emulsifier is added to the base liquid in the above step a. The emulsifier can be a conventional emulsifier, for example, it can be at least one of sodium dodecylbenzenesulfonate, sodium lauryl sulfate, triethanolamine, sorbitan fatty acid ester, polyoxyethylene laurate, sodium laurate, sodium carboxymethyl cellulose, and phenylethylphenol polyoxyethylene ether.

[0015] Furthermore, the concentration of the emulsifier is preferably 0.0052-0.0062 mol / L; the concentration of the emulsifier is more preferably 0.0057 mol / L.

[0016] The model of the polyvinyl alcohol described in step a above may be a conventional model, for example, the model may be polyvinyl alcohol 1788.

[0017] Furthermore, in order to improve the performance of the prepared resin-based aluminum-based granular adsorbent, 2 g of polyvinyl alcohol and 2 g of tricalcium phosphate are preferably added to 100 ml of the deionized water in step a above, the concentration of the porogen in the base liquid is 0.068-0.17 mol / L, and the concentration of polyvinyl alcohol in the base liquid is preferably 1.72 wt%.

[0018] The coupling agent in step b may be a conventional coupling agent, such as A151, A171, KH540, KH550, KH51, KH560 or KH570.

[0019] Wherein, the alcohol described in the above step b is preferably methanol, ethanol and / or isopropanol.

[0020] Furthermore, in order to improve the performance of the prepared resin-based aluminum-based granular adsorbent, as a preferred technical solution, the concentration of sodium aluminate in the liquid A in step b is 1.07-1.50 mol / L, the concentration of sodium hydroxide is 0.32 mol / L, the concentration of alcohol is 2.05 mol / L, and the concentration of the coupling agent is 0.4 mol / L.

[0021] Wherein, the lithium halide described in the above step c can be at least one of LiCl, LiBr, and LiI.

[0022] The resin monomer described in step d above may be a conventional resin monomer, such as methacrylate, styrene, divinylbenzene or sodium p-styrenesulfonate.

[0023] The initiator described in step d above may be a conventional initiator, such as at least one of benzoyl peroxide, tert-butyl benzoyl peroxide, dicumyl peroxide, and methyl ethyl ketone peroxide.

[0024] Wherein, the solvent described in the above step d is preferably toluene, 1,2-dichlorobenzene solvent, benzene, n-heptane, dibutyl phthalate and / or liquid paraffin.

[0025] Among them, the protective gas described in the above step e can be any gas as long as it can discharge oxygen after being introduced to prevent oxygen from participating in the reaction. For example, it can be at least one of nitrogen, carbon dioxide, hydrogen, and helium. Furthermore, in order to reduce costs, the protective gas is preferably nitrogen.

[0026] In the above step e, the temperature for pouring liquid C into the reaction vessel containing the base liquid, stirring, and adding liquid A and liquid B to the reaction is preferably 60-100°C, and more preferably 60-80°C.

[0027] In the above step e, liquid C is poured into the reaction vessel containing the base liquid and stirred at a conventional stirring speed, for example, the stirring speed can be 200-1000 rpm, preferably 200-400 rpm.

[0028] Furthermore, to improve the performance of the prepared resin-based aluminum-based particulate adsorbent, in step e, Liquid A and Liquid B are preferably added dropwise using a peristaltic pump, with the peristaltic pump speed for Liquid A at 5-20 rpm and the peristaltic pump speed for Liquid B at 20-30 rpm. More preferably, the peristaltic pump speed for Liquid A is 8-12 rpm, and the peristaltic pump speed for Liquid B is 22-25 rpm. Furthermore, in step e, when Liquid A and Liquid B are added dropwise in parallel, the pH of the solution is preferably maintained at 4-5.

[0029] In the above step e, after adding liquid A and liquid B, the reaction can be continued until the reaction is completed, generally 10-60 minutes, preferably 20 minutes.

[0030] In the above step e, after adding liquid A and liquid B, the reaction is continued until the reaction is completed, and the reaction temperature is lowered to harden the mixture, generally to 80-100° C., and preferably to 95° C.

[0031] Furthermore, in order to improve the performance of the prepared resin-based aluminum-based granular adsorbent, in the above step e, the volume ratio of the base liquid, liquid A, liquid B, and liquid C is preferably 10-12:32-34:16-18:4-6; the volume ratio of the base liquid, liquid A, liquid B, and liquid C is more preferably 11:33:17:5.

[0032] The present invention also provides a resin-based aluminum-based particle adsorbent prepared by the above method.

[0033] The resin-based aluminum-based particle adsorbent of the present invention has good Li + Performance, its + The adsorption capacity can reach 3-5 mg / g.

[0034] The present invention also provides the resin-based aluminum-based particle adsorbent for adsorbing Li + Purpose.

[0035] Furthermore, the resin-based aluminum particle adsorbent of the present invention can be used for Li + adsorption, especially the adsorption concentration of 0.4 ~ 1.0g / L in salt lake brine + .

[0036] The beneficial effects of the present invention are:

[0037] 1. The preparation method of the resin-based aluminum-based granular adsorbent of the present invention is that the aluminum-based adsorbent is fixed on the resin-based carrier through the intermolecular force formed with the coupling agent, so that it will not separate from the matrix during the cyclic adsorption experiment and will not affect the adsorption effect.

[0038] 2. The preparation method of the resin-based aluminum-based granular adsorbent of the present invention adopts a one-step method to in-situ synthesize the aluminum-based adsorbent and the resin-based carrier, and at the same time fixes the aluminum-based adsorbent on the resin-based carrier through the amphiphilicity of the coupling agent. The process steps are simple, easy to mass produce, and have good social and economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 Scanning electron microscope image of the resin-based aluminum-based particle adsorbent prepared by the present invention DETAILED DESCRIPTION

[0040] The embodiments of the present invention are described in detail below in conjunction with specific examples, but it will be understood by those skilled in the art that the following examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. Where specific conditions are not specified in the examples, conventional conditions shall be followed.

[0041] Example 1

[0042] Base solution: Add 100 mL of deionized water to a 300 mL beaker, heat to 70°C, add 2 g of polyvinyl alcohol 1788 (PVA), dissolve it, then add 2 g of tricalcium phosphate, 2 g of sodium dodecylbenzenesulfonate (SDBS), and 4 g of NaCl, stir until evenly dispersed, and place it in a 1000 mL three-necked flask as the base solution.

[0043] Solution A: Weigh 22g NaAlO2, 3.2g NaOH, 30mL anhydrous ethanol, and 25g silane coupling agent KH550 into a beaker filled with 250mL deionized water, stir until completely dissolved, and set aside.

[0044] Solution B: Weigh 21g AlCl3 and 7.5g LiCl into 125mL of deionized water, stir until completely dissolved, then add 17mL HCl, disperse evenly, and set aside.

[0045] Liquid C: Add 30 mL of styrene monomer, 25 mL of divinylbenzene, 20 mL of 1,2-dichlorobenzene solvent, and 1 g of benzoyl peroxide into a 100 mL dropping funnel, shake well, and set aside.

[0046] After heating the three-necked flask containing the base liquid to 70°C, nitrogen was introduced to expel the remaining oxygen in the flask, and liquid C was poured in. The rotation speed was adjusted to 200-250rpm to disperse the oil phase solution into small droplets as much as possible under high shear. Liquids A and B were then dripped into the three-necked flask in parallel through a peristaltic pump. The dripping time was controlled at 8-10 minutes to ensure that the pH of the solution was 4-5. After the dripping was complete, the reaction was carried out for 20 minutes, and then the temperature was adjusted to 95°C. After the reaction for 2 hours, the degree of ball formation was observed. After hardening, the mixture was cooled to room temperature and stirred continuously. Finally, the granular aluminum adsorbent was removed, and the excess reagents were washed off with ethanol and deionized water, and the mixture was dried at 60°C for 24 hours.

[0047] Example 2

[0048] Base liquid: Add 100 mL of deionized water to a 300 mL beaker, heat to 70°C, add 2 g of polyvinyl alcohol 1788 (PVA), dissolve it, then add 2 g of tricalcium phosphate, 2 g of sodium laurate, and 4 g of PEG-6000, stir until evenly dispersed, and place it in a 1000 mL three-necked flask as the base liquid.

[0049] Solution A: Weigh 30g NaAlO2, 3.2g NaOH, 50mL anhydrous ethanol, 25g silane coupling agent KH570, and 30mL anhydrous ethanol into a beaker containing 250mL deionized water, stir until completely dissolved, and set aside.

[0050] Solution B: Weigh 25g AlCl3 and 10g LiCl and add them to 125mL deionized water. Stir until completely dissolved. Then add 20mL HCl and disperse evenly. Set aside.

[0051] Liquid C: Measure 15 mL of methacrylate monomer, 20 mL of styrene, 15 mL of diethylbenzene, 30 mL of toluene, and 1.5 g of tert-butyl benzoyl peroxide, add them into a 100 mL dropping funnel, shake evenly, and set aside.

[0052] After heating the three-necked flask containing the base liquid to 70°C, nitrogen was introduced to expel the remaining oxygen in the flask, and liquid C was poured in. The rotation speed was adjusted to 200-250rpm to disperse the oil phase solution into small droplets as much as possible under high shear. Liquids A and B were then dripped into the three-necked flask in parallel through a peristaltic pump. The dripping time was controlled at 8-10 minutes to ensure that the pH of the solution was 4-5. After the dripping was complete, the reaction was carried out for 20 minutes, and then the temperature was adjusted to 95°C. After the reaction for 2 hours, the degree of ball formation was observed. After hardening, the mixture was cooled to room temperature and stirred continuously. Finally, the granular aluminum adsorbent was removed, and the excess reagents were washed off with ethanol and deionized water, and the mixture was dried at 60°C for 24 hours.

[0053] Example 3

[0054] Base liquid: Add 100 mL of deionized water to a 300 mL beaker, heat to 70°C, add 2 g of polyvinyl alcohol (PVA), dissolve it, then add 2 g of tricalcium phosphate, 2 g of sodium lauryl sulfate, and 4 g of NaHCO3, stir until evenly dispersed, and place it in a 1000 mL three-necked flask as the base liquid.

[0055] Solution A: Weigh 35g NaAlO2, 3.2g NaOH, 25mL anhydrous ethanol, 25g silane coupling agent KH560, and 30mL methanol into a beaker containing 250mL deionized water, stir until completely dissolved, and set aside.

[0056] Solution B: Weigh 25g AlCl3 and 15g LiCl into 125mL deionized water, stir until completely dissolved, then add 25mL HCl, disperse evenly, and set aside.

[0057] Liquid C: Add 40 mL of styrene, 30 mL of pentaerythritol triacrylate, 35 mL of 1,2-dichlorobenzene solvent monomer, and 2 g of benzoyl peroxide into a 100 mL dropping funnel, shake well, and set aside.

[0058] After heating the three-necked flask containing the base liquid to 70°C, nitrogen was introduced to expel the remaining oxygen in the flask, and liquid C was poured in. The rotation speed was adjusted to 200-250rpm to disperse the oil phase solution into small droplets as much as possible under high shear. Liquids A and B were then dripped into the three-necked flask in parallel through a peristaltic pump. The dripping time was controlled at 8-10 minutes to ensure that the pH of the solution was 4-5. After the dripping was complete, the reaction was carried out for 20 minutes, and then the temperature was adjusted to 95°C. After the reaction for 2 hours, the degree of ball formation was observed. After hardening, the mixture was cooled to room temperature and stirred continuously. Finally, the granular aluminum adsorbent was removed, and the excess reagents were washed off with ethanol and deionized water, and the mixture was dried at 60°C for 24 hours.

[0059] Example 4

[0060] Base solution: Add 100 mL of deionized water to a 300 mL beaker, heat to 80°C, add 2 g of polyvinyl alcohol (PVA), dissolve it, then add 2 g of tricalcium phosphate, 2 g of sodium dodecylbenzenesulfonate (SDBS), and 4 g of NaCl, stir until evenly dispersed, and place it in a 1000 mL three-necked flask as the base solution.

[0061] Solution A: Weigh 22g NaAlO2, 3.2g NaOH, 30mL methanol, and 25g silane coupling agent KH550 into a beaker filled with 250mL deionized water, stir until completely dissolved, and set aside.

[0062] Solution B: Weigh 21g AlCl3 and 7.5g LiCl into 125mL of deionized water, stir until completely dissolved, then add 17mL HCl, disperse evenly, and set aside.

[0063] Liquid C: Add 50 mL of styrene monomer, 20 mL of 1,2-n-heptane, and 1 g of benzoyl peroxide into a 100 mL dropping funnel, shake well, and set aside.

[0064] After heating the three-necked flask containing the base liquid to 80°C, nitrogen was introduced to expel the remaining oxygen in the flask, and liquid C was poured in. The rotation speed was adjusted to 200-250rpm to disperse the oil phase solution into small droplets as much as possible under high shear. Liquids A and B were then dripped into the three-necked flask in parallel through a peristaltic pump. The dripping time was controlled at 8-10 minutes to ensure that the pH of the solution was 4-5. After the dripping was complete, the reaction was carried out for 20 minutes, and then the temperature was adjusted to 95°C. After the reaction for 2 hours, the degree of ball formation was observed. After hardening, the mixture was cooled to room temperature and stirred continuously. Finally, the granular aluminum adsorbent was removed, and the excess reagents were washed off with ethanol and deionized water, and the mixture was dried at 60°C for 24 hours.

[0065] Example 5

[0066] The difference from Example 4 is that the reaction temperature is 90°C.

[0067] Example 6

[0068] The difference from Example 4 is that the reaction temperature is 95°C.

[0069] Comparative Example 1

[0070] The difference from Example 1 is that no silane coupling agent is added.

[0071] Comparative Example 2

[0072] Base liquid: Add 100 mL of deionized water as the base liquid to a 1 L reactor and heat to 70 °C.

[0073] Solution A: Weigh 22g NaAlO2 and 3.2g NaOH into a beaker containing 250mL deionized water, stir until completely dissolved, and set aside.

[0074] Solution B: Weigh 21g AlCl3 and 7.5g LiCl into 125mL of deionized water, stir until completely dissolved, then add 17mL HCl, disperse evenly, and set aside.

[0075] Liquid A and liquid B are slowly dripped into the base liquid through a peristaltic pump. The pH of the mixed solution is always maintained at 4-5. After the dripping of liquids AB, the reaction is continued for 2 hours. The product is filtered, washed, dried, ground and set aside.

[0076] Add 100 mL of deionized water to a 500 mL three-necked flask, heat it to 70 ° C, add 2 g of polyvinyl alcohol (PVA), dissolve it, then add 2 g of tricalcium phosphate, 2 g of sodium dodecylbenzenesulfonate (SDBS), 4 g of PEG-6000, 25 g of silane coupling agent KH550, 4 g of NaCl, 20 g of adsorbent powder prepared by reaction of AB liquid, 30 mL of styrene monomer, 20 mL of 1,2-dichlorobenzene solvent, and 1 g of benzoyl peroxide. Stir evenly, then adjust the temperature to 80-100 ° C, react for 2 h, observe the degree of ball formation, cool to room temperature after hardening, continue stirring, and finally take out the granular aluminum adsorbent, wash off the excess reagents with ethanol and deionized water, and dry at 60 ° C for 24 h.

[0077] Comparative Example 3

[0078] The difference from Example 1 is that the reaction temperature of the aluminum salt is 40°C.

[0079] Comparative Example 4

[0080] The difference from Example 1 is that the reaction temperature of the aluminum salt is 60°C.

[0081] Comparative Example 5

[0082] The difference from Example 1 is that the pH of the aluminum salt reaction is 7-8.

[0083] Comparative Example 6

[0084] The difference from Example 1 is that the pH of the aluminum salt reaction is 2-3.

[0085] The scanning electron microscope image of a resin-based aluminum-based particle adsorbent obtained by the method of the present invention is as follows: Figure 1 As shown, from Figure 1 The scanning electron microscope image shows that the surface of the adsorbent prepared by the synthesis method of the present invention is loose and porous, with a pore size of micron level.

[0086] Adsorption and desorption experiments: The prepared resin-based aluminum granular adsorbent was loaded into the adsorption-desorption column, and the Li-containing + Salt lake brine with a concentration of 0.4-1.0 g / L was passed through the adsorbent column and analyzed with water when the adsorption capacity reached saturation. The Li content in the solution before and after adsorption was determined by atomic absorption spectroscopy. + The adsorption capacity is calculated using the following formula:

[0087] Q=(Co-Ct)V / m

[0088] Where Q represents the adsorption capacity, Co represents the initial Li + concentration, Ct represents the concentration of the solution after adsorption, V is the volume of the solution, and m is the mass of the adsorbent.

[0089] After 50 consecutive cycles, the adsorbent was dried and weighed, and the dissolution loss rate was calculated using the following formula:

[0090] L=(mo-mt) / mo×100%

[0091] Where L is the dissolution loss rate, mo is the initial column mass of the adsorbent, and mt is the mass of the adsorbent after the cycle.

[0092] Table 1 Adsorption capacity, capacity reduction rate after 50 cycles, and dissolution loss rate of the adsorbents obtained in Examples 1-6 and Comparative Examples 1-6

[0093]

[0094]

[0095] As can be seen from Table 1, the adsorbents synthesized by the methods of Examples 1-3 have high adsorption capacity, cyclic stability and low dissolution loss. It can be seen from Examples 1-3 and Comparative Example 1 that the addition of a silane coupling agent can increase the interaction between aluminum hydroxide and the resin, reduce dissolution loss, and improve the adsorption capacity. It can be seen from Examples 1-3 and Comparative Example 2 that the one-step synthesis method and the multi-step synthesis method have the same adsorption capacity and low dissolution rate, but have greater advantages in terms of time cost. It can be seen from Examples 1-6 and Comparative Examples 3 and 4 that when the synthesis temperature is higher than 60°C, the adsorbent has a higher adsorption capacity and cyclic stability. It can be seen from Examples 1-3 and Comparative Examples 5 and 6 that the adsorption capacity and stability of the synthesized product are higher under neutral pH conditions.

[0096] This specific embodiment is only an explanation of the present invention and is not a limitation of the present invention. After reading the description of the present invention, those skilled in the art may make some modifications or improvements based on the present invention. However, as long as they are within the scope of the claims of the present invention, they are protected by patent law.

Claims

1. A method for preparing a resin-based aluminum-based particle adsorbent, characterized in that: The following steps are involved: a. Prepare a base solution: Add polyvinyl alcohol, tricalcium phosphate, and a porogen to deionized water and stir until uniformly dispersed to obtain a base solution; wherein, based on 100 ml of deionized water, add 1.8-2.2 g of polyvinyl alcohol and 1.8-2.2 g of tricalcium phosphate; the concentration of the porogen in the base solution is 0.068-0.17 mol / L; and the concentration of polyvinyl alcohol in the base solution is 1.6-1.9 wt %; b. Prepare Solution A: Prepare a solution containing sodium metaaluminate, sodium hydroxide, alcohol, and a coupling agent. The concentration of sodium metaaluminate, sodium hydroxide, alcohol, and coupling agent in Solution A is 1.07-1.50 mol / L, 0.26-0.4 mol / L, 1.8-2.2 mol / L, and 0.35-0.45 mol / L, respectively. c. Prepare Solution B: Prepare a solution containing aluminum chloride, lithium halide, and HCl. The concentration of aluminum chloride in Solution B is 0.54-0.90 mol / L, the concentration of lithium halide is 0.70-1.42 mol / L, and the concentration of HCl is 2.20-3.28 mol / L. d. Prepare Liquid C: Mix the resin monomer, solvent, and initiator in a weight ratio of 30-36:18-22:0.8-1.2 to obtain Liquid C; e. Pour liquid C into a reaction vessel containing a bottom liquid and stir evenly, then add liquid A and liquid B dropwise in parallel, maintain the solution pH at 4-5, form amorphous aluminum hydroxide with lithium halide intercalation, and fix the adsorbent on the resin-based carrier through the action of a coupling agent. After adding liquid A and liquid B, continue the reaction until the reaction is completed, lower the reaction temperature to harden it, and obtain a resin-based granular adsorbent; wherein, during the reaction, a protective gas is continuously introduced to discharge oxygen in the reaction vessel, and the protective gas is a gas that does not participate in the reaction. The volume ratio of the bottom liquid, liquid A, liquid B, and liquid C is 9-13: 28-35: 14-20: 3-7; In step e, the reaction temperature of adding liquid A and liquid B is 70-100°C.

2. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: The weight ratio of the resin monomer, solvent and initiator is 32-34:19-21:0.9-1.

1.

3. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: The weight ratio of the resin monomer, solvent and initiator is 33:20:

1.

4. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: The porogen described in step a is at least one of sodium chloride, potassium chloride, sodium bicarbonate, ammonium bicarbonate, and polyethylene glycol-6000.

5. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: An emulsifier is also added to the base liquid in step a, and the emulsifier is at least one of sodium dodecylbenzene sulfonate, sodium lauryl sulfate, triethanolamine, sorbitan fatty acid ester, polyoxyethylene laurate, sodium laurate, sodium carboxymethyl cellulose, and phenylethylphenol polyoxyethylene ether.

6. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 5, wherein: The concentration of the emulsifier is 0.0052-0.0062 mol / L.

7. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 6, wherein: The concentration of the emulsifier is 0.0057 mol / L.

8. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: The model of the polyvinyl alcohol is polyvinyl alcohol 1788.

9. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: In step a, 2 g of polyvinyl alcohol and 2 g of tricalcium phosphate are added to 100 ml of the deionized water. The concentration of the porogen in the base solution is 0.068-0.17 mol / L, and the concentration of the polyvinyl alcohol in the base solution is 1.72 wt%.

10. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: The coupling agent in step b is A151, A171, KH540, KH550, KH51, KH560 or KH570.

11. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: The alcohol described in step b is at least one of methanol, ethanol and isopropanol.

12. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: In step b, the concentration of sodium aluminate in solution A is 1.07-1.50 mol / L, the concentration of sodium hydroxide is 0.32 mol / L, the concentration of alcohol is 2.05 mol / L, and the concentration of coupling agent is 0.4 mol / L.

13. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: The lithium halide described in step c is at least one of LiCl, LiBr, and LiI.

14. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: The resin monomer in step d is methacrylate, styrene, divinylbenzene or sodium p-styrenesulfonate.

15. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: The initiator in step d is at least one of benzoyl peroxide, tert-butyl benzoyl peroxide, dicumyl peroxide, and methyl ethyl ketone peroxide.

16. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: The solvent in step d is at least one of toluene, 1,2-dichlorobenzene solvent, benzene, n-heptane, dibutyl phthalate, and liquid paraffin.

17. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: The protective gas in step e is at least one of nitrogen, carbon dioxide, hydrogen and helium.

18. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: In step e, liquid C is poured into the reaction vessel containing the base liquid, stirred, and liquid A and liquid B are added. The reaction temperature is 70-80°C.

19. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 18, wherein: In step e, liquid C is poured into the reaction vessel containing the base liquid, and the stirring speed is 200-1000 rpm.

20. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 19, wherein: The stirring speed is 200-400rpm.

21. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: In step e, liquid A and liquid B are dripped in using a peristaltic pump, the speed of the peristaltic pump for liquid A is 5-20 rpm, and the speed of the peristaltic pump for liquid B is 20-30 rpm.

22. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 21, wherein: The speed of the peristaltic pump for liquid A is 8-12 rpm.

23. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 21, wherein: The speed of the peristaltic pump for liquid B is 22-25rpm.

24. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: In step e, the time from the addition of solution A and solution B to the completion of the reaction is 10-60 minutes.

25. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 24, wherein: In step e, the time from the addition of solution A and solution B to the completion of the reaction is 20 min.

26. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: In step e, after adding liquid A and liquid B, continue until the reaction is complete, and then lower the reaction temperature to 80-100°C to harden it.

27. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 26, wherein: In step e, after adding liquid A and liquid B, continue until the reaction is complete, and then lower the reaction temperature to 95°C to harden it.

28. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 1, wherein: In step e, the volume ratio of the base liquid, liquid A, liquid B, and liquid C is 10-12: 32-34: 16-18: 4-6.

29. The method for preparing a resin-based aluminum-based particle adsorbent according to claim 28, wherein: In step e, the volume ratio of the base liquid, liquid A, liquid B, and liquid C is 11:33:17:

5.

30. A resin-based aluminum-based particulate adsorbent prepared by the method according to any one of claims 1 to 29.

31. The resin-based aluminum-based particle adsorbent according to claim 30, characterized in that: The Li + The adsorption capacity is 3-5 mg / g.

32. The resin-based aluminum-based particle adsorbent according to claim 30 or 31 is used for adsorbing Li + Purpose.

33. The use according to claim 32, characterized in that: The adsorbed Li + For the adsorption of Li in salt lake brine with a concentration of 0.4-1.0 g / L + .

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