CN113578252B - Preparation method of lithium extraction adsorbent - Google Patents
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Abstract
The invention belongs to the technical field of chemical industry, and discloses a preparation method of a lithium extraction adsorbent, which utilizes strong acid wastewater generated in fine chemical production to react with suspension aqueous solution mixed by aluminum hydroxide and lithium chloride, then adds a precipitant to separate out solidified matters of aluminum lithium ions under the action of coprecipitation, and then performs drying, powdering and wet granulation to obtain the lithium extraction adsorbent. The method can change waste into valuables, can utilize the waste acid to achieve the purpose of producing the lithium extraction adsorbent, and simultaneously can remove waste acid water generated in the production of fine chemicals such as medical raw medicine intermediates, resin and the like, and directly adopts aluminum hydroxide as a raw material, so that the cost is lower than that of adopting aluminum chloride hydrate as an aluminum-based raw material in industrial production, the comprehensive benefit is higher, and the adsorbent obtained by the method is matched with the continuous ion exchange technology described in US3879287, so that the difficult problems of high energy consumption, high cost, low lithium recovery rate and the like in the extraction of lithium from salt lake brine can be effectively solved.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of a lithium extraction adsorbent.
Background
Lithium resources are the most light metal known in nature, and are widely applied to the fields of military, batteries, medicines, nuclear energy and the like because of high conductivity, high heat ratio and good physicochemical properties, so that the development of new energy resources in the future certainly generates strong competition for the lithium resources.
The existing lithium extraction methods include a combustion leaching method, a carbonization method, a precipitation method, a solvent extraction method, a membrane separation technology, an adsorption method and the like. Although the combustion leaching method and the precipitation method have simple process, the method has strong corrosion to equipment, and the method is only suitable for salt lake brine with low magnesium-lithium ratio. Both carbonization and solvent extraction are relatively long processes, the former being relatively energy-intensive and the latter being relatively corrosive to equipment, resulting in excessive costs. The electrodialysis method and the membrane separation technology are not easy to industrialize, compared with the method, the method for extracting the salt lake brine lithium by adopting the adsorbent is more reliable, the salt lake brine generally contains rich B, br, mg, na, K, ca and other elements, the grades of various elements contained in salt lakes in different areas are different, especially the development difficulty of the salt lake with high grade Mg/Li is extremely high, the adsorption method can realize the purpose of specifically extracting lithium ions from the salt lake brine consisting of different elements in different areas on the premise of low cost, no environmental pollution and good safety and selectivity, and the problem of high development difficulty of the salt lake brine with high grade Mg/Li ratio is effectively solved.
In the field of adsorption and extraction of lithium, the technology adopted in patent CN201710235736 is to mix and react aluminum chloride solution and lithium compound to form initial reaction body LiCl 2.2-2.8 Al (OH) 3 ·2.7～3.9H 2 O, then solid-liquid separation, drying, grinding and crushing, colloid bonding, adding liquid chlorine, mixing and granulating, and screening out a finished product.
Lithium extraction adsorbent LiX published in U.S. Pat. No. 3,182,2B 2 X ·2Al(OH) 3 And nH2O, wherein boehmite AlO (OH) is used as a raw material, potassium aluminate, sodium aluminate, ammonia water, sodium hydroxide and potassium hydroxide are used as alkaline precursors, aluminum sulfate, aluminum trichloride, aluminum nitrate, sulfuric acid, hydrochloric acid and nitric acid are used as acid precursors, the precursor slurry is prepared, then lithium chloride solution is added for stirring reaction, and a series of operations such as suction filtration and drying are performed, an adhesive is not needed in the process, but high-pressure steam is used for activating the adsorbent in the later period, so that the operation is complicated and the energy consumption is high.
In patent CN202010028091, aluminum salt, lithium salt and a third component MX salt are mutually mixed and dissolved, then alkali liquor is added to adjust pH to separate out solid, and then the solid is dried, ground and crushed, glued and screened to obtain the finished product.
The patent CN201811331549 lithium adsorbent or precursor powder thereof, a plurality of polymers, a pore-forming agent and an organic solvent are mixed and stirred for 1-120 min under the conditions of normal pressure and 10-190 ℃, the mixture is dripped into the solution or extruded, molded and crushed, and the granular lithium adsorbent is obtained through washing.
In the synthesis process of the lithium extraction adsorbent, the cost of adopting the hydroxyl aluminum oxide or aluminum salt as the raw material is higher than that of aluminum hydroxide, and if a pore-forming agent, a plurality of polymers and other components are used, the preparation process is more complicated, and the cost is increased.
In contrast, the lithium extraction adsorbent synthesized by the invention belongs to an environment-friendly adsorption material, the selected aluminum hydroxide participates in the reaction by the alkaline characteristic, the synthesis process is different from that of the traditional lithium adsorbent, the invention takes various strong acid wastewater generated in fine chemical industry as a starting material to react with a mixed suspension system of aluminum hydroxide powder and lithium chloride aqueous solution, and after reaching a full-solution state, precipitant is added to enable aluminum lithium ions to generate coprecipitation action to separate out solidified matters, part of COD in acid water can be attached to the separated out adsorbent precursor in the process of coprecipitating aluminum lithium ions to separate out solids, so that COD in acid water is reduced, and part of organic matters in waste acid water are attached to the finally obtained adsorbent, but the specific adsorption performance of the adsorbent on brine lithium ions is not greatly influenced, and the organic matters in COD can be used as a molecular skeleton of the adsorbent to improve the mechanical strength of the adsorbent, thereby reducing the dissolution loss rate in the use process of the adsorbent. The traditional method is to prepare aqueous solutions by aluminum trichloride and lithium hydroxide respectively and then mix and react the aqueous solutions. Compared with the combination of aluminum trichloride and lithium hydroxide, the combination of aluminum hydroxide and lithium chloride has low cost, and the lithium chloride has higher solubility in water than lithium hydroxide, so that the reaction is more sufficient, the cost is lower than that of the traditional aluminum-based adsorbent while the specific adsorption of lithium ions is achieved, the comprehensive benefit is higher, and the adsorption capacity of the lithium extraction adsorbent is also greatly improved compared with that of the traditional lithium extraction adsorbent.
Disclosure of Invention
Aiming at the defects of the existing lithium extraction technology, the invention adopts aluminum hydroxide and lithium chloride as direct raw materials from the aspects of cost and environmental protection, forms a suspension system by preparing the molar ratio of the aluminum hydroxide to the lithium chloride, introduces industrial strong acid wastewater into the suspension system to enable the suspension to reach a fully-dissolved state, then adds a precipitant into the fully-dissolved solution to precipitate solid by a coprecipitation principle, and lithium ions in the precipitated solid can be embedded and loaded in amorphous aluminum hydroxide, and finally is dried, powdered and wet granulated to obtain the finished product.
In the initial stage of dripping the precipitant, less cations are carried by the precipitant, so that lithium ions in the reaction liquid can be well connected in the carrier aluminum hydroxide by virtue of coprecipitation, but the process of inserting the lithium ions into the carrier can be influenced to a certain extent along with the increase of the cations carried by the precipitant. Therefore, the pH value of the system can be adjusted by selecting the lithium hydroxide solution as the precipitant, and lithium ions can be added into the system, so that the lithium ions are finally more effectively inserted into the amorphous aluminum hydroxide. And the ratio of the molar concentration of each material is regulated, so that the final finished product can form good specific surface area, pore volume and crystal form, thereby achieving the optimal adsorption effect when lithium ions in brine are adsorbed.
The invention also aims to change various strong acid waste water generated in chemical production into valuable while preparing the lithium extraction adsorbent by an environment-friendly and efficient method, so that the waste water becomes the main raw material for preparing the adsorbent.
The technical process for synthesizing the lithium extraction adsorbent comprises the following steps:
1) Configuration of suspension system: preparing a suspension by tap water and aluminum hydroxide powder with the concentration of 2-3 mol/L in a reaction bottle according to a calculated proportion, preparing a lithium chloride solution with the concentration of 3-5 mol/L by anhydrous lithium chloride or hydrate thereof and deionized water according to the calculated proportion, and then pouring the lithium chloride aqueous solution into the aluminum hydroxide suspension according to an optimized aluminum-lithium molar concentration ratio for mixing and stirring;
2) Preparing a full solution: adding a proper amount of industrial strong acid wastewater into the suspension mixture in the step 1) until the pH value is 2-3, wherein the suspension system can reach a fully-dissolved state, and the temperature is controlled between 15-50 ℃ and is preferably 25 ℃;
3) Solid precipitation stage: dropwise adding the precipitant alkaline solution into the step 2)The solid double salt is precipitated by controlling the temperature between 15 and 50 ℃ and preferably 25 ℃ to reach the pH near neutral, and the solid double salt can be LiX.2Al (OH) 3 ·nH 2 O、LiY·2Al(OH) 3 ·nH 2 O、LiZ g ·2Al(OH) 3 ·nH 2 One or more of the components O is also possibly mixed, and is specifically determined by the type of negative acid radical ions contained in strong acid water, wherein X, Y, Z is NO 3 -、Cl - 、SO 4 -2 And when the ion is a divalent anion, g is 0.5. The solidified material combination takes amorphous aluminum hydroxide as a carrier, and part of lithium salt is embedded on the carrier.
4) Solid-liquid separation: and 3) carrying out solid-liquid separation on the filter pressing in the step 3), wherein part of lithium ions contained in the separated mother liquor can be removed from the next batch, and the solids are dried and powdered.
5) Wet granulation stage: mixing and heating the adhesive and the organic solvent according to a certain proportion in a wet granulator, then pouring the powder into colloid, stirring and mixing, distilling and recovering part of the organic solvent, and then forming.
6) And (3) a finished product manufacturing stage: and (3) drying the extruded particles, and sieving the particles to obtain a finished product with the granularity of 0.5-3 mm.
Specifically, in the step 1), the concentration of the prepared lithium chloride solution is 2mol/L, the prepared aluminum hydroxide suspension is 1.35mol/L, and 1.5-3 bv of the lithium chloride solution is mixed with 1bv of the aluminum hydroxide suspension, so that the quantity ratio of aluminum lithium substances in the suspension mixture is 1:1.5-4.5. Preferably in a ratio of 1:3.
Specifically, in the step 2), the added strong acid wastewater is generated in the fine chemical production. Which contains NO 3 - 、Cl - 、SO 4 -2 And (3) mixing the isochoric strong acid ions or a plurality of isochoric strong acid ions, wherein the adding amount of the isochoric strong acid ions is used for enabling the mixed suspension in the step 1) to reach a full-dissolution state.
Specifically, in the step 3), the precipitating agent added dropwise may be one or a mixture of several of liquid alkali, triethylamine, ammonia water and lithium hydroxide solution, and the lithium hydroxide solution is preferred in view of not introducing other cations into the system.
Specifically, the adhesive in the wet granulation in the step 5) is characterized by being a single-component solvent type or a multi-component solvent type, specifically being one or a mixture of more than one of polyvinylpyrrolidone, polyvinyl chloride, polypropylene chloride, chlorinated polyvinyl chloride and perchloroethylene, and being uniformly mixed with an organic solvent according to a ratio of 1:12, preferably a ratio of 1:10. The organic solvent is one or a combination of a plurality of chlorobenzene, cyclohexanone, toluene, dimethylbenzene, ethyl acetate, dichloroethane or chloroform. The ratio of the adhesive to the powder is 1:15-1:5, preferably 1:10.
Specifically, in step 6), if the particle size of the finished product is too large, the resistance of the brine to permeate into the particles is also larger, and meanwhile, the resistance of the lithium element in the particles to precipitate out of the surfaces of the particles during analysis is also increased, so that the adsorption and desorption are not facilitated, and the particle size of the finished product is too small, so that the stacking density of a bed layer is too large, the requirements on energy consumption and equipment are high, and the adsorption and desorption are also not facilitated. The final particle size is preferably 2.5mm, combining the above analyses.
The beneficial effects of the invention are as follows:
1. the invention directly changes the strong acid wastewater generated in chemical production into the main raw material, if the waste acid water contains COD, organic matters in the waste acid water can be attached to the adsorbent in the coprecipitation process of aluminum and lithium ions, and can be used as a molecular framework of the adsorbent to indirectly improve the mechanical strength of the adsorbent on the premise of not influencing the performance of the adsorbent, thereby reducing the cost of the raw material and assisting in treating the wastewater, and achieving the effects of saving the production cost and achieving green and environment-friendly win-win effect.
2. Under the condition of replacing main raw materials, the prepared lithium extraction adsorbent still has good adsorption effect in performance, and the dissolution loss rate of the adsorbent is basically the same as that of the adsorbent prepared by the traditional method, so that no difference in performance exists.
3. Compared with the traditional dry granulation, the wet granulation adopted in the granulating aspect of the finished product has the advantages that the lithium adsorption capacity of the finished product is obviously higher than that of the finished product obtained by the traditional dry granulation, compared with the prior art, the wet granulation technology is simpler and more convenient to operate, the market prevalence rate is higher, and the practicability is stronger.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As shown in FIG. 1, in the embodiment of the invention, a preparation method of a lithium extraction adsorbent is provided, the adsorbent is prepared by adding a precipitator to adjust proper pH value to precipitate solid in the synthesis process, and then filtering, drying and wet granulating to form solid particles, wherein the components of the solid particles are that aluminum lithium ions are subjected to coprecipitation to enable lithium salts to be inserted into amorphous aluminum hydroxide, and then deionized water is used for washing the solid particles to remove part of the lithium salts, so that the adsorbent with part of lithium ion active sites is formed, the activated granular adsorbent is formed, lithium ions in brine can be effectively attached to the empty part of the adsorbent, and other ions in the brine can not be attached to the empty part of the adsorbent, thus the aim of selectively extracting lithium ions in salt lake brine with high grade magnesium-lithium ratio can be achieved.
The following describes the preparation method of the lithium extraction adsorbent of the present invention by way of a number of examples, and is not limited to the other limitations of the present invention.
Example 1:
152.88g of aluminum hydroxide powder and 201.37g of lithium chloride are added into a reaction bottleAdding 5L deionized water, stirring to obtain suspension, adding sulfuric acid wastewater generated in industrial production of tert-butyl peroxide into a reaction bottle, diluting, adding the suspension, measuring pH to 1.8 after reaching full-solution state, dripping lithium hydroxide solution with precipitant concentration of 50g/L to pH to 6.8, and separating out condensate, li (SO) 4 2- ) 0.5 ·2Al(OH) 3 ·nH 2 O, carrying out suction filtration and solid-liquid separation, drying the obtained solid at 60 ℃ overnight, and pulverizing to powder below 200 meshes.
Adding colloid with powder weight of 10% into wet granulator, mixing with powder, adding organic solvent to obtain slurry, shaping, granulating, and oven drying, and sieving with particle size of 2.5mm to obtain the final product.
10g of finished product is selected and put into 0.5L of pure water to be stirred for 2 hours for activation, then the obtained solid is put into 0.5L of brine mother liquor to be stirred for 2 hours for adsorption experiments, and the lithium adsorption amount is obtained by comprehensive calculation and is 3.4mg/g;
example 2:
adding 152.88g of aluminum hydroxide powder, 201.37g of lithium chloride and 5L of deionized water into a reaction bottle, stirring to prepare a suspension system, adding hydrochloric acid wastewater generated in the chloromethylation or Friedel-crafts reaction stage of resin white balls into the reaction bottle, measuring pH to be 2.3 after the suspension system reaches a fully-dissolved state, then dripping a lithium hydroxide solution with the concentration of 50g/L of a precipitant until the pH is 7, and separating out a solidified substance, liCl 2Al (OH) at the moment 3 ·nH 2 O, carrying out suction filtration and solid-liquid separation, drying the obtained solid at 60 ℃ overnight, and pulverizing to powder below 200 meshes.
Adding colloid with powder weight of 10% into wet granulator, mixing with powder, adding organic solvent to obtain slurry, shaping, granulating, and oven drying, and sieving with particle size of 2.5mm to obtain the final product. And evaporating, drying and recovering part of the solvent at 60 ℃, airing to obtain a finished product, and screening the finished product with the granularity of 2.5mm.
Selecting 10g of finished product, putting the finished product into 0.5L of pure water, stirring for 2 hours for activation, then performing suction filtration, putting the obtained solid into 0.5L of brine mother liquor, stirring for 2 hours for adsorption experiments, and comprehensively calculating to obtain the lithium adsorption quantity of 4.2mg/g;
example 3:
adding 152.88g of aluminum hydroxide powder, 201.37g of lithium chloride and 5L of deionized water into a reaction bottle, stirring to prepare a suspension system, adding mixed wastewater of hydrochloric acid and sulfuric acid (sulfate radical is easily oxidized into sulfate radical) generated after carboxylic acid is subjected to acyl chlorination in industrial production into the reaction bottle, measuring pH of the suspension system to be 2.3 after the suspension system reaches a full-solution state, then dripping lithium hydroxide solution with the concentration of 50g/L of precipitant until the pH reaches 7.1, and separating out a solidified substance at the moment, wherein the components are LiCl 2Al (OH) 3 ·nH 2 O、Li(SO 4 2- ) 0.5 ·2Al(OH) 3 ·nH 2 And (3) carrying out suction filtration and solid-liquid separation on the mixed system of O, drying the obtained solid at 60 ℃ overnight, and pulverizing the solid into powder of less than 200 meshes.
Adding colloid with powder weight of 10% into wet granulator, mixing with powder, adding organic solvent to obtain slurry, shaping, granulating, and oven drying, and sieving with particle size of 2.5mm to obtain the final product. And evaporating, drying and recovering part of the solvent at 60 ℃, airing to obtain a finished product, and screening the finished product with the granularity of 2.5mm.
10g of finished product is selected and put into 0.5L of pure water to be stirred for 2 hours for activation, then the obtained solid is put into 0.5L of brine mother liquor to be stirred for 2 hours for adsorption experiments, and the lithium adsorption amount is obtained by comprehensive calculation and is 3.3mg/g;
example 4:
adding 152.88g of aluminum hydroxide powder, 201.37g of lithium chloride and 5L of deionized water into a reaction bottle, stirring to prepare a suspension system, adding sulfuric acid and nitric acid mixed wastewater generated during nitration in industrial production into the reaction bottle, diluting, adding the suspension system, measuring pH to be 2 after reaching a fully-dissolved state, then dripping a lithium hydroxide solution with the concentration of a precipitant of 50g/L until the pH is 6.9, and precipitating a condensate at the moment, wherein the components are Li (SO 4 2- ) 0.5 ·2Al(OH) 3 ·nH 2 O、LiNO 3 ·2Al(OH) 3 ·nH 2 And (3) carrying out suction filtration and solid-liquid separation on the mixed system of O, drying the obtained solid at 60 ℃ overnight, and pulverizing the solid into powder of less than 200 meshes.
Adding colloid with powder weight of 10% into wet granulator, mixing with powder, adding organic solvent to obtain slurry, shaping, granulating, and oven drying, and sieving with particle size of 2.5mm to obtain the final product. And evaporating, drying and recovering part of the solvent at 60 ℃, airing to obtain a finished product, and screening the finished product with the granularity of 2.5mm.
10g of finished product is selected and put into 0.5L of pure water to be stirred for 2 hours for activation, then the obtained solid is put into 0.5L of brine mother liquor to be stirred for 2 hours for adsorption experiment, and the lithium adsorption capacity is obtained by comprehensive calculation and is 3.0mg/g;
it should be noted that, the salt lake mainly has a composition of a chloride type, a sulfate type and a carbonate type mainly of a Tibetan, wherein examples 1 to 4 can effectively solve the problem of lithium extraction from the sulfate type and the chloride type salt lake, while for the carbonate type salt lake, although the salt lake is equivalent to the sulfate type and the chloride type salt lake in the adsorption stage, the salt lake is difficult to extract lithium from the carbonate type salt lake in the analysis stage, because the ion lattice force formed by carbonate and lithium ions is larger in the adsorption stage of the adsorbent, the solubility of lithium carbonate accumulated in the adsorbent is low, and the solubility of lithium carbonate is lower than that of other lithium salts, so that the lithium carbonate is difficult to be eluted from the adsorbent in the analysis stage, the solubility of lithium carbonate is changed along with the temperature, and the higher the solubility of lithium carbonate is lower, so that the temperature of the adsorption stage is required to be 25 ℃ in the adsorption stage, and the temperature of the analysis stage is 0 ℃. And moreover, the lithium carbonate is easy to form a relatively soluble substance lithium bicarbonate in the presence of carbon dioxide, circulating carbon dioxide can be introduced into a continuous ion exchange system in an analysis stage, so that part of lithium carbonate on the adsorbent is converted into relatively soluble lithium bicarbonate to be eluted, and then the obtained lithium bicarbonate is heated and evaporated to be converted into lithium carbonate product again.
Comparative example:
adding 152.88g of aluminum hydroxide powder, 201.37g of lithium chloride and 5L of deionized water into a reaction bottle, stirring to prepare a suspension system, adding any one of waste acid water in examples 1-4 into the reaction bottle, enabling the suspension system to reach a full-solution state, measuring pH to be 2.2, then dripping a lithium hydroxide solution with the concentration of a precipitant of 50g/L until the pH is 7, and separating out a solidified substance, liX.2Al (OH) 3 ·nH 2 O, suction filtration, solid-liquid separation, inGranulating in a dry granulator, and returning the granules with the screening granularity of 2.0-2.5 mm serving as finished product non-standard particle size granules to the dry granulator and tabletting and granulating.
Selecting 10g of finished product, putting the finished product into 0.5L of pure water, stirring for 2 hours for activation, then performing suction filtration, putting the obtained solid into 0.5L of brine mother liquor, stirring for 2 hours for adsorption experiments, and comprehensively calculating to obtain the lithium adsorption capacity of 2.9mg/g;
in the above examples or comparative examples, if a part of COD is contained in the waste acid water, the waste acid water does not affect various properties of the final product within a certain range, and the organic matter contained in the adsorbent can also be used as a molecular skeleton of the adsorbent to enhance the mechanical strength of the adsorbent. The final product forming stages of examples 1 to 4 were obtained by wet granulation techniques, whereas the final product of the comparative example was obtained by dry granulation techniques. The comparison of the examples shows that the lithium adsorption capacity of the wet-process granulating lithium extraction adsorbent is obviously better than that of the dry-process granulating, because the dry-process granulating technology has larger compression pressure in the material compression process than that of the wet-process granulating technology, the stacking density of the granulating finished product is higher, and the flowing resistance of liquid in the granules is larger than that of the granules prepared by the wet process, so that the adsorption and the analysis are more unfavorable, and compared with the dry-process granulating technology, the wet-process granulating adopted by the invention has simpler operation, better quality and higher market prevalence.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A method of preparing a lithium extraction sorbent, characterized by: the method comprises the following steps:
preparing a suspension by using tap water and 2-3 mol/L aluminum hydroxide powder in a reaction bottle, and introducing 3-5 mol/L lithium chloride solution to prepare a suspension system;
introducing strong acid water into the reaction bottle until the suspension system in the reaction bottle is completely dissolved to obtain an acidic solution with the pH value of 2-3;
dripping precipitant into the reaction bottle and stirring until the pH reaches 6-8, thereby separating out LiX.2Al (OH) under the action of coprecipitation principle 3 ·nH 2 O、LiY·2Al(OH) 3 ·nH 2 O、LiZ g ·2Al(OH) 3 ·nH 2 One or more than one mixed solid of O component, wherein X, Y, Z is NO 3 - 、Cl-、SO 4 2- A negative strong acid ion, g being 0.5 when it is a divalent anion;
and (3) pulverizing the obtained solid, stirring and mixing the obtained solid with adhesive and powder, wherein the mass ratio of the adhesive to the powder is 1:15-1:5, then using a wet granulator for compression molding, and screening the powder with the granularity of 0.5-3 mm after drying to obtain the finished product.
2. The method for preparing a lithium extraction adsorbent according to claim 1, characterized in that: the screening granularity is 2.5mm after drying.
3. The method for preparing a lithium extraction adsorbent according to claim 1, characterized in that: the strong acid water can be industrial strong acid wastewater, and the composition components of the strong acid wastewater are one or a mixture of a plurality of hydrochloric acid, nitric acid, sulfuric acid and chloric acid.
4. A method for preparing a lithium extraction adsorbent according to claim 3, characterized in that: part of COD contained in the strong acid wastewater can be used as a molecular skeleton to be attached to a precipitated adsorbent precursor in the process of precipitating solids along with aluminum lithium ion coprecipitation under the action of a precipitator, so that the COD content in the waste acid water is reduced.
5. The method for producing a lithium extraction adsorbent according to claim 4, characterized in that: the precipitant is triethylamine, industrial liquid alkali or lithium hydroxide solution with the concentration of 1mol/L-5 mol/L.
6. The method for producing a lithium extraction adsorbent according to claim 5, characterized in that: the precipitant is lithium hydroxide solution with the concentration of 1mol/L-5 mol/L.
7. The method for preparing a lithium extraction adsorbent according to claim 1, characterized in that: adding strong acid water and precipitant into the reaction bottle, and controlling the temperature between 15 and 50 ℃.
8. The method for preparing a lithium extraction adsorbent according to claim 1, characterized in that: the adhesive is a single component solvent type polymer or a multi-component solvent type polymer.
9. The method for preparing a lithium extraction adsorbent according to claim 8, wherein: the polymer is one or a mixture of more of ethylene chloride-vinyl acetate copolymer, polyformaldehyde, polyvinyl pyrrolidone, polyvinyl chloride, perchloroethylene and epoxy resin, and the mixture is uniformly fused with an organic solvent according to the ratio of 1:12.
10. The method for preparing a lithium extraction adsorbent according to claim 9, characterized in that: the organic solvent is one or more of chlorobenzene, cyclohexanone, toluene, xylene, ethyl acetate, dichloroethane and chloroform.
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