CN114768775A - Preparation method of lithium adsorption material - Google Patents
Preparation method of lithium adsorption material Download PDFInfo
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- CN114768775A CN114768775A CN202210382624.9A CN202210382624A CN114768775A CN 114768775 A CN114768775 A CN 114768775A CN 202210382624 A CN202210382624 A CN 202210382624A CN 114768775 A CN114768775 A CN 114768775A
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Abstract
The invention provides a preparation method of a lithium adsorption material, which comprises the following steps: mixing the lithium adsorbent powder, the adhesive and the pore-forming agent, and then extruding and granulating by using an extruder to obtain a lithium adsorbing material; wherein the pore-forming agent comprises volatile organic compounds. According to the invention, a volatile organic compound is selected as a pore-forming agent, the pore-forming agent is uniformly mixed into lithium adsorbent powder by virtue of the super-strong shearing force and extrusion force of an extruder, and gas is rapidly volatilized in a high-temperature environment in an extrusion process to generate gas, so that the lithium adsorbent material has a porous structure, and thus has higher pores, specific surface area and stronger liquid absorption property, and meanwhile, the lithium adsorbent powder in the lithium adsorbent material has a porous structure formed by volatilization of a specific pore-forming agent without introducing an additional porous carrier, so that the occupation ratio of the lithium adsorbent powder in the lithium adsorbent material can be higher; based on the performances, the lithium adsorption material has higher adsorption equivalent weight, and is beneficial to reducing the lithium extraction cost of the brine.
Description
Technical Field
The invention relates to the technical field of lithium extraction, in particular to a preparation method of a lithium adsorption material.
Background
With the application of metallic lithium and its compounds in many fields such as materials and new energy, the demand of metallic lithium is increasing, and the traditional lithium extraction from lithium ore can not meet the market demand. Lithium in nature is also present in salt lake brine, and reserves are more abundant, so that the extraction of lithium from the salt lake becomes a main way for obtaining lithium in the future. The adsorption method is one of the common methods for extracting lithium from salt lakes, wherein a lithium adsorbent is used as an active ingredient for extracting lithium and is used in a large amount, so that the adsorption method becomes a key in the lithium extraction technology by the adsorption method.
Currently, a commonly used method for preparing a lithium adsorbent is to use a porous material as a carrier, granulate the porous material with adsorbent particles and a binder, and distribute the adsorbent particles in pores and surfaces of the porous material, wherein the ratio of the porous material in the lithium adsorbent prepared in this way is usually above 10%, resulting in a low effective content of active substances such as adsorbent particles, which affects the adsorption effect of the lithium adsorbent; in addition, the preparation method has complicated working procedures during granulation, and is not beneficial to large-scale industrial production. In addition, the adhesive adopted in the mode is usually an aqueous adhesive, and the aqueous adhesive is easy to age and crack in brine, so that the lithium adsorbent is ineffective, and the lithium extraction efficiency is influenced.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a lithium adsorbing material, and aims to solve the problem that the lithium adsorbing material prepared by the traditional preparation process is low in adsorption efficiency.
In order to achieve the purpose, the invention provides a preparation method of a lithium adsorbing material, which comprises the following steps:
mixing the lithium adsorbent powder, the adhesive and the pore-forming agent, and then extruding and granulating by using an extruder to obtain a lithium adsorbing material;
wherein the pore-forming agent comprises volatile organic compounds.
Optionally, the pore former comprises at least one of an alkane, an alkene, an alcohol, an aldehyde, an ether, a ketone, an aromatic hydrocarbon, and a halogenated hydrocarbon.
Optionally, the pore former comprises at least one of ethanol, isopropanol, and n-butanol.
Optionally, the weight ratio of the lithium adsorbent powder to the pore-forming agent is (90-95): (5-20).
Optionally, when performing extrusion granulation, the temperature range of the extruder is 100-260 ℃.
Optionally, the binder comprises PVDF; alternatively, the first and second liquid crystal display panels may be,
the adhesive includes PVDF and a first material including at least one of SBR, CMC, PVC, ABS, PPA 6.
Optionally, the lithium adsorbent powder comprises LiCl 2al (oh)3·nH2O。
Optionally, the weight ratio of the lithium adsorbent powder to the adhesive is (90-95): (2-5).
Optionally, the extruder is a twin screw extruder.
Optionally, after the step of performing extrusion granulation by using an extruder, the method further comprises:
and cooling the extruded material obtained by extrusion, and drying at 100-150 ℃ to obtain the lithium adsorbing material.
In the technical scheme provided by the invention, a volatile organic compound is selected as a pore-forming agent, the pore-forming agent is uniformly mixed into lithium adsorbent powder by utilizing the superstrong shearing force and extrusion force of an extruder, and the lithium adsorbent has a porous structure by vaporization expansion in a high-temperature environment in an extrusion process, so that the lithium adsorbent has higher pores, specific surface area and stronger liquid absorption property, and meanwhile, the lithium adsorbent has a porous structure formed by volatilization of a specific pore-forming agent without introducing an additional porous carrier, so that the lithium adsorbent in the lithium adsorbent can have a higher proportion; based on the performances, the lithium adsorption material has higher adsorption equivalent weight, and is beneficial to reducing the lithium extraction cost of the brine. The preparation method has simple process, easy operation and low granulation cost, and is more beneficial to industrial production.
In addition, based on the method, when the adhesive is selected, a non-aqueous adhesive such as PVDF (polyvinylidene fluoride) can be selected, so that the prepared lithium adsorbing material is not easily influenced by brine when used for extracting lithium from brine, and the service life of the material is prolonged.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other relevant drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is an electron microscope image of a lithium adsorbing material prepared by the preparation method of the lithium adsorbing material provided by the invention at a magnification of 3K;
fig. 2 is an electron microscope image of the lithium adsorbing material prepared by the method for preparing the lithium adsorbing material provided by the invention at a magnification of 50K.
The implementation, functional features and advantages of the present invention will be further described with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments.
It should be noted that those who do not specify specific conditions in the examples were performed under the conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between the various embodiments may be combined with each other, but must be based on the realization of the capability of a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
Currently, a commonly used method for preparing a lithium adsorbent is to use a porous material as a carrier, granulate the porous material with adsorbent particles and a binder, and distribute the adsorbent particles in pores and surfaces of the porous material, wherein the ratio of the porous material in the lithium adsorbent prepared in this way is usually above 10%, which results in a low effective content of active substances such as the adsorbent particles, and affects the adsorption effect of the lithium adsorbent; and the preparation method has complicated working procedures during granulation, and is not beneficial to large-scale industrial production. In addition, the adhesive adopted in the mode is usually an aqueous adhesive, and the aqueous adhesive is easy to age and crack in brine, so that the lithium adsorbent is ineffective, and the lithium extraction efficiency is influenced.
In view of this, the present invention provides a method for preparing a lithium adsorbing material, including the steps of:
step S100, mixing the lithium adsorbent powder, the adhesive and the pore-forming agent, and then extruding and granulating by using an extruder to obtain a lithium adsorbing material; wherein the pore-forming agent comprises volatile organic compounds.
In the present invention, the volatile organic compound means various organic compounds having a boiling point of 50 to 260 ℃ at normal temperature. The volatile organic compound has volatility in a certain temperature range, and the volatile organic compound is used as a pore-forming agent to be mixed with the lithium adsorbent powder and the adhesive; meanwhile, an extrusion process is adopted, on one hand, the pore-forming agent is uniformly mixed into the lithium adsorbent powder by utilizing the super-strong shearing force and the extrusion force of an extruder, the dispersion uniformity of the pore-forming agent in the lithium adsorbent powder is improved, and further, the distribution uniformity of pores is improved, on the other hand, the pore-forming agent is quickly volatilized to generate gas by utilizing a high-temperature environment accompanying the extrusion process, as shown in figures 1 and 2, so that the prepared lithium adsorption material has a porous structure, the porosity is more than 70%, a plurality of pores are uniformly distributed, and the prepared lithium adsorption material has high pores, a high specific surface area and high liquid absorption performance; meanwhile, the lithium adsorbing material is a porous structure formed by volatilization of a specific pore-forming agent, and no additional porous carrier is introduced, so that compared with the traditional method of using a porous material as a carrier, the method disclosed by the invention can ensure that the proportion of lithium adsorbent powder in the lithium adsorbing material is higher, namely the content of active ingredients with adsorption activity in the material is higher. In conclusion, the lithium adsorbing material prepared by the method has higher adsorption equivalent weight and high adsorption efficiency, and is beneficial to reducing the lithium extraction cost of the brine. In addition, the volatile organic compound is liquid, so that the volatile organic compound is more beneficial to being uniformly mixed with the lithium adsorbent powder and the adhesive, dense, small and uniform pores are formed at all positions of the material, and the adsorption efficiency of the lithium adsorption material is improved.
In addition, the preparation method has simple process, easy operation and low granulation cost, and is more beneficial to industrial production.
Wherein the lithium adsorbent powder comprises LiCl 2Al (OH)3·nH2O (basic lithium aluminum chloride), namely, basic lithium aluminum chloride is taken as a main adsorption component.
Wherein, the pore-forming agent comprises at least one of alkane, olefin, alcohol, aldehyde, ether, ketone, aromatic hydrocarbon and halogenated hydrocarbon. Specifically, the volatile organic compound may be an alkane, an alkene, an alcohol, an aldehyde, an ether, a ketone, an aromatic hydrocarbon, a halogenated hydrocarbon, or the like, and in actual use, any one of the above-listed organic compounds may be used as the pore-forming agent, or a combination of any two or more of the above-listed volatile organic compounds may be used as the pore-forming agent.
Furthermore, the pore-forming agent comprises at least one of ethanol, isopropanol and n-butyl alcohol, compared with other pore-forming agent selections, the ethanol, the isopropanol and the n-butyl alcohol have good volatility and belong to an environment-friendly organic solvent, and the pore-forming agent uses at least one of the ethanol, the isopropanol and the n-butyl alcohol as the pore-forming agent, so that the environment pollution can be avoided, the environment is protected, the production cost for environment protection is reduced, and the health of production personnel is facilitated.
The weight ratio of the lithium adsorbent powder to the pore-forming agent is (90-95): (5-20). When the addition amount of the pore-forming agent is too much, on one hand, the extrusion effect is affected, so that the uniformity of the pore structure of the product is reduced, and on the other hand, the product forming is also affected, and on the basis, the embodiment limits that 5-20 parts of the pore-forming agent is correspondingly added to every 90-95 parts of the lithium adsorbent powder, so that the adsorption performance of the product is improved as much as possible under the condition of ensuring the product forming and stable performance. Further, in this embodiment, the weight of the pore-forming agent is preferably: and adding 9-11 parts of pore-forming agent to every 90-95 parts of lithium adsorbent powder.
The weight ratio of the lithium adsorbent powder to the adhesive is (90-95): (2-5). Based on the mixture ratio, the lithium adsorbing material prepared by the process comprises the following components in percentage by weight: 90-95% of lithium adsorbent powder, 2-5% of adhesive and 1-5% of water (water is introduced by a cooling process, natural adsorption of water in air and the like). The process reduces the content limitation on the lithium adsorbent powder and the adhesive, so that the product can contain 90-95% of the lithium adsorbent powder, the content of effective adsorption components is far higher than that of the traditional preparation method, the adsorption equivalent is higher, and the adsorption efficiency is better.
In actual application, any common extruder in the market can be selected for extrusion granulation. Preferably, in this embodiment, the extruder is a twin-screw extruder. Compared with other extruders, the double-screw extruder has higher production efficiency and best extrusion effect, and can create a high-temperature environment enough for volatilizing the pore-forming agent.
And when extrusion granulation is carried out, the segmented temperature range of the extruder is 100-260 ℃. By setting the temperature range, the requirements on equipment of the extruder are not too high, too heavy burden on the extruder is not caused, and the requirements on full volatilization of the pore-forming agent and good extrusion effect of the extrudate can be met.
In addition, based on the method, when the adhesive is selected, a non-aqueous adhesive such as PVDF can be selected, so that the prepared lithium adsorption material is not easily influenced by brine when being used for extracting lithium from the brine, and the service life of the material is prolonged. Specifically, in this embodiment, the adhesive may be selected as follows: the binder comprises PVDF (polyvinylidene fluoride); alternatively, the adhesive comprises PVDF and a first material comprising at least one of SBR (styrene butadiene rubber), CMC (sodium carboxymethylcellulose), PVC (polyvinyl chloride), ABS (acrylonitrile butadiene styrene copolymer), PPA6 (nylon material). In other words, the adhesive may be one or more of SBR, CMC, PVDF, PVC, ABS, PPA6, and the adhesive necessarily contains PVDF.
Further, the method further comprises, after the step of performing extrusion granulation using an extruder:
and step S10, cooling the extruded material obtained by extrusion, and drying at 100-150 ℃ to obtain the lithium adsorption material.
Specifically, the step S100 may be performed as follows in actual operation: mixing the lithium adsorbent powder, the adhesive and the pore-forming agent, and then extruding and granulating by using an extruder to obtain an extrudate; and cooling the extrudate, and drying at 100-150 ℃ to obtain the lithium adsorbing material. Wherein, when cooling, air cooling or liquid cooling can be adopted; after the cooling, can use the pelleter to cut grain to the extrudate after the cooling, make the particulate matter, the particle size of particulate matter can be 1 ~ 4mm, and continuous gyro wheel pelleter can be chooseed for use to the pelleter. It should be noted that, a die design may also be utilized, and after extrusion, particles are obtained by direct granulation, and then cooling is performed. In addition, after cooling, drying is carried out at 100-150 ℃, so that on one hand, moisture in the material can be removed, the moisture content of the product can reach the preset requirement (for example, 1-5% of water), and on the other hand, the drying can also volatilize the residual pore-forming agent, thereby avoiding pollution to lithium salt in the subsequent lithium extraction process. Wherein, the drying step can be carried out by adopting a disc dryer or a belt dryer, the drying efficiency is high, and the industrial production is facilitated.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1
S1, selecting materials:
the lithium adsorbent powder is LiCl.2Al (OH)3·nH2O; the adhesive is PVDF; the pore-forming agent is ethanol; the weight ratio of the lithium adsorbent powder, the adhesive and the pore-forming agent is 92:3: 5.
S2, putting the materials into a high-speed mixer, and mixing for 15min at the rotating speed of 1500rpm to obtain a uniform mixed material.
S3, adding the mixed materials into a double-screw extruder, and setting the parameters of the extruder as follows: the temperature of the first section is 120 ℃, the temperature of the second section is 160 ℃, the temperature of the third section is 180 ℃, the temperature of the fourth section is 220 ℃, the temperatures of the fifth, sixth and seventh sections in sequence are all 220 +/-5 ℃, and the temperature of a die head is 240 ℃. And (4) obtaining an extruded strip through extrusion treatment, and cooling the extruded strip through water. The first section to the sixth section refer to six temperature zones which are distributed in sequence along the feeding direction.
And S4, using a roller granulator to granulate the extruded strips at the rotation speed of 1200rpm to obtain adsorbent particles with the particle size of 1-4 mm.
S5, drying the adsorbent particles at 120 ℃ by using a disc dryer to obtain the lithium adsorbent material with the porosity of more than 70%, wherein in the lithium adsorbent material, the content of the lithium adsorbent powder is 90% -95%, the content of the binder is 2% -5%, and the content of water is 1% -5%.
Example 2
The procedure was as in example 1 except that "the weight ratio of the lithium adsorbent powder, the binder and the pore-forming agent was adjusted to 92:3: 5" and "the weight ratio of the lithium adsorbent powder, the binder and the pore-forming agent was adjusted to 92:3: 6".
Example 3
The procedure was as in example 1 except that "the weight ratio of the lithium adsorbent powder, the binder and the pore-forming agent was adjusted to 92:3: 5" and "the weight ratio of the lithium adsorbent powder, the binder and the pore-forming agent was adjusted to 92:3: 7".
Example 4
The procedure was carried out in the same manner as in example 1 except that "the weight ratio of the lithium adsorbent powder to the binder to the pore-forming agent" was adjusted to 92:3:5 ", and" the weight ratio of the lithium adsorbent powder to the binder to the pore-forming agent "was adjusted to 92:3: 8".
Example 5
The procedure was as in example 1 except that "the weight ratio of the lithium adsorbent powder, the binder and the pore-forming agent was adjusted to 92:3: 5" and "the weight ratio of the lithium adsorbent powder, the binder and the pore-forming agent was adjusted to 92:3: 9".
Example 6
The procedure was carried out in the same manner as in example 1 except that "the weight ratio of the lithium adsorbent powder to the binder to the pore-forming agent" was adjusted to 92:3:5 ", and" the weight ratio of the lithium adsorbent powder to the binder to the pore-forming agent "was adjusted to 92:3: 10".
Example 7
The procedure was as in example 1 except that "the weight ratio of the lithium adsorbent powder, the binder and the pore-forming agent was adjusted to 92:3: 5" and "the weight ratio of the lithium adsorbent powder, the binder and the pore-forming agent was adjusted to 92:3: 11".
Example 8
The procedure was as in example 1 except that "the weight ratio of the lithium adsorbent powder, the binder and the pore-forming agent was adjusted to 92:3: 5" and "the weight ratio of the lithium adsorbent powder, the binder and the pore-forming agent was adjusted to 92:3: 12".
Example 9
The procedure was carried out in the same manner as in example 1 except that "the weight ratio of the lithium adsorbent powder to the binder to the pore-forming agent" was adjusted to 92:3:5 ", and" the weight ratio of the lithium adsorbent powder to the binder to the pore-forming agent "was adjusted to 92:3: 13".
Example 10
The procedure was as in example 1 except that "the weight ratio of the lithium adsorbent powder, the binder and the pore-forming agent was adjusted to 92:3: 5" and "the weight ratio of the lithium adsorbent powder, the binder and the pore-forming agent was adjusted to 92:3: 14".
Example 11
The procedure was as in example 1 except that "the weight ratio of the lithium adsorbent powder, the binder and the pore-forming agent was adjusted to 92:3: 5" and "the weight ratio of the lithium adsorbent powder, the binder and the pore-forming agent was adjusted to 92:3: 15".
Example 12
The procedure was carried out in the same manner as in example 1 except that "the weight ratio of the lithium adsorbent powder to the binder to the pore-forming agent" was adjusted to 92:3:5 ", and" the weight ratio of the lithium adsorbent powder to the binder to the pore-forming agent "was adjusted to 92:3: 20".
Example 13
The procedure of example 1 was repeated except that the type of the pore-forming agent was changed from ethanol to a mixture of isopropyl alcohol and n-butyl alcohol (volume ratio: 1).
Example 14
The procedure of example 1 was repeated except that the type of the binder was changed from PVDF to a mixture of PVDF, SBR and CMC (weight ratio: 1: 1).
Example 15
The procedure was as in example 1 except that the type of the adhesive was changed from PVDF to a mixture of PVDF, PVC, ABS and PPA6 (weight ratio: 1:1: 1).
Example 16
The procedure of example 1 was repeated, except that the first stage temperature of the extruder in S3 was adjusted to 100 ℃ and the die temperature was adjusted to 260 ℃.
Example 17
The same procedure as in example 1 was repeated except that the drying temperature in S5 was adjusted from 120 ℃ to 100 ℃.
Example 18
The same procedure as in example 1 was repeated except that the drying temperature in S5 was adjusted from 120 ℃ to 150 ℃.
Comparative example 1
Mixing Al (OH)3Adding the powder and LiOH solution into a sand mill according to the Li/Al molar ratio of 0.6 for sand milling activation for 1.5h, then dropwise adding hydrochloric acid at the speed of 15mL/min, controlling the reaction temperature at 75 ℃, adjusting the pH value to 5.5, aging for 1h, filtering the solid, then washing the solid twice with slurry, drying and crushing the solid to obtain the lithium adsorbent powder.
Preparing 25 wt% aqueous solution of lithium adsorbent powder, adding carboxymethyl cellulose (CMC) as water-based binder in an amount of 2 wt% of the lithium adsorbent powder, and stirring while adding to obtain a mixed solution of the adsorbent powder and the water-based binder. 5g of polyurethane foam with the porosity of 85 percent is immersed in the solution, the foam is given a certain pressure to fully absorb the solution, and then the solution is dried in a vacuum oven at the temperature of 80 ℃ to obtain the lithium adsorbent with uniformly distributed lithium adsorbent powder.
According to calculation, the adsorbent powder accounts for 74.90 wt%, the water-based adhesive accounts for 1.50 wt%, and the porous material accounts for 23.60 wt% in the lithium adsorbent.
Comparative example 2
The same procedure as in example 1 was repeated except that "the mixture was baked at 240 ℃ to obtain a lump-shaped adsorbent material, and the lump-shaped adsorbent material was crushed by a crusher to obtain adsorbent particles" in S3.
The lithium adsorbing materials prepared in the above examples and comparative examples were subjected to performance tests.
(1) Adsorption equivalent and desorption equivalent of lithium-adsorbing material
20L of salt solution containing 5mol/L of sodium chloride and 250ppm of lithium ions is prepared and used for simulating salt lake brine.
The lithium adsorbents obtained in the above examples and comparative examples were each taken at 1 kg. Placing a lithium adsorption material in the salt solution, and soaking for 4.5 h; then, taking out the lithium adsorption material, putting the lithium adsorption material into 20L of deionized water for soaking and desorbing for 4.5h, detecting the lithium element difference value in the adsorbed salt solution and the lithium element difference value in the desorbed deionized water, and then calculating the adsorption equivalent weight and the desorption equivalent weight of the lithium adsorption material. The results are reported in table 1 below.
(2) The lithium adsorbing materials prepared in the examples and the comparative examples are respectively marked, and then are soaked in a sodium chloride solution with the concentration of 5mol/L for 3 months (namely 90 days), then the lithium adsorbing materials are taken out and placed in a vibration table to vibrate for 7 days, then the powder dropping rate is calculated, and the strength of the lithium adsorbing materials is judged according to the powder dropping rate.
TABLE 1 Performance test
And (4) analyzing results:
firstly, as can be seen from the adsorption equivalent and the desorption equivalent, each example shows higher adsorption equivalent and desorption equivalent than those of the comparative example, which shows that the lithium adsorption material prepared by the method has higher adsorption performance and good adsorption and desorption effects on lithium; secondly, as can be seen from the comparison of the powder dropping rate, the lithium adsorbing material in each example has lower powder dropping rate compared with the comparative example, which shows that the lithium adsorbing material prepared by the method has higher strength and stability and longer service life in brine.
The above are only preferred embodiments of the present invention, and do not limit the scope of the present invention, and it is obvious to those skilled in the art that various modifications and variations can be made in the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (10)
1. The preparation method of the lithium adsorbing material is characterized by comprising the following steps of:
mixing the lithium adsorbent powder, the adhesive and the pore-forming agent, and then extruding and granulating by using an extruder to obtain a lithium adsorbing material;
wherein the pore-forming agent comprises volatile organic compounds.
2. The method for preparing a lithium-adsorbing material according to claim 1, wherein the pore-forming agent comprises at least one of an alkane, an olefin, an alcohol, an aldehyde, an ether, a ketone, an aromatic hydrocarbon, and a halogenated hydrocarbon.
3. The method for preparing a lithium-adsorbing material according to claim 2, wherein the pore-forming agent comprises at least one of ethanol, isopropanol, and n-butanol.
4. The method for preparing the lithium adsorbent according to claim 1, wherein the weight ratio of the lithium adsorbent powder to the pore-forming agent is (90-95): (5-20).
5. The method for producing a lithium-adsorbing material according to claim 1, wherein the temperature range of the extruder in the stage of extrusion granulation is 100 to 260 ℃.
6. The method for producing a lithium-adsorbing material according to claim 1, wherein the binder comprises PVDF; alternatively, the first and second electrodes may be,
the adhesive includes PVDF and a first material including at least one of SBR, CMC, PVC, ABS, PPA 6.
7. The method for preparing a lithium adsorbent according to claim 1, wherein the lithium adsorbent powder comprises licl.2al (oh)3·nH2O。
8. The method for preparing the lithium adsorbent material according to claim 1, wherein the weight ratio of the lithium adsorbent powder to the binder is (90-95): (2-5).
9. The method for producing a lithium-adsorbing material according to claim 1, wherein the extruder is a twin-screw extruder.
10. The method for preparing a lithium-adsorbing material according to claim 1, further comprising, after the step of performing extrusion granulation using an extruder:
and cooling the extruded material obtained by extrusion, and drying at 100-150 ℃ to obtain the lithium adsorbing material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115738892A (en) * | 2022-11-30 | 2023-03-07 | 中国科学院青海盐湖研究所 | Spherical combined lithium adsorbent and granulation method thereof |
| US11918971B1 (en) | 2023-08-11 | 2024-03-05 | Sunresin New Materials Co. Ltd. | Lithium adsorbent and preparation method therefor |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004025113A (en) * | 2002-06-27 | 2004-01-29 | Ind Technol Res Inst | Method of adsorbing lithium ion from lithium-containing aqueous solution with adsorbent |
| US20140239224A1 (en) * | 2009-11-13 | 2014-08-28 | Simbol Inc. | Sorbent for Lithium Extraction |
| CN108745276A (en) * | 2018-04-18 | 2018-11-06 | 南京工业大学 | A kind of preparation method of mixed-forming lithium ion adsorbent |
| CN108940181A (en) * | 2018-06-12 | 2018-12-07 | 南京工业大学 | A kind of titanium-type lithium ion sieve adsorbant and application |
| CN109225121A (en) * | 2018-08-27 | 2019-01-18 | 石河子大学 | The preparation method and brine of compound adsorbent propose lithium method |
| CN109225124A (en) * | 2018-11-09 | 2019-01-18 | 华东理工大学 | A kind of preparation method of particle lithium adsorbent |
| CN111215040A (en) * | 2020-01-10 | 2020-06-02 | 西安蓝深环保科技有限公司 | Preparation method of lithium extraction adsorbent |
| CN113351155A (en) * | 2021-06-11 | 2021-09-07 | 清华大学 | Adsorbing material and preparation method and application thereof |
-
2022
- 2022-04-12 CN CN202210382624.9A patent/CN114768775B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004025113A (en) * | 2002-06-27 | 2004-01-29 | Ind Technol Res Inst | Method of adsorbing lithium ion from lithium-containing aqueous solution with adsorbent |
| US20140239224A1 (en) * | 2009-11-13 | 2014-08-28 | Simbol Inc. | Sorbent for Lithium Extraction |
| CN108745276A (en) * | 2018-04-18 | 2018-11-06 | 南京工业大学 | A kind of preparation method of mixed-forming lithium ion adsorbent |
| CN108940181A (en) * | 2018-06-12 | 2018-12-07 | 南京工业大学 | A kind of titanium-type lithium ion sieve adsorbant and application |
| CN109225121A (en) * | 2018-08-27 | 2019-01-18 | 石河子大学 | The preparation method and brine of compound adsorbent propose lithium method |
| CN109225124A (en) * | 2018-11-09 | 2019-01-18 | 华东理工大学 | A kind of preparation method of particle lithium adsorbent |
| CN111215040A (en) * | 2020-01-10 | 2020-06-02 | 西安蓝深环保科技有限公司 | Preparation method of lithium extraction adsorbent |
| CN113351155A (en) * | 2021-06-11 | 2021-09-07 | 清华大学 | Adsorbing material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| JAE-WON LEE: "Highly crystalline lithium–manganese spinel prepared by a hydrothermal process with co-solvent", 《JOURNAL OF POWER SOURCES》, vol. 196 * |
| 罗绍华: "造粒工艺制备LiFePO4/C复合正极材料及其性能", 《电源技术》, no. 12 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115738892A (en) * | 2022-11-30 | 2023-03-07 | 中国科学院青海盐湖研究所 | Spherical combined lithium adsorbent and granulation method thereof |
| US11918971B1 (en) | 2023-08-11 | 2024-03-05 | Sunresin New Materials Co. Ltd. | Lithium adsorbent and preparation method therefor |
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