CN115594223A - Modified lithium ion sieve, manganese dioxide adsorbent, preparation method and application of manganese dioxide adsorbent, and method for extracting lithium from salt lake - Google Patents
Modified lithium ion sieve, manganese dioxide adsorbent, preparation method and application of manganese dioxide adsorbent, and method for extracting lithium from salt lake Download PDFInfo
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Abstract
The invention discloses a modified lithium ion sieve, a manganese dioxide adsorbent, a preparation method and application thereof, and a method for extracting lithium from a salt lake, and belongs to the technical field of metallurgy. The modified lithium ion sieve is MnO with a three-dimensional layered framework structure 2 The nano sheet material has larger specific surface area and stable layered structure, can provide more adsorption sites and shorter ion diffusion distance for Li + The adsorption capacity is large, the adsorption efficiency is high,is favorable for prolonging the cycle life of the adsorbent. The manganese dioxide adsorbent or chromatographic column further obtained by the modified lithium ion sieve has higher lithium adsorption capacity and longer service life, and is suitable for extracting lithium from salt lakes.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a modified lithium ion sieve, a manganese dioxide adsorbent, a preparation method and application thereof, and a method for extracting lithium from a salt lake.
Background
The lithium resource has wide application in the related fields of lithium ion batteries and the like, along with the rapid development of the lithium ion battery industry, the demand of the industrial production for the lithium resource is increased more and more rapidly, and even the situation that the supply of the lithium raw material is short of the demand has appeared in recent years.
The reserve of lithium resources in China is relatively large, and the lithium resources are mainly concentrated in salt lakes in Tibet and Qinghai regions, so how to efficiently and quickly extract lithium elements from the salt lakes is a scientific problem to be solved.
The content of lithium in the salt lake is low, the content of magnesium and other metals is high, and the difficulty of selectively extracting lithium resources from the salt lake is high due to the similar properties of magnesium and lithium. In the past, the methods for extracting lithium from salt lakes mainly include precipitation, calcination leaching, carbonization, nanofiltration, solvent extraction, adsorption and the like, wherein the adsorption method uses a lithium ion sieve to adsorb lithium ions, and is considered to be a promising method for extracting lithium from salt lakes due to large adsorption capacity and high selectivity.
The lithium ion can be classified into a metal oxide Type (TiO) according to its chemical composition 2 Or MnO 2 MO for short and metal phosphate type (MPO) 4 And M is Fe, mn or Ti, abbreviated as MPO). Compared with the latter, the MO type ion sieve has better adsorption effect on lithium and has certain industrial benefitTherefore, the method is gradually applied to the field of lithium extraction in salt lakes.
However, the traditional MO-based ion sieve has low lithium adsorption capacity and short cycle life.
In view of this, the invention is particularly proposed.
Disclosure of Invention
It is an object of the present invention to provide a modified lithium ion sieve which is resistant to Li + The adsorption capacity is large, the adsorption efficiency is high, and the cycle life of the adsorbent is prolonged.
The second purpose of the invention is to provide a preparation method of the modified lithium ion sieve.
The invention also aims to provide a manganese dioxide adsorbent containing the modified lithium ion sieve.
The fourth object of the present invention is to provide a method for preparing the manganese dioxide adsorbent.
The fifth object of the present invention is to provide a chromatographic column containing the manganese dioxide adsorbent.
The invention also aims to provide the application of the modified lithium ion sieve or manganese dioxide adsorbent in extracting lithium elements.
The seventh purpose of the invention is to provide a method for extracting lithium from a salt lake.
The application can be realized as follows:
in a first aspect, the present application provides a modified lithium ion sieve which is MnO of a three-dimensional layered framework structure 2 A nanosheet material.
In an alternative embodiment, the modified lithium ion sieve comprises multiple layers of MnO 2 The nanosheets are sequentially arranged in a main structure at intervals, and adjacent two layers of MnO are arranged 2 And a supporting framework is arranged between the nano sheets.
In alternative embodiments, mnO 2 The specific surface area of the nano sheet material is not less than 75m 2 /g。
In alternative embodiments, two adjacent layers of MnO 2 The gap between the nano sheets is more than 0nm and less than or equal to 100nm.
In a second aspect, the present application provides a method of preparing a modified lithium ion sieve according to the previous embodiment, comprising the steps of:
a is to be x MnO 2 The material is subjected to acid treatment, solid-liquid separation and drying to obtain HMnO 2 A material; wherein A is an alkali metal element, and x is more than 0 and less than 1;
HMnO 2 Mixing the material with an aqueous solution of a proppant, performing ultrasonic treatment, collecting nanosheet material to obtain MnO 2 A nanosheet.
In an alternative embodiment, A x MnO 2 The material is prepared by the following method: an alkali metal compound is mixed with an oxide of manganese and calcined.
In an alternative embodiment, the oxide of manganese comprises MnO 2 、Mn 2 O 3 And Mn 3 O 4 At least one of (1).
In alternative embodiments, the alkali metal in the alkali metal compound comprises at least one of lithium, sodium, and potassium.
In an alternative embodiment, the molar amount of alkali metal in the alkali metal compound does not exceed the molar amount of manganese in the oxide of manganese.
In an alternative embodiment, the molar ratio of alkali metal in the alkali metal compound to manganese in the oxide of manganese is from 0.5 to 0.8.
In an alternative embodiment, the calcination temperature is 700 to 1200 deg.C, preferably 800 to 1000 deg.C.
In an alternative embodiment, the calcination time is from 6 to 24 hours, preferably from 12 to 18 hours.
In alternative embodiments, pair A x MnO 2 The acid treatment of the material is carried out with an acid concentration of 0.1 to 6mol/L, preferably 0.3 to 1.5mol/L.
In an alternative embodiment, A x MnO 2 The solid-to-liquid ratio of the material to the acid is 1g:1-10mL; preferably 1g:2-5mL.
In an alternative embodiment, the acid treatment time is from 0.1 to 24 hours, preferably from 1 to 6 hours;
in an alternative embodiment, the drying temperature is 40-80 ℃, preferably 50-70 ℃;
in an alternative embodiment, the drying time is between 3 and 18h, preferably between 6 and 15h.
In an alternative embodiment, the concentration of proppant in the aqueous solution of proppant is from 0.01 to 5g/L, preferably from 0.1 to 3g/L.
In an alternative embodiment, HMnO 2 The solid-to-liquid ratio of the material to the aqueous solution of the proppant is 10-100g:1L, preferably 20 to 50g:1L of the compound.
In an alternative embodiment, the proppant comprises an organic ammonium species, preferably comprising at least one of tetra-n-butylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide.
In an alternative embodiment, the sonication time is between 0.5 and 24h, preferably between 1 and 6h.
In an alternative embodiment, collecting the nanoplatelet material comprises: centrifuging the material obtained after ultrasonic treatment at low speed, collecting the upper suspension to obtain deprotonated MnO 2 A nanosheet material.
In an alternative embodiment, collecting the nanoplatelet material further comprises: mnO to deprotonate 2 Centrifuging the nanosheet material at high speed, and collecting the solid phase to obtain MnO 2 Nanosheets.
In an alternative embodiment, after collecting the solid phase, drying the solid phase is further included.
In an alternative embodiment, the rotation speed of the low-speed centrifugation is 3000-10000r/min, preferably 5000-8000r/min.
In an alternative embodiment the rotation speed of the high speed centrifugation is 10000-20000r/min, preferably 14000-18000r/min.
In an alternative embodiment, the temperature at which the solid phase is dried is 40-80 deg.C, preferably 50-70 deg.C.
In an alternative embodiment, the solid phase is dried for a period of time ranging from 3 to 18 hours, preferably from 6 to 12 hours.
In a third aspect, the present application provides a manganese dioxide adsorbent that is an agglomerate of the modified lithium ion sieve of the previous embodiment and a binder.
In an alternative embodiment, the agglomerates are particulate matter having a particle size in the order of millimeters.
In a fourth aspect, the present application provides a method for preparing manganese dioxide adsorbent as in the previous embodiments, comprising the steps of: the modified lithium ion sieve according to the previous embodiment is mixed with a binder and an organic solvent, and then transferred to an aqueous phase to obtain an agglomerate.
In an alternative embodiment, drying the agglomerates is also included.
In an alternative embodiment, the mass ratio of the modified lithium ion sieve to the binder is 5 to 100, preferably 10 to 30.
In an alternative embodiment, the binder includes at least one of sodium carboxymethylcellulose (CMC), styrene Butadiene Rubber (SBR), polyvinyl alcohol (PVA), and polyvinyl chloride (PVC), and preferably includes at least one of polyvinyl alcohol (PVA) and polyvinyl chloride (PVC).
In an alternative embodiment, the feed-to-liquid ratio of the modified lithium ion sieve to the organic solvent is 1g:0.1-12mL, preferably 1g:1-6mL.
In an alternative embodiment, the drying of the agglomerates is carried out at a temperature of 40-80 deg.C, preferably 50-70 deg.C.
In an alternative embodiment, the agglomerates are dried for a period of time ranging from 3 to 18 hours, preferably from 6 to 12 hours.
In a fifth aspect, the present application provides a chromatography column, the adsorbent of which comprises the manganese dioxide adsorbent of the previous embodiment.
In an alternative embodiment, the manganese dioxide adsorbent is packed in the column in an amount of 30-80% by volume of the column.
In a sixth aspect, the present application provides the use of a modified lithium ion sieve according to any one of the preceding embodiments or a manganese dioxide adsorbent according to any one of the preceding embodiments for extracting lithium element.
In an alternative embodiment, modified lithium ion sieves or manganese dioxide adsorbents are used for lithium extraction in salt lakes.
In a seventh aspect, the present application provides a method for extracting lithium from a salt lake, including the following steps: and (3) introducing salt lake brine to be extracted into a chromatographic column filled with the manganese dioxide adsorbent, washing out the manganese dioxide adsorbent after the manganese dioxide adsorbent is adsorbed and saturated, and then carrying out desorption treatment to obtain desorption discharge liquid rich in lithium.
In alternative embodiments, the flow rate of the salt lake brine through the chromatography column is 1-100mL/min, preferably 10-30mL/min.
In an alternative embodiment, the adsorption time is from 0.1 to 6h, preferably from 0.5 to 3h.
In an alternative embodiment, the desorbing agent used in the desorbing process is an acid, preferably hydrochloric acid.
In an alternative embodiment, the flow rate of the desorbing agent is from 0.1 to 50mL/min, preferably from 1 to 6mL/min.
In an alternative embodiment, the concentration of the desorbing agent is from 0.1 to 10mol/L, preferably from 0.3 to 1.5mol/L.
In an alternative embodiment, the desorption time is between 0.3 and 9h, preferably between 1 and 3h.
The beneficial effect of this application includes:
the application provides MnO with a three-dimensional layered framework structure as a modified lithium ion sieve 2 Nanosheet material, which has large specific surface area, can provide more adsorption sites and shorter ion diffusion distance, and has good Li-ion affinity + The adsorption capacity is large; in addition, the modified lithium ion sieve has a framework between the sheet layers, so that the modified lithium ion sieve has a stable layered structure, is not easy to collapse even if the volume is expanded in the using process, and further has a long cycle life.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an SEM image of a synthetic modified lithium ion sieve of example 1;
fig. 2 is an SEM spectrum of an unmodified lithium ion sieve of comparative example 1.
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. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The modified lithium ion sieve, the manganese dioxide adsorbent, the preparation method and the application thereof, and the method for extracting lithium from the salt lake, which are provided by the application, are specifically described below.
The inventor researches and proposes that the main reason for the lower lithium adsorption capacity of the traditional MO-based ionic sieve is that the traditional MO-based ionic sieve has few lithium diffusion sites; the main reasons for the short cycle life of the traditional MO-based ionic sieve are that the volume expansion rate is high and the structure collapses quickly in the using process.
Based on the above, the application creatively provides a modified lithium ion sieve which is MnO with a three-dimensional layered framework structure 2 A nanosheet material.
Referably, the MnO 2 The nanosheet material comprising a multilayer MnO 2 The nano sheets are sequentially arranged at intervals and have main body structures, and two adjacent layers of MnO are 2 And a supporting framework is arranged between the nano sheets.
In some preferred embodiments, mnO is provided herein 2 The specific surface area of the nano sheet material is not less than 75m 2 A value of,/g, for example, 75m 2 /g、78m 2 /g、80m 2 /g、82m 2 /g、84m 2 /g、86m 2 /g、88m 2 /g、91m 2 /g、92m 2 /g、95m 2 G or 98m 2 In terms of/g, etc.
In alternative embodiments, two adjacent layers of MnO 2 The gap between the nano sheets is more than 0nm and less than or equal to 100nm, such as 0.1nm, 0.5nm, 1nm, 5nm, 10nm, 20nm, 50nm, 80nm or 100nm, and the like, and can also be any value within the range of more than 0nm and less than or equal to 100nm.
Note that if two adjacent layers of MnO are present 2 Gaps between the nanosheets exceed 100nm, which easily leads to collapse of the nanosheet structure.
In summary, the modified lithium ion sieve provided by the application has a larger specific surface area, can provide more adsorption sites and a shorter ion diffusion distance, and can be used for Li + The adsorption capacity is large; in addition, the modified lithium ion sieve has a framework between the sheets, so that the modified lithium ion sieve has a stable layered structure, is not easy to collapse even if the volume of the modified lithium ion sieve expands in the using process, and further has a long cycle life.
Accordingly, the present application also provides a preparation method of the modified lithium ion sieve, which can comprise the following steps:
s1: a is to be x MnO 2 The material is subjected to acid treatment, solid-liquid separation and drying to obtain HMnO 2 A material; wherein A is an alkali metal element, and x is more than 0 and less than 1;
s2: HMnO 2 Mixing the material with an aqueous solution of a proppant, performing ultrasonic treatment, and collecting nanosheet material to obtain MnO 2 Nanosheets.
For reference, the above A in S1 x MnO 2 The material is of a nanosheet structure containing alkali metal, and can be prepared by the following method: an alkali metal compound is mixed with an oxide of manganese and calcined.
Wherein the oxide of manganese may comprise MnO, for example 2 、Mn 2 O 3 And Mn 3 O 4 At least one of (1).
The alkali metal in the alkali metal compound may include, for example, at least one of lithium, sodium, and potassium.
In some alternative embodiments, the molar amount of alkali metal in the above alkali metal compound does not exceed the molar amount of manganese in the manganese oxide, which can be understood as: the molar ratio of the alkali metal in the alkali metal compound to manganese in the manganese oxide is 0 (excluded) -1, such as 0.1; preferably 0.5 to 0.8.
It should be noted that, in the following description,if the amount of the alkali metal compound is too large, subsequent acid H is liable to be generated + Extraction of alkali metal elements and proppant replacement H + It is not thorough. If the amount of the alkali metal compound is too small, the synthesis of A tends to be difficult x MnO 2 . The dosage of the alkali metal is controlled within the range of the application, so that the A is easier to synthesize x MnO 2 On the other hand, it is advantageous to increase the content of p-Li + The amount of adsorption of (3).
For reference, the calcination after the alkali metal compound is mixed with the manganese oxide may be performed at 700 to 1200 ℃. For example, the calcination temperature may be 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, or the like, or may be any other value within the range of 700 to 1200 ℃; preferably 800-1000 deg.C.
It should be noted that if the calcination temperature exceeds 1200 ℃, other phases may be formed or the product may have other morphologies, resulting in the subsequent inability to obtain HMnO of the nanosheets 2 A material; if the calcination temperature is lower than 800 ℃, the calcination time is greatly prolonged.
Correspondingly, the calcination time after the alkali metal compound is mixed with the manganese oxide can be 6-24h, such as 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h, and the like, and can also be any other value within the range of 6-24 h; preferably 12-18h.
For reference, in S1, pairs A x MnO 2 The acid used for acid treatment of the material is a dilute acid, and may be, for example, dilute hydrochloric acid, dilute sulfuric acid, dilute nitric acid, or dilute phosphoric acid.
By the pair A x MnO 2 The material is subjected to an acid treatment with H + By displacement of A x MnO 2 Alkali metal ions (i.e. H) in the material + Occupying the original alkali metal position) to obtain HMnO 2 A material (which remains in a nanosheet structure).
If the substitution pattern is not employed, A is directly removed x MnO 2 Alkali metal in the alloy can cause the material to subsequently collapse. By H in acids + Replacement is performed to balance the charge, so that the material will not collapseAnd, the subsequent replacement of the proppant is also facilitated.
The concentration of the diluted acid can be 0.1-6mol/L, such as 0.1mol/L, 0.2mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L, 5.5mol/L or 6mol/L, and the like, and can also be any value within the range of 0.1-6mol/L; preferably 0.3 to 1.5mol/L.
If the concentration of the dilute acid is too high, the shape and the structure of the material can be damaged.
A x MnO 2 The solid-to-liquid ratio of the material to the acid may be 1 to 10mL, and may be any other value within the range of 1g to 10mL, such as 1g; preferably 1g.
If the amount of the liquid is too low, the acid cannot react with the solid A x MnO 2 The materials are in sufficient contact and cannot completely displace A x MnO 2 Alkali metal ions in the material.
In this application, for A x MnO 2 The time for the material to be subjected to acid treatment is 0.1-24h, such as 0.1h, 0.5h, 1h, 2h, 5h, 8h, 10h, 15h, 20h or 24h, and the like, and can be any value within the range of 0.1-24 h; preferably 1-6h.
For reference, pair A x MnO 2 After the material is subjected to acid treatment, solid-liquid separation can be carried out by adopting a filtration mode.
The drying process after solid-liquid separation can be carried out at 40-80 deg.C, such as 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C or 80 deg.C, or other arbitrary values within 40-80 deg.C; preferably 50-70 deg.C.
The corresponding drying time can be 3-18h, such as 3h, 5h, 8h, 10h, 12h, 15h or 18h, and the like, and can also be any other value within the range of 3-18 h; preferably 6-15h.
The higher the drying temperature, the shorter the corresponding drying time. However, too high a drying temperature may cause the destruction of the material structure.
In S2, the concentration of the proppant in the aqueous solution of the proppant may be 0.01 to 5g/L, such as 0.01g/L, 0.05g/L, 1g/L, 1.5g/L, 2g/L, 2.5g/L, 3g/L, 3.5g/L, 4g/L, 4.5g/L or 5g/L, and the like, and may be any other value within the range of 0.01 to 5g/L; preferably 0.1 to 3g/L.
HMnO 2 The solid-liquid ratio of the material to the aqueous solution of the proppant may be 10 to 100g, such as 10g; preferably 20 to 50g.
It is noted that the proppant mainly plays a supporting role and can be inserted into two adjacent layers of MnO as a supporting framework 2 Between the nano-sheets, avoiding layered MnO 2 The nanoplatelets collapsed and overlapped together.
The concentration and amount of proppant is such that it will be able to convert HMnO 2 H in the material + And (4) complete replacement. If the concentration or the content of the propping agent is too high, the benefit is low, and the material is alkaline and is not beneficial to subsequent treatment; if the concentration or content of the proppant is too low, it will result in failure to introduce HMnO 2 H in the material + And completely replaced.
Illustratively, the proppant includes organic ammonium species such as tetra-n-butylammonium hydroxide (TBAOH), tetramethylammonium hydroxide (TMAOH), tetraethylammonium hydroxide (Et) 4 NOH) and tetrapropylammonium hydroxide (TPAOH), preferably comprising tetra-n-butylammonium hydroxide.
In S2, the ultrasonic treatment time can be 0.5-24h, such as 0.5h, 1h, 2h, 5h, 8h, 10h, 12h, 15h, 18h, 20h, 22h or 24h, and the like, and can also be any other value within the range of 0.5-24 h; preferably 1-6h.
By processing of S2, HMnO can be obtained 2 The material is fully stripped and deprotonated to obtain MnO 2 A nanosheet structure.
In S3, collecting the nanosheet material may include: centrifuging the material obtained after ultrasonic treatment at low speed, collecting the upper suspension to obtain deprotonated MnO 2 A nanosheet material.
Further, deprotonated MnO 2 Nanoplatelets materialPerforming high-speed centrifugation, and collecting solid phase to obtain MnO 2 Nanosheets.
After the solid phase is collected, the solid phase may be dried.
In the process of collecting the nano sheet material, the rotating speed of the low-speed centrifugation can be 3000-8000r/min, such as 3000r/min, 4000r/min, 5000r/min, 6000r/min, 7000r/min or 8000r/min, and the like, and can also be any other value within the range of 3000-8000 r/min; preferably 5000-8000r/min.
In the process of carrying out high-speed centrifugation on the suspension, the rotating speed of the high-speed centrifugation can be 10000-20000r/min, such as 10000r/min, 12000r/min, 15000r/min, 18000r/min or 20000r/min, and the like, and can also be any other value within the range of 10000-20000 r/min; preferably 14000 to 18000r/min.
For reference, the temperature for drying the solid phase may be 40-80 deg.C, such as 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C or 80 deg.C, or any other value within the range of 40-80 deg.C; preferably 50-70 deg.C.
Correspondingly, the time for drying the solid phase substance can be 3-18h, such as 3h, 5h, 8h, 10h12h, 15h or 18h, and can also be any other value within the range of 3-18 h; preferably 6-12h.
Similarly, the higher the drying temperature, the shorter the corresponding drying time. However, too high a drying temperature may cause the material structure to be damaged, and the nanosheet structure to collapse.
In addition, the application also provides a manganese dioxide adsorbent which is an agglomerate of the modified lithium ion sieve and a binder.
Preferably, the agglomerates are particulate matter having a particle size in the order of millimeters. Illustratively, the particles may have a particle size of 1-100mm.
Correspondingly, the application also provides a preparation method of the manganese dioxide adsorbent, which comprises the following steps: the modified lithium ion sieve is mixed with a binder and an organic solvent, and then transferred into a water phase to obtain an agglomerate, so that the adsorption capacity of the modified lithium ion sieve can be improved. For reference, the mass ratio of the modified lithium ion sieve to the binder can be 5 to 100, such as 5; preferably 10-30.
If the binder is too much, the proportion of the modified lithium ion sieve in the agglomerate can be reduced, and the adsorption capacity is reduced; if the binder is too little, a better binding effect cannot be achieved, and most of the modified lithium ion sieve is in a dispersed state and cannot be effectively agglomerated.
Illustratively, the binder may include at least one of sodium carboxymethylcellulose, styrene-butadiene rubber, polyvinyl alcohol, and polyvinyl chloride, and preferably includes at least one of polyvinyl alcohol and polyvinyl chloride.
For reference, the feed-to-liquid ratio of the modified lithium ion sieve to the organic solvent may be 1g:0.1-12mL, such as 1g:0.1mL, 1g:0.5mL, 1g:1mL, 1g:2mL, 1g:5mL, 1g:8mL, 1g:10mL or 1g:12mL, etc.; preferably 1g:1-6mL.
The organic solvent may illustratively include alcohols (e.g., methanol, ethanol, etc.) or N-methylpyrrolidone, and preferably includes N-methylpyrrolidone.
The modified lithium ion sieve is slurry after being mixed with the binder and the organic solvent, particles are not easy to form, the slurry is wholly transferred into water, on one hand, the organic solvent can be removed in the drying process, high pollution of the organic solvent to the subsequent lithium extraction process is avoided, and on the other hand, the modified lithium ion sieve can be agglomerated into uniform particles under the condition of the binder.
Further, the agglomerate is dried.
The drying of the agglomerate may be carried out at 40 to 80 ℃, for example, the drying temperature may be 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, or may be any other value within the range of 40 to 80 ℃; preferably 50-70 deg.C.
The time for drying the agglomerate is 3-18h, such as 3h, 5h, 8h, 10h, 12h, 15h or 18h, and can be any value within the range of 3-18 h; preferably 6 to 12.
In addition, the present application provides a chromatography column comprising an adsorbent comprising the manganese dioxide adsorbent described above.
For reference, the loading of the manganese dioxide adsorbent in the column may be 30-80% of the column volume, such as 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80%, etc., or any other value within the range of 30-80%.
In addition, the application also provides application of the modified lithium ion sieve or the manganese dioxide adsorbent in extracting lithium elements.
For example, modified lithium ion sieves or manganese dioxide adsorbents can be used for extracting lithium from salt lakes.
Correspondingly, the application also provides a method for extracting lithium from the salt lake, which comprises the following steps: and (3) introducing salt lake brine to be extracted into a chromatographic column filled with a manganese dioxide adsorbent, washing out the manganese dioxide adsorbent after the manganese dioxide adsorbent is adsorbed and saturated, and then carrying out desorption treatment to obtain a lithium-rich desorption discharge liquid.
For reference, the flow rate of the salt lake brine introduced into the chromatographic column can be 1-100mL/min, such as 1mL/min, 2mL/min, 5mL/min, 10mL/min, 20mL/min, 50mL/min, 80mL/min or 100mL/min, and the like, and can also be any other value within the range of 1-100 mL/min; preferably 10-30mL/min.
The flow rate can ensure that the manganese dioxide absorbent is fully contacted with the salt lake brine, and if the flow rate is too high, the manganese dioxide absorbent cannot be fully contacted with the salt lake brine; if the flow rate is too small, the adsorption efficiency is lowered.
The adsorption time can be 0.1-6h, such as 0.1h, 0.2h, 0.5h, 1h, 1.5h, 2h, 5.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h, and the like, and can also be any other value within the range of 0.1-6 h; preferably 0.5-3h.
Similarly, if the adsorption time is too short, the manganese dioxide adsorbent cannot be fully contacted with the salt lake brine; if the adsorption time is too long, the adsorption efficiency is lowered.
For reference, the desorption agent used for the above desorption treatment is an acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like, preferably hydrochloric acid.
The flow rate of the desorbing agent can be 0.1-50mL/min, such as 0.1mL/min, 0.2mL/min, 0.5mL/min, 1mL/min, 2mL/min, 5mL/min, 10mL/min, 15mL/min, 2mL/min, 25mL/min, 30mL/min, 35mL/min, 40mL/min, 45mL/min, or 50mL/min, or any other value within the range of 0.1-50 mL/min; preferably 1-6mL/min.
The concentration of the desorption reagent is 0.1-10mol/L, such as 0.1mol/L, 0.mol/L, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L or 10mol/L, and the like, and can be any other value in the range of 0.1-10 mol/L; preferably 0.3 to 1.5mol/L.
The desorption time is 0.3-9h, such as 0.3h, 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h or 9h, and the like, and can also be any other value within the range of 0.3-9 h; preferably 1-3 hours.
Through desorption, the manganese dioxide adsorbent can be recycled.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
This example provides a manganese dioxide adsorbent, which can be prepared as follows:
step (1): 5g of Mn 2 O 3 With 2.35g of Na 2 CO 3 Mixing, calcining at 800 deg.C for 12h to obtain Na x MnO 2 A material;
step (2): treating 5g of the material obtained in step (1) with 15mL of 1.5mol/L dilute hydrochloric acid for 3h, filtering, and drying at 55 deg.C for 12h to obtain HMnO 2 A material;
and (3): dispersing the material (5 g) prepared in the step (2) in 200mL of TBAOH aqueous solution with the concentration of 1g/L, and maintaining ultrasonic treatment for 5h to obtain MnO stripped into nanosheets 2 A material;
and (4): centrifuging the ultrasonically treated material at low speed at 7000r/min, collecting the upper suspension, centrifuging at high speed at 16000r/min, and collecting MnO 2 Drying the nanosheet solid material at 50 deg.C for 7h to obtain solid materialSEM images of (a) are shown in fig. 1);
and (5): and (5) uniformly mixing the solid material (5 g) dried in the step (4) with 0.17g of PVC binder in 20mL of NMP solvent to prepare slurry, gradually transferring the slurry into water to enable the solid material to be agglomerated into uniform particles under the condition of the binder, and then drying the uniform particles at 55 ℃ for 12 hours to obtain the manganese dioxide adsorbent.
After the manganese dioxide adsorbent is obtained, filling the adsorbent particles into a chromatographic column (the filling amount is 50% of the volume of the chromatographic column), and circulating the chromatographic column for 2 hours at the flow rate of 20mL/min to introduce salt lake brine; and after the adsorbent is adsorbed and saturated, introducing deionized water into the column for cleaning the adsorbent, keeping the speed of 1mL/min for 3h, and introducing 0.4mol/L hydrochloric acid for desorption treatment, wherein the desorption discharge liquid is a lithium-rich solution.
Example 2
This example provides a manganese dioxide adsorbent, which can be prepared as follows:
step (1): adding 10g of MnO 2 Mixing with 6.66g of CH3COONa, and calcining at 800 ℃ for 12h to obtain Na x MnO 2 A material;
step (2): 10g of the material obtained in the step (1) is treated with 20mL of dilute hydrochloric acid with the concentration of 3mol/L for 6h, filtered and dried at 60 ℃ for 8h to obtain HMnO 2 A material;
and (3): dispersing the material (10 g) prepared in the step (2) in 200mL of TBAOH aqueous solution with the concentration of 0.1g/L, and maintaining for 4h of ultrasonic treatment to obtain MnO peeled into nanosheets 2 A material;
and (4): centrifuging the ultrasonically treated material at 6000r/min at low speed, collecting upper suspension, centrifuging at high speed at 14000r/min, and collecting MnO 2 Drying the nanosheet solid material at 65 ℃ for 8 h;
and (5): and (3) uniformly mixing the solid material (10 g) dried in the step (4) with 0.5g of PVC binder in 30mL of NMP solvent to prepare slurry, gradually transferring the slurry into water to enable the solid material to be agglomerated into uniform particles under the condition of the binder, and then performing drying treatment at 70 ℃ for 6 hours to obtain the manganese dioxide adsorbent.
After the manganese dioxide adsorbent is obtained, filling the adsorbent particles into a chromatographic column (the filling amount is 50% of the volume of the chromatographic column), and then circulating the chromatographic column for 0.5h at the flow rate of 15mL/min to introduce salt lake brine; and after the adsorbent is adsorbed and saturated, introducing deionized water into the column for cleaning the adsorbent, keeping the speed of 2mL/min for 2h, and introducing 0.3mol/L hydrochloric acid for desorption treatment, wherein the desorption discharge liquid is a lithium-rich solution.
Example 3
This example provides a manganese dioxide adsorbent, which can be prepared as follows:
step (1): adding 8g of Mn 3 O 4 With 5.15g of KNO 3 Calcining at 900 ℃ for 16h after mixing to obtain K x MnO 2 A material;
step (2): treating 8g of the material obtained in step (1) with 28mL of 2mol/L dilute hydrochloric acid for 1h, filtering, and drying at 50 ℃ for 15h to obtain HMnO 2 A material;
and (3): dispersing the material (8 g) prepared in the step (2) in 240mL of TBAOH aqueous solution with the concentration of 0.5g/L, and maintaining the solution for 3h of ultrasonic treatment to obtain MnO stripped into nanosheets 2 A material;
and (4): centrifuging the ultrasonically treated material at low speed of 5000r/min, collecting upper suspension, centrifuging at high speed of 18000r/min, and collecting MnO 2 Drying the nanosheet solid material at 70 ℃ for 6h;
and (5): and (3) uniformly mixing the solid material (8 g) dried in the step (4) with 0.8g of PVC binder in 16mL of NMP solvent for pulping, gradually transferring into water to enable the solid material to be agglomerated into uniform particles under the condition of the binder, and then performing drying treatment at 60 ℃ for 8h to obtain the manganese dioxide adsorbent.
After the manganese dioxide adsorbent is obtained, the adsorbent particles are filled into a chromatographic column (the filling amount is 50% of the volume of the chromatographic column), and then salt lake brine is circulated for 1.2h to the chromatographic column at the flow rate of 25 mL/min; and after the adsorbent is adsorbed and saturated, introducing deionized water into the column for cleaning the adsorbent, keeping the speed of 3mL/min for 1h, and introducing 0.1mol/L hydrochloric acid for desorption treatment, wherein the desorption discharge liquid is a lithium-rich solution.
Example 4
This example provides a manganese dioxide adsorbent, which can be prepared as follows:
step (1): 7g of Mn 2 O 3 With 2.62g of Li 2 CO 3 Calcining for 14h at 1000 ℃ after mixing to obtain Li x MnO 2 A material;
step (2): treating 7g of the material obtained in the step (1) with 28mL of 2.4mol/L diluted hydrochloric acid for 2h, filtering, and drying at 65 ℃ for 9h to obtain HMnO 2 A material;
and (3): dispersing the material (7 g) prepared in the step (2) in 350mL of TBAOH aqueous solution with the concentration of 2g/L, and maintaining for 1h of ultrasonic treatment to obtain MnO peeled into nanosheets 2 A material;
and (4): centrifuging the ultrasonically treated material at low speed of 5500r/min, collecting upper suspension, centrifuging at high speed of 15000r/min, and collecting MnO 2 Drying the nano-sheet solid material at 55 ℃ for 12 h;
and (5): and (3) uniformly mixing the solid material (7 g) dried in the step (4) with 0.35g of PVC binder in 7mL of NMP solvent to prepare slurry, gradually transferring the slurry into water to enable the solid material to be agglomerated into uniform particles under the condition of the binder, and then performing drying treatment at 50 ℃ for 9 hours to obtain the manganese dioxide adsorbent.
After the manganese dioxide adsorbent is obtained, filling the adsorbent particles into a chromatographic column (the filling amount is 50% of the volume of the chromatographic column), and then circulating the chromatographic column for 2.5 hours at the flow rate of 30mL/min to introduce salt lake brine; after the adsorbent is adsorbed and saturated, deionized water is introduced into the column for cleaning the adsorbent, and then 0.5mol/L hydrochloric acid is introduced for desorption treatment at the speed of 4mL/min for 1.5h, and the desorption discharge liquid is a lithium-rich solution.
Example 5
This example provides a manganese dioxide adsorbent, which can be prepared as follows:
step (1): 15g of MnO 2 Mixing with 2.48g of LiOH and calcining at 1000 ℃ for 18h to obtain Li x MnO 2 A material;
step (2): treating 15g of the material obtained in step (1) with 75mL of 1mol/L diluted hydrochloric acid for 5h, filtering, and drying at 70 ℃ for 6h to obtain HMnO 2 A material;
and (3): dispersing the material (15 g) prepared in the step (2) in 750mL TBAOH aqueous solution with the concentration of 3g/L, and maintaining ultrasonic treatment for 2h to obtain MnO stripped into nanosheets 2 A material;
and (4): centrifuging the material after ultrasonic treatment at 8000r/min at low speed, collecting upper suspension, centrifuging at 17000r/min at high speed, and collecting MnO 2 Drying the nanosheet solid material at 60 ℃ for 9 h;
and (5): and (3) uniformly mixing the solid material (15 g) dried in the step (4) with 1g of PVC binder in 90mL of NMP solvent to prepare slurry, gradually transferring the slurry into water to enable the solid material to be agglomerated into uniform particles under the condition of the binder, and then performing drying treatment at 65 ℃ for 6 hours to obtain the manganese dioxide adsorbent.
After the manganese dioxide adsorbent is obtained, filling the adsorbent particles into a chromatographic column (the filling amount is 50% of the volume of the chromatographic column), and circulating the chromatographic column for 3 hours at the flow rate of 10mL/min to introduce salt lake brine; and after the adsorbent is adsorbed and saturated, introducing deionized water into the column for cleaning the adsorbent, keeping the speed of 6mL/min for 2.5h, and introducing 0.2mol/L hydrochloric acid for desorption treatment, wherein the desorption discharge liquid is a lithium-enriched solution.
Example 6
This example differs from example 1 in that: in the step (2), the proppant is TMAOH.
Example 7
This example differs from example 1 in that: in the step (1), the calcining temperature is 700 ℃ and the time is 24h.
Example 8
This example differs from example 1 in that: in the step (1), the calcining temperature is 1200 ℃ and the time is 6h.
Example 9
This example differs from example 1 in that: in the step (2), the concentration of the dilute acid is 0.1mol/L.
Example 10
This example differs from example 1 in that: in the step (2), the concentration of the dilute acid is 6mol/L.
Example 11
This example differs from example 1 in that: in the step (2), the liquid-solid ratio is 1mL:1g of the total weight of the composition.
Example 12
The present example differs from example 1 in that: in the step (2), the liquid-solid ratio is 10mL:1g of the total weight of the composition.
Example 13
The present example differs from example 1 in that: in the step (2), the drying temperature is 40 ℃, and the drying time is 18h.
Example 14
This example differs from example 1 in that: in the step (2), the drying temperature is 80 ℃, and the drying time is 3 hours.
Example 15
This example differs from example 1 in that: in the step (3), the concentration of TBAOH is 0.01g/L.
Example 16
The present example differs from example 1 in that: in the step (3), the concentration of TBAOH is 5g/L.
Example 17
This example differs from example 1 in that: in the step (3), the liquid-solid ratio is 10g:1L of the compound.
Example 18
This example differs from example 1 in that: in the step (3), the liquid-solid ratio is 100g:1L of the compound.
Example 19
The present example differs from example 1 in that: in the step (3), the ultrasonic treatment time is 0.5h.
Example 20
This example differs from example 1 in that: in the step (3), the ultrasonic treatment time is 24h.
Example 21
This example differs from example 1 in that: in the step (4), the rotating speed of the low-speed centrifugation is 3000r/min, and the rotating speed of the high-speed centrifugation is 10000r/min.
Example 22
This example differs from example 1 in that: in the step (4), the rotating speed of the low-speed centrifugation is 8000r/min, and the rotating speed of the high-speed centrifugation is 20000r/min.
Example 23
This example differs from example 1 in that: in the step (4), the drying temperature is 40 ℃, and the drying time is 18h.
Example 24
The present example differs from example 1 in that: in the step (4), the drying temperature is 80 ℃, and the drying time is 3h.
Example 25
This example differs from example 1 in that: in the step (5), the mass ratio of the solid material to the binder is 5:1.
example 26
This example differs from example 1 in that: in the step (5), the mass ratio of the solid material to the binder is 100:1.
example 27
The present example differs from example 1 in that: in the step (5), the solid-liquid ratio of the solid material to the organic solvent is 1g:0.1mL.
Example 28
The present example differs from example 1 in that: in the step (5), the solid-liquid ratio of the solid material to the organic solvent is 1g:12mL.
Example 29
This example differs from example 1 in that: in the step (5), the drying temperature is 40 ℃, and the drying time is 18h.
Example 30
This example differs from example 1 in that: in the step (5), the drying temperature is 80 ℃, and the drying time is 3 hours.
Comparative example 1
This comparative example differs from example 1 in that: direct MnO mixing 2 The nano-sheet is prepared into lithium ionSub-sieves (SEM picture shown in FIG. 2), i.e. not for MnO 2 And modifying the nanosheet.
Comparative example 2
This comparative example differs from example 1 in that: in the step (1), the calcination temperature is 500 ℃.
Comparative example 3
This comparative example differs from example 1 in that: in the step (1), the calcination temperature is 1500 ℃.
Comparative example 4
The comparative example differs from example 1 in that: in the step (2), the concentration of the dilute acid is 0.05mol/L.
Comparative example 5
The comparative example differs from example 1 in that: in the step (2), the concentration of the dilute acid is 8mol/L.
Comparative example 6
The comparative example differs from example 1 in that: in the step (2), the liquid-solid ratio is 0.5mL:1g of the total weight of the composition.
Comparative example 7
This comparative example differs from example 1 in that: in the step (2), the liquid-solid ratio is 15mL:1g of the total weight of the composition.
Comparative example 8
This comparative example differs from example 1 in that: in the step (2), the drying temperature is 100 ℃.
Comparative example 9
This comparative example differs from example 1 in that: in step (3), the TBAOH concentration was 0.005g/L.
Comparative example 10
This comparative example differs from example 1 in that: in the step (3), the concentration of TBAOH is 10g/L.
Comparative example 11
This comparative example differs from example 1 in that: in the step (3), the liquid-solid ratio is 5g:1L of the total amount of the active ingredients.
Comparative example 12
This comparative example differs from example 1 in that: in the step (3), the liquid-solid ratio is 120g:1L of the compound.
Comparative example 13
This comparative example differs from example 1 in that: in the step (4), only low-speed centrifugation is performed, and high-speed centrifugation is not performed.
Comparative example 14
This comparative example differs from example 1 in that: in the step (4), only high-speed centrifugation is carried out, and low-speed centrifugation is not carried out.
Comparative example 15
This comparative example differs from example 1 in that: in the step (4), the drying temperature is 100 ℃.
Comparative example 16
This comparative example differs from example 1 in that: in the step (5), the mass ratio of the solid material to the binder is 2:1.
comparative example 17
This comparative example differs from example 1 in that: in the step (5), the mass ratio of the solid material to the binder is 120:1.
comparative example 18
This comparative example differs from example 1 in that: in the step (5), the solid-liquid ratio of the solid material to the organic solvent is 1g:0.05mL.
Comparative example 19
This comparative example differs from example 1 in that: in the step (5), the solid-liquid ratio of the solid material to the organic solvent is 1g:15mL.
Comparative example 20
This comparative example differs from example 1 in that: in the step (5), the drying temperature is 100 ℃.
Test examples
The above examples 1 to 30 and comparative examples 1 to 20 all treated the same salt lake brine in which the concentrations of main elements are shown in table 1.
The specific surface areas of the lithium ion sieve materials of the respective examples and comparative examples are shown in table 2. The lithium adsorption amount per lithium ion sieve in each example and comparative example is shown in table 3, and the manganese elution rate per lithium ion sieve in each example and comparative example is shown in table 4.
TABLE 1 concentration of major elements in salt lake brine
| Main elements of | Concentration (mg/L) |
| Li + | 389 |
| Na + | 9120 |
| Mg 2+ | 6550 |
| K + | 2770 |
TABLE 2 specific surface area of lithium ion sieve material
TABLE 3 unit lithium ion sieve lithium adsorption
TABLE 4 Unit manganese dissolution rate of lithium ion sieve
From the above, the manganese dioxide adsorbent prepared from the modified lithium ion sieve provided by the application can be improved by more than 30% in adsorption capacity compared with the manganese dioxide adsorbent prepared from unmodified lithium ion sieve, the dissolution rate of Mn is also obviously reduced, the use value of the MO-based lithium ion sieve is greatly improved, and the use cost is fully reduced.
Further, as can be seen by comparing each example with the comparative example, the effect corresponding to example 2 is the best, and the conditions in this example are best illustrated. When the preparation conditions are changed, the corresponding effects are deteriorated.
In summary, the modified lithium ion sieve provided by the application has a larger specific surface area, and the corresponding lithium adsorption capacity is remarkably improved; and the modified lithium ion sieve provided by the application has a three-dimensional layered framework structure, provides better circulation stability and has longer service life.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The modified lithium ion sieve is characterized by being MnO with a three-dimensional layered framework structure 2 A nanosheet material.
2. The modified lithium ion of claim 1A sieve, characterized in that the modified lithium ion sieve comprises multiple layers of MnO 2 The nanosheets are sequentially arranged in a main structure at intervals, and adjacent two layers of MnO are arranged 2 A supporting framework is arranged between the nano sheets;
preferably, the MnO 2 The specific surface area of the nano sheet material is not less than 75m 2 /g；
Preferably, two adjacent layers of MnO 2 The gap between the nano sheets is more than 0nm and less than or equal to 100nm.
3. The method of preparing a modified lithium ion sieve according to claim 1 or 2, comprising the steps of: a is to be x MnO 2 The material is subjected to acid treatment, solid-liquid separation and drying to obtain HMnO 2 A material; wherein A is an alkali metal element, and x is more than 0 and less than 1;
HMnO 2 Mixing the material with an aqueous solution of a proppant, performing ultrasonic treatment, and collecting nanosheet material to obtain MnO 2 Nanosheets;
preferably, A is x MnO 2 The material is prepared by the following method: mixing an alkali metal compound with an oxide of manganese, and calcining;
preferably, the oxide of manganese comprises MnO 2 、Mn 2 O 3 And Mn 3 O 4 At least one of;
preferably, the alkali metal in the alkali metal compound comprises at least one of lithium, sodium and potassium;
preferably, the molar amount of alkali metal in the alkali metal compound does not exceed the molar amount of manganese in the oxide of manganese, more preferably, the molar ratio of alkali metal in the alkali metal compound to manganese in the oxide of manganese is from 0.5 to 0.8;
preferably, the calcination temperature is 700-1200 deg.C, more preferably 800-1000 deg.C;
preferably, the calcination time is from 6 to 24 hours, more preferably from 12 to 18 hours.
4. The method according to claim 3, wherein A is x MnO 2 Acids for acid treatment of materialsThe concentration of (A) is 0.1-6mol/L; and/or, in the aqueous solution of the proppant, the concentration of the proppant is 0.01-5g/L;
preferably, the concentration of the acid is 0.3 to 1.5mol/L; and/or the concentration of the proppant is 0.1-3g/L;
preferably, said A is x MnO 2 The solid-to-liquid ratio of the material to the acid is 1g:1-10mL; more preferably 1g:2-5mL;
preferably, the acid treatment time is 0.1-24h, more preferably 1-6h;
preferably, the drying temperature is 40-80 ℃, more preferably 50-70 ℃;
preferably, the drying time is 3-18h, more preferably 6-15h;
preferably, HMnO 2 The solid-to-liquid ratio of the material to the aqueous solution of the proppant is 10-100g:1L, more preferably 20-50g:1L;
preferably, the proppant comprises an organic ammonium species, more preferably at least one of tetra-n-butylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide;
preferably, the sonication time is between 0.5 and 24h, more preferably between 1 and 6h.
5. The method of manufacturing of claim 3, wherein collecting the nanoplatelets comprises: centrifuging the material obtained after ultrasonic treatment at low speed, collecting the upper suspension to obtain deprotonated MnO 2 A nanosheet material;
preferably, collecting the nanoplatelets further comprises: mnO to be deprotonated 2 Centrifuging the nanosheet material at high speed, and collecting the solid phase to obtain MnO 2 A nanosheet;
preferably, after collecting the solid phase, drying the solid phase;
preferably, the rotating speed of the low-speed centrifugation is 3000-8000r/min, more preferably 5000-8000r/min;
preferably, the rotating speed of the high-speed centrifugation is 10000-20000r/min, more preferably 14000-18000r/min;
preferably, the temperature for drying the solid phase is 40-80 ℃, more preferably 50-70 ℃;
preferably, the drying time of the solid phase is 3 to 18 hours, more preferably 6 to 12 hours.
6. A manganese dioxide adsorbent, wherein the manganese dioxide adsorbent is an agglomerate of the modified lithium ion sieve of claim 1 or 2 and a binder;
preferably, the agglomerates are particulate matter having a particle size in the order of millimeters.
7. The method of preparing manganese dioxide adsorbent of claim 6, comprising the steps of: mixing the modified lithium ion sieve of claim 1 or 2 with a binder and an organic solvent, followed by transferring into an aqueous phase to obtain an agglomerate;
preferably, drying the agglomerate;
preferably, the mass ratio of the modified lithium ion sieve to the binder is 5-100, more preferably 10-30;
preferably, the binder comprises at least one of sodium carboxymethylcellulose, styrene-butadiene rubber, polyvinyl alcohol and polyvinyl chloride, and more preferably comprises at least one of polyvinyl alcohol and polyvinyl chloride;
preferably, the feed-liquid ratio of the modified lithium ion sieve to the organic solvent is 1g:0.1-12mL, more preferably 1g:1-6mL;
preferably, the drying of the agglomerates is carried out at a temperature of from 40 to 80 ℃, more preferably from 50 to 70 ℃;
preferably, the agglomerates are dried for a period of time ranging from 3 to 18 hours, more preferably from 6 to 12 hours.
8. A chromatography column, wherein the adsorbent of the chromatography column comprises manganese dioxide as claimed in claim 6;
preferably, the manganese dioxide adsorbent is filled in the column in an amount of 30-80% by volume of the column.
9. Use of the modified lithium ion sieve of any one of claims 1-2 or the manganese dioxide adsorbent of claim 6 for extracting lithium element;
preferably, the modified lithium ion sieve or the manganese dioxide adsorbent is used for extracting lithium in a salt lake.
10. A method for extracting lithium from a salt lake is characterized by comprising the following steps: introducing salt lake brine to be extracted into a chromatographic column filled with the manganese dioxide adsorbent of claim 6, washing out the manganese dioxide adsorbent after the manganese dioxide adsorbent is adsorbed and saturated, and then carrying out desorption treatment to obtain a desorption effluent rich in lithium;
preferably, the flow rate of the salt lake brine introduced into the chromatographic column is 1-100mL/min, preferably 10-30mL/min;
preferably, the adsorption time is 0.1-6h, more preferably 0.5-3h;
preferably, the desorbing agent used in the desorbing treatment is an acid, more preferably hydrochloric acid;
preferably, the flow rate of the desorption reagent is 0.1-50mL/min, more preferably 1-6mL/min;
preferably, the concentration of the desorption reagent is 0.1-10mol/L, more preferably 0.3-1.5mol/L;
preferably, the desorption time is from 0.3 to 9h, more preferably from 1 to 3h.
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