CN113845143A - Bentonite modified metatitanic acid type lithium ion sieve precursor and preparation method thereof - Google Patents
Bentonite modified metatitanic acid type lithium ion sieve precursor and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a bentonite modified metatitanic acid type lithium ion sieve precursor, which comprises the following steps: respectively adding Ti (SO)4)2And C2H7LiO4Dissolving to obtain Ti (SO)4)2Solutions and C2H7LiO4A solution; to Ti (SO)4)2Dripping precipitator into the solution to obtain white TiO (OH)2Precipitating, then adding TiO (OH)2Washing the precipitate with deionized water until no SO is formed4 2‑Residual; washing the TiO (OH)2Diluting the precipitate with water, pulping, and adding C dropwise into the slurry2H7LiO4After the solution is uniformly mixed, dropwise adding a complexing agent into the mixed solution, and stirring to obtain transparent yellow sol after dropwise adding; and adding bentonite into the transparent yellow sol, stirring, ageing, drying to obtain dry gel, grinding the dry gel, and calcining to obtain the dry gel. The precursor can effectively solve the problems of small specific surface area and small adsorption capacity of the existing precursor.
Description
Technical Field
The invention belongs to the technical field of lithium ion sieves, and particularly relates to a bentonite modified metatitanic acid type lithium ion sieve precursor and a preparation method thereof.
Background
The method for extracting lithium from salt lake brine generally comprises the steps of preparing a proper precursor, and removing Li in the precursor by acid washing+The lithium ion sieve is obtained, so that the synthesis of the titanium lithium ion sieve precursor by adopting a proper method is the key for preparing the lithium ion sieve. At present, methods for synthesizing titanium lithium ion sieve precursors mainly include a high-temperature solid phase method, a hydrothermal method, a sol-gel method, a precipitation peptization method, a template method and the like.
Among them, the precipitation peptization method is a method improved on the basis of the sol-gel method. The method comprises the steps of enabling a titanium source to exist in a precipitation form by using a precipitator, adding a lithium source, complexing the lithium source and the titanium source by using a complexing agent, aging for a period of time to obtain transparent sol, aging the sol for a period of time at room temperature, drying to obtain dry gel, and calcining to obtain the titanium-lithium ionic sieve precursor. However, the existing lithium ion sieve precursor has small specific surface area and limited adsorption capacity, so that the adsorption effect is general.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a bentonite modified metatitanic acid type lithium ion sieve precursor and a preparation method thereof, and the precursor can effectively solve the problems of small specific surface area and small adsorption capacity of the existing precursor.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a bentonite modified metatitanic acid type lithium ion sieve precursor comprises the following steps:
(1) respectively adding Ti (SO)4)2And C2H7LiO4Dissolving to obtain Ti (SO)4)2Solutions and C2H7LiO4A solution;
(2) to Ti (SO)4)2Dripping precipitator into the solution to obtain white TiO (OH)2Precipitating, then adding TiO (OH)2Washing the precipitate with deionized water until no SO is formed4 2-Residual;
(3) the TiO (OH) cleaned in the step (2)2Diluting the precipitate with water, pulping, and adding C obtained in step (1) dropwise into the slurry2H7LiO4After the solution is uniformly mixed, dropwise adding a complexing agent into the mixed solution, and stirring to obtain transparent yellow sol after dropwise adding;
(4) and (4) adding bentonite into the transparent yellow sol obtained in the step (3), stirring, ageing, drying to obtain dry gel, grinding the dry gel, and calcining to obtain the transparent yellow sol.
In the above scheme, Ti (SO)4)2Is a source of titanium, C2H7LiO4Preparing precursor sol of the titanium lithium ion sieve for a lithium source, adding bentonite into the precursor sol, calcining to obtain a bentonite modified metatitanic acid type lithium ion sieve precursor with uniform mesoporous morphology, wherein the bentonite has larger specific surface area, good adsorption performance, large storage capacity and low price, and can be used for modifying the precursor of the titanium lithium ion sieve, and the bentonite can be inserted into Li2TiO3In the structure, the metatitanic acid type lithium ion sieve with remarkably improved specific surface area and adsorption capacity is prepared, and the lithium extraction efficiency of the traditional lithium ion sieve can be improved.
Further, the precipitator in the step (2) is ammonia water, and the ammonia water is dripped until the pH value of the solution is 7-9.
Further, the dropping speed of the precipitating agent in the step (2) is 8-12 s/drop.
Further, the complexing agent in the step (3) is H with the volume concentration of 25-35 percent2O2。
Further, the complexing agent in the step (3) is H with the volume concentration of 30 percent2O2。
Further, in the step (3), H2O2The molar ratio of the Ti to the Ti in the mixed solution is 5-7: 1.
Further, in the step (3), H2O2The molar ratio of Ti in the mixed solution is 6: 1.
In the above scheme, H2O2The molar ratio of Ti in the mixed solution is too small, so that the prepared sample has a cracked and incomplete surface and a relatively smooth and gapless structureH2O2The molar ratio of the Ti to the Ti in the mixed solution is increased, the surface of the sample gradually takes on a porous structure when H2O2When the molar ratio of Ti in the mixed solution is too large, the pores on the surface of the sample decrease, and the pores are accompanied by H2O2Increase in amount of Li2TiO3The diffraction peak intensity of the characteristic crystal face in the crystal is gradually enhanced, which proves that H2O2In an amount to Li2TiO3Grain growth is important, H2O2The main principle of the function is as follows: h2O2In the preparation process, the main component is decomposed into peroxy radicals (. O-O. to complex TiO (OH) to obtain TiO (OH) - (O-TiO-O) n-TiO (OH) with stable structure, and Li is inserted to obtain crystal with the structural formula of Li [ Li ]1/3Ti2/3]O2When the complexing agent is H2O2When the amount is very small, the generated peroxy radicals (. O-O. cndot.) will be reduced correspondingly, and the effect of complexing TiO (OH) will be reduced correspondingly, thus being unfavorable for the growth of crystal face and leading to incomplete structure of sample.
Further, the solid-to-liquid ratio of the bentonite to the transparent yellow sol in the step (4) is 1g: 0.5-0.7L.
Further, the solid-to-liquid ratio of the bentonite to the transparent yellow sol in the step (4) is 1g: 0.6L.
In the scheme, the modification treatment of the bentonite is performed on Li along with the increase of the solid-liquid ratio2TiO3The diffraction crystal face of the precursor is influenced and changes towards the direction beneficial to the oriented growth of the characteristic crystal face, when the liquid-solid ratio reaches 1g:0.6L, the characteristic diffraction peak intensity of the crystal face is highest, namely the crystal intensity is the largest, the crystallinity is the best, and therefore, the Li is more convenient+Elution and adsorption of (3); however, as the using amount of the bentonite is increased, part of elements in the bentonite replace Li in the Li2 layer of the precursor, so that the crystal structure integrity of the precursor is reduced, and Li is caused+The elution rate of (2) is reduced, the adsorption sites of Li are correspondingly reduced, and the elution rate of (2) is reduced for Li+The adsorption capacity of (a) is thus reduced.
And (3) further, adding bentonite in the step (4), stirring for 2-4h, aging for 10-14h, and drying at 70-90 ℃ to obtain xerogel.
Further, after the dry gel in the step (4) is ground, the temperature is raised to 600-900 ℃ at the speed of 2-4 ℃/min, and the temperature is maintained for 1.5-3 h.
Further, after the dry gel is ground in the step (4), the temperature is raised to 750 ℃ at the speed of 3 ℃/min, and the temperature is kept for 2 h.
In the scheme, with the increase of the calcination temperature, the titanium lithium ion sieve precursor is subjected to crystal form transformation and is converted into a beta-monoclinic phase, crystal grains are in a growth trend, the crystal structure is in an integrity trend, when the temperature reaches 750 ℃, the characteristic diffraction peak of each crystal face reaches the maximum value, and the Li modified by the surface bentonite2TiO3Li in the host crystal layer+The stable and highly ordered crystal structure is completely formed, and when the temperature is continuously increased, the diffraction peak intensity of each crystal face is weakened, so that the crystal structure is most stable when the calcining temperature is 750 ℃.
The beneficial effects produced by the invention are as follows:
1. the bentonite modified metatitanic acid type lithium ion sieve precursor has higher thermal stability, and the bentonite is introduced to play a role in blocking so that the thermal stability of the bentonite modified metatitanic acid type lithium ion sieve precursor is improved.
2. Porous structures are uniformly distributed on the surface of the bentonite modified metatitanic acid type lithium ion sieve precursor, the specific surface area of a sample can be increased, the adsorption capacity and the adsorption rate of the lithium ion sieve are further improved, and the adsorption capacity can reach 45.49 mg/g.
3. The bentonite modified metatitanic acid type lithium ion sieve precursor has complete crystal growth and uniformly distributed pore structure on the surface, and is more favorable for Li+Elution of (2), increasing Li+The elution equilibrium time of the elution is 6h, Li after 6h+The elution rate of (2) is as high as 99.85%.
Drawings
Fig. 1 is an SEM image of a metatitanic acid type lithium ion sieve precursor prepared in example 1;
fig. 2 is an SEM image of a metatitanic acid type lithium ion sieve precursor prepared in comparative example 2;
fig. 3 is an SEM image of a metatitanic acid type lithium ion sieve precursor prepared in comparative example 3;
fig. 4 is an XRD pattern of the metatitanic acid type lithium ion sieve precursor in example 1;
FIG. 5 is an XRD pattern of a lithium titanate type lithium ion sieve precursor in example 1 after acid washing;
FIG. 6 is an XRD pattern of the adsorbent of example 1 after adsorption;
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings.
Example 1
A bentonite modified metatitanic acid type lithium ion sieve precursor comprises the following steps:
(1) respectively adding Ti (SO)4)2And C2H7LiO4Dissolving to obtain Ti (SO)4)2Solutions and C2H7LiO4A solution;
(2) to Ti (SO)4)2Dropwise adding ammonia water into the solution at the dropping speed of 10 s/drop until the pH value of the solution is 8 to obtain white TiO (OH)2Precipitating, then adding TiO (OH)2Washing the precipitate with deionized water until no SO is formed4 2-Residual;
(3) the TiO (OH) cleaned in the step (2)2Diluting the precipitate with 100ml of water, pulping, and adding C obtained in step (1) dropwise into the slurry2H7LiO4Uniformly mixing the solution, and dropwise adding H with the volume concentration of 30% into the mixed solution2O2，H2O2The molar ratio of the Ti to the Ti in the mixed solution is 6:1, and the transparent yellow sol is obtained by stirring after the dripping is finished;
(4) and (3) adding bentonite into the transparent yellow sol in the step (3), wherein the solid-to-liquid ratio of the bentonite to the transparent yellow sol is 1g:0.6L, stirring for 3h, then aging for 12h, then drying at 80 ℃ to obtain dry gel, grinding the dry gel, then heating to 750 ℃ at the speed of 3 ℃/min, calcining, and preserving heat for 2h to obtain the transparent yellow sol.
Example 2
A bentonite modified metatitanic acid type lithium ion sieve precursor comprises the following steps:
(1) respectively adding Ti (SO)4)2And C2H7LiO4Dissolving to obtain Ti (SO)4)2Solutions and C2H7LiO4A solution;
(2) to Ti (SO)4)2Dropwise adding ammonia water into the solution at the dropping speed of 10 s/drop until the pH value of the solution is 7 to obtain white TiO (OH)2Precipitating, then adding TiO (OH)2Washing the precipitate with deionized water until no SO is formed4 2-Residual;
(3) the TiO (OH) cleaned in the step (2)2Diluting the precipitate with 100ml of water, pulping, and adding C obtained in step (1) dropwise into the slurry2H7LiO4Uniformly mixing the solution, and dropwise adding H with the volume concentration of 25% into the mixed solution2O2，H2O2The molar ratio of the mixed solution to Ti in the mixed solution is 5:1, and the transparent yellow sol is obtained by stirring after the dripping is finished;
(4) and (3) adding bentonite into the transparent yellow sol in the step (3), wherein the solid-to-liquid ratio of the bentonite to the transparent yellow sol is 1g:0.5L, stirring for 2h, then aging for 10h, then drying at 70 ℃ to obtain dry gel, grinding the dry gel, then heating to 600 ℃ at the speed of 3 ℃/min, calcining, and preserving heat for 2h to obtain the transparent yellow sol.
Example 3
A bentonite modified metatitanic acid type lithium ion sieve precursor comprises the following steps:
(1) respectively adding Ti (SO)4)2And C2H7LiO4Dissolving to obtain Ti (SO)4)2Solutions and C2H7LiO4A solution;
(2) to Ti (SO)4)2Dropwise adding ammonia water into the solution at the dropping speed of 10 s/drop until the pH value of the solution is 9 to obtain white TiO (OH)2Precipitating, then adding TiO (OH)2Washing the precipitate with deionized water until no SO is formed4 2-Residual;
(3) the TiO (OH) cleaned in the step (2)2Precipitation ofDiluting with 100ml of water, pulping, and adding C obtained in step (1) dropwise into the slurry2H7LiO4Uniformly mixing the solution, and dropwise adding H with the volume concentration of 35% into the mixed solution2O2，H2O2The molar ratio of the Ti to the Ti in the mixed solution is 7:1, and the transparent yellow sol is obtained by stirring after the dripping is finished;
(4) and (3) adding bentonite into the transparent yellow sol in the step (3), wherein the solid-to-liquid ratio of the bentonite to the transparent yellow sol is 1g:0.7L, stirring for 4h, then aging for 14h, then drying at 90 ℃ to obtain dry gel, grinding the dry gel, then heating to 900 ℃ at the speed of 4 ℃/min, calcining, and preserving heat for 2h to obtain the transparent yellow sol.
Comparative example 1
A metatitanic acid type lithium ion sieve precursor is prepared by the following steps:
(1) respectively adding Ti (SO)4)2And C2H7LiO4Dissolving to obtain Ti (SO)4)2Solutions and C2H7LiO4A solution;
(2) to Ti (SO)4)2Dropwise adding ammonia water into the solution at the dropping speed of 10 s/drop until the pH value of the solution is 8 to obtain white TiO (OH)2Precipitating, then adding TiO (OH)2Washing the precipitate with deionized water until no SO is formed4 2-Residual;
(3) the TiO (OH) cleaned in the step (2)2Diluting the precipitate with 100ml of water, pulping, and adding C obtained in step (1) dropwise into the slurry2H7LiO4Uniformly mixing the solution, and dropwise adding H with the volume concentration of 30% into the mixed solution2O2，H2O2The molar ratio of the sol to Ti in the mixed solution is 6:1, stirring is carried out after the dropwise addition is finished to obtain transparent yellow sol, the transparent yellow sol is aged for 12 hours at room temperature, then drying is carried out at 80 ℃ to obtain dry gel, the dry gel is ground, then the temperature is increased to 750 ℃ at the speed of 3 ℃/min for calcination, and the heat preservation is carried out for 2 hours, so that the titanium dioxide sol is prepared.
Comparative example 2
A bentonite modified metatitanic acid type lithium ion sieve precursor comprises the following steps:
(1) respectively adding Ti (SO)4)2And C2H7LiO4Dissolving to obtain Ti (SO)4)2Solutions and C2H7LiO4A solution;
(2) to Ti (SO)4)2Dropwise adding ammonia water into the solution at the dropping speed of 10 s/drop until the pH value of the solution is 8 to obtain white TiO (OH)2Precipitating, then adding TiO (OH)2Washing the precipitate with deionized water until no SO is formed4 2-Residual;
(3) the TiO (OH) cleaned in the step (2)2Diluting the precipitate with 100ml of water, pulping, and adding C obtained in step (1) dropwise into the slurry2H7LiO4Uniformly mixing the solution, and dropwise adding H with the volume concentration of 30% into the mixed solution2O2，H2O2The molar ratio of the Ti to the Ti in the mixed solution is 3:1, and the transparent yellow sol is obtained by stirring after the dripping is finished;
(4) and (3) adding bentonite into the transparent yellow sol in the step (3), wherein the solid-to-liquid ratio of the bentonite to the transparent yellow sol is 1g:0.3L, stirring for 3h, then aging for 12h, then drying at 80 ℃ to obtain dry gel, grinding the dry gel, then heating to 750 ℃ at the speed of 3 ℃/min, calcining, and preserving heat for 2h to obtain the transparent yellow sol.
Comparative example 3
A bentonite modified metatitanic acid type lithium ion sieve precursor comprises the following steps:
(1) respectively adding Ti (SO)4)2And C2H7LiO4Dissolving to obtain Ti (SO)4)2Solutions and C2H7LiO4A solution;
(2) to Ti (SO)4)2Dropwise adding ammonia water into the solution at the dropping speed of 10 s/drop until the pH value of the solution is 8 to obtain white TiO (OH)2Precipitating, then adding TiO (OH)2Washing the precipitate with deionized water until no SO is formed4 2-Residual;
(3) the TiO (OH) cleaned in the step (2)2Diluting the precipitate with 100ml of water, pulping, and adding C obtained in step (1) dropwise into the slurry2H7LiO4Uniformly mixing the solution, and dropwise adding H with the volume concentration of 30% into the mixed solution2O2，H2O2The molar ratio of the Ti to the Ti in the mixed solution is 8:1, and the transparent yellow sol is obtained by stirring after the dripping is finished;
(4) and (3) adding bentonite into the transparent yellow sol in the step (3), wherein the solid-to-liquid ratio of the bentonite to the transparent yellow sol is 1g:1L, stirring for 3h, aging for 12h, drying at 80 ℃ to obtain dry gel, grinding the dry gel, heating to 750 ℃ at the speed of 3 ℃/min, calcining, and preserving heat for 2h to obtain the transparent yellow sol.
Comparative example 4
A bentonite modified metatitanic acid type lithium ion sieve precursor comprises the following steps:
(1) respectively adding Ti (SO)4)2And C2H7LiO4Dissolving to obtain Ti (SO)4)2Solutions and C2H7LiO4A solution;
(2) to Ti (SO)4)2Dropwise adding ammonia water into the solution at the dropping speed of 10 s/drop until the pH value of the solution is 8 to obtain white TiO (OH)2Precipitating, then adding TiO (OH)2Washing the precipitate with deionized water until no SO is formed4 2-Residual;
(3) the TiO (OH) cleaned in the step (2)2Diluting the precipitate with 100ml of water, pulping, and adding C obtained in step (1) dropwise into the slurry2H7LiO4Uniformly mixing the solution, and dropwise adding H with the volume concentration of 30% into the mixed solution2O2，H2O2The molar ratio of the Ti to the Ti in the mixed solution is 6:1, and the transparent yellow sol is obtained by stirring after the dripping is finished;
(4) and (3) adding bentonite into the transparent yellow sol in the step (3), wherein the solid-to-liquid ratio of the bentonite to the transparent yellow sol is 1g:0.6L, stirring for 3h, then aging for 12h, then drying at 80 ℃ to obtain dry gel, grinding the dry gel, then heating to 1000 ℃ at the speed of 3 ℃/min, calcining, and preserving heat for 2h to obtain the transparent yellow sol.
Test examples
The metatitanic acid type lithium ion sieve precursors obtained in examples 1 to 3 and comparative examples 1 to 4 were acid-washed with 0.2mol/L hydrochloric acid solution, respectively, at 50 ℃ for 6 hours, at a molar ratio of hydrogen ions in hydrochloric acid to lithium ions in the precursors of 1:1, and the acid-washed precursors were dried to obtain different adsorbents.
1. Respectively carrying out adsorption tests on different adsorbents and lithium hydroxide solution with the concentration of 2g/L according to the solid-to-liquid ratio of 2g:100ml, wherein the adsorption time is 24h, measuring the lithium ion concentration in the adsorbed solution after adsorption equilibrium, calculating the adsorption capacity, carrying out acid washing treatment on the solution for 6h by using 0.204mol/L HCl under the constant temperature condition of 50 ℃, taking the solution, diluting the solution, and measuring Li in the solution by using an atomic absorption spectrophotometer+And (4) calculating the lithium ion elution rate of each sample, wherein the specific results are shown in the table 1.
Table 1: adopting different adsorbents to adsorb the lithium ion concentration in the solution
| Adsorption capacity (mg/g) | Elution Rate (%) | |
| Example 1 | 45.49 | 99.85 |
| Example 2 | 45.12 | 99.45 |
| Example 3 | 44.59 | 99.67 |
| Comparative example 1 | 30.62 | 94.21 |
| Comparative example 2 | 32.35 | 94.98 |
| Comparative example 3 | 31.01 | 95.21 |
| Comparative example 4 | 34.12 | 95.36 |
As is clear from the data in the above table, the adsorption capacity and the elution rate in examples 1 to 3 are larger than those in comparative examples 1 to 4.
2. The pore structure characteristics of different adsorbents were determined separately, and the specific results are shown in table 2.
Table 2: structural characteristics of different samples
As can be seen from the data in the above table, the specific surface areas of the adsorbents in examples 1 to 3 are all larger than those of the adsorbents in comparative examples 1 to 4, the pore diameters of the adsorbents in examples 1 to 3 are all much smaller than those of the adsorbents in comparative examples 1 to 4, and the adsorption capacities of examples 1 to 3 are all larger than those of the adsorbents in comparative examples 1 to 4.
As can be seen from fig. 1 to 3, the sample surface of example 1 has a uniform pore structure; the samples of comparative examples 2 and 3 had less surface porosity.
As can be seen from the attached FIGS. 4-6, the sample before pickling has a complete structure and a uniform porous structure on the surface; the structure of the sample after acid washing is destroyed, and the phenomenon of grain aggregation is obvious, which is caused by the Li with larger diameter after acid washing+Is enclosed by H with smaller radius+Replacement, which causes crystal structure change, crystal face spacing reduction, unit cell volume shrinkage, ion arrangement damage and lattice energy increase, and finally causes a crystal grain polymerization phenomenon; after adsorption, the surface of the sample has no obvious uniform pore structure, and the phenomenon of grain aggregation is obvious as that of the sample after acid washing, so that the sample does not cause any new structural change on lithium adsorption.
Claims (10)
1. A preparation method of a bentonite modified metatitanic acid type lithium ion sieve precursor is characterized by comprising the following steps:
(1) respectively adding Ti (SO)4)2And C2H7LiO4Dissolving to obtain Ti (SO)4)2Solutions and C2H7LiO4A solution;
(2) to Ti (SO)4)2Dripping precipitator into the solution to obtain white TiO (OH)2Precipitating, then adding TiO (OH)2Washing the precipitate with deionized water until no SO is formed4 2-Residual;
(3) the TiO (OH) cleaned in the step (2)2Diluting the precipitate with water, pulping, and adding C obtained in step (1) dropwise into the slurry2H7LiO4After the solution is uniformly mixed, dropwise adding a complexing agent into the mixed solution, and stirring to obtain transparent yellow sol after dropwise adding;
(4) and (4) adding bentonite into the transparent yellow sol obtained in the step (3), stirring, ageing, drying to obtain dry gel, grinding the dry gel, and calcining to obtain the transparent yellow sol.
2. The method for preparing a bentonite-modified lithium metatitanic acid type lithium ion sieve precursor according to claim 1, wherein the precipitant in the step (2) is ammonia water, and is added dropwise until the solution has a pH value of 7 to 9.
3. The method for preparing a bentonite-modified lithium metatitanic acid type lithium ion sieve precursor according to claim 1, wherein the complexing agent in the step (3) is H with a volume concentration of 25-35%2O2。
4. The method for preparing a bentonite-modified metatitanic acid type lithium ion sieve precursor according to claim 3, wherein H in the step (3)2O2The molar ratio of the Ti to the Ti in the mixed solution is 5-7: 1.
5. The method for preparing a bentonite-modified metatitanic acid type lithium ion sieve precursor according to claim 1, wherein the solid-to-liquid ratio of the bentonite to the transparent yellow sol in the step (4) is 1g:0.5 to 0.7L.
6. The method for preparing a bentonite-modified metatitanic acid type lithium ion sieve precursor according to claim 5, wherein the solid-to-liquid ratio of the bentonite to the transparent yellow sol in the step (4) is 1g to 0.6L.
7. The method for preparing a bentonite-modified metatitanic acid type lithium ion sieve precursor according to claim 1, wherein the bentonite is added in the step (4), and then the bentonite is stirred for 2 to 4 hours, then aged for 10 to 14 hours, and then dried at 70 to 90 ℃ to obtain xerogel.
8. The method for preparing the bentonite modified metatitanic acid type lithium ion sieve precursor as claimed in claim 1, wherein the temperature is raised to 600-900 ℃ at a speed of 2-4 ℃/min after the dry gel is ground in the step (4), and the temperature is maintained for 1.5-3 h.
9. The method for preparing a bentonite-modified metatitanic acid type lithium ion sieve precursor according to claim 8, wherein the temperature is raised to 750 ℃ at a speed of 3 ℃/min after the dry gel is ground in the step (4), and the temperature is maintained for 2 hours.
10. A bentonite-modified lithium ion sieve precursor of metatitanic acid type, which is prepared by the method of any one of claims 1 to 9.
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