CN109317087B - Doped lithium titanate adsorbent and preparation method thereof - Google Patents
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Abstract
The invention relates to an adsorption material for separating and extracting lithium from brine, and particularly relates to a doped lithium titanate adsorbent and a preparation method thereof. The doped lithium titanate adsorbent HxLi4‑xMyTi5‑yO12Is doped from M to Li4Ti5O12Form a precursor Li in the crystal lattice of4MyTi5‑ yO12And then the alloy is obtained by acid washing and lithium removal, wherein M is one or a mixture of more of Ce, Sn and Hf, the value range of x is 0.0-4.0, x is not 0, and the value range of y is 0.05-2.0. The doped lithium titanate adsorbent is obtained by uniformly mixing a titanium source, a lithium source and M salt, drying, calcining, cooling and acid washing. The doped lithium titanate adsorbent prepared by the method can adsorb and extract lithium from brine with the magnesium-lithium ratio of more than 100, and has the lithium adsorption rate of more than 75 percent and the magnesium removal rate of more than 99 percent; the desorption solution has high acidity, about 1-7 times of lithium enrichment times and low titanium dissolution loss rate, and has industrial application prospect.
Description
Technical Field
The invention relates to an adsorption material for separating and extracting lithium from brine, and particularly relates to a doped lithium titanate adsorbent and a preparation method thereof.
Background
With the wide application of lithium batteries in the fields of automobiles, wind power, IT and the like, the demand of lithium and compounds serving as key raw materials is increased sharply. The current demand for lithium products in the international market continues to increase at a rate of more than 10% per year on average, resulting in a double surge in the market price of lithium products. More than 60% of the lithium resource is stored in the salt lake, and the extraction of lithium from the salt lake brine has become a main way for producing lithium salt at home and abroad. The salt lake brine in China is rich in resources, and occupies the second place in the proven lithium resource reserves in the world, wherein the liquid state mine lithium resources account for about 80% of the lithium resources in China. However, most of the salt lake brine in China has the characteristics of high magnesium and low lithium, the magnesium-lithium ratio is greater than 30 (mass ratio), a small amount of lithium ions and a large amount of magnesium ions coexist, and the properties of the magnesium ions and the lithium ions are similar, so that the lithium extraction from the salt lake brine with the high magnesium-lithium ratio becomes a recognized technical problem, and the development and utilization of lithium resources in China are severely restricted.
The process for extracting lithium from salt lake mainly includes precipitation method, solvent extraction method, calcination extraction method, membrane method and adsorption method. The precipitation method is mature in technology, but is not suitable for treating brine containing a large amount of magnesium ions and low-lithium brine; the solvent extraction method has good selectivity, but the extractant has high volatility, is easy to generate emulsification and foaming phenomena, and has poor engineering implementation effect; the calcination leaching method can better separate magnesium and lithium, but has high energy consumption, low lithium recovery rate (less than 40 percent) and poor economic benefit; the membrane method has good effect of separating magnesium and concentrating lithium from salt lake brine, but the membrane belongs to consumable goods and has high cost, and the prior art needs to be perfected. The adsorption method is widely researched due to the advantages of simple process, good selectivity, high lithium recovery rate, small pollution and the like, and is one of the most accepted methods with industrial prospects.
Currently, manganese lithium oxide (LiMn) is the main inorganic adsorbent studied by adsorption method2O4、Li1.33Mn1.67O4、Li1.6Mn1.6O4、Li4Mn5O12) And titanium lithium oxide (Li)2TiO3、Li4Ti5O12) And the like. The manganese lithium oxide has the advantages of large adsorption capacity, high adsorption efficiency and the like, but the adsorption material has poor acid and alkali resistance and is not suitable for extracting lithium from alkaline brine or lithium carbonate lithium precipitation mother liquor. The titanium lithium oxide adsorbent has good acid and alkali resistance, but the migration speed of lithium ions in the adsorbent is slow, and the adsorption efficiency is low. Patent CN102049238A in Li4Ti5O12Other metals such as V, Fe, Co, Mn, Al and the like are doped in the lithium ion adsorbent, so that the adsorption capacity of the lithium ion adsorbent is improved; in the process of absorbing and extracting lithium, the potential of the system is adjusted by adding an oxidant or external circuit voltage to lead Li+The adsorbent is inserted or removed, and the dissolving loss of the adsorbent caused by acid-base conditions is avoided. The method has the problems that the cost of the added oxidant is high, and the process of regulating the potential of the system by an external circuit is complicated. The patent CN108212074A is obtained by doping magnetic elements (iron, cobalt and nickel) in lithium metatitanate to replace partial titanium positions, and then eluting lithium with acidA magnetically separable Ti-series adsorbent can be quickly separated out by the action of external magnetic field after adsorbing Li, but has the problems of high dissolving loss rate, quick performance attenuation and long adsorption time.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a doped lithium titanate adsorbent, and the doped lithium titanate adsorbent HxLi4-xMyTi5-yO12Is doped from M to Li4Ti5O12Form a precursor Li in the crystal lattice of4MyTi5-yO12And then the alloy is obtained by acid washing and lithium removal, wherein M is one or a mixture of more of Ce, Sn and Hf, the value range of x is 0.0-4.0, x is not 0, and the value range of y is 0.05-2.0.
In the present invention, the M element replaces Li4Ti5O12The position of the medium titanium element is random and is not limited to a specific position.
The invention also provides a preparation method of the doped lithium titanate adsorbent, which comprises the following main steps: mixing titanium source, lithium source and M salt uniformly, drying, calcining, cooling and acid-washing.
The titanium source is titanium dioxide (rutile type or anatase type) or metatitanic acid; the lithium source is lithium acetate, lithium hydroxide or lithium carbonate, the M salt is soluble salt of one or more metals of Ce, Sn and Hf, such as acetate or nitrate, and the raw materials are mixed.
In the mixing process, the adding amount of a lithium source and a titanium source is added according to the mol ratio of Li to Ti = 4.0-4.2 to 5.0, M salt is added according to the stoichiometric ratio of chemical reaction, and when M is a plurality of metal elements, y is the sum of the atomic numbers of each metal element; the molecular formula of the hydrogen type lithium titanate adsorbent formed by acid washing and lithium removal of the doped lithium titanate adsorbent precursor is HxLi4-xMyTi5-yO12(ii) a Mixing a solid titanium source, a lithium source, M salt and water at a solid-to-liquid ratio of 1: 0.5-7 (mass ratio), stirring at 10-95 ℃ for 0.5-10 h, and drying the material.
The drying process is carried out by at least one of spray drying, vacuum drying and forced air drying, the drying temperature is 80-300 ℃, the drying time is 1-24 hours, and the material is calcined.
And in the calcining process, the dried raw material is calcined at 700-850 ℃ for 10-70 h, preferably 12-50 h, so as to obtain the doped lithium titanate adsorbent precursor.
The acid washing process is to use 0.1-3.0 mol/L HCl or H for the doped lithium titanate adsorbent precursor2SO4Soaking and stirring for 0.5-12H, and changing the shape to obtain the hydrogen-type doped lithium titanate adsorbent HxLi4-xMyTi5-yO12。
The hydrogen-type doped lithium titanate adsorbent can be directly applied to salt lake original brine or brine after evaporation and concentration, and the principle is as follows:
loaded adsorption of Li+The process is as follows: H-SO (hydrogen form) + Li+→ Li-SO (lithium form) + H+
Elution of displaced Li+The process is as follows: Li-SO (lithium form) + H+→ H-SO (hydrogen form) + Li+
The application method of the hydrogen-type doped lithium titanate adsorbent comprises the following steps: adjusting the initial pH value of salt lake brine or a lithium-containing solution to be more than 6.5 by using caustic soda, adding the hydrogen-type adsorbent into the brine, stirring for a period of time, and filtering and separating to obtain adsorption mother liquor and a lithium-loaded adsorbent; putting the lithium-loaded adsorbent into acid liquor to desorb lithium, stirring for a period of time, filtering and separating to obtain a filtrate, namely a lithium-rich solution, and a filter cake, namely a converted and recovered hydrogen-type adsorbent, which can be repeatedly used.
The invention has the advantages that:
(1) h proposed by the inventionxLi4-xMyTi5-yO12The metal ions M are doped in the lithium titanate, so that the microporous structure of the adsorbent is improved, the lithium adsorption capacity and the selectivity are improved, and when the lithium is extracted from the brine with the magnesium-lithium ratio of more than 100, the lithium adsorption rate is more than 75 percent, and the magnesium removal rate is more than 99 percent;
(2) the doped lithium titanate adsorbent provided by the invention has good adaptability to acid-base environments, is suitable for extracting lithium from sulfate salt lake brine, and is also suitable for extracting lithium from carbonate salt lake brine with high alkalinity or lithium carbonate lithium precipitation mother liquor, and the manganese lithium adsorbent does not have the characteristic;
(3) the desorption liquid obtained by the doped lithium titanate adsorbent in the lithium desorption process has high acidity, the lithium enrichment times are about 1-7 times, the titanium dissolution rate is low, and the doped lithium titanate adsorbent has great industrial application prospects.
Detailed description of the invention
In order to explain the present invention in more detail, the following examples are given for illustration, but the present invention is not limited to these examples.
Example 1
LiOH·H2O、SnC2O4And H2TiO3Mixing in a molar ratio of 4.05:0.09:4.91, adding 55.0g LiOH. H2O (analytically pure), 6.1g SnC2O4(chemically pure) and 156.3g H2TiO3Adding 435g of deionized water into the mixture according to the solid-liquid ratio of 1:2, and stirring the mixture in a water bath at 60 ℃ for 3 hours; drying the obtained slurry at 110 deg.C for 5h by blowing, grinding, calcining at 750 deg.C for 15h, cooling, grinding to obtain Li4Sn0.09Ti4.91O12And (3) an adsorbent precursor. Taking 100 g of the Li4Sn0.09Ti4.91O12Placing the solution in HCl 3.0L with the concentration of 1.0 mol/L, stirring and soaking for 4h, and filtering to obtain the hydrogen type lithium ion adsorbent. Then 1000 mL of brine with the composition shown in Table 1 was taken, the pH was adjusted to 8.0 with 0.1mol/L NaOH solution, 42 g (dry weight) of the hydrogen-type lithium ion adsorbent was added, the mixture was soaked for 60min with stirring, and filtration was carried out to obtain an adsorption mother liquor L1Determination of Li+ 、Mg2+Content of the obtained product is1Namely, the load of Li+The adsorbent of (4); at S1Adding 100 mL of hydrochloric acid with concentration of 1.0 mol/L, soaking for 50min under stirring, and filtering to obtain desorption solution L2Determination of Li+ 、Mg2+To give a filter cake S2Namely the hydrogen type adsorbent, and the hydrogen type adsorbent can be recycled. The measurement results are shown in tables 4 and 5.
TABLE 1 composition of the raw brine used in example 1
Example 2
C2H3O2Li、Zr(NO3)4·5H2O and rutile TiO2Mixing at a molar ratio of 4.04:1.2:3.8, and mixing with 78.5g C2H3O2Li (analytically pure), 151.7g Zr (NO)3)4·5H2O (analytically pure) and 89.4g of rutile TiO2(analytically pure) adding 480g of deionized water according to the solid-liquid ratio of 1:1.5, and stirring for 8 hours at 25 ℃; drying the obtained slurry at 120 deg.C for 4h by blowing, grinding, calcining at 800 deg.C for 16h, cooling, grinding to obtain Li4Zr1.2Ti3.8O12And (3) an adsorbent precursor. Taking 100 g of the Li4Zr1.2Ti3.8O12Soaking in 1.8L HCl 1.5 mol/L for 5h, filtering to obtain hydrogen type lithium ion adsorbent, adding 70 g (dry weight) of hydrogen type lithium ion adsorbent into 1000 mL bittern (pH = 9.5) shown in Table 2, soaking under stirring for 80min, and filtering to obtain adsorption mother liquor L3Determination of Li+ 、Mg2+Content of the obtained product is3Namely, the load of Li+The adsorbent of (1). At S3Adding 1.0 mol/L hydrochloric acid 200mL, soaking for 60min under stirring, and filtering to obtain desorption solution L4Determination of Li+ 、Mg2+To give a filter cake S4Namely the hydrogen type adsorbent, and the hydrogen type adsorbent can be recycled. The measurement results are shown in tables 4 and 5.
Table 2 composition of carbonate brine used in example 2
Example 3
Li2CO3、Ce(NO3)3·6H2O and anatase type TiO2The molar ratio of the raw materials is 2.03:0.05:4.95 mixing, 48.7g Li2CO3(analytically pure), 7.0g Ce (NO)3)3·6H2O (analytically pure) and 128.3g TiO2Adding 460g of deionized water according to the solid-liquid ratio of 1:2.5, and stirring in a water bath at 50 ℃ for 4 hours; drying the obtained slurry at 105 deg.C for 8h by blowing, grinding, calcining at 700 deg.C for 18h, cooling, and grinding to obtain Li4Ce0.05Ti4.95O12And (3) an adsorbent precursor. Taking 100 g of the Li4Ce0.05Ti4.95O12Soaking in 3.0mol/L HCl 1.0L for 6h, filtering to obtain hydrogen type lithium ion adsorbent, adding hydrogen type lithium ion adsorbent 45g (dry weight) into brine 200mL (pH > 14) shown in Table 3, soaking under stirring for 70min, and filtering to obtain adsorption mother liquor L5Determination of Li+ 、Mg2+Content of the obtained product is5Namely, the load of Li+The adsorbent of (1). At S5Adding 160 mL of hydrochloric acid with the concentration of 1.0 mol/L, soaking for 80min under stirring, and filtering to obtain desorption solution L6Determination of Li+ 、Mg2+To give a filter cake S6Namely the hydrogen type adsorbent, and the hydrogen type adsorbent can be recycled. The measurement results are shown in tables 4 and 5.
Table 3 lithium deposition mother liquor composition of lithium carbonate used in example 3
TABLE 4 magnesium lithium separation of the adsorption process of examples 1-3
TABLE 5 lithium recovery in examples 1-3 desorption procedures
Claims (7)
1. The preparation method of the doped lithium titanate adsorbent is characterized in that the doped lithium titanate adsorbent HxLi4- xMyTi5-yO12Is doped from M to Li4Ti5O12Form a precursor Li in the crystal lattice of4MyTi5-yO12The lithium-removing catalyst is obtained by acid-washing and lithium-removing, wherein M is one or a mixture of more of Ce, Sn and Hf, x is 0.0-4.0 and is not 0, and y is 0.05-2.0;
the M element replaces Li4Ti5O12The position of the medium titanium element is random and is not limited by a specific position;
the adsorbent is prepared by the following method:
uniformly mixing a titanium source, a lithium source and M salt, drying, calcining, cooling and acid washing to synthesize the doped lithium titanate adsorption material HxLi4-xMyTi5-yO12(ii) a Adding lithium source and titanium source according to the mol ratio of Li to Ti = 4.0-4.2 to 5.0, adding M salt according to the stoichiometric ratio of chemical reaction, and when M is multiple metal elements, y is the sum of the atomic numbers of each metal element; and in the calcining process, the dried raw material is calcined at 700-850 ℃ for 10-70 h to obtain the doped lithium titanate adsorbent precursor.
2. The method of claim 1, wherein the titanium source is titanium dioxide or metatitanic acid; the titanium dioxide is rutile type or anatase type; the lithium source is lithium acetate, lithium hydroxide or lithium carbonate, and the M salt is soluble salt of one or more metals of Ce, Sn and Hf.
3. The method of claim 1, wherein the M salt is an acetate or nitrate.
4. The method according to claim 1, wherein the solid titanium source, the lithium source and the M salt are mixed with water or an acetic acid solution at a solid-liquid mass ratio of 1: 0.5-7, stirred at 10-95 ℃ for 0.5-10 h, and then the material is dried.
5. The method of claim 1, wherein the drying is performed by at least one of spray drying, vacuum drying and forced air drying, wherein the drying temperature is 80 ℃ to 300 ℃ and the drying time is 1h to 24 h.
6. The method of claim 1, wherein the calcination time is 12 to 50 hours.
7. The method of claim 1, wherein the acid washing process is performed by using 0.1-3.0 mol/L HCl or H for the doped lithium titanate adsorbent precursor2SO4Soaking and stirring for 0.5-12H, and changing the shape to obtain a hydrogen-type doped lithium titanate adsorbent HxLi4-xMyTi5-yO12。
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| CN110028099A (en) * | 2019-05-24 | 2019-07-19 | 江苏特丰新材料科技有限公司 | A kind of preparation method of powder-type high capacity titanium based lithium-ion exchanger |
| CN110090614B (en) * | 2019-05-28 | 2021-08-27 | 湖南大学 | Preparation method of lithium ion sieve adsorbent, product and application thereof |
| CN110180489B (en) * | 2019-06-25 | 2021-12-07 | 四川泛宇锂能新材料科技有限公司 | Sulfur-doped lithium-rich manganese lithium adsorbent and preparation method and application thereof |
| CN110860270A (en) * | 2019-11-29 | 2020-03-06 | 成都泰利创富锂业科技有限公司 | Lithium-rich lithium metatitanate doped adsorption material and preparation method thereof |
| CN110918044A (en) * | 2019-12-02 | 2020-03-27 | 尚鹏 | Doped lithium-rich spinel type titanium lithium oxide adsorption material and preparation method thereof |
| CN111533146A (en) * | 2020-05-07 | 2020-08-14 | 四川泛宇锂能新材料科技有限公司 | Method for recovering lithium in lithium carbonate lithium precipitation mother liquor |
| CN112717468A (en) | 2020-12-09 | 2021-04-30 | 西安蓝晓科技新材料股份有限公司 | Method for recovering lithium in lithium precipitation mother liquor |
| CN112705156B (en) * | 2020-12-21 | 2022-06-21 | 四川大学 | Porous doped titanium lithium adsorbent and preparation method thereof |
| CN115301196B (en) * | 2022-04-27 | 2023-06-16 | 南京工业大学 | Titanium-doped modified manganese-series lithium ion sieve and preparation method thereof |
| CN115253999B (en) * | 2022-07-13 | 2023-06-23 | 中国科学院青海盐湖研究所 | Lithium adsorption material and preparation method and application thereof |
| CN116983948A (en) * | 2023-09-27 | 2023-11-03 | 赣州市力道新能源有限公司 | Preparation method of titanium lithium ion adsorption material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049238A (en) * | 2010-11-19 | 2011-05-11 | 中南大学 | Ion sieve for selectively extracting lithium and application thereof |
| CN103991908A (en) * | 2014-05-08 | 2014-08-20 | 华东理工大学 | Method for regulating and controlling stability of lithium ion sieve by cation doping |
| JP2017131863A (en) * | 2016-01-29 | 2017-08-03 | 国立研究開発法人量子科学技術研究開発機構 | Lithium permselective membrane, lithium recovery apparatus, lithium recovery method, hydrogen production method |
| KR20170142661A (en) * | 2016-06-20 | 2017-12-28 | 연세대학교 산학협력단 | Lithium absorbent and method of manufacturing the same |
| CN108187606A (en) * | 2018-01-22 | 2018-06-22 | 天津市职业大学 | A kind of electric conductivity titanium based lithium-ion sieve and preparation method thereof |
| CN108212074A (en) * | 2016-12-12 | 2018-06-29 | 中国科学院过程工程研究所 | It is a kind of can the metatitanic acid type lithium ion sieve of Magnetic Isolation, preparation method and applications |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140069874A (en) * | 2012-11-30 | 2014-06-10 | 한국화학연구원 | Method for recovering indium from indium containing solution or mixture |
| CN102983319B (en) * | 2012-12-18 | 2015-08-26 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of modified lithium titanate material and preparation method thereof |
-
2018
- 2018-09-14 CN CN201811072111.8A patent/CN109317087B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049238A (en) * | 2010-11-19 | 2011-05-11 | 中南大学 | Ion sieve for selectively extracting lithium and application thereof |
| CN103991908A (en) * | 2014-05-08 | 2014-08-20 | 华东理工大学 | Method for regulating and controlling stability of lithium ion sieve by cation doping |
| JP2017131863A (en) * | 2016-01-29 | 2017-08-03 | 国立研究開発法人量子科学技術研究開発機構 | Lithium permselective membrane, lithium recovery apparatus, lithium recovery method, hydrogen production method |
| KR20170142661A (en) * | 2016-06-20 | 2017-12-28 | 연세대학교 산학협력단 | Lithium absorbent and method of manufacturing the same |
| CN108212074A (en) * | 2016-12-12 | 2018-06-29 | 中国科学院过程工程研究所 | It is a kind of can the metatitanic acid type lithium ion sieve of Magnetic Isolation, preparation method and applications |
| CN108187606A (en) * | 2018-01-22 | 2018-06-22 | 天津市职业大学 | A kind of electric conductivity titanium based lithium-ion sieve and preparation method thereof |
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