CN101985098A - Method for preparing manganese series lithium-ion sieve adsorbent H4Mn5O12 and precursor thereof - Google Patents
Method for preparing manganese series lithium-ion sieve adsorbent H4Mn5O12 and precursor thereof Download PDFInfo
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- CN101985098A CN101985098A CN 201010285009 CN201010285009A CN101985098A CN 101985098 A CN101985098 A CN 101985098A CN 201010285009 CN201010285009 CN 201010285009 CN 201010285009 A CN201010285009 A CN 201010285009A CN 101985098 A CN101985098 A CN 101985098A
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Abstract
The invention provides a method for preparing a manganese series lithium-ion sieve adsorbent H4Mn5O12 and a precursor thereof, relating to a preparation method of an inorganic adsorbent for absorbing lithium from liquid lithium resources such as salt brine, seawater, geothermal water and the like. In the preparation method, manganese salts and lithium salts with low melting points are taken as raw materials, organic carboxylic acid is used as an ingredient, the precursor Li4Mn5O12 is obtained through soft chemical synthesis and low-temperature roasting; acid treatment is carried out on the precursor, and Li in the precursor is extracted to be converted to an H-type ion sieve represented by H4Mn5O12 or MnO2.0.31H2O; and the H-type ion sieve H4Mn5O12 is filtered, washed and dried to obtain the adsorbent capable of sieving lithium ions. The method of the invention has simple process, and the obtained ion sieve has the advantages of small dissolving loss, fast adsorption rate and high adsorption capacity.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion sieve adsorbant, particularly prepare lithium ion sieve H
4Mn
5O
12(or MnO
20.31H
2O) and the method for precursor.
Background technology
Lithium and compound thereof are widely used, and in fields such as metallurgy, pharmacy, electrochmical power source, alloy material and nuclear fusion generatings important purposes are arranged all, and the market demand is vigorous.Yet the lithium ore reserve does not satisfy the market demand far away in the world, and it is exhausted day by day.Contain huge lithium resource in salt lake bittern, underground water, the seawater, become in recent years the developmental research emphasis of lithium industry both at home and abroad, the liquid lithium mineral resources will become the main resource of carrying lithium.
China is a salt lake resources big country, and research resource such as comprehensive reutilization lithium from the salt lake has crucial meaning for the improvement of China's salt lake resources comprehensive utilization and ecological environment.The method of extracting lithium from liquid lithium resources such as salt lake mainly contains the precipitation method, solvent extraction, ion exchange adsorption.Wherein ion exchange adsorption, particularly lithium ion sieve method especially are fit to extract lithium the bittern low from lithium content, that calcium-magnesium content is high.And the Mn oxide lithium ion sieve is considered to one of best inorganic lithium sorbing material of absorption property and application prospect.Reported Mn oxide lithium ion sieve mainly contains λ-MnO
2, H
4Mn
5O
12(or MnO
20.31H
2O) and MnO
20.5H
2O, they are respectively by precursor LiMn
2O
4, Li
1.33Mn
1.67O
4And Li
1.6Mn
1.6O
4Make.Li
1.33Mn
1.67O
4And Li
1.6Mn
1.6O
4Because Mn wherein is+4 valencys, be in the process of ion sieve the molten damage of disproportionation not to take place in transition, and than LiMn
2O
4Have better structural stability and absorption property.But the much more synthetic of these two kinds of materials adopted through hydro-thermal method synthetic mesophase products, and complex process, condition harshness, production cost height, output are little, are unfavorable for large-scale production.
Summary of the invention
The objective of the invention is to overcome existing preparation H
4Mn
5O
12The deficiency of lithium ion sieve, provide a kind of raw material be simple and easy to, the simply softening synthetic method of learning of reaction condition gentleness, technical process.Prepare the lithium ion sieve that molten damage is little, adsorption rate is fast, adsorption capacity is high.
A kind of preparation lithium ion sieve H of the present invention
4Mn
5O
12And the method for precursor, be soft chemical method.Technical scheme of the present invention may further comprise the steps:
(1) be 0.6～1.0 with lithium acetate and manganese acetate according to lithium manganese mol ratio: 1 is dissolved in the water;
(2) the compounding ingredient citric acid is dissolved in the water;
(3) solution with step (1), (2) reacts.Reacted product carries out evaporation drying, grinding;
(4) drying composite that step (3) is obtained promptly obtains ion sieve precursor Li at 300 ℃ of-500 ℃ of following roasting 10-15h
4Mn
5O
12
(5) with inorganic acid with the lithium stripping in the precursor after filtration, washing, drying, promptly obtain H-type lithium ion sieve H
4Mn
5O
12
Preferred lithium acetate and manganese acetate according to lithium manganese mol ratio be 0.8: 1 soluble in water.
Citric acid of the present invention is 0.5～1.5: 1 with (lithium+manganese) preferred mol ratio.
Described water is pure water, distilled water or deionized water.
Inorganic acid preferably adopts hydrochloric acid, sulfuric acid or nitric acid, concentration 0.2mol/L～1mol/L.
The advantage and the good effect of invention
(1) the present inventor finds that through the long-term test and the accumulation of practical experience the lithium source of selecting for use is that lithium acetate, manganese source are manganese acetate, is low-melting compound (70 ℃ of lithium acetate fusing points, 80 ℃ of manganese acetate fusing points).This can guarantee (300-500 ℃) the fully fusion in product synthesis temperature scope of lithium source and manganese source, evenly diffusion.If adopt lithium hydroxide (450 ℃ of fusing points), lithium carbonate (723 ℃ of fusing points), manganese dioxide (390 ℃ of fusing points), manganese carbonate (350 ℃) then occur the Mn oxide dephasign in the product easily; In addition,, avoid adopting nitrate, sulfate, chloride etc. to contain anionic raw materials such as N, S, Cl, also can effectively guarantee degree of purity of production because the present invention adopts acetate to do lithium source and manganese source; The more important thing is that the inventor passes through repetition test, also find adopting citric acid is compounding ingredient, and this material can be fully forms complex, distributes from the lithium atom and the manganese atom of atomic level homogenizing product with lithium ion and manganese ion, makes product Li not occur
2MnO
3Etc. rich lithium lithium manganese oxide dephasign.Also have a bit, what the inventor need further specify is that citric acid and acetate in the raw material that the present invention adopts can discharge a large amount of heat in roasting process, be beneficial to reaction and carry out, and discharge a large amount of nontoxic CO simultaneously
2Gas makes product form the porous pattern that small grains constitutes, and this effect is difficult to realize by other solid phase methods.
(2) method of the present invention's employing is for cooperating the softening synthetic method of learning, and experiment condition, product proportioning are convenient to control;
(3) the present invention has successfully obtained lithium ion sieve precursor material Li
4Mn
5O
12, it has spinel structure, stable in properties;
(4) the present invention has successfully obtained lithium ion sieve material H
4Mn
5O
12, it can be used for carrying lithium in the lithium-containing solutions such as salt lake bittern, seawater, and has good cycling stability, advantage that adsorption capacity is big.
Description of drawings
Fig. 1 is a synthesis step schematic diagram of the present invention.
Fig. 2 is the embodiment of the invention 1 gained lithium ion sieve precursor Li
4Mn
5O
12Before the acidleach and the XRD figure after the acidleach.
Fig. 3 is the embodiment of the invention 1 gained lithium ion sieve precursor Li
4Mn
5O
12SEM figure before the acidleach.
Fig. 4 is the embodiment of the invention 1 gained lithium ion sieve precursor Li
4Mn
5O
12SEM figure after the acidleach.
The specific embodiment
The present invention will be further described below by embodiment, and its purpose only is better to understand content of the present invention, but protection scope of the present invention is not limited by the cases cited.
Embodiment 1:
Shown in accompanying drawing 1 synthesis flow, accurately take by weighing lithium acetate 4.0808g and manganese acetate 12.255g, the adding distil water dissolving obtains mixed solution.This mixed solution is dropwise added in the citric acid solution that contains citric acid 18.912g 80 ℃ of water bath with thermostatic control reaction 1h.Then product is put into 120 ℃ of dryings of baking oven, obtained yellow solid.Rise to 400 ℃ of insulation 12h with putting into the programming rate of batch-type furnace with 5 ℃/min after this yellow solid grinding, cooling naturally promptly obtains spinel-type lithium-ion sieve precursor Li subsequently
4Mn
5O
12, as shown in Figure 2.With this lithium ion sieve precursor Li
4Mn
5O
12HCl acidleach 24h with 0.5mol/L promptly obtains lithium ion sieve H
4Mn
5O
12, as shown in Figure 2.Fig. 3 and Fig. 4 are respectively gained lithium ion sieve precursor Li
4Mn
5O
12SEM figure before and after the acidleach.Take by weighing 0.3g lithium ion sieve H
4Mn
5O
12Put into certain salt lake bittern that 30ml contains Li+250mg/L, after the 24h adsorption equilibrium, record its first adsorption capacity be about 14mg/g.
Embodiment 2
Shown in Fig. 1 synthesis flow, accurately take by weighing lithium acetate 4.0808g and manganese acetate 12.255g, the adding distil water dissolving obtains mixed solution.This mixed solution is dropwise added in the citric acid solution that contains citric acid 9.456g 80 ℃ of water bath with thermostatic control reaction 1h.Then product is put into 120 ℃ of dryings of baking oven, obtained yellow solid.Rise to 350 ℃ of insulation 12h with putting into the programming rate of batch-type furnace with 5 ℃/min after this yellow solid grinding, cooling naturally promptly obtains lithium ion sieve precursor Li subsequently
4Mn
5O
12With this lithium ion sieve precursor Li
4Mn
5O
12HCl acidleach 24h with 0.7mol/L promptly obtains lithium ion sieve H
4Mn
5O
12Take by weighing 0.3g lithium ion sieve H
4Mn
5O
12Put into 30ml and contain Li
+In certain salt lake bittern of 250mg/L, after the 24h adsorption equilibrium, recording its adsorption capacity is 10mg/g.
Claims (9)
1. one kind prepares manganese based lithium-ion sieve adsorbant H
4Mn
5O
12Method, it is characterized in that, may further comprise the steps:
(1) be 0.6～1.0 with lithium acetate and manganese acetate according to lithium manganese mol ratio: 1 is dissolved in the water;
(2) the compounding ingredient citric acid is dissolved in the water;
(3) solution with step (1), (2) reacts; Reacted product evaporation drying, grinding;
(4) drying composite that step (3) is obtained promptly obtains ion sieve precursor Li at 300 ℃ of-500 ℃ of following roasting 10-15h
4Mn
5O
12
(5) with inorganic acid with the lithium stripping in the precursor after filtration, washing, drying, promptly obtain H-type lithium ion sieve H
4Mn
5O
12
2. method according to claim 1 is characterized in that, the mol ratio of citric acid and lithium+manganese is 0.5～1.5: 1.
3. method according to claim 1 is characterized in that, lithium acetate and manganese acetate according to lithium manganese mol ratio be 0.8: 1 soluble in water.
4. according to claim 1 or 2 or 3 described methods, it is characterized in that described water is pure water, distilled water or deionized water.
5. according to claim 1 or 2 or 3 described methods, it is characterized in that described inorganic acid is hydrochloric acid or nitric acid or the sulfuric acid of 0.2mol/L～1.0mol/L.
6. one kind prepares manganese based lithium-ion sieve adsorbant precursor Li
4Mn
5O
12Method, it is characterized in that, may further comprise the steps:
(1) be 0.6～1.0 with lithium acetate and manganese acetate according to lithium manganese mol ratio: 1 is dissolved in the water;
(2) the compounding ingredient citric acid is dissolved in the water;
(3) solution with step (1), (2) reacts, and reacted product carries out evaporation drying, grinding;
(4) drying composite that step (3) is obtained promptly obtains ion sieve precursor Li at 300 ℃ of-500 ℃ of following roasting 10-15h
4Mn
5O
12
7. method according to claim 6 is characterized in that, the mol ratio of citric acid and lithium+manganese is 0.5～1.5: 1.
8. method according to claim 6 is characterized in that, lithium acetate and manganese acetate are to be dissolved in distilled water at 0.8: 1 according to lithium manganese mol ratio.
9. according to claim 6 or 7 or 8 described methods, it is characterized in that described water is pure water, distilled water or deionized water.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104925836A (en) * | 2015-05-22 | 2015-09-23 | 中国科学院青海盐湖研究所 | Method for extracting lithium from lithium-containing brine |
| CN105883927A (en) * | 2016-04-07 | 2016-08-24 | 黄冈师范学院 | Method for desorption of lithium manganate series adsorbent precursor |
| CN106311190A (en) * | 2016-08-18 | 2017-01-11 | 佛山科学技术学院 | Preparation method of porous manganese-based lithium ion sieve adsorbent |
| CN107243318A (en) * | 2017-05-11 | 2017-10-13 | 南京工业大学 | A kind of preparation method of titanium-type lithium ion sieve adsorbant |
| CN108199104A (en) * | 2017-11-30 | 2018-06-22 | 湖南邦普循环科技有限公司 | A kind of lithium manganate battery waste material prepares the method and its lithium ion sieve of lithium ion sieve |
| CN108543516A (en) * | 2018-03-31 | 2018-09-18 | 毛强平 | A kind of lithium ion selective absorbent, preparation method and the technique for carrying lithium from brine |
| CN108745276A (en) * | 2018-04-18 | 2018-11-06 | 南京工业大学 | A kind of preparation method of mixed-forming lithium ion adsorbent |
| CN109384262A (en) * | 2018-11-12 | 2019-02-26 | 南京工业大学 | A kind of sheet Li4Mn5O12The preparation method of ion sieve presoma and ion sieve |
| CN110639507A (en) * | 2019-09-27 | 2020-01-03 | 华南理工大学 | Li-Mn bimetallic oxide composite denitration catalyst and preparation method and application thereof |
| CN111017999A (en) * | 2019-12-13 | 2020-04-17 | 中国科学院山西煤炭化学研究所 | Molten salt three-step method for preparing lithium ion sieve precursor Li1.6Mn1.6O4And applications thereof |
| CN113663638A (en) * | 2021-08-02 | 2021-11-19 | 中国科学院武汉岩土力学研究所 | Lithium ion adsorption caisson and preparation method and application thereof |
| CN115837265A (en) * | 2022-11-28 | 2023-03-24 | 云汇环保科技南通有限公司 | Manganese-based oxide lithium ion sieve and preparation method and application thereof |
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| CN1810353A (en) * | 2005-12-15 | 2006-08-02 | 北京矿冶研究总院 | Method for preparing lithium ion sieve adsorbent |
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Cited By (18)
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|---|---|---|---|---|
| CN103991908B (en) * | 2014-05-08 | 2016-04-20 | 华东理工大学 | By the method for cation doping regulation and control lithium ion sieve stability |
| 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 |
| CN104925836A (en) * | 2015-05-22 | 2015-09-23 | 中国科学院青海盐湖研究所 | Method for extracting lithium from lithium-containing brine |
| CN105883927A (en) * | 2016-04-07 | 2016-08-24 | 黄冈师范学院 | Method for desorption of lithium manganate series adsorbent precursor |
| CN106311190A (en) * | 2016-08-18 | 2017-01-11 | 佛山科学技术学院 | Preparation method of porous manganese-based lithium ion sieve adsorbent |
| CN106311190B (en) * | 2016-08-18 | 2018-11-23 | 佛山科学技术学院 | The preparation method of porous manganese systems lithium ion sieve adsorbant |
| CN107243318A (en) * | 2017-05-11 | 2017-10-13 | 南京工业大学 | A kind of preparation method of titanium-type lithium ion sieve adsorbant |
| CN108199104A (en) * | 2017-11-30 | 2018-06-22 | 湖南邦普循环科技有限公司 | A kind of lithium manganate battery waste material prepares the method and its lithium ion sieve of lithium ion sieve |
| CN108543516B (en) * | 2018-03-31 | 2020-12-18 | 青海跨界分离技术有限公司 | Lithium ion selective adsorbent, preparation method and process for extracting lithium from brine |
| CN108543516A (en) * | 2018-03-31 | 2018-09-18 | 毛强平 | A kind of lithium ion selective absorbent, preparation method and the technique for carrying lithium from brine |
| CN112342378A (en) * | 2018-03-31 | 2021-02-09 | 南京霄祥工程技术有限公司 | Lithium ion adsorbent and preparation method thereof |
| CN108745276A (en) * | 2018-04-18 | 2018-11-06 | 南京工业大学 | A kind of preparation method of mixed-forming lithium ion adsorbent |
| CN109384262A (en) * | 2018-11-12 | 2019-02-26 | 南京工业大学 | A kind of sheet Li4Mn5O12The preparation method of ion sieve presoma and ion sieve |
| CN110639507A (en) * | 2019-09-27 | 2020-01-03 | 华南理工大学 | Li-Mn bimetallic oxide composite denitration catalyst and preparation method and application thereof |
| CN111017999A (en) * | 2019-12-13 | 2020-04-17 | 中国科学院山西煤炭化学研究所 | Molten salt three-step method for preparing lithium ion sieve precursor Li1.6Mn1.6O4And applications thereof |
| CN111017999B (en) * | 2019-12-13 | 2021-11-30 | 中国科学院山西煤炭化学研究所 | Molten salt three-step method for preparing lithium ion sieve precursor Li1.6Mn1.6O4And applications thereof |
| CN113663638A (en) * | 2021-08-02 | 2021-11-19 | 中国科学院武汉岩土力学研究所 | Lithium ion adsorption caisson and preparation method and application thereof |
| CN115837265A (en) * | 2022-11-28 | 2023-03-24 | 云汇环保科技南通有限公司 | Manganese-based oxide lithium ion sieve and preparation method and application thereof |
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Application publication date: 20110316 |