CN109289756B - Porous manganese-based lithium ion sieve adsorbent and preparation method thereof - Google Patents
Porous manganese-based lithium ion sieve adsorbent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a porous manganese-based lithium ion sieve adsorbent, which comprises the following steps: adding a manganese source and a lithium source into water, and stirring to obtain a first mixed solution; adding an organic polyol compound into the first mixed solution, and stirring to obtain a second mixed solution; placing the second mixed solution into a microwave reactor, reacting at 120-200 ℃ for 10-120 min, and then carrying out solid-liquid separation on solid and liquid in the second mixed solution to obtain LiMnO2Particles; subjecting the obtained LiMnO to2Calcining the particles at 450-600 ℃ for 3-8 h to obtain Li1.6Mn1.6O4Porous manganese-based lithium ion sieve adsorbent. The invention adopts a microwave hydrothermal reaction method to prepare the porous manganese-based lithium ion sieve adsorbent, adopts organic polyol as a structure regulating agent and a reducing agent for regulating growth, has simple raw materials and simple preparation process, and obtains the product with high purity, high yield, uniform particle size and stable performance.
Description
Technical Field
The invention relates to a lithium ion sieve adsorbent, in particular to a porous manganese series lithium ion sieve adsorbent and a preparation method thereof.
Background
Lithium is mainly present in the salt lake brine and seawater as pegmatite ore such as spodumene and lepidolite or as lithium ions in nature. In recent years, much attention is paid to the extraction of lithium from liquid ores at home and abroad, nearly 80% of lithium salt is a product for extracting lithium from brine at present, and the comprehensive development and utilization of brine lithium resources become the mainstream of the development of the lithium industry. The salt lakes in the middle and western parts of China are numerous and rich in lithium, sodium, potassium, magnesium and other resources, so that the economic value is high. The method for extracting lithium ions from brine mainly comprises the following steps: the method comprises a precipitation method, an evaporation crystallization method, a solvent extraction method, a calcination leaching method, a salting-out method, a carbonization method, a selective semi-permeable membrane method, a 'schwann' method and an adsorption method, wherein the traditional 'precipitation-crystallization method' is not suitable for extracting lithium from salt lakes due to low Li content and high Mg/Li ratio in most of salt lake brine in China, the adsorption method has simple process and low cost, and is an effective method for extracting lithium from low-concentration lithium-containing solution, and the main medium for extracting lithium by the adsorption method is a lithium ion sieve adsorbent.
The lithium manganese spinel type lithium adsorbent has the advantages of wide research and high adsorption capacity, and is expected to be used for extracting lithium from salt lakes with high magnesium-lithium ratio. The spinel type adsorbent mainly comprises LiMnO4，Li1.33Mn1.66O4And Li1.6Mn1.6O4Wherein Li1.6Mn1.6O4The adsorption capacity is large, and the solvent loss resistance is good, so that the adsorption material is widely concerned. The existing preparation method mainly adopts a manganese source high-temperature solid phase method to prepare an intermediate LiMnO2Then preparing Li by a second high-temperature solid-phase method with aluminum salt1.6Mn1.6O4。
For example, CN101961634, adopts lithium salt and manganese oxide as raw materials, adds acetone or absolute ethyl alcohol as dispersing agent, grinds and mixes uniformly; calcining at constant temperature in inert atmosphere to obtain powdery LiMnO2Intermediate, then calcining with lithium source to prepare Li1.6Mn1.6O4An adsorbent. It mainly adopts a solid phase sintering method.
For another example, CN101985098, Li is prepared by sintering lithium acetate, manganese acetate and citric acid as raw materials1.33Mn1.66O4An adsorbent. It mainly adopts a solid phase sintering method.
For another example, CN103121724, which is an intermediate product of LiMnO preparation by mixing a permanganate solution, a lithium hydroxide solution and a divalent manganese salt, adding lithium hydroxide and hydrothermal reaction2Preparation of Li by high-temperature calcination1.6Mn1.6O4An adsorbent. It mainly employs a conventional hydrothermal method.
The prior art is currently preparing Li1.6Mn1.6O4In the adsorbent process, it obtains intermediate LiMnO2In the prior art, two methods are mainly used, one method is high-temperature sintering, and the method is difficult to effectively control the morphology and the dispersity of particles. The other is a traditional hydrothermal method, which mainly adopts a high-valence manganese source and a low-valence manganese source to add an oxidant to prepare MnOOH particles, and then prepares LiMnO through hydrothermal method2Each time of the traditional hydrothermal reaction is maintained for more than 12 hours, and the growth of the crystal is lack of regulation and control. The existing method has overlarge energy consumption, and an effective method is not adopted to control the uniformity and the dispersity of the particles and regulate and control the crystal growth process of the particles.
Disclosure of Invention
The invention mainly aims to provide a porous manganese-based lithium ion sieve adsorbent and a preparation method thereof, thereby overcoming the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a porous manganese-based lithium ion sieve adsorbent comprises the following steps:
(1) adding a manganese source and a lithium source into water, and stirring to obtain a first mixed solution;
(2) adding an organic polyol compound into the first mixed solution, and stirring to obtain a second mixed solution;
(3) placing the second mixed solution into a microwave reactor, reacting at 120-200 ℃ for 10-120 min, and then carrying out solid-liquid separation on solid and liquid in the second mixed solution to obtain LiMnO2Particles;
(4) subjecting the obtained LiMnO to2Calcining the particles at 450-600 ℃ for 3-8 h to obtain Li1.6Mn1.6O4Porous manganese-based lithium ion sieve adsorbent.
The embodiment of the invention also provides the porous manganese-based lithium ion sieve adsorbent prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts a microwave hydrothermal reaction method, adopts simple raw materials, only adopts a high-price manganese source, adds an organic structure directing agent organic polyol compound and simultaneously serves as a reducing agent, and prepares LiMnO rapidly in one step2Preparing porous flower-shaped Li after sintering1.6Mn1.6O4An adsorbent. The preparation process is simple, the prepared product has high purity, short heating time, high reaction speed, high preparation efficiency of the product and uniform particles. The reaction steps and the preparation cost are effectively reduced, the microwave hydrothermal reaction condition is easy to control, the large-scale industrial production is favorably realized, and the obtained product has high purity, high yield, uniform grain diameter and stable performance.
(2) The invention adopts common organic polyol as a structure regulator and a reducer for regulating growth, synthesizes an intermediate and prepares Li by a high-temperature solid phase method1.6Mn1.6O4The lithium ion sieve adsorbent has high purity, good quality, controllable surface, high dispersibility and high adsorption capacity, and the product presents hexagonal star-shaped particles, and the observation of a scanning electron microscope shows that the product of the invention is porous flower-shaped growing Li with different shapes1.6Mn1.6O4Lithium ion adsorbent crystals.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is an XRD diffractogram of a porous manganese-based lithium ion sieve adsorbent product prepared in the first example of the present invention;
FIG. 2 is an SEM scan of a porous manganese-based lithium ion sieve adsorbent product prepared according to one embodiment of the present invention;
FIG. 3 is an SEM scan of a porous manganese-based lithium ion sieve adsorbent product prepared according to example two of the present invention;
FIG. 4 is an XRD diffractogram of a first solid obtained in comparative example one of the present invention;
FIG. 5 is a SEM scan of a second solid lithium ion adsorbent obtained in comparative example I of the present invention;
FIG. 6 is a SEM scan of a lithium ion adsorbent obtained in comparative example two of the present invention.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to propose the technical solution of the present invention, and further explain the technical solution, the implementation process and the principle thereof, etc.
The invention provides the porous flower-shaped Li with high product purity, good quality and controllable surface1.6Mn1.6O4A preparation method of the adsorbent.
As one aspect of the technical scheme of the invention, the invention relates to a preparation method of a porous manganese-based lithium ion sieve adsorbent, which comprises the following steps:
(1) adding a manganese source and a lithium source into water, and stirring to obtain a first mixed solution;
(2) adding an organic polyol compound into the first mixed solution, and stirring to obtain a second mixed solution;
(3) placing the second mixed solution into a microwave reactor, reacting at 120-200 ℃ for 10-120 min, and then carrying out solid-liquid separation on solid and liquid in the second mixed solution to obtain LiMnO2Particles;
(4) subjecting the obtained LiMnO to2Calcining the particles at 450-600 ℃ for 3-8 h to obtain Li1.6Mn1.6O4Porous manganese-based lithium ion sieve adsorbent.
In some embodiments, the manganese source comprises any one or a combination of two or more of potassium permanganate, sodium permanganate, ammonium permanganate, zinc permanganate, magnesium permanganate, and calcium permanganate.
In some embodiments, the lithium source comprises any one or a combination of two or more of lithium hydroxide, lithium hydroxide monohydrate, lithium chloride, lithium carbonate, lithium sulfate, and lithium nitrate.
In some embodiments, the manganese source and the lithium source are present in a mass ratio of 0.15: 1.0 to 0.8: 1.0.
In some embodiments, the organic polyol compound includes any one or a combination of two or more of ethylene glycol, 1, 2-propanediol, 1, 4-butanediol, glycerol, xylitol, pentaerythritol, and sorbitol.
In some embodiments, the mass ratio of the organic polyol compound to the manganese source is 5: 1 to 50: 1.
In some embodiments, step (3) comprises: carrying out solid-liquid separation on the solid and the liquid in the second mixed solution to obtain a solid, cleaning and drying the solid to obtain LiMnO2And (3) granules.
In some preferred embodiments, the cleaning comprises: and (4) exchanging and cleaning with deionized water and ethanol.
In some embodiments, the stirring in step (1) and step (2) is magnetic stirring.
In some specific embodiments, the method for preparing the porous manganese-based lithium ion sieve adsorbent comprises:
(1) adding a manganese source and a lithium source into deionized water according to a proportion, and magnetically stirring to obtain a first mixed solution.
(2) Adding organic polyol compounds in a certain proportion into the first mixed solution, mixing and magnetically stirring to obtain a second mixed solution.
(3) Placing the second mixed solution into a microwave reactor at the temperature of 120-200 ℃, reacting for 10 minutes to 2 hours, after the reaction is finished, carrying out solid-liquid separation on the solid and liquid mixture to obtain a solid, cleaning and drying the solid to obtain pure LiMnO2And (3) granules.
(4) The obtained LiMnO2Calcining at 450-600 ℃ for 3-8 hours to obtain Li1.6Mn1.6O4Porous manganese-based lithium ion sieve adsorbent.
In another aspect of the present invention, the present invention relates to a porous manganese-based lithium ion sieve adsorbent, which is prepared by the method.
The technical solutions of the present invention will be described in further detail with reference to several preferred embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions.
Example 1
(1) Adding potassium permanganate and anhydrous lithium hydroxide into deionized water according to the mass ratio of 0.15: 1, and magnetically stirring to obtain a first mixed solution.
(2) And adding glycerol into the first mixed solution, wherein the weight ratio of the glycerol to the potassium permanganate is 5: 1, mixing and magnetically stirring to obtain a second mixed solution.
(3) Putting the second mixed solution into a microwave reactor, reacting for 10 minutes at the temperature of 120 ℃, after the reaction is finished, carrying out solid-liquid separation on the solid and liquid mixture to obtain a solid, and cleaning and drying to obtain pure LiMnO2And (3) granules.
(4) The obtained LiMnO2Calcining at 450 ℃ for 8 hours to obtain Li1.6Mn1.6O4A lithium ion adsorbent.
(5) The obtained Li1.6Mn1.6O4The lithium ion adsorbent was washed three times with deionized water and ethanol exchange.
The XRD diffraction pattern of the porous manganese-based lithium ion sieve adsorbent product is shown in figure 1, and the SEM scanning pattern of the porous manganese-based lithium ion sieve adsorbent product is shown in figure 2. By comparing the XRD diffraction analysis result with a diffraction spectrogram, the positions of all peaks are well matched, no other impurity peaks exist, and the product prepared by the preparation method is high in purity.
The observation of a scanning electron microscope can find that the product is porous flower-shaped growing Li with different shapes1.6Mn1.6O4Lithium ion adsorbent crystals.
Example 2
(1) Adding potassium permanganate and anhydrous lithium hydroxide into deionized water according to the mass ratio of 0.8:1, and magnetically stirring to obtain a first mixed solution.
(2) And adding glycerol into the first mixed solution, wherein the weight ratio of the glycerol to the potassium permanganate is 50: 1, mixing and magnetically stirring to obtain a second mixed solution.
(3) Putting the second mixed solution into a microwave reactor, reacting for 2 hours at the temperature of 200 ℃, after the reaction is finished, carrying out solid-liquid separation on the solid and liquid mixture to obtain a solid, cleaning and drying the solid to obtain pure LiMnO2And (3) granules.
(4) The obtained LiMnO2Calcining at 600 ℃ for 8 hours to obtain Li1.6Mn1.6O4A lithium ion adsorbent.
(5) The obtained Li1.6Mn1.6O4The lithium ion adsorbent was washed three times with deionized water and ethanol exchange.
SEM scanning picture of porous manganese series lithium ion sieve adsorbent product is shown in figure 3, and observation of scanning electron microscope shows that the product is porous flower-shaped growing Li with different shapes1.6Mn1.6O4Lithium ion adsorbent crystals.
Example 3
(1) Adding sodium permanganate and lithium chloride into deionized water according to the mass ratio of 0.15: 1, and magnetically stirring to obtain a first mixed solution.
(2) And adding ethylene glycol into the first mixed solution, wherein the mass ratio of the ethylene glycol to the potassium permanganate is 5: 1, mixing and magnetically stirring to obtain a second mixed solution.
(3) Putting the second mixed solution into a microwave reactor, reacting for 10 minutes at the temperature of 120 ℃, after the reaction is finished, carrying out solid-liquid separation on the solid and liquid mixture to obtain a solid, cleaning and drying the solid to obtain pure LiMnO2And (3) granules.
(4) The obtained LiMnO2Calcining at 450 deg.C for 8 hr to obtainLi1.6Mn1.6O4A lithium ion adsorbent.
(5) The obtained Li1.6Mn1.6O4The lithium ion adsorbent was washed three times with deionized water and ethanol exchange.
Example 4
(1) Adding ammonium permanganate and lithium chloride into deionized water according to the mass ratio of 0.8:1, and magnetically stirring to obtain a first mixed solution.
(2) And adding ethylene glycol into the first mixed solution, wherein the mass ratio of the ethylene glycol to the potassium permanganate is 50: 1, mixing and magnetically stirring to obtain a second mixed solution.
(3) Putting the second mixed solution into a microwave reactor, reacting for 2 hours at the temperature of 200 ℃, after the reaction is finished, carrying out solid-liquid separation on the solid and liquid mixture to obtain a solid, cleaning and drying the solid to obtain pure LiMnO2And (3) granules.
(4) The obtained LiMnO2Calcining at 600 ℃ for 3 hours to obtain Li1.6Mn1.6O4A lithium ion adsorbent.
(5) The obtained Li1.6Mn1.6O4The lithium ion adsorbent was washed three times with deionized water and ethanol exchange.
Comparative example 1
(1) Adding potassium permanganate and anhydrous lithium hydroxide into deionized water according to the mass ratio of 0.15: 1, and magnetically stirring to obtain a first mixed solution.
(2) And (3) putting the first mixed solution into a microwave reactor, reacting for 10 minutes at the temperature of 120 ℃, carrying out solid-liquid separation on the solid and liquid mixture after the reaction is finished to obtain a solid, and cleaning and drying to obtain first solid particles.
(3) And calcining the obtained first solid particles at the high temperature of 450 ℃ for 8 hours to obtain a second solid lithium ion adsorbent.
(4) The resulting second solid was washed three times with deionized water and ethanol exchange.
The reaction conditions were similar to those of example 1, and the XRD diffraction pattern of the first solid of the obtained product is shown in FIG. 4, and it can be seen thatIn the absence of added organic alcohol, only a portion of the LiMnO in the sample was present2The major component is Mn3O4This is due to the fact that in the absence of organic alcohols, the particles do not have sufficient reducing agent to result in a product first solid with mostly tetravalent Mn3O4And after finishing the high-temperature calcination, the product Mn3O4The product purity is lower and the impurities are more because of no change. The product LiMnO obtained at the same time2The second solid lithium ion adsorbent is rod-shaped particles, and the SEM scanning image of the second solid lithium ion adsorbent is shown in FIG. 5.
Comparative example 2
(1) Adding potassium permanganate and anhydrous lithium hydroxide into deionized water according to the mass ratio of 0.15: 1, and magnetically stirring to obtain a first mixed solution.
(2) And adding glycerol into the first mixed solution, wherein the weight ratio of the glycerol to the potassium permanganate is 5: 1, mixing and magnetically stirring to obtain a second mixed solution.
(3) Putting the second mixed solution into a conventional reaction kettle, putting the reaction kettle into an oven, reacting for 24 hours at the temperature of 120 ℃, after the reaction is finished, carrying out solid-liquid separation on the solid and liquid mixture to obtain a solid, cleaning and drying to obtain pure LiMnO2And (3) granules.
(4) The obtained LiMnO2Calcining at 450 ℃ for 8 hours to obtain Li1.6Mn1.6O4A lithium ion adsorbent.
(5) The obtained Li1.6Mn1.6O4The lithium ion adsorbent was washed three times with deionized water and ethanol exchange.
The obtained product can be observed by XRD and scanning electron microscope to be flower-shaped particles, but under the reaction condition, the product is mainly Li with irregular flower-shaped growth1.6Mn1.6O4The lithium ion adsorbent is crystalline and has poor uniformity, and the SEM scanning image is shown in figure 6.
In addition, the inventor also carries out corresponding tests by using other process conditions and the like listed in the foregoing to replace the corresponding process conditions in the examples 1 to 4, and the contents to be verified are similar to the products of the examples 1 to 4. Therefore, the contents of the verification of each example are not described herein one by one, and only examples 1 to 4 are used as representatives to describe the excellent points of the present invention.
It should be noted that, in the present document, in a general case, an element defined by the phrase "includes.
It should be understood that the above preferred embodiments are only for illustrating the present invention, and other embodiments of the present invention are also possible, but those skilled in the art will be able to adopt the technical teaching of the present invention and equivalent alternatives or modifications thereof without departing from the scope of the present invention.
Claims (5)
1. A preparation method of a porous manganese-based lithium ion sieve adsorbent is characterized by comprising the following steps:
(1) adding a manganese source and a lithium source into water, and stirring to obtain a first mixed solution, wherein the mass ratio of the manganese source to the lithium source is 0.15: 1.0-0.8: 1.0;
(2) adding an organic polyol compound into the first mixed solution, wherein the mass ratio of the organic polyol compound to the manganese source is 5: 1-50: 1, stirring to obtain a second mixed solution;
(3) placing the second mixed solution into a microwave reactor, reacting at 120-200 ℃ for 10-120 min, and then carrying out solid-liquid separation on solid and liquid in the second mixed solution to obtain LiMnO2Particles;
(4) subjecting the obtained LiMnO to2Calcining the particles at 450-600 ℃ for 3-8 h to obtain Li1.6Mn1.6O4A porous manganese-based lithium ion sieve adsorbent;
wherein the manganese source is selected from any one or the combination of more than two of potassium permanganate, sodium permanganate, ammonium permanganate, zinc permanganate, magnesium permanganate and calcium permanganate;
the lithium source comprises any one or the combination of more than two of lithium hydroxide, lithium hydroxide monohydrate, lithium chloride, lithium carbonate, lithium sulfate and lithium nitrate;
the organic polyol compound is selected from one or a combination of more than two of ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, glycerol, xylitol, pentaerythritol and sorbitol.
2. The method of claim 1, wherein step (3) comprises: carrying out solid-liquid separation on the solid and the liquid in the second mixed solution to obtain a solid, cleaning and drying the solid to obtain LiMnO2And (3) granules.
3. The method of claim 2, wherein the cleaning comprises: and (4) exchanging and cleaning with deionized water and ethanol.
4. The method of claim 1, wherein: the stirring in the step (1) and the step (2) is magnetic stirring.
5. The porous manganese-based lithium ion sieve adsorbent prepared by the method according to any one of claims 1 to 4.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1702043A (en) * | 2005-04-12 | 2005-11-30 | 武汉理工大学 | Preparation of spinel type Li-Mn-oxide lithium ion screening materials by hydrothermal method |
| CN101898113A (en) * | 2010-08-11 | 2010-12-01 | 华东理工大学 | Spherical manganese dioxide type lithium ionic sieve |
| CN101961634A (en) * | 2010-09-16 | 2011-02-02 | 中南大学 | Manganese series lithium ion sieve adsorbent and preparation method of precursor thereof |
| CN103121724A (en) * | 2012-12-24 | 2013-05-29 | 华东理工大学 | Method for preparing lithium ion sieve MnO2.0.5H2O and precursor thereof Li1.6Mn1.6O4 |
| KR20160147632A (en) * | 2015-06-15 | 2016-12-23 | 명지대학교 산학협력단 | Polyvinyl alcohol composite foam comprising lithium ion sieve and preparing method thereof |
| CN107051369A (en) * | 2017-03-16 | 2017-08-18 | 南京工业大学 | In situ oxidation-reduction for HMn production2O4Method (2) |
-
2018
- 2018-12-07 CN CN201811494510.3A patent/CN109289756B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1702043A (en) * | 2005-04-12 | 2005-11-30 | 武汉理工大学 | Preparation of spinel type Li-Mn-oxide lithium ion screening materials by hydrothermal method |
| CN101898113A (en) * | 2010-08-11 | 2010-12-01 | 华东理工大学 | Spherical manganese dioxide type lithium ionic sieve |
| CN101961634A (en) * | 2010-09-16 | 2011-02-02 | 中南大学 | Manganese series lithium ion sieve adsorbent and preparation method of precursor thereof |
| CN103121724A (en) * | 2012-12-24 | 2013-05-29 | 华东理工大学 | Method for preparing lithium ion sieve MnO2.0.5H2O and precursor thereof Li1.6Mn1.6O4 |
| KR20160147632A (en) * | 2015-06-15 | 2016-12-23 | 명지대학교 산학협력단 | Polyvinyl alcohol composite foam comprising lithium ion sieve and preparing method thereof |
| CN107051369A (en) * | 2017-03-16 | 2017-08-18 | 南京工业大学 | In situ oxidation-reduction for HMn production2O4Method (2) |
Non-Patent Citations (1)
| Title |
|---|
| Microwave assisted hydrothermal synthesis of MnO2·0.5H2O ion-sieve for lithium ion selective adsorption;Lifang Chen et al.;《Separation Science and Technology》;20151124;第51卷(第5期);第874-882页 * |
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