CN102160992A - Lithium adsorbent forming process using sponge as vector - Google Patents
Lithium adsorbent forming process using sponge as vector Download PDFInfo
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- CN102160992A CN102160992A CN 201110039893 CN201110039893A CN102160992A CN 102160992 A CN102160992 A CN 102160992A CN 201110039893 CN201110039893 CN 201110039893 CN 201110039893 A CN201110039893 A CN 201110039893A CN 102160992 A CN102160992 A CN 102160992A
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Abstract
The invention provides a lithium adsorbent forming process using sponge as a vector, and relates to a lithium adsorbent forming method which is used for adsorbing lithium in salt lake brine, seawater, well brine and other lithium-containing solutions. The forming process comprises the following steps: foaming powdered adsorbent and a sponge raw material, wherein the chemical characteristics of the adsorbent are not changed in the foaming process; and preparing blocky sponge by the powdered adsorbent to adsorb lithium ions in the salt lake brine. The forming process has the advantages that: by the blocky sponge lithium adsorbent prepared by the process, the problems that the powdered adsorbent is easily lost and operation is hard in the adsorbing process are fundamentally solved; and the sponge lithium adsorbent has high adsorption speed, larger specific surface area and long service life.
Description
Technical field
The present invention relates to be used for the moulding process of the powdered absorbent of salt lake bittern, seawater, well halogen absorption lithium ion, mainly be a kind of be the moulding process of the lithium adsorbent of carrier with the sponge.
Background technology
China is traditional lithium resource big country, also be salt lake lithium resource big country, salt lake lithium resource reserves (amounting to lithium carbonate) are above 300,0000 tons, be that the world's four Great Salt lake's lithium resource reserves surpass one of saline lake deposit of 1,000,000 tons, have good resources supplIes and DEVELOPMENT PROSPECT.But China carried lithium to the salt lake and paid little attention to the past, and the technology input also not have the extensive equipment of carrying lithium from salt lake bittern at present very little, and the extraction of lithium also concentrates on from ore and refines.And mine resources is limited, adds that in recent years the demand to lithium increases, and lithium already develops and is restricted.In recent years, the big great development of lithium technology was proposed in the salt lake, and China also is in the research and development stage, and the device and the technology of large-scale production also do not arranged, and therefore carrying lithium from salt lake bittern is the task of top priority that China's lithium already develops.
In the lithium adsorbent research field, abroad just begin as far back as the 1980s, domestic starting late, existing technical merit is also not very high.From experimental viewpoint, so far, the ion exchange absorbent of discovering better performances all is a powder.Although it is better that experimental study shows absorption property,, do not solve the granulation problem and can't realize suitability for industrialized production because the flowability and the permeability of powder are all very poor.
Some researchers adopt aluminium hydroxide, manganese dioxide or titanium dioxide as the powder adsorbent, with silica gel, waterglass, cellulose acetate, polyvinyl chloride, polyacrylamide, macromolecular compounds such as polyacrylic hydrazide are as carrier, carry out extruder grain with organic solvent as binding agent, the method only is in experimental stage, and the adsorbance of adsorbent reduces with the quality increase of macromolecular compound, and the addition of macromolecular compound has determined the stability of absorbent particles, so the method is restricted always.Also there is the researcher to adopt ion exchange resin, be that ion exchange resin is joined in the reactor of synthetic powder adsorbent, because ion exchange resin has big duct, therefore micromolecular inorganic matter enters into the duct, forms the adsorbent precipitation with precipitating reagent in the duct.The method is because difficult operation, and can't measure the content of fertile absorber in the duct, thereby the adsorbance of adsorbent is less.
Summary of the invention
Purpose of the present invention will overcome the deficiency of above-mentioned technology just, and provide a kind of is the moulding process of the lithium adsorbent of carrier with the sponge, the present invention adopts has the sponge of macropore structure as carrier, with LiMn2O4 as the load adsorbent, purpose is that the powder adsorbent is injected in the macropore sponge, the ion of adsorbent can free in and out, and has realized the effect of ion-exchange absorption like this.Through measuring, adsorbent of the present invention has bigger specific area, and absorption property is good.
The present invention solves the technical scheme that its technical problem adopts: this is the moulding process of the lithium adsorbent of carrier with the sponge, the activity that the preparation technology of this method is simple, the sponge foaming does not influence adsorbent, adsorbent after the moulding has bigger specific area, absorption property is good, and the concrete steps of this technology are as follows:
(1), presoma LiMn2O4 adopts LiCl and MnO2 to mix, according to Li: the Mn mol ratio is 0.45-0.6, and LiCl and MnO2 are mixed in beaker;
(2), add 10-20mL water, make mixture become pasty state, be heated to 50-90 ℃, stir 0.5-2h;
(3), above-mentioned pastel is put into Muffle furnace, temperature is set to 200-800 ℃ and calcines 1-3h, obtains powdery lithium adsorbent LiMn2O4;
(4), account for the 10%-40% of sponge gross mass, powdered absorbent is joined foaming together in the sponge foaming body according to the quality of LiMn2O4;
(5), with foam sponge, obtain lithium adsorbent after the pickling.
As preferably, adopting concentration of hydrochloric acid is that 0.1-0.5mol/L carries out pickling, and the pickling time is 0.5-1h, obtains lithium adsorbent.
Described method, can be used for the sponge is that the moulding process of powder adsorbent of carrier can comprise powder adsorbents such as aluminium hydroxide, titanium dioxide.
The effect that the present invention is useful is: method of the present invention, employing is the moulding process of the powdered absorbent of carrier with the sponge, be based on theory with macropore structure, because macromolecular compound is as the little and easy broken problem of the adsorbents adsorb amount that carrier brought, and the quantity of sorbent of carried ion exchange resin is few, finally causes the adsorbents adsorb amount after the moulding little.The sponge of therefore adopting the macropore structure, its advantage have following some: 1. before the sponge foaming powder is injected into wherein, foaming back adsorbent all is wrapped in the foam sponge, makes the active ingredient increase of adsorbent like this; 2. in the sponge foaming process, its raw material not with adsorbent generation chemical reaction, can not influence the absorption property of adsorbent; 3. because sponge has macropore, effectively increase the specific area of adsorbent, reduced the discrepancy resistance of adsorbent, made adsorbent be more prone to be adsorbed wash-out; 4. the adsorbents adsorb amount is big, and adsorption time is short.
The specific embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with for example.Should be appreciated that described hereinly, and be not used in qualification the present invention for example only in order to explaining the present invention.
Of the present invention this be the moulding process of the lithium adsorbent of carrier with the sponge, the concrete steps of this technology are as follows:
(1), according to Li: the Mn mol ratio is 0.45-0.6, and LiCl and MnO2 are mixed in beaker;
(2), add 10-20mL water, make mixture become pasty state, be heated to 50-90 ℃, stir 0.5-2h;
(3), above-mentioned pastel is put into Muffle furnace, temperature is set to 200-800 ℃ and calcines 1-3h, obtains powdery lithium adsorbent LiMn2O4;
(4), account for the 10%-40% of sponge gross mass, powdered absorbent is joined foaming together in the sponge foaming body according to the quality of LiMn2O4;
(5), with the foam sponge that obtains, adopting concentration of hydrochloric acid is that 0.1-0.5mol/L carries out pickling, the pickling time is 0.5-1h, obtains lithium adsorbent.
Embodiment 1
At first in the 100mL crucible, add 30g MnO2 solid, add 10.41g LiClH2O then, after mixing, add the 10mL deionized water, on electric furnace, be heated to 50 ℃, stir 1h.Crucible is put into Muffle furnace, and temperature is set to 200 ℃, and calcining 3h takes out crucible behind the 3h, solid absorbent is pulverized, and obtains presoma LiMn2O4.According to the sponge formula rate, add the powdered absorbent of mass fraction 10%, carry out mixed foaming with the sponge foaming raw material, obtain foam sponge body adsorbent.Adopt the hydrochloric acid of 0.1mol/L to carry out pickling 0.5h, the pickling rate reaches 75%, and the sponge after the pickling is put into bittern and carries out adsorption experiment, and through flame spectrophotometer measuring, adsorbance is 2.5mg/g.
Embodiment 2
At first add the 30gMnO2 solid in the 100mL crucible, weighing 9.37g LiClH2O is dissolved in the 20mL water, lithium chloride solution is joined in the crucible mix with manganese dioxide, crucible is placed on is heated to 80 ℃ on the electric furnace then, stirs 0.5h.Crucible is put into Muffle furnace, and temperature is set to 500 ℃, and calcining 2h takes out crucible behind the 2h, solid absorbent is pulverized, and obtains presoma LiMn2O4.According to the sponge formula rate, add the powdered absorbent of mass fraction 20%, carry out mixed foaming with the sponge foaming raw material, obtain foam sponge body adsorbent.Adopt the hydrochloric acid of 0.2mol/L to carry out pickling 0.5h, the pickling rate reaches 80%, and the sponge after the pickling is put into bittern and carries out adsorption experiment, and through flame spectrophotometer measuring, adsorbance is 2.6mg/g.
Embodiment 3
At first add the 30gMnO2 solid in the 100mL crucible, weighing 12.49g LiClH2O is dissolved in the 20mL water, lithium chloride solution is joined in the crucible mix with manganese dioxide, crucible is placed on is heated to 90 ℃ on the electric furnace then, stirs 0.5h.Crucible is put into Muffle furnace, and temperature is set to 800 ℃, and calcining 1h takes out crucible behind the 1h, solid absorbent is pulverized, and obtains presoma LiMn2O4.According to the sponge formula rate, add the powdered absorbent of mass fraction 40%, carry out mixed foaming with the sponge foaming raw material, obtain foam sponge body adsorbent.Adopt the hydrochloric acid of 0.2mol/L to carry out pickling 0.5h, the pickling rate reaches 81%, and the sponge after the pickling is put into bittern and carries out adsorption experiment, and through flame spectrophotometer measuring, adsorbance is 2.8mg/g.
Be understandable that, for a person skilled in the art, technical scheme of the present invention and inventive concept be equal to replacement or change the protection domain that all should belong to the appended claim of the present invention.
Claims (2)
1. one kind is the moulding process of the lithium adsorbent of carrier with the sponge, and it is characterized in that: the concrete steps of this technology are as follows:
(1), according to Li: the Mn mol ratio is 0.45-0.6, and LiCl and MnO2 are mixed in beaker;
(2), add 10-20mL water, make mixture become pasty state, be heated to 50-90 ℃, stir 0.5-2h;
(3), above-mentioned pastel is put into Muffle furnace, temperature is set to 200-800 ℃ and calcines 1-3h, obtains powdery lithium adsorbent LiMn2O4;
(4), account for the 10%-40% of sponge gross mass, powdered absorbent is joined foaming together in the sponge foaming body according to the quality of LiMn2O4;
(5), with foam sponge, obtain lithium adsorbent after the pickling.
2. according to claim 1 is the moulding process of the lithium adsorbent of carrier with the sponge, it is characterized in that: adopting concentration of hydrochloric acid is that 0.1-0.5mol/L carries out pickling, and the pickling time is 0.5-1h, obtains lithium adsorbent.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109126750A (en) * | 2017-06-27 | 2019-01-04 | 比亚迪股份有限公司 | Support type lithium adsorbent and preparation method thereof |
| CN110961070A (en) * | 2018-09-30 | 2020-04-07 | 比亚迪股份有限公司 | Lithium adsorbent and preparation method thereof |
| CN111330540A (en) * | 2020-03-06 | 2020-06-26 | 旬阳领盛新材料科技有限公司 | Preparation method of graphene oxide composite aluminum lithium adsorbent |
| CN112216894A (en) * | 2020-10-15 | 2021-01-12 | 天齐锂业（江苏）有限公司 | Method for preparing lithium ion sieve composite material by recycling negative electrode of waste lithium ion battery |
| CN112237905A (en) * | 2020-10-10 | 2021-01-19 | 西安蓝深环保科技有限公司 | Lithium extraction adsorbent for raw halogen and preparation method thereof |
| CN118719026A (en) * | 2024-06-19 | 2024-10-01 | 四川泰利兴坤新材料有限公司 | A manganese-based adsorbent for lithium extraction from salt lakes and a foaming preparation method thereof |
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| CN101157480A (en) * | 2007-09-18 | 2008-04-09 | 华东理工大学 | Manganese dioxide ion sieve |
| CN101829538A (en) * | 2010-05-19 | 2010-09-15 | 浙江海虹控股集团有限公司 | Preparation method of high-performance lithium adsorbent |
| CN101898113A (en) * | 2010-08-11 | 2010-12-01 | 华东理工大学 | Spherical manganese dioxide lithium ion sieve |
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2011
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| CN101157480A (en) * | 2007-09-18 | 2008-04-09 | 华东理工大学 | Manganese dioxide ion sieve |
| CN101829538A (en) * | 2010-05-19 | 2010-09-15 | 浙江海虹控股集团有限公司 | Preparation method of high-performance lithium adsorbent |
| CN101898113A (en) * | 2010-08-11 | 2010-12-01 | 华东理工大学 | Spherical manganese dioxide lithium ion sieve |
Non-Patent Citations (1)
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| 《Journal of Solid State Chemistry》 20021231 Ramesh Chitrakar et al. Synthesis of orthorhombic LiMnO2 by solid-phase reaction under steam atmosphere and a study of its heat and acid-treated phases 参见第67页 1-2 第169卷, * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109126750A (en) * | 2017-06-27 | 2019-01-04 | 比亚迪股份有限公司 | Support type lithium adsorbent and preparation method thereof |
| CN109126750B (en) * | 2017-06-27 | 2020-08-07 | 比亚迪股份有限公司 | Supported lithium adsorbent and preparation method thereof |
| CN110961070A (en) * | 2018-09-30 | 2020-04-07 | 比亚迪股份有限公司 | Lithium adsorbent and preparation method thereof |
| CN111330540A (en) * | 2020-03-06 | 2020-06-26 | 旬阳领盛新材料科技有限公司 | Preparation method of graphene oxide composite aluminum lithium adsorbent |
| CN112237905A (en) * | 2020-10-10 | 2021-01-19 | 西安蓝深环保科技有限公司 | Lithium extraction adsorbent for raw halogen and preparation method thereof |
| CN112237905B (en) * | 2020-10-10 | 2022-02-15 | 西安蓝深新材料科技有限公司 | Lithium extraction adsorbent for raw halogen and preparation method thereof |
| CN112216894A (en) * | 2020-10-15 | 2021-01-12 | 天齐锂业（江苏）有限公司 | Method for preparing lithium ion sieve composite material by recycling negative electrode of waste lithium ion battery |
| CN112216894B (en) * | 2020-10-15 | 2021-11-19 | 天齐锂业（江苏）有限公司 | Preparation method and recovery method of lithium ion sieve composite material |
| CN118719026A (en) * | 2024-06-19 | 2024-10-01 | 四川泰利兴坤新材料有限公司 | A manganese-based adsorbent for lithium extraction from salt lakes and a foaming preparation method thereof |
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Effective date of registration: 20191219 Address after: 314000 401, building 32, Hangzhou bay new economic Park, Jiaxing Port Area, Zhejiang Province Patentee after: Zhejiang Haiti New Material Technology Co., Ltd Address before: 311113 Liangzhu Town, Yuhang District, Zhejiang, Hangzhou Patentee before: Zhejiang Haihong Holding Co.,Ltd. |