CN101062473A - Preparation method of three-dimensional ordered large-hole manganese oxygen 'lithium ionic sieve' - Google Patents
Preparation method of three-dimensional ordered large-hole manganese oxygen 'lithium ionic sieve' Download PDFInfo
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- CN101062473A CN101062473A CNA2007100347036A CN200710034703A CN101062473A CN 101062473 A CN101062473 A CN 101062473A CN A2007100347036 A CNA2007100347036 A CN A2007100347036A CN 200710034703 A CN200710034703 A CN 200710034703A CN 101062473 A CN101062473 A CN 101062473A
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Abstract
The invention relates to the making of 3DOM. It is made through synthesizing polymethyl methacryate or polystyrene pattern lumber, using Li and Mn front drive solution to stuff glue crystalline, through two sections of constant temperature baking to get 3DOM, using acid or peroxy-disulfate to perform acid etch. The result is that the product is the low density material in small blocks, unnecessary to add adhesive with high adhesive feature, using ammonium peroxy-disulfate to remove Li, reduced in Mn ion damage, improved adhesive feature, showing three dimensional porous frame structure, significantly improved in drive power inside the screen and the outside surface of the micro hole adhesive, being a dual hole channel with both macro and micro holes.
Description
Technical field
The present invention relates to a kind of preparation method of ion sieve preparation of adsorbent method, particularly a kind of lithium ion sieve adsorbant.
Background technology
Lithium is the lightest silvery white metal of occurring in nature, be widely used in industries such as glass, pottery, lubricant, cold-producing medium, metallurgy and pharmacy, particularly the progress aspect electrochmical power source, alloy material and nuclear fusion generating research is particularly noticeable, be acknowledged as " energy metal that promotes world's progress ", the title of " 21 century new forms of energy " is arranged.Yet land lithium resource total amount (being mainly ore lithium resource and salt lake lithium resource) is about 1,700 ten thousand tons (folding lithium metals) in the world, far can not satisfy the distant view market demand of lithium, lithium resource is very huge in the seawater by contrast, is about 2,600 hundred million tons, contains 0.17 milligram of lithium in every liter of seawater.Therefore, inquire into that to extract lithium seawater from low concentration, the salt lake bittern be the important subject in fields such as current chemistry, chemical industry and material subject.Extract lithium and mainly adopt absorption method from the seawater of low concentration, salt lake bittern, the lithium ion sieve that uses is pulverulent material, need to add binding agent and make graininess, so adsorbance is low, and it is not fine putting forward the lithium effect.
Summary of the invention
The manganese oxygen ' lithium ionic sieve ' that the purpose of this invention is to provide a kind of high adsorption capacity.
The objective of the invention is to realize in the following way: a kind of preparation method of three-dimensional ordered large-hole manganese oxygen ' lithium ionic sieve ':
1), methyl methacrylate or styrene solution, add initator, carry out emulsion polymerization, generate polymethyl methacrylate or polystyrene emulsion, prepare regular polymer colloid crystal template with centrifugal settling method;
2), with lithium salts and manganese salt, be made into precursor solution together by Li/Mn mol ratio 0.5-1.2 and citric acid, fill colloidal crystal template, after the drying the colloidal crystal template compound;
3), the colloidal crystal template compound is carried out 2 roastings, heating rate 1-10 ℃/minute, the 1st time at 280-320 ℃ of constant temperature calcining 1-4 hour, and the 2nd time at 500-700 ℃ of constant temperature calcining 2-5 hour, the 3DOM lithium manganese oxide;
4), carry out acidleach with acid or peroxy-disulfuric acid salt pair 3DOM lithium manganese oxide and take off lithium, three-dimensional ordered large-hole manganese oxygen ' lithium ionic sieve '.
Initator is a persulfate.
Persulfate is potassium persulfate and sodium persulfate.
Lithium salts is chloride or the nitrate or the acetate of lithium.
Manganese salt is chloride or the nitrate or the acetate of manganese.
Taking off the lithium agent is hydrochloric acid or ammonium peroxydisulfate.
The present invention has following beneficial effect, and the one, manganese oxygen ' lithium ionic sieve ' is low-density material, is little bulk material, does not need adding additives, the adsorbance height, high adsorption capacity reaches 50mg/g; The 2nd, adopt ammonium peroxydisulfate as taking off the lithium agent, reduced the molten damage of manganese ion, molten loss rate is minimum to be 4%, has improved absorption property; The 3rd, manganese oxygen ' lithium ionic sieve ' is three-dimensional ordered macroporous skeleton structure, having improved the mass transfer driving force of ion sieve inside and the surfaces externally and internally of micro-porous adsorption position amasss, having significantly improved the absorption property of manganese oxygen ' lithium ionic sieve ', is a kind of double hole channel material that has macropore and micropore concurrently.
Description of drawings
Fig. 1 is preparation technology's flow chart of the present invention;
Fig. 2 is the SEM photo of the embodiment of the invention 1 gained 3DOM lithium manganese oxide;
Fig. 3 is the XRD figure spectrum of the embodiment of the invention 1 gained 3DOM lithium manganese oxide;
Fig. 4 is the SEM photo of the embodiment of the invention 1 gained manganese oxygen ' lithium ionic sieve ';
Fig. 5 is the SEM photo of the embodiment of the invention 2 gained 3DOM lithium manganese oxides;
Fig. 6 is the XRD figure spectrum of the embodiment of the invention 2 gained 3DOM lithium manganese oxides;
Fig. 7 is the SEM photo of the embodiment of the invention 2 gained manganese oxygen ' lithium ionic sieve 's;
The specific embodiment
Embodiment 1:
As Fig. 1, Fig. 2, Fig. 3, shown in Figure 4, use methyl methacrylate and deionized water in 1: 10 the ratio adding there-necked flask, feed nitrogen protection, under 70 ℃ of temperature and mixing speed, add the potassium persulfate initator and carry out in-situ polymerization; Realize the oriented and ordered arrangement of microballoon with centrifugal settling method, get colloidal crystal template; Accurately take by weighing analytically pure lithium chloride (LiClH
2O) 0.6041g, manganese chloride (MnCl
24H
2O) 3.9541g and citric acid (C
6H
8O
7H
2O) the 4.2027g material is used dissolved in distilled water, with the pH value of concentrated ammonia liquor regulator solution, is made into the precursor solution of 20ml; Colloidal crystal template was immersed in the precursor solution about 3 minutes, treat that solution fully infilters microballoon gap, template complete wetting after, suction filtration is removed excessive solution, obtains the colloidal crystal template compound after the drying; The colloidal crystal template compound is carried out 2 ℃/minute of two sections constant temperature calcinings, heating rates, and the 1st time 300 ℃ of constant temperature calcinings 3 hours, remove organic formwork respectively and promote crystalline phase to generate 600 ℃ of constant temperature calcinings 3 hours for the 2nd time; Obtain 3DOM (three-dimensionally orderedmacropores) lithium manganese oxide; This 3DOM lithium manganese oxide is three-dimensional ordered macroporous spinel-type LiMn through SEM and XRD test conclusive evidence
2O
4, this lithium manganese oxide is taken off lithium with the peroxy-disulfuric acid ammonium salt solution handle, make three-dimensional ordered large-hole manganese oxygen ' lithium ionic sieve '.
Embodiment 2:
As Fig. 1, Fig. 5, Fig. 6, shown in Figure 7, use styrene and deionized water in 1: 10 the ratio adding there-necked flask, feed nitrogen protection, under 70 ℃ of temperature and mixing speed, add the potassium persulfate initator and carry out in-situ polymerization; Realize the oriented and ordered arrangement of microballoon with centrifugal settling method, get colloidal crystal template; Accurately take by weighing analytically pure lithium nitrate (LiNO
3) 0.9193g, 50% manganese nitrate [Mn (NO
3)
2] solution 7.1578g and citric acid (C
6H
8O
7H
2O) the 4.2027g material is used dissolved in distilled water, with the pH value of concentrated ammonia liquor regulator solution, is made into the precursor solution of 20ml; Colloidal crystal template was immersed in the precursor solution about 3 minutes, treat that solution fully infilters microballoon gap, template complete wetting after, suction filtration is removed excessive solution, obtains the colloidal crystal template compound after the drying; The colloidal crystal template compound is carried out 2 ℃/minute of two sections constant temperature calcinings, heating rates, and the 1st time 300 ℃ of constant temperature calcinings 3 hours, remove organic formwork respectively and promote crystalline phase to generate 600 ℃ of constant temperature calcinings 3 hours for the 2nd time; Obtain the 3DOM lithium manganese oxide; This 3DOM lithium manganese oxide is three-dimensional ordered macroporous spinel-type Li through SEM and XRD test conclusive evidence
4Mn
5O
12, this lithium manganese oxide is taken off lithium with the peroxy-disulfuric acid ammonium salt solution handle, make three-dimensional ordered large-hole manganese oxygen ' lithium ionic sieve '.
Claims (6)
1, a kind of preparation method of three-dimensional ordered large-hole manganese oxygen ' lithium ionic sieve ' is characterized in that:
1), methyl methacrylate or styrene solution, add initator, carry out emulsion polymerization, generate polymethyl methacrylate or polystyrene emulsion, prepare regular polymer colloid crystal template with centrifugal settling method;
2), with lithium salts and manganese salt, be made into precursor solution together by Li/Mn mol ratio 0.5-1.2 and citric acid, fill colloidal crystal template, after the drying the colloidal crystal template compound;
3), the colloidal crystal template compound is carried out 2 roastings, heating rate 1-10 ℃/minute, the 1st time at 280-320 ℃ of constant temperature calcining 1-4 hour, and the 2nd time at 500-700 ℃ of constant temperature calcining 2-5 hour, the 3DOM lithium manganese oxide;
4), carry out acidleach with acid or peroxy-disulfuric acid salt pair 3DOM lithium manganese oxide and take off lithium, three-dimensional ordered large-hole manganese oxygen ' lithium ionic sieve '.
2, the preparation method of three-dimensional ordered large-hole manganese oxygen ' lithium ionic sieve ' according to claim 1 is characterized in that: initator is a persulfate.
3, the preparation method of three-dimensional ordered large-hole manganese oxygen ' lithium ionic sieve ' according to claim 2 is characterized in that: persulfate is potassium persulfate and sodium persulfate.
4, the preparation method of three-dimensional ordered large-hole manganese oxygen ' lithium ionic sieve ' according to claim 1 is characterized in that: lithium salts is chloride or the nitrate or the acetate of lithium.
5, the preparation method of three-dimensional ordered large-hole manganese oxygen ' lithium ionic sieve ' according to claim 1 is characterized in that: manganese salt is chloride or the nitrate or the acetate of manganese.
6, the preparation method of three-dimensional ordered large-hole manganese oxygen ' lithium ionic sieve ' according to claim 1 is characterized in that: taking off the lithium agent is hydrochloric acid or ammonium peroxydisulfate.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101937989A (en) * | 2010-08-13 | 2011-01-05 | 上海中科深江电动车辆有限公司 | Three-dimensional nanoporous metal-oxide electrode material of lithium ion battery and preparation method thereof |
| CN101955210A (en) * | 2010-09-14 | 2011-01-26 | 华东理工大学 | Granular lithium ion sieve |
| CN101985098A (en) * | 2010-09-16 | 2011-03-16 | 中南大学 | Method for preparing manganese series lithium-ion sieve adsorbent H4Mn5O12 and precursor thereof |
| CN102558410A (en) * | 2012-01-20 | 2012-07-11 | 齐齐哈尔大学 | Preparation method of self-assembled three-dimensional ordered polystyrene colloidal crystal |
| CN102935299A (en) * | 2012-09-29 | 2013-02-20 | 上海空间电源研究所 | Method for extracting lithium ions by manganese oxide adsorbing material |
| CN104689858A (en) * | 2013-12-10 | 2015-06-10 | 上海空间电源研究所 | Preparation method of lithium manganate ion sieve separation membrane |
| CN112871126A (en) * | 2021-01-18 | 2021-06-01 | 江苏特丰新材料科技有限公司 | Preparation method of lithium ion sieve particles with high adsorption capacity |
-
2007
- 2007-04-10 CN CNA2007100347036A patent/CN101062473A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101937989A (en) * | 2010-08-13 | 2011-01-05 | 上海中科深江电动车辆有限公司 | Three-dimensional nanoporous metal-oxide electrode material of lithium ion battery and preparation method thereof |
| CN101955210A (en) * | 2010-09-14 | 2011-01-26 | 华东理工大学 | Granular lithium ion sieve |
| CN101985098A (en) * | 2010-09-16 | 2011-03-16 | 中南大学 | Method for preparing manganese series lithium-ion sieve adsorbent H4Mn5O12 and precursor thereof |
| CN102558410A (en) * | 2012-01-20 | 2012-07-11 | 齐齐哈尔大学 | Preparation method of self-assembled three-dimensional ordered polystyrene colloidal crystal |
| CN102558410B (en) * | 2012-01-20 | 2013-10-30 | 齐齐哈尔大学 | Preparation method of self-assembled three-dimensional ordered polystyrene colloidal crystal |
| CN102935299A (en) * | 2012-09-29 | 2013-02-20 | 上海空间电源研究所 | Method for extracting lithium ions by manganese oxide adsorbing material |
| CN102935299B (en) * | 2012-09-29 | 2015-09-30 | 上海空间电源研究所 | A kind of method using manganese oxide sorbing material to extract lithium ion |
| CN104689858A (en) * | 2013-12-10 | 2015-06-10 | 上海空间电源研究所 | Preparation method of lithium manganate ion sieve separation membrane |
| CN112871126A (en) * | 2021-01-18 | 2021-06-01 | 江苏特丰新材料科技有限公司 | Preparation method of lithium ion sieve particles with high adsorption capacity |
| CN112871126B (en) * | 2021-01-18 | 2023-08-11 | 江苏特丰新材料科技有限公司 | Preparation method of lithium ion sieve particles with high adsorption capacity |
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