CN102512983A - Lithium ion sieve membrane and preparation method thereof - Google Patents
Lithium ion sieve membrane and preparation method thereof Download PDFInfo
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- CN102512983A CN102512983A CN2011104453473A CN201110445347A CN102512983A CN 102512983 A CN102512983 A CN 102512983A CN 2011104453473 A CN2011104453473 A CN 2011104453473A CN 201110445347 A CN201110445347 A CN 201110445347A CN 102512983 A CN102512983 A CN 102512983A
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Abstract
The invention discloses a preparation method of a lithium ion sieve membrane. The lithium ion sieve membrane is prepared by using a membrane casting gel made mainly from a soluble lithium salt and a manganese salt and by using a ceramic tube as a carrier, wherein the lithium permeation flux of the lithium ion sieve membrane is 1 to 10*10<-2>mg.cm<-2>mg.min<-1>. The preparation method comprises the following preparation steps: adding LiNO3 and Mn(NO3)2 into a glycol solution of citric acid, heating under reflux, evaporating water and glycol and obtaining gel; immersing the ceramic tube into the gel, drying the ceramic tube and firing the ceramic tube; and repeating the previous steps one again to obtain a lithium ion sieve precursor membrane; treating the precursor membrane with hydrochloric acid or a solution of ammonium persulfate, removing lithium and obtaining the lithium ion sieve membrane which has certain permselectivity for lithium in a lithium-containing solution. The method disclosed by the invention adopts a simple process and readily available raw materials, and the obtained lithium ion sieve membrane has a great application prospect in the field of continuous lithium extraction from sea water.
Description
Technical field
The present invention relates to a kind of lithium ion sieve membrane and preparation method thereof.
Technical background
Lithium is the very active alkali metal of chemical property, and only the form with compound is distributed widely in occurring in nature, and in rock, soil, salt lake, seawater and living organism, but content all seldom, so lithium is also divided into the row of rare element.And the lithium in the salt lake bittern, seawater accounts for more than 2/3rds of world's lithium reserves, usually and sylvite class and the symbiosis of halogen mineral products.See that from long-range sustainable development solid lithium minerals resource is fewer and feweri, can not satisfy growing demand, therefore press for liquid lithium resources such as exploitation salt lake bittern, seawater and GEOTHERMAL WATER.From rare lithium solution, extract lithium with extraction, ion-exchange or absorption method the most green economy become common recognition.The Mn oxide ion sieve material of spinel structure has very high selectivity and bigger exchange capacity to lithium in solution, and has the characteristics of economy, environmental protection, thereby this material has become the focus of domestic and international research.But this ion sieve mainly is a pulverulent material, is unfavorable for that industrialization proposes lithium production; Even process granular or organic membranaceously, also there is long or bad mechanical strength of operation cycle in the practical application and operates problems such as discontinuous.If is carrier with the inorganic ceramic pipe, film on the surface, it is membranaceous to process film, then applicable to proposing the lithium production operation, and is expected to realize that by ion sieve effect serialization proposes the lithium operation.
Summary of the invention
The object of the present invention is to provide a kind of lithium ion sieve membrane and preparation method thereof, can overcome the defective of prior art.It can satisfy the membranaceous lithium ion sieve that extracts lithium production demand.This method is a prop carrier by the earthenware that the surface is micropore mainly; Make the very thin lithium ion sieve of one deck through sol-gel process at its outer surface; And then the form of employing film absorber; Tube side and shell side feed eluant, eluent and adsorbent respectively, if absorption and wash-out can carry out simultaneously, can realize that then the lithium operation is proposed in serialization from lithium-containing solution.Method technology of the present invention is simple, low in raw material cost is easy to get, and the lithium ion sieve membrane of acquisition is carried the lithium field at the serialization seawater and had broad application prospects.
Lithium ion sieve membrane provided by the invention is to use the solubility lithium salts and manganese salt processes the casting film gel as primary raw material and earthenware is preparing carriers, and the lithium ion sieve membrane is 1-10 * 10 to the permeation flux of lithium
-2Mgcm
-2Min
-1Preparation process: in the ethylene glycol solution of citric acid, add LiNO
3And Mn (NO
3)
2, reflux, distillation dewaters, forms gel behind the ethylene glycol then; Earthenware immerses gel, and drying is accompanied burning, repeats said process at least one time, obtains lithium ion sieve precursor film, handles with hydrochloric acid or ammonium persulfate solution again, takes off lithium, can get the lithium ion sieve membrane.
Wherein, citric acid and ethylene glycol are 1: 3～5 in molar ratio; LiNO
3And Mn (NO
3)
2Mol ratio be 1: 1.5～2.5; Citric acid and Mn (NO
3)
2Mol ratio be 1: 1.The surface apertures of earthenware is 0.1～1.0 μ m.
Alternatively, the size of earthenware (being not limited to this size but particularly point out): the length of earthenware is about 5cm, and outer tube diameter is about 1.3cm, and interior caliber is about 0.9cm.
The preparation process of lithium ion sieve membrane specifically comprises the steps: among the present invention
1) with citric acid and ethylene glycol in molar ratio 1: mix (3～5), is heated with stirring to citric acid and dissolves fully.
2) with LiNO
3And Mn (NO
3)
2In molar ratio 1: mix (1.5～2.5), joins in the above-mentioned solution, makes citric acid and Mn (NO
3)
2Mol ratio be 1: 1, continue reflux 1.5～2.5h, form light yellow vitreosol.
3) with the colloidal sol air-distillation dewater, decompression distillation forms the dark brown gel after removing ethylene glycol, pour in the evaporating dish.
4) earthenware handled well is immersed in the gel, 3-5 back of extracting is dry in about 70 ℃, places Muffle furnace with the heating that heats up of the speed of 5～10 ℃/min again, at 300～350 ℃ of insulation 0.5～1.5h down, 800 ℃ be incubated down cool off naturally behind 4～8h the film pipe.Be positioned in the evaporating dish, the coagulant liquid that makes is watered be poured on the earthenware, and dipping a period of time.
5) be prop carrier with membranaceous lithium ion sieve precursor, repeat above-mentioned steps, can get twice or the lithium ion sieve precursor film of film forming repeatedly;
6) HCl or the 0.2mol/L ammonium persulfate solution with the effective 0.1～0.5mol/L of film that makes carries out wash-out, can get the lithium ion sieve membrane.
7) lithium-containing solution with 0.01～0.05mol/L is an adsorption liquid, can investigate the selection through performance of film to lithium.
The thickness of the lithium ion sieve precursor film of gained of the present invention is 0.1-15 μ m.The thickness of optional film is 1-5 μ m.
(precursor is LiMn to the product of gained of the present invention
2O
4) have pure spinel structure, form homogeneous, overcome other precursor (like Li
1.6Mn
1.6O
4) be prone to contain the deficiency of dephasign or amorphous phase in the composition.On the earthenware through after homogeneous is not filmed; Handle all and can have even, the continuous rete that certain selection sees through with different eluant, eluents lithium in the lithium-containing solution; Whole mechanical strength, hear resistance and antifouling ability more organic (carrier) film of film pipe has significant superiority; And can well form assembly apparatus, satisfy the needs of commercial Application.The lithium ion sieve membrane that lithium in the lithium-containing solution is had certain selection permeability that the present invention obtains, preparation method's technology is simple, low in raw material cost is easy to get, and the lithium ion sieve membrane of acquisition is carried the lithium field at the serialization seawater and is had broad application prospects.
Description of drawings
Fig. 1 is a lithium ion sieve film preparation process chart of the present invention.
Fig. 2 is the assembly apparatus sketch of embodiment of the invention film pipe when carrying out wash-out and adsorption treatment.
Fig. 3 is embodiment of the invention gained lithium ion sieve precursor (Li
2MnO
4) the XRD photo of film.
Fig. 4 is the SEM photo on embodiment of the invention gained tubulose lithium ion sieve precursor film surface.
Fig. 5 is the SEM photo of embodiment of the invention gained tubulose lithium ion sieve membrane precursor section.
The specific embodiment
Embodiment one:
Surface apertures is about 0.1 μ m earthenware, and ((length is about 5cm in the inferior membrane separation technique in sky, Nanjing Co., Ltd; Outer tube diameter is about 1.3cm, and interior caliber is about 0.9cm), smooth with 600 orders, 1000 order sand paperings; Put into ultrasonic cleaner and clean 15min; To remove surface impurity, the sodium hydroxide solution of putting into concentration again and be 2.5mol/L soaks 24h, then with deionized water rinsing to neutral 70 ℃ of oven dry; Put into the temperature programming stove and rise to 320 ℃, cooling naturally behind the constant temperature calcining 4h with 5 ℃/min speed.
With citric acid 15.9g, ethylene glycol 14.1g joins in the there-necked flask, and heated and stirred to citric acid dissolves fully.Take by weighing 50%Mn (NO
3)
227.5g LiNO with 3.2mol/L
3Solution 36.0ml together adds in the there-necked flask, and ebuillition of heated is after a period of time, and solution is slowly deepened by light yellow; Temperature maintenance is at 105 ℃～115 ℃, and backflow 1.5h forms the buff vitreosol; Dewater carrying out air-distillation, decompression distillation removes ethylene glycol, the dark brown gel is poured in the evaporating dish.Earthenware is immersed in the gel 70 ℃ of oven dry after the extracting 3 times; Put into the speed intensification of Muffle furnace with 5 ℃/min, be incubated 0.5h down at 300 ℃, 800 ℃ are incubated 4h down; Naturally cool off then membranaceous lithium ion sieve precursor (the about 1 μ m of thickness), repeat above-mentioned steps once.The film pipe is put into wash-out and adsorption treatment assembly apparatus (installing as shown in Figure 2) carries out pickling, and the HCl solution that shell side (film tube outer surface) feeds 0.1mol/L carries out pickling, and flow velocity is 1ml/min; After the pickling, feed the lithium liquid of 0.01mol/L to tube side with 1ml/min under the normal temperature, shell side feeds the HCl solution of 0.1mol/L with 1ml/min, through measuring the content that flows out lithium in the liquid, the lithium ion sieve membrane is 1.70 * 10 to the permeation flux of lithium
-2Mgcm
-2Min
-1
Embodiment two:
It is smooth with 600 orders, 1000 order sand paperings that surface apertures is about 0.1 μ m earthenware, puts into ultrasonic cleaner and clean 15min, to remove surface impurity.It is that the sodium hydroxide solution of 2.5mol/L soaks 24h that earthenware is put into concentration.To neutral, the 70 ℃ of oven dry earlier of flushing back are put into the temperature programming stove then and are calcined with deionized water rinsing.
With citric acid 16.8g, ethylene glycol 19.9g joins in the there-necked flask, and heated and stirred to citric acid dissolves fully.Take by weighing 50%Mn (NO
3)
228.7g LiNO with 3.2mol/L
3Solution 53.4ml together adds in the there-necked flask, and ebuillition of heated is after a period of time, and solution is slowly deepened by light yellow; Temperature maintenance is at 105 ℃～115 ℃, and backflow 2h forms the buff vitreosol; Dewater carrying out air-distillation, decompression distillation removes ethylene glycol, the dark brown gel is poured in the evaporating dish.Earthenware is immersed in the gel 70 ℃ of oven dry after the extracting 4 times; Put into the speed intensification of Muffle furnace with 10 ℃/min; At 300 ℃ of following insulation 1h, 800 ℃ of insulation 6h down, cool off naturally then membranaceous lithium ion sieve precursor; Once (the XRD figure spectrum is as shown in Figure 3, and the SEM photo of outer surface is as shown in Figure 4 to repeat above-mentioned steps; The SEM photo of section is as shown in Figure 5).The film pipe is put into special assembly carry out pickling, the HCl solution that shell side (film tube outer surface) feeds 0.5mol/L carries out pickling, and flow velocity is 1ml/min; After the pickling, feed the lithium liquid of 0.02mol/L with 1ml/min to tube side under the normal temperature, shell side feeds the HCl solution of 0.5mol/L with 1ml/min, through measuring the content that flows out lithium in the liquid, the lithium ion sieve membrane is 6.57 * 10 to the permeation flux of lithium
-2Mgcm
-2Min
-1
Embodiment three:
It is smooth with 600 orders, 1000 order sand paperings that surface apertures is about 1.0 μ m earthenwares, puts into ultrasonic cleaner and clean 15min, to remove surface impurity.It is that the sodium hydroxide solution of 2.5mol/L soaks 24h that earthenware is put into concentration.To neutral, the 70 ℃ of oven dry earlier of flushing back are put into the temperature programming stove then and are calcined with deionized water rinsing.
With citric acid 15.4g, ethylene glycol 22.7g joins in the there-necked flask, and heated and stirred to citric acid dissolves fully.Take by weighing 50%Mn (NO
3)
226.2g LiNO with 3.2mol/L
3Solution 57.2ml together adds in the there-necked flask, and ebuillition of heated is after a period of time, and solution is slowly deepened by light yellow; Temperature maintenance is at 105 ℃～115 ℃, and backflow 2.5h forms the buff vitreosol; Dewater carrying out air-distillation, decompression distillation removes ethylene glycol, the dark brown gel is poured in the evaporating dish.Earthenware is immersed in the gel 70 ℃ of oven dry after the extracting 4 times, puts into Muffle furnace and heat up with the speed of 10 ℃/min, at 300 ℃ of insulation 1.5h down, 800 ℃ of insulation 8h down, cool off naturally then membranaceous lithium ion sieve precursor, the repetition above-mentioned steps is once.The ammonium persulfate solution that film shell journey (film tube outer surface) is fed 0.2mol/L carries out pickling, and flow velocity is 1ml/min; After the pickling, feed the lithium liquid of 0.05mol/L with 1ml/min to tube side under the normal temperature, shell side feeds the ammonium persulfate solution of 0.2mol/L with 1ml/min, through measuring the content that flows out lithium in the liquid, the lithium ion sieve membrane is 4.35 * 10 to the permeation flux of lithium
-2Mgcm
-2Min
-1
Claims (9)
1. a lithium ion sieve membrane uses solubility lithium salts and manganese salt to process the casting film gel as primary raw material, it is characterized in that it is is carrier loaded membranaceous lithium ion sieve with earthenware, and the lithium ion sieve membrane is 1-10 * 10 to the permeation flux of lithium
-2Mgcm
-2Min
-1Preparation process is: in the ethylene glycol solution of citric acid, add LiNO
3And Mn (NO
3)
2, reflux, distillation dewaters, forms behind the ethylene glycol dark brown gel then; Earthenware immerses gel, and drying is accompanied burning, repeats said process at least one time, obtains lithium ion sieve precursor film, handles with watery hydrochloric acid or ammonium persulfate solution again, takes off lithium, can get the lithium ion sieve membrane.
2. lithium ion sieve membrane according to claim 1 is characterized in that described citric acid and ethylene glycol are 1: 3～5 in molar ratio; LiNO
3And Mn (NO
3)
2Mol ratio be 1: 1.5～2.5; Citric acid and Mn (NO
3)
2Mol ratio be 1: 1.
3. lithium ion sieve membrane according to claim 1, the surface apertures that it is characterized in that described earthenware are 0.1～1.0 μ m.
4. lithium ion sieve membrane according to claim 1, the thickness that it is characterized in that described lithium ion sieve precursor film are 0.1-15 μ m.
5. lithium ion sieve membrane according to claim 1, the thickness that it is characterized in that described lithium ion sieve precursor film are 1-5 μ m.
6. lithium ion sieve membrane according to claim 1, the length that it is characterized in that described earthenware is 5cm, and outer tube diameter is 1.3cm, and interior caliber is 0.9cm.
7. the preparation method of the described lithium ion sieve membrane of claim 1 is characterized in that it comprises the steps:
1) by metering citric acid and ethylene glycol are mixed, be heated with stirring to citric acid and dissolve fully;
2) with LiNO
3And Mn (NO
3)
2Mix, join in the above-mentioned solution, continue reflux 1.5～2.5h, form light yellow vitreosol;
3) with the colloidal sol air-distillation dewater, decompression distillation forms the dark brown gel after removing ethylene glycol, pour in the evaporating dish;
4) earthenware is immersed in the gel, extracting 3-5 time back is in 70 ℃ of dryings, places the Muffle furnace heating that heats up again, at 300～350 ℃ of insulation 0.5～1.5h down, 800 ℃ cool off naturally behind insulation 4～8h down the film pipe;
5) be prop carrier with membranaceous lithium ion sieve precursor, repeating step 4) once or twice more than, obtain lithium ion sieve precursor film;
6) HCl solution or the 0.2mol/L ammonium persulfate solution with the effective 0.1～0.5mol/L of film that makes carries out wash-out, can get the lithium ion sieve membrane;
7) lithium-containing solution with 0.01～0.05mol/L is an adsorption liquid, can investigate the selection through performance of film to lithium.
8. the preparation method of lithium ion sieve membrane according to claim 7 is characterized in that described LiNO
3And Mn (NO
3)
2Mol ratio be 1: 1.5～2.5; Citric acid and Mn (NO
3)
2Mol ratio be 1: 1; Return time 1.5～2.5h.
9. the preparation method of lithium ion sieve membrane according to claim 7 is characterized in that the described heating rate of step 4) is 5～10 ℃/min.
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Cited By (10)
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|---|---|---|---|---|
| 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 |
| CN106310961A (en) * | 2016-10-08 | 2017-01-11 | 天津科技大学 | Preparation method of lithium ion sieve acid-resistant blend membrane |
| CN106435220A (en) * | 2016-09-06 | 2017-02-22 | 南京工业大学 | Method for reducing magnesium-lithium ratio of salt lake brine |
| CN107261860A (en) * | 2017-06-23 | 2017-10-20 | 哈尔滨工业大学 | A kind of method that sol-gal process prepares metal oxide membrane for water treatment |
| CN108046368A (en) * | 2018-01-07 | 2018-05-18 | 天津市职业大学 | Glass-loaded lithium ion sieve filler of a kind of open celled foam and preparation method thereof |
| CN108114693A (en) * | 2018-01-07 | 2018-06-05 | 天津市职业大学 | A kind of glass fibre is lithium ion sieve adsorbed film of matrix and preparation method thereof |
| CN108160024A (en) * | 2018-01-11 | 2018-06-15 | 南京工业大学 | Preparation method of ceramic tube support body loaded 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 |
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| CN113559829A (en) * | 2021-08-16 | 2021-10-29 | 海南大学 | Preparation method and application of uranium/lithium synchronous adsorption material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH038443A (en) * | 1989-06-02 | 1991-01-16 | Agency Of Ind Science & Technol | Lithium adsorbent and method for recovering lithium with the same |
| JP2002167626A (en) * | 2000-11-28 | 2002-06-11 | National Institute Of Advanced Industrial & Technology | Apparatus and method for recovering lithium |
| JP2011074410A (en) * | 2009-09-29 | 2011-04-14 | Jx Nippon Mining & Metals Corp | Method for separating and recovering nickel and lithium |
| CN102211012A (en) * | 2010-09-10 | 2011-10-12 | 中国海洋大学 | Lithium ion sieve membrane and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3008443B2 (en) * | 1990-05-11 | 2000-02-14 | 松下電器産業株式会社 | Manufacturing method of printed circuit board mounting pin connector |
-
2011
- 2011-12-28 CN CN201110445347.3A patent/CN102512983B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH038443A (en) * | 1989-06-02 | 1991-01-16 | Agency Of Ind Science & Technol | Lithium adsorbent and method for recovering lithium with the same |
| JP2002167626A (en) * | 2000-11-28 | 2002-06-11 | National Institute Of Advanced Industrial & Technology | Apparatus and method for recovering lithium |
| JP2011074410A (en) * | 2009-09-29 | 2011-04-14 | Jx Nippon Mining & Metals Corp | Method for separating and recovering nickel and lithium |
| CN102211012A (en) * | 2010-09-10 | 2011-10-12 | 中国海洋大学 | Lithium ion sieve membrane and preparation method thereof |
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|---|---|---|---|---|
| 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 |
| CN106435220A (en) * | 2016-09-06 | 2017-02-22 | 南京工业大学 | Method for reducing magnesium-lithium ratio of salt lake brine |
| CN106310961A (en) * | 2016-10-08 | 2017-01-11 | 天津科技大学 | Preparation method of lithium ion sieve acid-resistant blend membrane |
| CN107261860A (en) * | 2017-06-23 | 2017-10-20 | 哈尔滨工业大学 | A kind of method that sol-gal process prepares metal oxide membrane for water treatment |
| CN108114693B (en) * | 2018-01-07 | 2020-07-17 | 天津市职业大学 | Lithium ion sieve adsorption membrane with glass fiber as matrix and preparation method thereof |
| CN108114693A (en) * | 2018-01-07 | 2018-06-05 | 天津市职业大学 | A kind of glass fibre is lithium ion sieve adsorbed film of matrix and preparation method thereof |
| CN108046368A (en) * | 2018-01-07 | 2018-05-18 | 天津市职业大学 | Glass-loaded lithium ion sieve filler of a kind of open celled foam and preparation method thereof |
| CN108046368B (en) * | 2018-01-07 | 2020-08-11 | 天津市职业大学 | Lithium ion sieve filler loaded by open-cell foam glass and preparation method thereof |
| CN108160024A (en) * | 2018-01-11 | 2018-06-15 | 南京工业大学 | Preparation method of ceramic tube support body loaded 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 |
| 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 |
| 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 |
| CN113559829A (en) * | 2021-08-16 | 2021-10-29 | 海南大学 | Preparation method and application of uranium/lithium synchronous adsorption material |
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