CN107174962A - A kind of preparation method and use of lithium ion blotting membrane - Google Patents
A kind of preparation method and use of lithium ion blotting membrane Download PDFInfo
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- CN107174962A CN107174962A CN201710420925.5A CN201710420925A CN107174962A CN 107174962 A CN107174962 A CN 107174962A CN 201710420925 A CN201710420925 A CN 201710420925A CN 107174962 A CN107174962 A CN 107174962A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28035—Membrane, sheet, cloth, pad, lamellar or mat with more than one layer, e.g. laminates, separated sheets
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
- C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
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- C08J7/16—Chemical modification with polymerisable compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/044—Elimination of an inorganic solid phase
- C08J2201/0444—Salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
Abstract
The invention provides a kind of preparation method and use of lithium ion blotting membrane, synthesize as follows：Kynoar powder and polyvinylpyrrolidone are added in N, N ' dimethyl acetamides, under constant temperature after mechanical agitation, keeping temperature is constant to be stood, and by phase-inversion technologies formation PVDF basement membranes, this PVDF basement membrane is put and preserved in deionized water；PVDF basement membranes are immersed in Tris HCl solutions, dopamine are added, at room temperature mechanical oscillation, obtaining surface has the PVDF basement membranes of poly-dopamine layer；12 crown ethers 4 are added in methanol with lithium chloride, the PVDF basement membranes that the surface has poly-dopamine layer are immersed in mixed solution, GDMA and azodiisobutyronitrile is added, forms mixed liquor, sealed after logical inert gas, be placed in thermostatic control oscillator vibration and react；The film obtained after reaction is taken off with pickling, lithium ion blotting membrane is obtained.Material prepared by this method is to Li+Selectivity is high, and separating effect is notable.
Description
Technical field
The invention belongs to field of material preparation, it is related to a kind of preparation method of lithium ion blotting membrane.
Background technology
Seperation film (separation membrane), refers to the membrane material with Selective Separation function, it can make in fluid
One or more of material permeances, and other materials can not be passed through, so as to play a part of separation, purifying and concentrate.Film can be with
It is homogeneous or heterogeneous, symmetric figure or unsymmetrical, solid-state or liquid, neutrality or charge.Envelope point
From flowing material can be liquid, can also be gaseous, film has selective penetrated property, and this is also film and membrane separating process
Inherent characteristic.The scope that seperation film is applicable separation is extremely wide, and from microsize grade to microbial cells, or even ion level has it to use force
Ground, key is to select different film types, thus membrane separation technique desalinization, drink water purifying, industrial wastewater and
The field such as sanitary sewage disposal and the separation of the industry such as reuse and chemical industry, medicine, food, purifying and concentration obtains extensively should
With being that recycling economy, clean manufacturing etc. provide technical guarantee, it has also become promote industry development, improve human being's production environment
One of general character support technology.
Molecular imprinting technology (Molecularly imprinted technique, MIT) is to simulate in nature such as：Enzyme
With the Molecular Recognization of substrate, antibody and antigen etc., being prepared by template molecule of target molecule has special choosing to the molecule
A kind of skill of the macromolecule imprinted polymer (Molecularly Imprinted Polymers, MIPs) of selecting property identification function
Art.Ionic imprinting technique (Ion imprinted technique, IIT) is the branch of molecular imprinting technology, it with yin, yang from
Son is template, is interacted by the action and function such as electrostatic, coordination monomer, and template ion is removed after cross-linked polymeric and is just obtained
Rigid polymer with special groups arrangement, fixed cavitation size and shape, the three-dimensional hole of formation has to object ion
Special compatibility and identity, are more and more used for separation, the enrichment aspect of metal ion.Ion blotting film (Ion
Imprinted membranes, IIMs) ionic imprinting technique is coupled with membrane separation technique, have as one kind and used compared with usury
Rate is while the small new material of environmental pollution, is widely applied to separation, purification art.
Conventional organic fluoride-containing polymer material of preparing mainly has polytetrafluoroethylene (PTFE) (PTFE) and Kynoar (PVDF).
Wherein PVDF is current comparatively ideal milipore filter and the material of preparing of microfiltration membranes.PVDF is a kind of white powder crystallinity polymerization
Thing, with excellent uvioresistant, weatherability and resistance tocrocking, dissolves in polar organic solvent such as dimethylformamide
(DMF), dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO), 1-METHYLPYRROLIDONE (NMP).PVDF have it is good into
Film processing characteristics, both can be also film-made using the shaping of solution phase inversion using melt spinning or thermally induced phase separation.So choosing
With the material as the film of substrate to well adapting to property of environment.
Lithium (lithium) and its compound be widely used in its excellent performance Lithium Battery Industry, electronics, metallurgy,
The fields such as chemical industry, medicine, the energy, have important strategic position in national economy and national defense construction, are described as that " 21 century is new
The energy ".Lithium also plays significant role in life science, and lithium can not only improve hematopoiesis function and improve human immunologic function, right
Neural activity also has good adjustment effect, and energy is calm, calms the nerves and controls neurological disorders, also can prevention and cure of cardiovascular disease.
Lithium consumption figure is increased with annual 7%-11% speed in recent years, but existing lithium resource is but increasingly exhausted.Wherein Bolivia,
The reserves basis of China and Chile accounts for more than the 80% of world gross reserves basis.Compared to the lithium resource of land, seawater and lake water
Amount containing lithium it is quite huge.Data shows, more than the 80% of 66% and lithium the reserves basis of salt lake Li Zhan worlds lithium reserves.Cause
This, the rate of recovery for improving lithium is necessary.Selectivity in view of simple seperation film is not high, introduces ion blotting skill
Art, imprinted layer is formed on its surface, to improve the selectivity of film, and a class new method is provided for lithium ion separation, purge process,
And constantly isolate and purify the irreplaceable effect of field performance in large industrial goods.
The content of the invention
It is an object of the invention to provide a kind of lithium ion blotting membrane, and for Li+、Mg2+、Na+Coexisted etc. different kinds of ions
Selective recognition and separation.
The present invention is achieved through the following technical solutions：
A kind of synthetic method of lithium ion blotting membrane, step is as follows：
Step 1, Kynoar (PVDF) powder and polyvinylpyrrolidone (PVP) be added to N, N '-dimethyl second
In acid amides (DMAC), mechanical agitation under constant temperature, after the completion of mechanical agitation, keeping temperature is constant to be stood, and passes through phase-inversion technologies shape
Into PVDF basement membranes, this PVDF basement membrane is put and preserved in deionized water；
Step 2, the PVDF basement membranes that step 1 is obtained are immersed in Tris-HCl solution, add dopamine, at room temperature machine
Tool vibrates, and obtaining surface has the PVDF basement membranes of poly-dopamine layer；
12- crown ethers -4 and lithium chloride are added in methanol, the PVDF basement membranes that the surface has poly-dopamine layer are soaked
Enter into the mixed solution, add GDMA (EGDMA) and azodiisobutyronitrile (AIBN), formed
Mixed liquor, leads to after inert gas and seals, be placed in thermostatic control oscillator vibration and react；
Step 3, step 2 is reacted after obtained film taken off with pickling, obtain lithium ion blotting membrane.
In step 1, the Kynoar, polyvinylpyrrolidone, N, the amount ratio of N '-dimethyl acetamide is 4g：
(0.01~0.04) g：25~40mL；The constant temperature is 30 DEG C, and the churned mechanically time is 12h；The time of repose is
24h。
In step 2, the dopamine is 2~4mg/mL, the Tris-HCl with the concentration in the Tris-HCl solution
The concentration of solution is 10~30mM, PH=8.5；In the mixed liquor, used 12- crown ethers -4, lithium chloride, dimethyl allene
Sour glycol ester, azodiisobutyronitrile, the amount ratio of methanol are 0.6~1.2g：0.3g：0.4~0.8mmol：8~10mg：
50mL；The inert gas is nitrogen；The temperature of the thermostatic control oscillator vibration is 60 DEG C, and the time of the reaction is 18h.
In step 3, described acid is HCl, and concentration is 0.2-0.5mol L-1。
Described lithium ion blotting membrane is used to adsorb lithium ion.
The synthesis of nonionic blotting membrane (NIMs) is that to be added without template Li+ remaining step same as above.
Kynoar powder described in above-mentioned technical proposal, it is used as synthesizing basal lamina material.
Lithium chloride described in above-mentioned technical proposal, it act as template ion.
12- crown ether -4 described in above-mentioned technical proposal, it act as function monomer.
GDMA described in above-mentioned technical proposal, it act as crosslinking agent.
Azodiisobutyronitrile described in above-mentioned technical proposal, it act as initiator.
In above-mentioned technical scheme, 12- crown ethers -4 and lithium chloride in methanol solution prepolymerization so that function monomer and mould
Chelation is produced between plate ion Li+, ion imprinted polymer is formed.
Beneficial effect：
The product, as function monomer, directly forms ion imprinted polymer with lithium ion to improve spy with 12- crown ethers -4
Different identity.From dopamine as basement membrane and the articulamentum of imprinted layer, it can significantly increase imprinted sites, so as to carry
The selectivity of high film.Due to adding after dopamine articulamentum, the recycling rate of waterused of membrane material is greatly increased.The blotting membrane is to Li+
With selective height, the significant advantage of separating effect.
Brief description of the drawings
Fig. 1 is the Staticadsorption experiment figure of embodiment 1, wherein, curve a is lithium ion blotting membrane, and curve b prints for non-lithium ion
Mark film；
Fig. 2 is the blotting membrane selective absorption lab diagram of embodiment 1, wherein, curve a is magnesium ion, and curve b is sodium ion；
Fig. 3 be the non-blotting membrane selective absorption lab diagram of embodiment 1, wherein, curve a be magnesium ion, curve b be sodium from
Son；
Fig. 4 is the Staticadsorption experiment figure of embodiment 2, wherein, curve a is lithium ion blotting membrane, and curve b prints for non-lithium ion
Mark film；
Fig. 5 is the blotting membrane selective absorption lab diagram of embodiment 2, wherein, curve a is magnesium ion, and curve b is sodium ion；
Fig. 6 be the non-blotting membrane selective absorption lab diagram of embodiment 2, wherein, curve a be magnesium ion, curve b be sodium from
Son.
Embodiment
With reference to specific implementation example, the present invention will be further described.
Heretofore described absorption property analysis test method is specially：
(1) Static Adsorption is tested
The IIMs and NIMs of the quality such as selection are added in corresponding test solution, stood in constant temperature waters, test fluid is put
Ion concentration after the adsorbance of trace and non-blotting membrane, adsorption equilibrium is investigated after standing certain time respectively in 25 DEG C of water-bath
Determined with Atomic Absorption Spectrometer (AAS).If the test solution added is VmL, the initial concentration for matching somebody with somebody solution is C0, a timing
Between balance after its concentration be Ct, the quality of film is m, then the adsorbance Q for having film is：
(2) selective absorption is tested
Choose Li+、Mg2+、Na+For competitive Adsorption substrate, the aqueous solution of several compounds of the above is respectively configured.Take and match somebody with somebody in right amount
The solution put is added in conical flask, is separately added into a piece of load weighted trace and non-blotting membrane, test fluid is placed on 25 DEG C
Water-bath in stand 8.0h respectively；After the completion of time of repose, take out each ion concentration after trace and non-blotting membrane, adsorption equilibrium and use
Atomic Absorption Spectrometer (AAS) is determined.
Embodiment 1
1. take 4g Kynoar powder (PVDF) to be blended with 0.04g polyvinylpyrrolidones (PVP), add 40mlN,
N '-dimethyl acetamide (DMAc) solution, mechanical agitation 12 hours under the conditions of 30 DEG C, keeping temperature takes off for constant static 24 hours
Bubble, passes through phase-inversion technologies formation PVDF basement membranes.This pvdf membrane is put and preserved in deionized water, in case next step is tested.
2. PVDF basement membranes are immersed in 50ml 25mM PH=8.5 Tris-HCl solution, take 180mg dopamines
(Dopamine) it is added in above-mentioned solution, at room temperature mechanical oscillation 6h, in the formation of PVDF membrane surfaces, one layer there is bonding to make
Poly-dopamine thin layer (PDA).1.2g 12- crown ethers -4,0.3gLiCl, which are added in 50ml methanol solutions, forms ion blotting
Polymer.Pvdf membrane with poly-dopamine thin layer is immersed in above-mentioned solution, 0.8mmol GDMAs are taken
(EGDMA), 10mg azodiisobutyronitriles (AIBN) be added in above-mentioned solution, lead to after nitrogen 20min and seal, be placed in 60 degree of constant temperature
18h is reacted in water bath chader.
3. taken the film out after reacting, with HCl eluted template ions, wherein HCl concentration is 0.5mol L-1, by Li+It is de-
Remove, then deionized water carries out cyclic washing until washing into neutrality, prepares ion blotting macroporous membrane (IIMs), non-trace
The synthesis of film (NIMs) is that to be added without lithium ion remaining step same as above.
4. Static Adsorption is tested
10mg/L LiCl solution is prepared, solvent deionized water takes a piece of trace and non-blotting membrane to be respectively put into 10mL's
In solution, stand at room temperature after 8.0h, determine residue Li in solution+Concentration.
As a result show：The adsorbance of blotting membrane is the adsorbance 19.2mg/g, such as Fig. 1 that 27.1mg/g is much larger than non-blotting membrane
It is shown.
5. selective absorption is tested
Select Mg2+、Na+For competitive Adsorption substrate, Li is prepared+、Mg2+、Na+The aqueous solution of three kinds of compounds, every kind of substrate
Concentration all be 10mg/L；Respectively take a piece of trace and non-blotting membrane to be put into 10mL solution, stood respectively in 25 DEG C of water-bath
8.0h；After the completion of time of repose, each ion concentration is determined with Atomic Absorption Spectrometer (AAS).
As a result show：Blotting membrane is to Mg2+、Na+Separation factor reach 4.42 and 4.01, rather than blotting membrane separation factor
Only 1.73 and 1.65, show blotting membrane to Li+There are specific selectivity evident characteristics, as shown in Figure 2 and Figure 3.
Embodiment 2
1. 4g Kynoar powder (PVDF) is blended with 0.15g polyvinylpyrrolidones (PVP), and addition 25mlN, N '-
Dimethyl acetamide (DMAc) solution, mechanical agitation 12 hours under the conditions of 30 DEG C, the constant static deaeration in 24 hours of keeping temperature is led to
Cross phase-inversion technologies formation PVDF basement membranes.This pvdf membrane is put and preserved in deionized water, in case next step is tested.
2. PVDF basement membranes are immersed in 50ml 10mM PH=8.5 Tris-HCl solution, take 100mg dopamines
(Dopamine) it is added in above-mentioned solution, at room temperature mechanical oscillation 6h, in the formation of PVDF membrane surfaces, one layer there is bonding to make
Poly-dopamine thin layer (PDA).0.6g12- crown ethers -4,0.3gLiCl are added in 50ml methanol solutions and form ion blotting
Polymer.Pvdf membrane with poly-dopamine thin layer is immersed in above-mentioned solution, 0.4mmol GDMAs are taken
(EGDMA), 8mg azodiisobutyronitriles (AIBN) be added in above-mentioned solution, lead to after nitrogen 10~20min and seal, be placed in 60 degree
18h is reacted in thermostatic control oscillator vibration.
3. taken the film out after reacting, with HCl eluted template ions, wherein HCl concentration is 0.2mol L-1, by Li+It is de-
Remove, then deionized water carries out cyclic washing until washing into neutrality, prepares ion blotting macroporous membrane (IIMs), non-trace
The synthesis of film (NIMs) is that to be added without lithium ion remaining step same as above.
4. Static Adsorption is tested
10mg/L LiCl solution is prepared, solvent deionized water takes a piece of trace and non-blotting membrane to be respectively put into 10mL's
In solution, stand at room temperature after 8.0h, determine residue Li in solution+Concentration.
As a result show：The adsorbance of blotting membrane is the adsorbance 14.2mg/g, such as Fig. 4 that 23.6mg/g is much larger than non-blotting membrane
It is shown.
5. selective absorption is tested
Select Mg2+、Na+For competitive Adsorption substrate, Li is prepared+、Mg2+、Na+The aqueous solution of three kinds of compounds, every kind of substrate
Concentration all be 10mg/L；Respectively take a piece of trace and non-blotting membrane to be put into 10mL solution, stood respectively in 25 DEG C of water-bath
8.0h；After the completion of time of repose, each ion concentration is determined with Atomic Absorption Spectrometer (AAS).
As a result show：Blotting membrane is to Mg2+、Na+Separation factor reach 3.63 and 3.49, rather than blotting membrane separation factor
Only 1.56 and 1.48, show blotting membrane to Li+There are specific selectivity evident characteristics, as shown in Figure 5, Figure 6.
Claims (5)
1. a kind of synthetic method of lithium ion blotting membrane, it is characterised in that step is as follows：
Step 1, Kynoar powder and polyvinylpyrrolidone be added in N, N '-dimethyl acetamide, machine under constant temperature
Tool is stirred, after the completion of mechanical agitation, and keeping temperature is constant to be stood, by phase-inversion technologies formation PVDF basement membranes, this PVDF base
Film is put to be preserved in deionized water；
Step 2, the PVDF basement membranes that step 1 is obtained are immersed in Tris-HCl solution, add dopamine, machinery shakes at room temperature
Swing, obtaining surface has the PVDF basement membranes of poly-dopamine layer；
12- crown ethers -4 and lithium chloride are added in methanol, the PVDF basement membranes that the surface has poly-dopamine layer are immersed in
In the mixed solution, GDMA and azodiisobutyronitrile are added, mixed liquor is formed, leads to inert gas
After seal, be placed in thermostatic control oscillator vibration react；
Step 3, step 2 is reacted after obtained film taken off with pickling, obtain lithium ion blotting membrane.
2. the synthetic method of a kind of lithium ion blotting membrane according to claim 1, it is characterised in that in step 1, described poly-
Vinylidene, polyvinylpyrrolidone, N, the amount ratio of N '-dimethyl acetamide is 4g：(0.01~0.04) g：25~40mL；
The constant temperature is 30 DEG C, and the churned mechanically time is 12h；The time of repose is 24h.
3. the synthetic method of a kind of lithium ion blotting membrane according to claim 1, it is characterised in that described many in step 2
Bar amine is 2~4mg/mL with the concentration in the Tris-HCl solution, and the concentration of the Tris-HCl solution is 10~30mM, PH
=8.5；In the mixed liquor, used 12- crown ethers -4, lithium chloride, GDMA, the isobutyl of azo two
Nitrile, the amount ratio of methanol are 0.6~1.2g：0.3g：0.4~0.8mmol：8~10mg：50mL；The inert gas is nitrogen；
The temperature of the thermostatic control oscillator vibration is 60 DEG C, and the time of the reaction is 18h.
4. the synthetic method of a kind of lithium ion blotting membrane according to claim 1, it is characterised in that described in step 3
Acid is HCl, and concentration is 0.2-0.5mol L-1。
5. lithium ion blotting membrane prepared by the method described in Claims 1 to 4 any one is used for the purposes for adsorbing lithium ion.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108246269A (en) * | 2018-01-10 | 2018-07-06 | 山东大学 | A kind of lithium ion adsorbent and preparation method and application |
| CN110862568A (en) * | 2019-12-04 | 2020-03-06 | 石河子大学 | Preparation method and application of molecularly imprinted membrane for separating phenylethanoid glycosides |
| CN111229174A (en) * | 2020-01-13 | 2020-06-05 | 江苏大学 | Preparation method and application of Li-IIMs (lithium-ion organic Compounds) ion imprinting membrane |
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| CN108246269A (en) * | 2018-01-10 | 2018-07-06 | 山东大学 | A kind of lithium ion adsorbent and preparation method and application |
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| CN111229174A (en) * | 2020-01-13 | 2020-06-05 | 江苏大学 | Preparation method and application of Li-IIMs (lithium-ion organic Compounds) ion imprinting membrane |
| CN111545172A (en) * | 2020-05-11 | 2020-08-18 | 清华大学 | Supported adsorbent and preparation method and application thereof |
| CN111545172B (en) * | 2020-05-11 | 2021-05-28 | 清华大学 | Supported adsorbent and preparation method and application thereof |
| CN113019337A (en) * | 2021-02-01 | 2021-06-25 | 江苏大学 | Preparation method of polytetrafluoroethylene boron affinity imprinted membrane and application of polytetrafluoroethylene boron affinity imprinted membrane in selective separation of shikimic acid |
| CN113351180A (en) * | 2021-06-08 | 2021-09-07 | 东北电力大学 | Preparation method and application of temperature response type bionic lithium ion imprinting composite membrane |
| CN113522061A (en) * | 2021-07-21 | 2021-10-22 | 昆明理工大学 | Preparation method of high-adsorption-capacity lithium ion imprinting nano composite membrane |
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