CN108854934A - lithium adsorbent and preparation method thereof - Google Patents
lithium adsorbent and preparation method thereof Download PDFInfo
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- CN108854934A CN108854934A CN201710318647.2A CN201710318647A CN108854934A CN 108854934 A CN108854934 A CN 108854934A CN 201710318647 A CN201710318647 A CN 201710318647A CN 108854934 A CN108854934 A CN 108854934A
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
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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
- B01D67/0039—Inorganic membrane manufacture
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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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
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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
- B01D71/02—Inorganic material
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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
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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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/2626—Absorption or adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
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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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Abstract
The invention discloses lithium adsorbents and preparation method thereof.Wherein, which includes：Basilar memebrane；And composite layer, the composite layer include：Adhesive layer, the adhesive layer are formed on the surface of the basilar memebrane；Adsorption layer, the adsorption layer are formed on the surface of the adhesive layer.The problems such as lithium adsorbent is efficiently solved and relies on a large amount of binder during existing graininess or blocky adsorbent-shaping by the way that adsorbent to be formed on basilar memebrane, and the usage ratio of adsorbent is low, and adsorption capacity is poor, easy to fall off and rupture.The intensity of the lithium adsorbent of the embodiment of the present invention is high, washes away more resistant to solution, not cracky, and solution transmitance is fast, and the capacity of absorption and the efficiency of absorption also significantly improve, meanwhile, service life is also longer.
Description
Technical field
The present invention relates to Material Fields, and in particular, to lithium adsorbent, and the method for preparing the lithium adsorbent.
Background technique
Without molding powder lithium adsorbent, there are poor fluidity, difficult the disadvantages of separating.To overcome these problems, go out
Show and has added powder in absorbent powder in product and patent, such as patent CN1302844C after some powder adsorbent-shapings
The polyvinyl-chloride binders of weight 8% to 10%, and the mixing of solvent liquid methyl chloride is added, cream paste is generated by squeezing, then
Particle is refined into be granulated.Another powder adsorbent-shaping is at block-like patent, as used in patent CN102160992A
Powdered absorbent foams together with sponge raw material, does not change the chemical property of adsorbent in foaming process, by the absorption of powder
Agent is prepared into blocky sponge adsorbent.But there are still Railway Projects for such product：(1) when binder amount used in forming is larger,
Adsorbance decline is obvious, however reduces consumption of binder, and adsorbent is washed away and is easy to fall off by solution；(2) spherical adsorbent makes
With will appear rupture in the process, service life is reduced.
Existing lithium adsorbent has much room for improvement as a result,.
Summary of the invention
The present invention is directed at least solve one of the technical problems existing in the prior art.For this purpose, one object of the present invention
It is to propose a kind of lithium adsorbent, which keeps the intensity of lithium adsorbent aobvious by the way that adsorbent to be formed on basilar memebrane
It writes and improves, washed away more resistant to solution, not cracky, and solution transmitance is fast, the capacity of absorption and the efficiency of absorption also significantly mention
It is high.
According to the first aspect of the invention, the present invention provides a kind of lithium adsorbents.According to an embodiment of the invention, the lithium
Adsorbent includes：Basilar memebrane；And composite layer, the composite layer include：Adhesive layer, the adhesive layer are formed in the basilar memebrane
Surface on；Adsorption layer, the adsorption layer are formed on the surface of the adhesive layer.
Lithium adsorbent according to an embodiment of the present invention is efficiently solved existing by the way that adsorbent to be formed on basilar memebrane
Graininess or blocky adsorbent-shaping during rely on a large amount of binder, the usage ratio of adsorbent is low, and adsorption capacity is poor,
The problems such as easy to fall off and rupture.The intensity of the lithium adsorbent of the embodiment of the present invention is high, washes away more resistant to solution, not cracky, and
Solution transmitance is fast, and the capacity of absorption and the efficiency of absorption also significantly improve, meanwhile, service life is also longer.According to the present invention
Even if the usage ratio of the binder of the lithium adsorbent of embodiment is relatively high, solution penetrating power is also had little influence on, and have
Higher intensity, more resistant to washing away, adsorbent hardly happens loss in long-time use；In addition, adsorbent amount ratio is high
Composite membrane has higher adsorption efficiency, bigger adsorption capacity, while composite membrane becomes more flexible less cracky.
According to the second aspect of the invention, the present invention provides a kind of methods for preparing lithium adsorbent above-mentioned.According to this
The embodiment of invention, this method include：(1) basilar memebrane is provided；And (2) form composite layer on the surface of the basilar memebrane,
The adsorption layer that the composite layer contains adhesive layer and is formed on the adhesive layer, to obtain the lithium adsorbent.
The method according to an embodiment of the present invention for preparing lithium adsorbent makes to prepare by forming composite layer on basilar memebrane
The intensity of the obtained lithium adsorbent is high, washes away more resistant to solution, not cracky, meanwhile, solution transmitance is fast, the capacity of absorption and
What is adsorbed is high-efficient, and service life is also longer.In addition, it should be noted that, the lithium adsorbent of this method preparation, has aforementioned lithium
The all technical features and advantage of adsorbent, this is no longer going to repeat them.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures
Obviously and it is readily appreciated that, wherein：
Fig. 1 shows the structural schematic diagram of lithium adsorbent according to an embodiment of the invention；
Fig. 2 shows the structural schematic diagram of the lithium adsorbent of another embodiment according to the present invention；
Fig. 3 shows the method flow schematic diagram according to an embodiment of the invention for forming the composite layer in multilayer.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, and for explaining only the invention, and is not considered as limiting the invention.
It should be noted that term " first ", " second " are used for description purposes only, it is not understood to indicate or imply phase
To importance or implicitly indicate the quantity of indicated technical characteristic.Define " first " as a result, the feature of " second " can be with
Explicitly or implicitly include one or more of the features.Further, in the description of the present invention, unless otherwise saying
Bright, the meaning of " plurality " is two or more.
Lithium adsorbent
According to the first aspect of the invention, the present invention provides a kind of lithium adsorbents.According to an embodiment of the invention, with reference to
The lithium adsorbent is explained in Fig. 1 and 2, which may include basilar memebrane 100 and composite layer 200.Composite layer
200 may include：Adhesive layer and adsorption layer, wherein adhesive layer can be formed on the surface of basilar memebrane；Adsorption layer can be formed
On the surface of adhesive layer.
Adsorption layer is formed on the surface of adhesive layer.Wherein, it should be noted that two surfaces of basilar memebrane 100
To form composite layer 200, that is to say, that composite layer 200 can be formed on a surface of basilar memebrane 100, can also be with shape
At on two surfaces of basilar memebrane 100, those skilled in the art can voluntarily select according to needs of production.Its
In, the adsorbent for needing to illustrate can be in powdery, i.e. adsorbent powder.Also it should be further noted that the embodiment of the present invention
Basilar memebrane in membranaceous, the transmitance of water and ion is higher.
Lithium adsorbent according to an embodiment of the present invention is efficiently solved existing by the way that adsorbent to be formed on basilar memebrane
Graininess or blocky adsorbent-shaping during rely on a large amount of binder, the usage ratio of adsorbent is low, and adsorption capacity is poor,
The problems such as easy to fall off and rupture.The intensity of the lithium adsorbent of the embodiment of the present invention is high, washes away more resistant to solution, not cracky, and
Solution transmitance is fast, and the capacity of absorption and the efficiency of absorption also significantly improve, meanwhile, service life is also longer.
According to an embodiment of the invention, basilar memebrane 100 has the first micropore.Be conducive to water as a result, and ion penetrates.According to
The preferred embodiment of the present invention, the first micropore are nano through holes.Water and ion are easy to penetrate as a result, make the transmitance of solution
It is higher.
According to an embodiment of the invention, composite layer 200 further comprises：Adhesive layer, the adhesive layer are formed by binder
, and the adsorption layer is formed on the surface of adhesive layer.The interior contact of binder and adsorbent is few as a result, convenient for absorption
Agent is exposed to the surface of composite layer after molding, enhances absorption property.
According to an embodiment of the invention, point of different adsorption layer and adhesive layer can be formed using different coverage modes
Cloth structure.According to some embodiments of the present invention, composite layer 200 may include an adhesive layer and an adsorption layer, the i.e. lithium
Adsorbent sequentially consists of basilar memebrane, adhesive layer, adsorption layer.The adsorption capacity of lithium adsorbent is strong as a result,.According to the present invention
Other embodiment, composite layer 200 also may include multiple adhesive layers and multiple adsorption layers, and adhesive layer and adsorption layer alternating
Stacking forms multilayered structure.For example, the lithium adsorbent sequentially consists of adsorption layer/adhesive layer/adsorption layer/adhesive layer/base
Counterdie/adhesive layer/adsorption layer；Basilar memebrane/adhesive layer/adsorption layer/adhesive layer/adsorption layer；Adsorption layer/adhesive layer/basilar memebrane/viscous
Tie layer/adsorption layer etc..It is contacted between each adsorption layer on a small quantity inside the adsorbent in adsorption layer and binder with bonding as a result,
The form that layer mutually bonds can effectively reduce active material surface covering binder, to make the absorption property of lithium adsorbent
More preferably.Term " multiple " mentioned herein refers at least two, it can is two, three, is also possible to more.
According to an embodiment of the invention, the ratio of adsorbent and binder in composite layer is not particularly limited, ability
Field technique personnel can carry out condition with the method for preparation according to production needs.Preferred embodiment in accordance with the present invention, composite layer
The binder of 200 adsorbents containing 80-90 mass parts and 10-20 mass parts.The usage ratio of adsorbent is high as a result, absorption
Ability is strong, and solution transmitance is fast, the capacity of absorption and absorption it is more efficient.
According to an embodiment of the invention, the ratio of adsorbent and binder in adsorption layer is not also particularly limited, this
Field technical staff can carry out condition with the method for preparation according to production needs.Preferred embodiment in accordance with the present invention, absorption
The binder of the layer adsorbent containing 70-99 mass parts and 1-30 mass parts.The ratio of binder is small as a result, can effectively reduce
Active material surface covers binder, to make the absorption property of lithium adsorbent more preferably.
According to an embodiment of the invention, the raw material of basilar memebrane is not particularly limited, those skilled in the art can basis
Needs of production is selected.Preferred embodiment in accordance with the present invention, basilar memebrane can be by being selected from polyethersulfone resin membrane, gathering
At least one formation of tetrafluoroethylene and ceramic membrane.Wherein, according to some embodiments of the present invention, ceramic material can wrap
Include at least one of aluminium oxide, zirconium oxide and titanium oxide.Basilar memebrane and adsorbent are firmly combined as a result, also, basilar memebrane
Good penetrability.According to an embodiment of the invention, the type of adsorbent is not particularly limited, those skilled in the art can basis
Needs of production is selected.Preferred embodiment in accordance with the present invention, adsorbent can be for selected from aluminum salt adsorbents, lithium manganese oxygen
Compound adsorbent, de- lithium aluminum salt adsorbent, takes off the lithium manganese oxide adsorbent of lithium and the lithium titanium of de- lithium at Li-Ti oxide adsorbent
At least one of oxide adsorbent.The absorption property to lithium of adsorbent is good as a result, and saturated adsorption capacity is high.
According to an embodiment of the invention, the type of binder is not particularly limited, those skilled in the art can basis
Needs of production is selected.Preferred embodiment in accordance with the present invention, binder can be selected from polyvinyl formal, gather
Vinylidene, ethylene-vinyl acetate copolymer (EVA), polyolefin copolymer (PO), polyamide (PA), thermoplastic polyurethane bullet
Property body rubber (TPU), ultra high molecular polyethylene, vinyl chloride-vinyl acetate copolymer, polyvinyl fluoride, polyvinyl chloride and poly- second
At least one of enol butyral (PVB).The adhesive property of binder is good as a result,.
According to some embodiments of the present invention, adsorption layer can further contain：The content of pore creating material, the pore creating material is little
In 2 mass parts.Inventor's discovery makes composite layer in microcosmic porous, to make using compaction treatment compound by addition pore creating material
Density, the adsorbent caking property on basilar memebrane of layer are significantly increased.According to an embodiment of the invention, the type of pore creating material not by
Special limitation, can voluntarily select according to actual needs.Preferred embodiment in accordance with the present invention, pore creating material can be for selected from carbon
Sour hydrogen ammonium, urea, polyvinylpyrrolidone (PVP), sodium chloride, potassium chloride, polyethylene glycol (PEG) and polyvinyl alcohol (PVA)
It is at least one.Thus composite layer density and adsorbent caking property on basilar memebrane are good.
According to an embodiment of the invention, composite layer has the second micropore.Wherein, it should be noted that the micropore is nanometer
Grade and/or micron-sized micropore, and dense distribution is easier to water and ion through composite layer, transmitance is fast on composite layer.
It further illustrates, the aperture for the micropore that different adsorbent is formed and distribution density are different, and those skilled in the art can be with
Different adsorbents is selected according to demand.
According to some embodiments of the present invention, composite layer 200 may include：Adsorption layer and adhesive layer, wherein adsorption layer contains
There are adsorbent, binder and pore creating material；Adhesive layer contains the binder and optionally pore creating material.Binder and absorption as a result,
The interior contact of agent is few, and the surface of composite layer after molding is exposed to convenient for adsorbent, enhances absorption property.
According to an embodiment of the invention, basilar memebrane 100 with a thickness of 0.05-500 μm；Composite layer 200 with a thickness of
0.011-10.1mm；Adsorption layer with a thickness of 0.01-10mm and adhesive layer with a thickness of 0.001-0.1mm.Lithium adsorbent as a result,
Has suitable aqueous solution time of penetration, adsorption efficiency is high.
The method for preparing lithium adsorbent
According to the second aspect of the invention, the present invention provides a kind of methods for preparing lithium adsorbent above-mentioned.This passes through
Composite layer is formed on basilar memebrane, is kept the intensity for the lithium adsorbent being prepared high, is washed away more resistant to solution, not cracky, together
When, solution transmitance is fast, the capacity of absorption and absorption it is high-efficient, service life is also longer.In addition, it should be noted that, should
The lithium adsorbent of method preparation, has all technical features and advantage of aforementioned lithium adsorbent, this is no longer going to repeat them.
The above-mentioned method for preparing lithium adsorbent in order to facilitate understanding, with reference to Fig. 3, according to an embodiment of the invention, to wherein
It is formed and is explained further below explanation in the method for the composite layer of multilayer, this method includes：
S100 provides basilar memebrane
According to an embodiment of the invention, providing basilar memebrane.According to some embodiments of the present invention, which can have
Nanometer through-hole.Nanometer through-hole makes water and ion be easy to keep the transmitance of the solution of basilar memebrane higher through basilar memebrane as a result,.
S200 forms composite layer
According to an embodiment of the invention, forming composite layer on the surface of basilar memebrane, which contains adhesive layer and shape
At the adsorption layer on adhesive layer, the lithium adsorbent is obtained.As a result, by different covering methods, not similar shape can be formed
The adsorption layer of formula reduces active material surface and covers binder, make adsorbent to reduce contact of the adsorbent with binder
Absorption property is more preferably.
It may further include according to an embodiment of the invention, S200 forms composite layer adsorption layer：
(a) binder is used, the adhesive layer is formed.Specifically, adhesive layer is in addition to containing binder, as needed, also
Pore creating material can be contained, pore creating material makes composite layer in microcosmic porous, to make the density of composite layer and adsorbent exist using pressure roller
Caking property is significantly increased on basilar memebrane.
(b) adsorbent is used, forms adsorption layer on the surface of adhesive layer.Specifically, adsorption layer is except containing in addition to adsorbent,
According to actual needs, it is also an option that property add binder and pore creating material.
(c) it will be dried after the basilar memebrane for forming adsorption layer elution, obtain dry composite membrane.According to the present invention
Some embodiments, elution can for water elute.
(d) dry composite membrane is subjected to compaction treatment, forms the lithium adsorbent.As a result, by compaction treatment, make multiple
The density for closing layer is higher, combines composite layer and basilar memebrane stronger.
According to an embodiment of the invention, this method may further include：
(g) the lithium adsorbent after roll process is subjected to slicing treatment, to obtain the suitable lithium absorption of shapes and sizes
Body.
According to an embodiment of the invention, can use one of following methods in step (a) and form adhesive layer：
(I) it is covered on basilar memebrane after mixing binder with solvent；
(II) it is covered on basilar memebrane after binder being heated to half melt.
Further, according to an embodiment of the invention, in step (I), binder is 1 by solid-to-liquid ratio with solvent：(1-3) into
The row mixing.The consistency of binder slurries is suitable as a result, convenient for being covered on basilar memebrane, and the adhesive layer thickness formed
It is suitable for.
Further, according to an embodiment of the invention, providing the method for two kinds of formation composite layers herein, and every kind of method
The composite layer of formation also differs from one another, specific as follows：
Method one：
According to an embodiment of the invention, composite layer includes that one layer of adhesive layer and one layer of adsorption layer, the adhesive layer can be free of
There is pore creating material.As a result, using the binder coated in advance by adsorbent and binder anchoring base film, to keep adsorbent big
Amount is exposed to the surface of composite membrane after molding.
According to an embodiment of the invention, being in mass ratio (80- by adsorbent and binder and pore creating material in step (b)
99)：(1-20)：(0-2) multi-fold forms adsorption layer on the surface of adhesive layer, wherein it is optionally added pore creating material,
Pore creating material makes composite layer in microcosmic porous, to keep the density of composite layer and adsorbent caking property on basilar memebrane equal using pressure roller
It significantly improves.The binder content of adsorption layer is few as a result, and adsorbent is made largely to be exposed to the surface of composite membrane after molding.
According to an embodiment of the invention, this method further comprises：It (f), will be described in formation between in step (b) and (c)
The basilar memebrane of adsorption layer carries out extrusion process, to obtain lithium absorption intermediate after extruding.Make adsorbent solid securely as a result,
It is scheduled on binder.
According to an embodiment of the invention, the extrusion process can be the pressure in 20-200 degrees Celsius and 0.01MPa-30MPa
It is carried out under power.Extruding efficiency is high as a result, and effect is good, and binder is securely fixed on basilar memebrane.
Inventor has found that binder is first applied to the surface of basilar memebrane by method one, then adsorbent is pressed in binder
On basilar memebrane, it is adsorption layer on adhesive layer, which can make adsorbent largely sudden and violent that the bottom of the composite layer of formation, which is adhesive layer,
It is exposed at the surface of composite membrane after molding, to make the absorption property of lithium adsorbent more preferably.
Method two：According to an embodiment of the invention, the method for forming composite layer adsorption layer includes：Before step (c), repeat
Step (a)~(b) at least once, is alternately stacked the adhesive layer of composite layer and adsorption layer.This method substep is more on basilar memebrane
Layer film forming is formed inside each layer adsorbent and binder and contacts the form mutually bonded between multilayer with binder on a small quantity, i.e., multiple
The adsorption layer and the alternatively distributed form of adhesive layer for closing layer can effectively reduce active material surface covering binder, to make
The absorption property of lithium adsorbent is more preferably.
According to a particular embodiment of the invention, in step (a), by the binder of 90-100 mass parts and 0-10 mass parts
It is 1 that pore creating material and solvent, which press solid-liquid mass ratio,：Be covered on basilar memebrane after 0-3 mixing and form adhesive layer, make between adsorption layer with
Adhesive layer mutually bonds, and is bonded and fixed at each adsorption layer on basilar memebrane, meanwhile, pore creating material is selectively added, keeps coating micro-
It sees porous.
According to a particular embodiment of the invention, in step (b), by the adsorbent of 70 mass parts, the bonding of 3-30 mass parts
It is 1 that the pore creating material of agent and 0-2 mass parts and the solvent, which press solid-liquid mass ratio,：The table of the adhesive layer is covered on after 0-3 mixing
The adsorption layer is formed on face, the interior contact of adsorbent and binder is few as a result, can effectively reduce active material surface covering
Binder, to make the absorption property of lithium adsorbent more preferably.
Inventors have found that two substep of method multilayer on basilar memebrane forms a film, formed few inside each layer adsorbent and binder
The form mutually bonded between amount contact and multilayer with binder, the i.e. adsorption layer of composite layer and the alternatively distributed form of adhesive layer,
Active material surface covering binder can be effectively reduced, to make the absorption property of lithium adsorbent more preferably.
According to an embodiment of the invention, the type of solvent is not particularly limited, it can be according to the type and reality of raw material
Production needs voluntarily to select.Preferred embodiment in accordance with the present invention, solvent can be for selected from water, N-Methyl pyrrolidone, n-formyl sarcolysine
Yl acetamide (DMAC), N-methyl formamide (DMF), acetone, dimethylbenzene, methylene chloride, chloroform, tetrachloromethane, toluene,
At least one of ethyl alcohol and methyl chloride.Adsorbent, binder and pore creating material are easy to evenly dispersed in above-mentioned solvent as a result,.
According to an embodiment of the invention, the method for covering may include slope flow coating and extrusion coated.Wherein, slope flow coating
It can be realized pre-measured coating, high-speed coating, even spread is multi-layer coated etc., and extrusion coated is suitable for high viscosity mixed liquor, energy
Enough deal with painting and measure big operation, while can enhance the impact resistance of composite layer, those skilled in the art can according to need into
Row selection.
According to an embodiment of the invention, composite layer with a thickness of 0.01mm-10mm.The thickness range composite layer has as a result,
Standby suitable aqueous solution time of penetration, adsorption efficiency are high.Below with reference to specific embodiment, the present invention will be described, needs
Bright, these embodiments are merely illustrative, and are not considered as limiting the invention.
Embodiment 1
Lithium adsorbent is prepared using the method for the embodiment of the present invention and detects adsorbance, and specific step is as follows：
(1) it weighs binder (PVC) 100g to be added in 30g acetone in slush state, blade coating is in ceramic membrane surface and ties up
Hold slush state.
(2) powder aluminum salt adsorbent (mLiCl2Al (OH) is weighed3·nH2O) 400g, binder (PVC) 10g and
0.5g ammonium hydrogen carbonate obtains mixture with high speed mixer mixing 1h.
(3) surface that step (1) obtains is coated with the mixture that step on the substrate adhesion of binder (2) obtains, with
0.5MPa pressure extrusion film, operation temperature are 120 DEG C.
(4) product that step (3) obtains is crossed after water elution and is heated to 100 DEG C of drying, adsorbent coating layer thickness, which is made, is
The composite membrane of 2mm.
(5) composite membrane is cut into suitable size, obtains the lithium adsorbent product of strip substrate.
2, adsorbance detects
(1) lithium adsorbent is uniformly cut into wide 4cm × long 8cm compound film sheet, contained active material quality is MIt is living；
(2) compound film sheet is washed by 0.5h using the deionized water of flowing, lithium eluting rate is 39%；
(3) prepare V volume brine, be C with lithium concentration in flame spectrophotometer measuring brine0；
(4) it by the compound film sheet fixation after elution and is completely soaked in above-mentioned brine carries out adsorption experiment vertically, through fire
Lithium concentration is C in flame photometric determination brinee, wherein adsorbance presses formula：
It calculates,
Front and back brine lithium variation is adsorbed through flame spectrophotometer measuring, the adsorbance of lithium adsorbent is 9.3mg/g.
Embodiment 2
Lithium adsorbent is prepared using the method for the embodiment of the present invention and detects adsorbance, and specific step is as follows：
(1) it weighs ethylene-vinyl acetate copolymer 100g to be added in 30g acetone in slush state, scratch in ceramic membrane
Positive and negative two surfaces simultaneously maintain slush state.
(2) powder aluminum salt adsorbent (mLiCl2Al (OH) is weighed3·nH2O) 400g, partly to melt state ethene-vinyl acetate total
Polymers 30g obtains mixture with mixer mixing 3h.
(3) mixing that step (2) obtains in the adhesion for the substrate that two surfaces that step (1) obtains are coated with binder
Material, with 0.8MPa pressure extrusion film, operation temperature is 120 DEG C.
(4) product that step (3) obtains is crossed after water elution and is heated to 100 DEG C of drying, monolayer adsorption agent is made and applies thickness
Degree is that the two sides of 1.8mm has the composite membrane of adsorption layer.
(5) composite membrane is cut into suitable size, obtains the lithium adsorbent product of the strip substrate of specific two-sided composite layer.
The lithium adsorbent is detected using the absorption quantity measuring method of embodiment 1, it is as a result as follows：Using going for flowing
Ion water washing 0.5h, lithium eluting rate are 42%, and the compound film sheet after elution, which is put into brine, carries out adsorption experiment, through flame light
Degree meter measurement absorption front and back brine lithium variation, adsorbance 9.0mg/g.
Embodiment 3
Lithium adsorbent is prepared using the method for the embodiment of the present invention and detects adsorbance, and specific step is as follows：
(1) it weighs binder (EVA) 100g to be added in 30g toluene in slush state, mixture A is made.
(2) powder aluminum salt adsorbent (mLiCl2Al (OH) is weighed3·nH2O) 400g, binder (EVA) 30g and 1g
Urea obtains mixture B with high speed mixer mixing 1h.
(3) by the sequence of mixture B, mixture A, PTFE film surface is coated to extrusion coated technology, and apply repeatedly
Cloth 3 times, operation temperature is 130 DEG C, forms composite layer intermediate.
(4) product that step (3) obtains is crossed after water elution and is heated to 90 DEG C of drying, adsorbent coating layer thickness, which is made, is
The composite membrane of 6mm.
(5) composite membrane is cut into suitable size, obtains the lithium adsorbent product of strip substrate.
The lithium adsorbent is detected using the absorption quantity measuring method of embodiment 1, it is as a result as follows：Using going for flowing
Ion water washing 0.5h, lithium eluting rate are 34%, and the compound film sheet after elution, which is put into brine, carries out adsorption experiment, through flame light
Degree meter measurement absorption front and back brine lithium variation, adsorbance 8.4mg/g.
Embodiment 4
Lithium adsorbent is prepared using the method for the embodiment of the present invention and detects adsorbance, and specific step is as follows：
(1) it weighs binder polyamide (PA) 100g to be added in 80g methylene chloride in slush state, mixture A is made.
(2) powder aluminum salt adsorbent (mLiCl2Al (OH) is weighed3·nH2O) 400g, binder polyamide (PA) 28g,
300g methylene chloride and 8g urea obtain mixture B with high speed mixer mixing 1h.
(3) by the sequence of mixture B, mixture A, mixing A and B usage ratio is 1:10, with the coating of extrusion coated technology
It is coated with 3 times to positive and negative two surfaces of alumina ceramic membrane, and repeatedly, operation temperature is 120 DEG C, forms composite layer intermediate.
(4) product that step (3) obtains is crossed after water elution and is heated to 80 DEG C of drying, adsorbent coating layer thickness, which is made, is
The composite membrane of 6mm.
(5) composite membrane is cut into suitable size, obtains the lithium adsorbent product of the strip substrate of specific two-sided composite layer.
The lithium adsorbent is detected using the absorption quantity measuring method of embodiment 1, it is as a result as follows：Using going for flowing
Ion water washing 0.5h, lithium eluting rate are 39%, and the compound film sheet after elution, which is put into brine, carries out adsorption experiment, through flame light
Degree meter measurement absorption front and back brine lithium variation, adsorbance 9.1mg/g.
Comparative example
Powdered absorbent is shaped to by spherical adsorbent using orifice coagulating bath method, specific manufacturing process is as follows：
(1) it weighs Kynoar (PVDF) 100g and dissolution in 300g N-Methyl pyrrolidone (NMP) is added, add
Powder aluminum salt adsorbent (mLiCl2Al (OH)3·nH2O) 300g, high-speed stirred mixes 6h at room temperature, obtains uniformly mixed
Slurry.
(2) slurry is fitted into syringe, is squeezed by needle point and is instilled in pure water dropwise, form graininess.By being taken in water
Out, 100 DEG C of drying are warming up to, spherical molding absorbent particles are obtained.
The absorbent particles are detected using the absorption quantity measuring method of embodiment 1, it is as a result as follows：Using flowing
Deionized water washs 0.5h, and lithium eluting rate is 33%, and the spherical adsorbent after elution, which is put into brine, carries out adsorption experiment, through fire
The brine lithium variation of flame photometric determination absorption front and back, adsorbance 7.1mg/g.Obviously, the adsorbance of the absorbent particles is significant
The lithium adsorbent being prepared lower than the embodiment of the present invention 1 and 3.Lithium adsorbent is adsorbed and is desorbed to lithium in cited embodiment
Ability is all substantially better than testing in comparative example as a result, lithium elution efficiency improves 3%~18%, while adsorption capacity improves
18%~31%.Also, the adsorbance of the lithium adsorbent of the specific two-sided composite layer of embodiment 2 and 4 is also higher, illustrates two-sided formation
Composite layer has no effect on the adsorbance of composite layer, to further increase lithium adsorbent adsorption capacity.Furthermore it is also observed in experiment
Solution becomes cloudy after stirring a period of time in the spherical adsorbent brine obtained to comparative example, and in embodiment is not in this
Phenomenon illustrates that the intensity of the lithium adsorbent of the embodiment of the present invention is high, washes away more resistant to solution.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
Centainly refer to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be any
One or more embodiment or examples in can be combined in any suitable manner.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that：Not
A variety of change, modification, replacement and modification can be carried out to these embodiments in the case where being detached from the principle of the present invention and objective, this
The range of invention is defined by the claims and their equivalents.
Claims (23)
1. a kind of lithium adsorbent, which is characterized in that including：
Basilar memebrane；And
Composite layer, the composite layer include：
Adhesive layer, the adhesive layer are formed on the surface of the basilar memebrane；
Adsorption layer, the adsorption layer are formed on the surface of the adhesive layer.
2. lithium adsorbent according to claim 1, which is characterized in that the composite layer includes multiple adhesive layers and more
A adsorption layer, and the adhesive layer and the adsorption layer are alternately stacked to form multilayered structure.
3. lithium adsorbent composite membrane according to claim 1, which is characterized in that the basilar memebrane has the first micropore.
4. lithium adsorbent according to claim 1, which is characterized in that the adsorption layer contains the absorption of 70-99 mass parts
The binder of agent and 1-30 mass parts.
5. lithium adsorbent according to claim 1, which is characterized in that the composite layer contains the absorption of 80-90 mass parts
The binder of agent and 10-20 mass parts.
6. lithium adsorbent according to claim 1, which is characterized in that the basilar memebrane be by selected from polyethersulfone resin membrane,
At least one formation of polytetrafluoroethylene film and ceramic membrane.
7. lithium adsorbent according to claim 6, which is characterized in that the ceramic membrane includes aluminium oxide, zirconium oxide and oxygen
Change the one or more of titanium.
8. lithium adsorbent according to claim 4 or 5, which is characterized in that the adsorbent is selected from aluminum salt adsorbent, lithium
Oxides of manganese sorbent, takes off lithium aluminum salt adsorbent, the lithium manganese oxide adsorbent of de- lithium and de- lithium at Li-Ti oxide adsorbent
At least one of Li-Ti oxide adsorbent.
9. lithium adsorbent according to claim 4 or 5, which is characterized in that the binder is selected from polyvinyl alcohol contracting first
Aldehyde, Kynoar, ethylene-vinyl acetate copolymer, polyolefin copolymer, polyamide, thermoplastic polyurethane elastomer rubber,
Ultra-high molecular weight polyethylene, vinyl chloride-vinyl acetate copolymer, polyvinyl fluoride, polyvinyl chloride and polyvinyl butyral
It is at least one.
10. lithium adsorbent according to claim 1, which is characterized in that the adsorption layer further contains：
The content of pore creating material, the pore creating material is not more than 2 mass parts.
11. lithium adsorbent according to claim 10, which is characterized in that the pore creating material be selected from ammonium hydrogen carbonate, urea,
At least one of polyvinylpyrrolidone, sodium chloride, potassium chloride, polyethylene glycol and polyvinyl alcohol.
12. lithium adsorbent according to claim 10, which is characterized in that the composite layer has the second micropore.
13. lithium adsorbent according to claim 1, which is characterized in that the basilar memebrane with a thickness of 0.05-500 μm；It is multiple
Close the layer adsorption layer with a thickness of 0.01-10mm and the adhesive layer with a thickness of 0.001-0.1mm.
14. a kind of method for preparing the described in any item lithium adsorbents of claim 1-13, which is characterized in that including：
(1) basilar memebrane is provided；And
(2) composite layer is formed on the surface of the basilar memebrane, the composite layer contains adhesive layer and is formed in the adhesive layer
On adsorption layer, to obtain the lithium adsorbent.
15. according to the method for claim 14, which is characterized in that step (2) further comprises：
(a) binder is used, the adhesive layer is formed；
(b) adsorbent is used, forms adsorption layer on the surface of the adhesive layer；
(c) it will be dried after the basilar memebrane for forming adsorption layer elution, to obtain dry composite membrane；And
(d) composite membrane of the drying is subjected to compaction treatment, to form the lithium adsorbent.
16. according to the method for claim 15, which is characterized in that in step (a), using described in the formation of one of following methods
Adhesive layer：
(I) it is covered on after mixing the binder with solvent on the basilar memebrane；
(II) binder is heated to being covered on the basilar memebrane after half melt.
17. according to the method for claim 16, which is characterized in that in step (I), the binder and the solvent are by solid
Liquor ratio is 1：(1-3) carries out the mixing.
18. according to the method for claim 17, which is characterized in that in step (b), by the adsorbent and the binder
It is in mass ratio with pore creating material (80-99)：(1-20)：(0-2) is covered on the surface of the adhesive layer and forms adsorption layer.
19. according to the method for claim 18, which is characterized in that further comprise：
(f) between in step (b) and (c), the basilar memebrane for forming the adsorption layer is subjected to extrusion process, after obtaining extruding
Lithium adsorb intermediate.
20. according to the method for claim 16, which is characterized in that step (2) further comprises：
(e) before step (c), step (a)~(b) is repeated at least once.
21. according to the method for claim 20, which is characterized in that in step (a), by the bonding of 90-100 mass parts
It is 1 that the pore creating material of agent and 0-10 mass parts and the solvent, which press solid-liquid mass ratio,：The basilar memebrane is covered on after 0-3 mixing
It is upper to form the adhesive layer,
It, will be described in the adsorbent of 70 mass parts, the binder of 3-30 mass parts and 0-2 mass parts in step (b)
It is 1 that pore creating material and the solvent, which press solid-liquid mass ratio,：It is covered on the surface of the adhesive layer after 0-3 mixing and forms the absorption
Layer.
22. the described in any item methods of 6-21 according to claim 1, which is characterized in that the method for the covering includes slope flow coat
Cloth and extrusion coated.
23. the described in any item methods of 6-21 according to claim 1, which is characterized in that the solvent is selected from water, N- methyl pyrrole
Pyrrolidone, n-formyl sarcolysine yl acetamide, N-methyl formamide, acetone, dimethylbenzene, methylene chloride, chloroform, tetrachloromethane, toluene,
At least one of ethyl alcohol and methyl chloride.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019209011A1 (en) * | 2018-04-23 | 2019-10-31 | 주식회사 포스코 | Lithium-adsorptive molded object and manufacturing method therefor |
| CN113083040A (en) * | 2021-04-23 | 2021-07-09 | 兰州理工大学 | Preparation method of soot carbon-based composite membrane material |
| CN114870809A (en) * | 2022-05-31 | 2022-08-09 | 南京林业大学 | Preparation method of wood film for adsorbing copper ions |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000071360A (en) * | 1998-09-02 | 2000-03-07 | Toto Ltd | Multifunctional material and manufacture thereof |
| CN102211012A (en) * | 2010-09-10 | 2011-10-12 | 中国海洋大学 | Lithium ion sieve membrane and preparation method thereof |
| JP2017040518A (en) * | 2015-08-18 | 2017-02-23 | 東洋クロス株式会社 | Strontium adsorption sheet |
-
2017
- 2017-05-08 CN CN201710318647.2A patent/CN108854934A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000071360A (en) * | 1998-09-02 | 2000-03-07 | Toto Ltd | Multifunctional material and manufacture thereof |
| CN102211012A (en) * | 2010-09-10 | 2011-10-12 | 中国海洋大学 | Lithium ion sieve membrane and preparation method thereof |
| JP2017040518A (en) * | 2015-08-18 | 2017-02-23 | 東洋クロス株式会社 | Strontium adsorption sheet |
Non-Patent Citations (1)
| Title |
|---|
| 张文等: ""液态锂资源提锂的吸附材料及性能"", 《化学进展》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019209011A1 (en) * | 2018-04-23 | 2019-10-31 | 주식회사 포스코 | Lithium-adsorptive molded object and manufacturing method therefor |
| CN112313006A (en) * | 2018-04-23 | 2021-02-02 | 株式会社Posco | Lithium-adsorbing molded article and method for producing same |
| CN112313006B (en) * | 2018-04-23 | 2023-10-13 | 浦项股份有限公司 | Lithium-adsorbing molded article and method for producing same |
| CN113083040A (en) * | 2021-04-23 | 2021-07-09 | 兰州理工大学 | Preparation method of soot carbon-based composite membrane material |
| CN113083040B (en) * | 2021-04-23 | 2022-03-01 | 兰州理工大学 | Preparation method of soot carbon-based composite membrane material |
| CN114870809A (en) * | 2022-05-31 | 2022-08-09 | 南京林业大学 | Preparation method of wood film for adsorbing copper ions |
| CN114870809B (en) * | 2022-05-31 | 2023-08-22 | 南京林业大学 | Preparation method of wood film for adsorbing copper ions |
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