CN204625733U - Lithium ion adsorption column - Google Patents

Lithium ion adsorption column Download PDF

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Publication number
CN204625733U
CN204625733U CN201520340183.1U CN201520340183U CN204625733U CN 204625733 U CN204625733 U CN 204625733U CN 201520340183 U CN201520340183 U CN 201520340183U CN 204625733 U CN204625733 U CN 204625733U
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China
Prior art keywords
lithium ion
adsorption column
presoma
lithium
cylinder
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Expired - Fee Related
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CN201520340183.1U
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Chinese (zh)
Inventor
张全有
李�杰
贾永忠
张丽芬
孙进贺
景燕
谢绍雷
姚颖
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ZHEJIANG JING QUAN WATER TREATMENT EQUIPMENT CO Ltd
Qinghai Institute of Salt Lakes Research of CAS
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ZHEJIANG JING QUAN WATER TREATMENT EQUIPMENT CO Ltd
Qinghai Institute of Salt Lakes Research of CAS
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Priority to CN201520340183.1U priority Critical patent/CN204625733U/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The utility model discloses a kind of lithium ion adsorption column, comprise and to be tangled the hollow cylinder formed by thermoplastic polymer fibers, be bonded with lithium ion sorbent material in described cylinder, wherein, lithium ion sorbent material obtains after adsorbing presoma wash-out lithium ion by lithium ion.Simple according to lithium ion adsorption column preparation method of the present utility model, the lithium ion adsorption column prepared is without interior axle, and adopt interior close outer thin design, physical strength is good; And in use, efflorescence does not occur under the Circulation containing lithium bittern and desorbing agent, stability of flow, resistance are constant, long service life; Meanwhile, this lithium ion adsorption column also has the features such as adsorptive capacity is high, adsorption rate is fast.

Description

Lithium ion adsorption column
Technical field
The utility model belongs to lithium ion separating device technical field, specifically, relates to a kind of lithium ion adsorption column.
Background technology
Metallic lithium has very strong chemically reactive, and its simple substance or compound are widely used in the fields such as metallurgy, pottery, battery material, nuclear industry, aerospace because of the advantage of uniqueness.In national economy and national defense construction, lithium is significant strategic resource.
Lithium has solid and liquid two kinds at the occurrence form of occurring in nature.Solid lithium mineral reserve are mainly the pegmatite such as triphane, lithionite ore deposit; Liquid lithium ore deposit is mainly present in salt lake brine, seawater, GEOTHERMAL WATER and oil-field water with lithium ion form.From the development and production situation in the whole world, the lithium rule of origin of 80% is in liquid lithium resource, and bittern carries lithium becomes lithium industrial expansion main flow.The focus that lithium is carried by China concentrates on western salt lake, and put forward lithium method and mainly contain the precipitator method, calcination method, carborization, solvent extration and absorption method etc., wherein ionic adsorption method puies forward the most effectual way of lithium.
The single lithium ion specific adsorbent of current synthesis is pulverulence, and the compound adsorbent that itself and organic polymer are made is small-particle state; Carry out in adsorption-desorption process being packed into fixed bed, the former particle diameter is tiny, mobility and poor permeability, and the latter easily efflorescence occurs again under the Circulation of bittern and elutriant, and fixed bed resistance increases, and brings difficulty to proposing lithium industrialization.
Utility model content
For solving above-mentioned prior art Problems existing, the utility model provides a kind of lithium ion adsorption column, and this lithium ion adsorption column, from containing when adsorbing lithium ion in lithium bittern, has the features such as adsorptive capacity is high, adsorption rate is fast.
In order to reach above-mentioned utility model object, the utility model have employed following technical scheme:
A kind of lithium ion adsorption column, comprises and to be tangled the cylinder formed by thermoplastic polymer fibers, be bonded with lithium ion sorbent material in described cylinder; Wherein, described lithium ion sorbent material obtains after adsorbing presoma wash-out lithium ion by lithium ion.
Further, described cylinder also adds grid beam, to increase structural strength and the withstand voltage properties of described cylinder.
Further, the mass ratio of described lithium ion absorption presoma and described thermoplastic polymer is 0.2 ~ 1:1.
Further, described lithium ion sorbent precursor body is selected from LiMn 2o 4, Li 4mn 5o 12, Li 1.6mn 1.6o 4, Li 2ti 3o 7, Li 4ti 5o 12, LiAlO 2in any one.
Further, described thermoplastic, polymeric materials is selected from any one in polypropylene, polyester, polymeric amide, polyethylene, tetrafluoroethylene, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer.
Further, described cylinder presents hollow columnar.
The utility model is by the process being wound around bonding thermoplastic polymer fibers entanglement formation cylinder, lithium ion being adsorbed presoma sprinkling is bonded on thermoplastic polymer fibers, and the cylinder obtained obtains the lithium ion adsorption column with absorption lithium ion performance through wash-out lithium ion again; This lithium ion adsorption column is without interior axle, and adopt interior close outer thin design, physical strength is good; In use procedure, under the Circulation containing lithium bittern and desorbing agent, efflorescence does not occur, stability of flow, resistance are constant, long service life.In addition, the lithium ion adsorption column that the utility model relates to also has the features such as adsorptive capacity is high, adsorption rate is fast, corrosion-resistant, high pressure resistant.
Accompanying drawing explanation
The following description carried out in conjunction with the drawings, the above-mentioned and other side of embodiment of the present utility model, feature and advantage will become clearly, in accompanying drawing:
Fig. 1 is the structural representation of the lithium ion adsorption column according to embodiment 1 of the present utility model;
Fig. 2 is the flow chart of steps of the preparation method of lithium ion adsorption column according to embodiment 1 of the present utility model;
Fig. 3 is the use schematic diagram of the lithium ion adsorption column according to embodiment 1 of the present utility model.
Embodiment
Below, embodiment of the present utility model is described in detail with reference to the accompanying drawings.But, the utility model can be implemented in many different forms, and the utility model should not be interpreted as being limited to the specific embodiment of setting forth here.On the contrary, provide these embodiments to be to explain principle of the present utility model and practical application thereof, thus enable others skilled in the art understand various embodiment of the present utility model and be suitable for the various amendments of certain expected application.In the accompanying drawings, for the sake of clarity, the shape and size of element can be exaggerated, and identical label will be used to indicate same or analogous element all the time.
Embodiment 1
With reference to Fig. 1, the lithium ion adsorption column of the present embodiment, comprises and to be tangled the cylinder formed by thermoplastic polymer fibers, be bonded with lithium ion sorbent material in described cylinder; Wherein, described lithium ion sorbent material obtains after adsorbing presoma wash-out lithium ion by lithium ion.
Preferably, described cylinder also adds grid beam, to increase structural strength and the withstand voltage properties of described cylinder, as shown in Figure 1, wherein, 1 is lithium ion adsorption column to the structural representation of the lithium ion adsorption column obtained, and 2 is grid beam.
This lithium ion adsorption column utilizes thermoplastic polymer fibers around forming post, not only makes cylinder have huge specific surface area, increases the active area of sorbent material and bittern on cylinder, improves adsorption efficiency; Can also according to the concrete shape of adsorption column or any moulding of size dimension, convenient and practical.
Below, introduce the preparation method of the lithium ion adsorption column of the present embodiment, comprise the steps:
In step 110, heating and melting polypropylene at 265 DEG C, and form polypropylene fibre through spray silk.
Particularly, polypropylene fusion temperature general control is 260 DEG C ~ 270 DEG C, and spray silk pressure is 0.1MPa, but usually, it is 0.03MPa ~ 0.7MPa that spinning process controls spray silk pressure by air compressor machine.Thread diameter through the polypropylene fibre of spray silk formation is about 0.03mm, namely 34, and this Fibre diameter character is determined by the bore of spinning jet, does not do special stipulation.
In the step 120, LiMn is adopted 2o 4as lithium ion absorption presoma, spray LiMn to polypropylene fibre surface uniform 2o 4powder, draws polypropylene fibre simultaneously, utilizes the viscosity of the polypropylene fibre self compared with Warm status that lithium ion is adsorbed presoma LiMn 2o 4bonding.Along with traction is constantly carried out, polypropylene fibre tangles formation cylinder gradually, lithium ion absorption presoma LiMn 2o 4also be bonded in described cylinder thereupon.Wherein, lithium ion absorption presoma LiMn 2o 4consumption for itself and polyacrylic mass ratio be 0.2:1.
In the present embodiment, in order to optimize utility model effect, described polypropylene fibre draws around a buttress shaft, so the cylinder obtained has hollow columnar structures, described cylinder is had " inwall " and " outer wall "; What deserves to be explained is, in the process of traction, without the need to considering pulling speed, only need ensure that this polypropylene fibre is in comparatively high temps and forms the object of cylinder to reach to tangle.
In step 130, grid beam is installed additional at " inwall " and " outer wall " of cylinder.
It should be noted that described cylinder after shaping temperature be still in higher state, preferably now install plastic wire screen work additional at " inwall " and " outer wall " of described cylinder, cooling after grid beam be fixed on cylinder, to increase structural strength and the withstand voltage properties of cylinder.In the present embodiment, the two grid dome that grid beam can be made up of some engineering plastics is formed, and the length of side of grid is preferably 0.5cm.
In step 140, the cylinder having installed grid beam additional obtains lithium ion adsorption column through cooling, wash-out lithium ion, washing, drying.
Particularly, the cylinder adding grid beam after the cooling period, is immersed 40h in the ammoniumsulphate soln of the 0.01mol/L of 20 DEG C, to make lithium ion presoma LiMn 2o 4in lithium ion obtain wash-out, formed and there is the lithium ion sorbent material NH of lithium ion adsorptive power 4mn 2o 4.Then use deionized water wash again, and at 70 DEG C dry 2h, obtain the utility model product lithium ion adsorption column.
What deserves to be explained is, in the present embodiment, LiMn 2o 4as lithium ion absorption presoma, the ammonium sulfate solution of 0.01mol/L is as the elutriant of wash-out lithium ion, and certainly, lithium ion absorption presoma can also be Li 4mn 5o 12, Li 1.6mn 1.6o 4, Li 2ti 3o 7, Li 4ti 5o 12, LiAlO 2in any one, the hydrochloric acid of can also to be concentration the be 0.01mol/L ~ 1mol/L of the elutriant for wash-out lithium ion, sulfuric acid or sulfuric acid; The process of above-mentioned wash-out lithium ion its essence is, between the positively charged ion in lithium ion absorption presoma and elutriant, replacement(metathesis)reaction occurs, thus obtains lithium ion sorbent material.
In order to verify the absorption property of the above-mentioned lithium ion adsorption column prepared, lithium ion being adsorbed from lithium-containing solution to it and tests.
First, the above-mentioned lithium ion adsorption column prepared is installed in sleeve, and four lithium ion adsorption column series connection are obtained lithium ion adsorption unit, as shown in Figure 3.In Fig. 3,10 represent lithium-containing solution when adsorbing, desorbing agent is represented when desorption, 20 represent sleeve, 30 represent lithium ion adsorption column, 40 represent adsorption tail liquid when adsorbing, and represent rich lithium desorption liquid (being about to obtain after the lithium ion desorption be adsorbed with on the lithium ion adsorption column of lithium ion is transferred to desorbing agent) when desorption.
Then, to concentration be 0.01mol/L the LiCl aqueous solution in lithium ion adsorb and (use NH 3h 2o-NH 4pH is adjusted to 9 ~ 11 by Cl buffered soln), and with the salpeter solution of 0.01mol/L for desorbing agent, desorption is carried out to the lithium ion adsorption column having adsorbed lithium ion.
Lithium concentration in adsorption tail liquid and rich lithium desorption liquid is analyzed, calculate known, now the equilibrium adsorption capacity of this lithium ion adsorption column is 3.35mmol/g, desorption rate reaches 94.3%, this performance powder shaped lithium ion performance of the adsorbent corresponding with it is basically identical, and in this adsorption-desorption process, the column flow of lithium ion adsorption column is stable, constant resisting force, withstand voltage properties are good, long service life.
Embodiment 2
In the description of embodiment 2, do not repeat them here with the something in common of embodiment 1, only describe the difference with embodiment 1.Embodiment 2 is with the difference of embodiment 1, and in step 110, tetrafluoroethylene hot melt at 400 DEG C forms polytetrafluoroethylene fiber; In the step 120, Li is adopted 2ti 3o 7as lithium ion absorption presoma, spray Li to polytetrafluoroethylene fiber surface uniform 2ti 3o 7powder, draws polytetrafluoroethylene fiber simultaneously, utilizes the viscosity of the polytetrafluoroethylene fiber self compared with Warm status that lithium ion is adsorbed presoma Li 2ti 3o 7bonding.Along with traction is constantly carried out, described polytetrafluoroethylene fiber tangles formation cylinder gradually, described lithium ion absorption presoma Li 2ti 3o 7also be bonded in described cylinder thereupon; Wherein, Li 2ti 3o 7be 0.75:1 with the mass ratio of tetrafluoroethylene; In step 130, the stainless (steel) wire screen work that the grid that " inwall " and " outer wall " of cylinder to install additional by some length of sides be 1.5cm is formed; In step 140, by install grid beam additional cylinder bubble to 20h, wash-out Li in the hydrochloric acid soln of the 0.5mol/L of 50 DEG C 2ti 3o 7in lithium ion, then through deionized water wash, dry 1h obtains lithium ion adsorption column at 80 DEG C.
Equally the lithium ion absorption property of the lithium ion adsorption column of above-mentioned acquisition is tested, from the LiCl aqueous solution of 0.01mol/L, adsorb lithium ion (use NH 3h 2o-NH 4pH is adjusted to 9 ~ 11 by Cl buffered soln), and with the hydrochloric acid soln of 0.5mol/L for desorbing agent carries out desorption; Be 3.86mmol/g through calculating its equilibrium adsorption capacity known, desorption rate is 95.0%; This performance powder lithium ion performance of the adsorbent corresponding with it is basically identical, and column flow is stable, constant resisting force, withstand voltage properties are good, long service life.
Embodiment 3
In the description of embodiment 3, do not repeat them here with the something in common of embodiment 1, only describe the difference with embodiment 1.Embodiment 3 is with the difference of embodiment 1, and in step 110, polyethylene hot melt at 160 DEG C forms polyethylene fibre; In the step 120, Li is adopted 1.6mn 1.6o 4as lithium ion absorption presoma, spray Li to polyethylene fibre surface uniform 1.6mn 1.6o 4powder, draws polyethylene fibre simultaneously, utilizes the viscosity of the polyethylene fibre self compared with Warm status that lithium ion is adsorbed presoma Li 1.6mn 1.6o 4bonding.Along with traction is constantly carried out, described polyethylene fibre tangles formation cylinder gradually, described lithium ion absorption presoma Li 1.6mn 1.6o 4also be bonded in described cylinder thereupon; Wherein, Li 1.6mn 1.6o 4be 1:1 with poly mass ratio; In step 130, at " inwall " and " the stainless (steel) wire screen work that the grid that outer wall to install additional by some length of sides be 1cm is formed of cylinder; In step 140, the cylinder installing grid beam additional is dipped to 1h in the aqueous nitric acid of the 1mol/L of 80 DEG C, wash-out Li 1.6mn 1.6o 4in lithium ion, then through deionized water wash, dry 40h obtains lithium ion adsorption column at 50 DEG C.
Equally the lithium ion absorption property of the lithium ion adsorption column of above-mentioned acquisition is tested, from the LiCl aqueous solution of 0.01mol/L, adsorb lithium ion (use NH 3h 2o-NH 4pH is adjusted to 9 ~ 11 by Cl buffered soln), and with the ammonium sulfate solution of 1mol/L for desorbing agent carries out desorption; Be 4.66mmol/g through calculating its equilibrium adsorption capacity known, desorption rate is 96.1%; This performance powder lithium ion performance of the adsorbent corresponding with it is basically identical, and column flow is stable, constant resisting force, withstand voltage properties are good, long service life.
Thermoplastic polymer in above-described embodiment 1-3 is respectively polypropylene, tetrafluoroethylene and polyethylene, and lithium ion absorption presoma is respectively LiMn 2o 4, Li 2ti 3o 7and Li 1.6mn 1.6o 4, but the utility model is not restricted to this, and any one also in optional autopolyester, polymeric amide, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer of thermoplastic polymer, lithium ion absorption presoma also can be selected from Li 4mn 5o 12, Li 4ti 5o 12, LiAlO 2in any one.Meanwhile, in above-mentioned three embodiments, the lithium ion absorption forerunner scapus prepared is immersed in the wash-out carrying out lithium ion in ammonium sulfate solution, hydrochloric acid and nitric acid respectively, but the utility model is not restricted to this, concentration is the elutriant that the sulphuric acid soln of 0.01mol/L ~ 1mol/L also can be used as wash-out lithium ion.
Although illustrate and describe the utility model with reference to specific embodiment, but it should be appreciated by those skilled in the art that: when not departing from the spirit and scope of the present utility model by claim and equivalents thereof, the various changes in form and details can be carried out at this.

Claims (6)

1. a lithium ion adsorption column, is characterized in that, comprises and to be tangled the cylinder formed by thermoplastic polymer fibers, be bonded with lithium ion sorbent material in described cylinder; Wherein, described lithium ion sorbent material obtains after adsorbing presoma wash-out lithium ion by lithium ion.
2. adsorption column according to claim 1, is characterized in that, described cylinder also adds grid beam, to increase structural strength and the withstand voltage properties of described cylinder.
3. adsorption column according to claim 1 and 2, is characterized in that, the mass ratio of described lithium ion absorption presoma and described thermoplastic polymer is 0.2 ~ 1:1.
4. adsorption column according to claim 1 and 2, is characterized in that, described lithium ion absorption presoma is selected from LiMn 2o 4, Li 4mn 5o 12, Li 1.6mn 1.6o 4, Li 2ti 3o 7, Li 4ti 5o 12, LiAlO 2in any one.
5. adsorption column according to claim 3, it is characterized in that, described thermoplastic, polymeric materials be selected from polypropylene, polyester, polymeric amide, polyethylene, tetrafluoroethylene, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer any one.
6. adsorption column according to claim 1, is characterized in that, described cylinder presents hollow columnar.
CN201520340183.1U 2015-05-22 2015-05-22 Lithium ion adsorption column Expired - Fee Related CN204625733U (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104928471A (en) * 2015-05-22 2015-09-23 中国科学院青海盐湖研究所 Lithium-ion adsorption column and preparing method thereof
CN110586203A (en) * 2019-10-25 2019-12-20 萱柯氢能科技(北京)有限公司 Full-life-cycle deionized resin tank and use method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104928471A (en) * 2015-05-22 2015-09-23 中国科学院青海盐湖研究所 Lithium-ion adsorption column and preparing method thereof
CN104928471B (en) * 2015-05-22 2017-12-08 中国科学院青海盐湖研究所 Lithium ion adsorption column and preparation method thereof
CN110586203A (en) * 2019-10-25 2019-12-20 萱柯氢能科技(北京)有限公司 Full-life-cycle deionized resin tank and use method thereof

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Granted publication date: 20150909

Termination date: 20200522