WO2024058764A1 - Nano fibre material and production method to be used as a filter for lithium recovery - Google Patents

Nano fibre material and production method to be used as a filter for lithium recovery Download PDF

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Publication number
WO2024058764A1
WO2024058764A1 PCT/TR2023/050970 TR2023050970W WO2024058764A1 WO 2024058764 A1 WO2024058764 A1 WO 2024058764A1 TR 2023050970 W TR2023050970 W TR 2023050970W WO 2024058764 A1 WO2024058764 A1 WO 2024058764A1
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Prior art keywords
lithium
fibre material
nano fibre
polyurethane
producing
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PCT/TR2023/050970
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French (fr)
Inventor
Benan YAZICI KARABULUT
Mustafa Muammer DEMİR
Mehmet İrfan YEŞİLNACAR
Alper BABA
Seyra TOPRAK
Original Assignee
İzmi̇r Yüksek Teknoloji̇ Ensti̇tüsü Rektörlüğü
Harran Üni̇versi̇tesi̇ Bi̇li̇msel Araştirma Kordi̇natörlüğü
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Priority claimed from TR2022/014324 external-priority patent/TR2022014324A1/en
Application filed by İzmi̇r Yüksek Teknoloji̇ Ensti̇tüsü Rektörlüğü, Harran Üni̇versi̇tesi̇ Bi̇li̇msel Araştirma Kordi̇natörlüğü filed Critical İzmi̇r Yüksek Teknoloji̇ Ensti̇tüsü Rektörlüğü
Publication of WO2024058764A1 publication Critical patent/WO2024058764A1/en

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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
    • 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
    • B01D67/0004—Organic membrane manufacture by agglomeration of particles
    • B01D67/00042—Organic membrane manufacture by agglomeration of particles by deposition of fibres, nanofibres or nanofibrils
    • 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
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • 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
    • B01D71/54—Polyureas; Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/08—Nanoparticles or nanotubes

Definitions

  • the invention relates to the development of a flexible nano fibre material coated with y-MnO2 using the electro-spinning method for the recovery of lithium from water for use in the fields of materials science, filtration systems and membrane technologies.
  • Lithium (Li + ) is the metal with the lowest density, following hydrogen and helium in the periodic table. The average concentration of lithium in the earth is about 0.006% and it is believed that seawater contains about 0.1 ppm lithium.
  • Lithium hydride is used in hydrogen gas production, lithium hydroxide in motor oil and grease production, lithium chloride and bromide in cooling systems. Lithium is most commonly used as lithium carbonate. The most common use is in the aluminum industry. The second largest use of lithium is in the glass industry. It also has a very serious use in the battery and battery industry. As lithium is a commercially valuable element, its recovery is important. Filters and various techniques have been developed in the known technique for lithium recovery. The data obtained with the known technique are given below.
  • PCT patent document number W02020033668 (A1 ) describes a process for concentrating an aqueous solution containing lithium.
  • a water-permeable hydrophilic polymer is used.
  • the hydrophilic polymer is interposed between two solutions, and the osmotic pressure difference between a dilute solution (such as a LiCI solution) and a highly concentrated salt solution (such as naturally occurring brine) is used as a driving force to transfer water from the dilute solution to the concentrated solution. This increases the lithium content of the solution.
  • PCT patent document WO2013182749A1 found during the literature search, describes obtaining a lithium solution by precipitating calcium and lithium in a solution containing calcium, magnesium and lithium by sequential process steps.
  • European patent document number EP3382043A1 found in the literature search describes a lithium recovery device that can be moved on land, eliminating the need to install a plant at sea.
  • Patent document number EP3478406 (A1 ), found during the literature search, describes a study for the extraction of lithium from brine solutions, where the solid material makes it possible to limit the formation of fine particles.
  • solvent selection was found to be one of the driving factors to control the morphology of polyurethane electrospun nanofibre membranes.
  • the solution properties were influenced by solvent properties such as dielectric constant, dipole moment and solvent vapor pressure.
  • solvent properties such as dielectric constant, dipole moment and solvent vapor pressure.
  • the best results in terms of produced material morphology and mechanical properties were obtained in mats electrospun from a solution containing 50/50% DMF/THF. It can be concluded that the properly controlled morphology of electrospun polyurethane nano fibre membranes can be useful for many potential applications such as biomedical, smart textiles, nanofiltration and sensors [2],
  • MNNs mixed matrix nano fibres
  • PSf flat sheet electrospun polysulfone
  • LIS lithium ion sieves
  • a series of batch adsorption experiments were carried out to determine the effect of the PSf matrix on the performance of the LIS in terms of adsorption capacity, kinetics and selectivity.
  • MMN has been extensively investigated as a flow membrane adsorber through permeation and breakthrough studies. The potential for continuous Li+ recovery has been demonstrated through cyclic adsorption-desorption operations [3],
  • NF electrospun composite nano fibre
  • the filter consisted of a hydrophilic polyacrylonitrile (PAN) matrix grafted with lithium ion sieves (LIS) H1.6Mn1.6O4.
  • PAN hydrophilic polyacrylonitrile
  • LIS lithium ion sieves
  • the characterization of LIS/PAN NF confirmed suitable structural and surface properties for efficient Li+ adsorption.
  • LIS/PAN NF was found to be mechanically suitable as a microfiltration membrane with high water flux and low pressure requirements [4],
  • Pullanchiyodan et al. (2021 ) presented a stretchable fabric-based supercapacitor using Lycra fabric (a blend of nylon and spandex) as a substrate and PEDOTPSS as a current collector.
  • the capacitance and energy density of the developed SSC were significantly improved by electrochemical deposition of MnOx NFs and 3D conductive winding with PEDOTPSS.
  • three types of SSCs namely SP-SC (PEDOTPSS), SPM-SC (PEDOTPSS/MnOx) and SPMPSC (PEDOTPSS/MnOx/PEDOTPSS), were fabricated [8].
  • HTO H2TiOs
  • the invention is a new nano fibre material and a new production method for the recovery of lithium in lithium-containing water or solutions by filtration, which eliminates disadvantages and includes additional advantages based on the known background art.
  • the flexible material which is produced by the electro-spinning method using polyurethane and whose functionality is increased by coating with A-MnO2, can be used as a potential filter material for recovering lithium from cold water or other liquid lithium sources.
  • y-MnC designed for lithium adsorption is one of the most commonly used materials.
  • y-MnC adsorbent exhibits ion sieve properties. This makes y-MnO2 highly selective for Li + adsorption. Since y-MnC adsorbs Li + via cation exchange with H + , quantitative adsorption of Li + is easily achieved by pH oscillation.
  • this invention is superior to other applications as a highly elastic, composite, high adsorption capacity, high selectivity and chemical stability, low cost, reusable, environmentally friendly material.
  • Li + recovery is a very challenging and costly process.
  • the invention differs from other methods because the material produced is both cheaper and the Li + recovery process time is short.
  • the disclosure relates to the development of a flexible nano fibre material coated with A-MnO2 using the electrospinning method for the recovery of lithium from water for use in the fields of materials science, filtration systems and membrane technologies.
  • a mat with high elasticity is produced by applying an electro-spinning process to polyurethane, and the mat is coated with y-MnCh.
  • the y-MnC coating increases the lithium retention ability of the polyurethane.
  • the lithium retention capacity of the nano fibre material prepared with polyurethane and y-MnC was measured.
  • the steps for preparing the nano fibre material and measuring the lithium retention capacity are given below.
  • Polyurethane was purchased. Tetrahydro-furan (THF) and N,N-dimethylformamide (DMF) were obtained. Polymer and solvents were used without further purification.
  • the polyurethane solution was prepared at a concentration of 13 wt% by dissolving in 1 :1 w/w DMF/THF by stirring for 24 hours in a laboratory magnetic stirrer at a speed of 100 rpm/min.
  • the prepared solution was kept at room temperature for about 6 hours to evaporate the solvent.
  • the solution was then transferred into a 20 ml plastic syringe using a stainless steel needle (18 gauge) connected horizontally to a high voltage source at 15 kV (Gamma High Voltage Research Ormond Beach, FL, USA).
  • a microinfusion pump (New Era NE300 Infusion Pump, Farmingdale, NY, USA) was used to stabilize the flow rate at 2.0 ml/h and the distance from the tip to the collector was set at 15 cm.
  • Humidity and temperature were 41 % and 24 °C, respectively.
  • the electrospun nonwoven mats were collected on aluminum foil and the morphology of the mats was examined by scanning electron microscopy (SEM, FEI Quanta250 FEG, Oregon, USA); the thermal degradation profile was determined by Perkin-Elmer Diamond TG/DTA.
  • PU is currently a popular polymer material and electrospun polyurethane nano fibres have good elasticity and high toughness.
  • the produced mats were coated with y-MnO2 using the spraying method.
  • the spraying process was carried out using a MagicBrush air compressor. Firstly, 3 g of y-MnO2 was dissolved in 50 ml of pure water to obtain a dispersion.
  • the produced PU mats were coated with different ratios (1 , 1.5 and 2 g/L y-MnC ) and kept at room temperature for 8 hours to dry the dispersion.
  • a 50 ppm Li + solution was prepared.
  • the filtration performance of the PU mats was tested by vacuum filtration. Each filtration process was completed in approximately 40 seconds.
  • the Li + concentrations of the solution obtained after filtration were measured by Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES).
  • the lithium retention capacity of the nano fibre material produced by the invention was compared with other absorbents in the known art. Information about these absorbents can be found in the References section under the heading of Background Art.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention relates to a flexible material produced by the electro-spinning method using polyurethane and coated with y-MnO2 to be used as a potential filter material for lithium recovery from cold water or other liquid lithium sources.

Description

DESCRIPTION
NANO FIBRE MATERIAL AND PRODUCTION METHOD TO BE USED AS A FILTER FOR LITHIUM RECOVERY
Technological Field:
The invention relates to the development of a flexible nano fibre material coated with y-MnO2 using the electro-spinning method for the recovery of lithium from water for use in the fields of materials science, filtration systems and membrane technologies.
Background Art:
Lithium (Li+) is the metal with the lowest density, following hydrogen and helium in the periodic table. The average concentration of lithium in the earth is about 0.006% and it is believed that seawater contains about 0.1 ppm lithium. Lithium hydride is used in hydrogen gas production, lithium hydroxide in motor oil and grease production, lithium chloride and bromide in cooling systems. Lithium is most commonly used as lithium carbonate. The most common use is in the aluminum industry. The second largest use of lithium is in the glass industry. It also has a very serious use in the battery and battery industry. As lithium is a commercially valuable element, its recovery is important. Filters and various techniques have been developed in the known technique for lithium recovery. The data obtained with the known technique are given below.
PCT patent document number W02020033668 (A1 ) describes a process for concentrating an aqueous solution containing lithium. In the mentioned method, a water-permeable hydrophilic polymer is used. The hydrophilic polymer is interposed between two solutions, and the osmotic pressure difference between a dilute solution (such as a LiCI solution) and a highly concentrated salt solution (such as naturally occurring brine) is used as a driving force to transfer water from the dilute solution to the concentrated solution. This increases the lithium content of the solution.
PCT patent document WO2013182749A1 , found during the literature search, describes obtaining a lithium solution by precipitating calcium and lithium in a solution containing calcium, magnesium and lithium by sequential process steps.
European patent document number EP3382043A1 found in the literature search describes a lithium recovery device that can be moved on land, eliminating the need to install a plant at sea.
Patent document number EP3478406 (A1 ), found during the literature search, describes a study for the extraction of lithium from brine solutions, where the solid material makes it possible to limit the formation of fine particles.
Park et al. (2014) prepared poly(acrylonitrile) (PAN) nanofibres mixed with H1.6Mn1.6O4 lithium ion sieve by electrospinning method. The prepared nanofibres have an adsorption capacity of 10.3 mg/g lithium. Similar electrospun mixed matrix nano fibres dispersed with lithium ion sieves containing H1.6Mn1.6O4 particles have been prepared to obtain superior adsorption capacity and selectivity towards Li+ [1],
In another study by Erdem et al. (2015), solvent selection was found to be one of the driving factors to control the morphology of polyurethane electrospun nanofibre membranes. The solution properties were influenced by solvent properties such as dielectric constant, dipole moment and solvent vapor pressure. The best results in terms of produced material morphology and mechanical properties were obtained in mats electrospun from a solution containing 50/50% DMF/THF. It can be concluded that the properly controlled morphology of electrospun polyurethane nano fibre membranes can be useful for many potential applications such as biomedical, smart textiles, nanofiltration and sensors [2],
In another study by Park et al. (2016), mixed matrix nano fibres (MMNs) based on flat sheet electrospun polysulfone (PSf) were combined with lithium manganese oxide (Li1 ,6Mn1 .604) as lithium ion sieves (LIS). A series of batch adsorption experiments were carried out to determine the effect of the PSf matrix on the performance of the LIS in terms of adsorption capacity, kinetics and selectivity. MMN has been extensively investigated as a flow membrane adsorber through permeation and breakthrough studies. The potential for continuous Li+ recovery has been demonstrated through cyclic adsorption-desorption operations [3],
In a study by Chung et al. (2017), an electrospun composite nano fibre (NF) was fabricated and used as an adsorbent membrane filter in a continuous Li+ mining process from seawater. The filter consisted of a hydrophilic polyacrylonitrile (PAN) matrix grafted with lithium ion sieves (LIS) H1.6Mn1.6O4. The characterization of LIS/PAN NF confirmed suitable structural and surface properties for efficient Li+ adsorption. LIS/PAN NF was found to be mechanically suitable as a microfiltration membrane with high water flux and low pressure requirements [4],
The flexible tactile sensor has received much attention due to its great flexibility, high sensitivity and wide operating range. In this review, Wang et al. (2018) provided a brief overview of the recent advances in PVDF nano fibres by electro-spinning for flexible tactile sensor applications [5],
In a study by Liu et al. (2019), elastic PU-Si3N4 composite nano fibre membranes were prepared by electro-spinning and used as filtration layers of composite window screens. The morphology, porous structure, air permeability and stress of the membrane were regulated by controlling only the concentration of electrode nanoparticles (NPs). It is noteworthy that the composite nano fibre membranes have excellent tensile strength. In addition, PU-Si3N4 window curtains provided a satisfactory filtration effect with favorable permeability and light transmission [6],
In a study by Avci et al. (2020), flexible poly(styrene-ethylene-butadiene-styrene)- SEBS hybrid composite nano fibres for bioengineering and water filtration applications were successfully prepared by electro-spinning method [7],
Pullanchiyodan et al. (2021 ) presented a stretchable fabric-based supercapacitor using Lycra fabric (a blend of nylon and spandex) as a substrate and PEDOTPSS as a current collector. The capacitance and energy density of the developed SSC were significantly improved by electrochemical deposition of MnOx NFs and 3D conductive winding with PEDOTPSS. To investigate the role of MnOx deposition and conductive winding, three types of SSCs, namely SP-SC (PEDOTPSS), SPM-SC (PEDOTPSS/MnOx) and SPMPSC (PEDOTPSS/MnOx/PEDOTPSS), were fabricated [8].
In another study by Zhao et al. (2022), a porous fibre supported H2TiOs (HTO) composite adsorbent was developed for lithium recovery from geothermal water. A commercial spinning apparatus combined with a wet spinning technique was used to prepare the fibre composite adsorbent. The PSF/HTO fibre showed high adsorption performance and stability when polysulfone was used as a support material [9],
In the known technical lithium recovery methods, the problems of low lithium recovery amount and rate and high cost are encountered. Although it is seen that electro-spinning technique is often used in recovery methods, it is difficult to adjust the polymer/solvent ratio to be used in nano fibre production. Therefore, a composite material cannot be obtained. The reusability of the obtained materials is limited.
As a result, there is a need for a new lithium recovery method that overcomes the known state of the art and eliminates its disadvantages.
References
[1 ] M.J. Park, G.M. Nisola, A.B. Beltran, R.E.C. Torrejos, J.G. Seo, S.P. Lee, H. Kim, W. J. Chung, Recyclable composite nanofiber adsorbent for Li+ recovery from seawater desalination retentate, Chem. Eng. J. 254 (2014) 73-81.
[2] R. Erdem, I. llsta, M. Akalin, 0. Atak, M. Yuksek, A. Pars, The impact of solvent type and mixing ratios of solvents on the properties of polyurethane based electrospun nanofibers, Appl. Surf. Sci. 334 (2015) 227-230.
[3] M.J. Park, G.M. Nisola, E.L. Vivas, L.A. Limjuco, C.P. Lawagon, J.G. Seo, H. Kim, H.K. Shon, W.J. Chung, Mixed matrix nanofiber as a flow-through membrane adsorber for continuous Li+ recovery from seawater, J. Membr. Sci. 510 (2016) 141-154.
[4] W.J. Chung, R.E.C. Torrejos, M.J. Park, E.L. Vivas, L.A. Limjuco, C.P. Lawagon, K.J. Parohinog, S.P. Lee, H.K. Shon, H. Kim, G.M. Nisola, Continuous lithium mining from aqueous resources by an adsorbent filter with a 3D polymeric nanofiber network infused with ion sieves, Chem. Eng. J. 309 (2017) 49-62.
[5] X. Wang, F. Sun, G. Yin, Y. Wang, B. Liu, M. Dong, Tactile-sensing based on flexible
PVDF nanofibers via electrospinning: a review, Sensors 18 (2) (2018) 330. [6] J. Liu, L. Gu, N. Cui, S. Bai, S. Liu, Q. Xu, Y. Qin, R. Yang, F. Zhou, Core-Shell Fiber-Based 2D Woven Triboelectric Nanogenerator for Effective Motion Energy Harvesting, Nanoscale Res. Lett. 14 (1 ) (2019) 311.
[7] H. Avci, E. Akkulak, et al., Flexible poly(styrene-ethylene-butadiene-styrene) hybrid nanofibers for bioengineering and water filtration applications, J. Appl. Polym. Sci. 137 (26) (2020).
[8] A. Pullanchiyodan, L. Manjakkal, M. Ntagios, R. Dahiya, MnOx-Electrodeposited Fabric-Based Stretchable Supercapacitors with Intrinsic Strain Sensing. ACS Applied Materials & Interfaces, 13 (40) (2021 ) 47581 -47592.
[9] K. Zhao, B. Tong, X. Yu, Y. Guo, Y. Xie, T. Deng, Synthesis of porous fiber-supported lithium ion-sieve adsorbent for lithium recovery from geothermal water, Chem. Eng. J. 430 (2022).
[10] L.A. Limjuco, G.M. Nisola, C.P. Lawagon, S.P. Lee, J.G. Seo, H. Kim, WJ. Chung, H2TiOs composite adsorbent foam for efficient and continuous recovery of Li+ from liquid resources, Colloid Surface A. 504 (2016) 267-279.
[11 ] H.-J. Hong, l.-S. Park, T. Ryu, J. Ryu, B.-G. Kim, K.-S. Chung, Granulation of Li1 ,33Mn1 .6704 (LMO) through the use of cross-linked chitosan for the effective recovery of Li+ from seawater, Chem. Eng. J. 234 (2013) 16-22.
[12] Z. Qiu, M. Wang, Y. Chen, T. Zhang, D. Yang, F. Qiu, Li4MnsOi2 doped cellulose acetate membrane with low Mn loss and high stability for enhancing lithium extraction from seawater, Desalination 506 (2021 ) 115003. [13] M.J. Park, G.M. Nisola, A.B. Beltran, R.E.C. Torrejos, J.G. Seo, et al, Recyclable composite nanofiber adsorbent for Li+ recovery from seawater desalination retentate, Chem. Eng. J. 254 (2014) 73-81.
[14] K. Zhao, B. Tong, X. Yu, Y. Guo, Y. Xie, T. Deng, Synthesis of porous fiber- supported lithium ion-sieve adsorbent for lithium recovery from geothermal water, Chem. Eng. J. 430 (2022).
Summary of the Invention
The invention is a new nano fibre material and a new production method for the recovery of lithium in lithium-containing water or solutions by filtration, which eliminates disadvantages and includes additional advantages based on the known background art.
In the invention, the flexible material, which is produced by the electro-spinning method using polyurethane and whose functionality is increased by coating with A-MnO2, can be used as a potential filter material for recovering lithium from cold water or other liquid lithium sources. y-MnC designed for lithium adsorption is one of the most commonly used materials. y-MnC adsorbent exhibits ion sieve properties. This makes y-MnO2 highly selective for Li+ adsorption. Since y-MnC adsorbs Li+ via cation exchange with H+, quantitative adsorption of Li+ is easily achieved by pH oscillation.
In addition, this invention is superior to other applications as a highly elastic, composite, high adsorption capacity, high selectivity and chemical stability, low cost, reusable, environmentally friendly material. Li+ recovery is a very challenging and costly process. The invention differs from other methods because the material produced is both cheaper and the Li+ recovery process time is short.
Disclosure of the Invention
In this detailed description, the inventive nano fibre material and the production method are explained only for a better understanding of the subject matter, with examples that will not have a limiting effect. The disclosure relates to the development of a flexible nano fibre material coated with A-MnO2 using the electrospinning method for the recovery of lithium from water for use in the fields of materials science, filtration systems and membrane technologies.
In the invention, a mat with high elasticity is produced by applying an electro-spinning process to polyurethane, and the mat is coated with y-MnCh. The y-MnC coating increases the lithium retention ability of the polyurethane.
In the invention, the lithium retention capacity of the nano fibre material prepared with polyurethane and y-MnC was measured. The steps for preparing the nano fibre material and measuring the lithium retention capacity are given below.
Step 1
Polyurethane was purchased. Tetrahydro-furan (THF) and N,N-dimethylformamide (DMF) were obtained. Polymer and solvents were used without further purification.
The polyurethane solution was prepared at a concentration of 13 wt% by dissolving in 1 :1 w/w DMF/THF by stirring for 24 hours in a laboratory magnetic stirrer at a speed of 100 rpm/min. The prepared solution was kept at room temperature for about 6 hours to evaporate the solvent. The solution was then transferred into a 20 ml plastic syringe using a stainless steel needle (18 gauge) connected horizontally to a high voltage source at 15 kV (Gamma High Voltage Research Ormond Beach, FL, USA). A microinfusion pump (New Era NE300 Infusion Pump, Farmingdale, NY, USA) was used to stabilize the flow rate at 2.0 ml/h and the distance from the tip to the collector was set at 15 cm. Humidity and temperature were 41 % and 24 °C, respectively. The electrospun nonwoven mats were collected on aluminum foil and the morphology of the mats was examined by scanning electron microscopy (SEM, FEI Quanta250 FEG, Oregon, USA); the thermal degradation profile was determined by Perkin-Elmer Diamond TG/DTA. PU is currently a popular polymer material and electrospun polyurethane nano fibres have good elasticity and high toughness.
The produced mats were coated with y-MnO2 using the spraying method. The spraying process was carried out using a MagicBrush air compressor. Firstly, 3 g of y-MnO2 was dissolved in 50 ml of pure water to obtain a dispersion. The produced PU mats were coated with different ratios (1 , 1.5 and 2 g/L y-MnC ) and kept at room temperature for 8 hours to dry the dispersion.
Step 2
A 50 ppm Li+ solution was prepared. The filtration performance of the PU mats was tested by vacuum filtration. Each filtration process was completed in approximately 40 seconds. The Li+ concentrations of the solution obtained after filtration were measured by Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES).
The highest Li+ recovery was obtained from the mat coated with 2 g/L y-MnO2.
Approximately 35.2 mg/g recovery was obtained. The data obtained in the studies carried out with different adsorbents used in the literature are given in the table below.
Adsorbent Sample Type [Li+] / (mg/g) Reference
PVA/HTO LiCI solution 12 [10]
CTS/LMO LiCI solution 11.4 [11 ]
PVA/CAM-HMO LiCI solution 23.26 [12]
PAN/HMO Desalinated seawater 10.3 [13]
PSF/HTO LiCI solution 30.83 [14]
PU/y-MnC Li+ solution 35.2 Invention
Table 1. Comparison of the material developed by the invention with other reported composite adsorbents.
The lithium retention capacity of the nano fibre material produced by the invention was compared with other absorbents in the known art. Information about these absorbents can be found in the References section under the heading of Background Art.

Claims

1. The invention relates to a method for the production of nano fibre material for the recovery of lithium from lithium-containing water or solutions by filtration, characterized in that
• obtaining a highly elastic mat of polyurethane (Pll) material by an electrospinning process,
• characterized in that the obtained mat is coated with y-MnCh.
2. A method for producing a nano fibre material according to claim 1 , characterized in that tetrahydrofuran (THF) is used as a solvent in the electro-spinning process of polyurethane.
3. A method of producing a nano fibre material according to claim 1 , characterized in that N,N-dimethylformamide (DMF) is used as a solvent in the electro-spinning process of polyurethane.
4. A method for producing a nano fibre material according to claim 1 , characterized in that a mixture of tetrahydrofuran (THF) and N,N-dimethylformamide (DMF) solvents in predetermined proportions is used as a solvent in the electro-spinning process of polyurethane.
5. A method for producing a nano fibre material according to claim 1 , characterized in that a mixture of tetrahydrofuran (THF) and N,N-dimethylformamide (DMF) solvents in predetermined proportions is used as a solvent in the electro-spinning process of polyurethane.
6. A method of producing a nano fibre material according to claim 1 , characterized in that the mat obtained is coated with y-MnC by spraying.
7. A method of producing a nano fibre material according to claim 6, characterized in that the obtained mat is coated with y-MnC by a drive from an air compressor.
8. A method of producing a nano fibre material according to claim 1 , characterized in that the polyurethane mat is coated with y-MnCh at 0 to 1 g/L.
9. A method of producing a nano fibre material according to claim 1 , characterized in that the polyurethane mat is coated with y-MnCh at 1 - 2 g/L.
10. A method of producing a nano fibre material according to claim 1 , characterized in that the polyurethane mat is coated with more than 2 g/L y-MnCh.
PCT/TR2023/050970 2022-09-16 2023-09-16 Nano fibre material and production method to be used as a filter for lithium recovery WO2024058764A1 (en)

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TR2022/014324 TR2022014324A1 (en) 2022-09-16 A NANO FIBER MATERIAL AND MANUFACTURING METHOD FOR USE AS A FILTER FOR LITHIUM RECOVERY
TR2022014324 2022-09-16

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04247834A (en) * 1991-01-25 1992-09-03 Showa Denko Kk Method for recovering lithium
US20190275473A1 (en) * 2018-03-08 2019-09-12 Ut-Battelle, Llc Lithium extraction composite for recovery of lithium from brines, and process of using said composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04247834A (en) * 1991-01-25 1992-09-03 Showa Denko Kk Method for recovering lithium
US20190275473A1 (en) * 2018-03-08 2019-09-12 Ut-Battelle, Llc Lithium extraction composite for recovery of lithium from brines, and process of using said composition

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ESKANDARPOUR NILOUFAR, SERESHTI HASSAN: "Electrospun polyurethane fibers doped with manganese oxide nanoparticles as an effective adsorbent for determination of priority pollutant mono-nitrophenols in water samples", JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING, ELSEVIER BV, NL, vol. 7, no. 1, 1 February 2019 (2019-02-01), NL , pages 102926, XP093150841, ISSN: 2213-3437, DOI: 10.1016/j.jece.2019.102926 *
LI-WEN MA; BAI-ZHEN CHEN; YA CHEN; XI-CHANG SHI;: "Preparation, characterization and adsorptive properties of foam-type lithium adsorbent", MICROPOROUS AND MESOPOROUS MATERIALS, ELSEVIER, AMSTERDAM ,NL, vol. 142, no. 1, 22 November 2010 (2010-11-22), Amsterdam ,NL , pages 147 - 153, XP028163801, ISSN: 1387-1811, DOI: 10.1016/j.micromeso.2010.11.028 *

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