**5.3 Liquid-liquid extraction method of recovery of lithium from seawater**

Scientists reported that liquid-liquid lithium extraction from seawater and liquid-liquid extraction are considered a potential process for extracting lithium from seawater. The use of liquid-liquid extraction to extract lithium from seawater is very limited, but the separation, purification and extraction of lithium by liquidliquid extraction have been considered by several authors [81]. On the basis of the reference liquid-liquid extraction of lithium from seawater discussed below.

Scientists have used several extractants, such as primary alcohol C3-C5 and aliphatic alcohol C6-C8, to extract lithium from seawater, but the most effective and promising is Isobutanol. Japanese scientists have developed the most interesting method of extraction and in fact the most modern technology [107, 115]. In these methods, lithium is first extracted with cyclohexane and trioctyloxyphosphine, then the lithium reacts with hydrochloric acid and potassium phosphate, followed by lithium precipitation. The product obtained by this method has a purity of more

**201**

world.

Li+

tion capacity of Li+

repeated desorption of Li+

In a small volume of acid solution, Li+

and a Kimtex® composite membrane.

*Lithium Recovery from Brines Including Seawater, Salt Lake Brine, Underground Water…*

than 95%. Synergistic extraction of lithium from seawater using a TTA-TOPO mixture has been reported by Harvianto et al. [123]. About 93% of the lithium can be recovered by TTA-TOPO. With acidic solutions, the lithium ion can be easily removed, but the removal efficiency decreases with increasing pH of acidic solutions. The type of acid does not affect the stripping efficiency. Similarly, by liquid-liquid extraction, 65% of lithium can be extracted from seawater, in the liquid-liquid extraction process, a magnesium ion is precipitated in advance. The recovery efficiency of lithium ions is negated by other metal ions in seawater [123].

In recent years a number of authors have studied lithium recovery using different types of membranes. The membrane process of lithium reduction is a fairly advanced process that is gaining the attention of various researchers around the

Polysulfone (PSf)-based mixed matrix nanofiber dispersed with particulate

 selectivity. At minimal trans-membrane pressure, the mixed matrix nanofiber membranes were very permeable to water. By supporting the dynamic adsorp-

cycle time (24 h) was successfully controlled by continuous streaming operations.

inorganic adsorbent containing a polymer membrane reservoir system, reported Chung et al. To extract lithium from seawater, Chung et al. used three different membranes: a PSf nonwoven membrane, a PSF nonwoven composite membrane

The proposed system has the advantage of direct application in the seawater eliminates the use of a pressurized flow system [124]. The proposed system can have a direct application in seawater using a pressure flow system. In addition, lithium extraction from seawater using an inorganic adsorbent containing a polymer membrane has been reported by Umeno et al. Lithium recovery from seawater desalination retentate using composite poly(acrylonitrile) nanofibers with H1.6Mn1.6O4 (HMO) lithium ion sieves was reported by Park et al. [110]. To obtain nanofibers, HMO/PAN dope solutions in N,N-dimethylformamide (DMF) with different HMO loads were used, and nanofibers were obtained by electrospinning. For efficient lithium extraction from seawater desalination retentate the material may be a potential membrane (Park et al.) [110]. The use of poly(vinyl chloride) (PVC) membrane adsorbent spinel-type manganese oxide by solvent exchange reported by Umeno et al. Poly(vinyl chloride) was dissolved in DMF solution, then lithium manganese oxide (spinel type) was mixed with DMF to obtain a suspension. The cured PVC film was prepared by applying a suspension to a thin film and immersed in water. To extract lithium obtained as a membrane type adsorbent the membrane was treated with HCl solution. Lithium extraction has been reported to be highly dependent on the method of preparation [109]. Hoshino reported on the recovery of lithium by dialysis and electrodialysis of seawater [111–113]. Selective extraction of lithium from seawater under laboratory conditions was investigated by electrodialysis using an ionic liquid (PP13-TFSI) impregnated with a membrane. The lithium recovery process was developed using

mixed matrix nanofibers, the shorter adsorption–desorption

[115]. Recovery of lithium from seawater using an

by Park et al. A mixed matrix of electro-spinning nanofibers was prepared by thermal annealing, where lithium-ion sieves were activated by acid pickling as Li0.67H0.96Mn1.58O4 or MO. PSF based mixed matrix nanofiber effectively improved

absorber has developed

enrichment was successfully achieved by

**5.4 Membrane process recovery of lithium from seawater**

lithium ion sieves as a flow-through membrane Li<sup>+</sup>

*DOI: http://dx.doi.org/10.5772/intechopen.90371*

*Lithium Recovery from Brines Including Seawater, Salt Lake Brine, Underground Water… DOI: http://dx.doi.org/10.5772/intechopen.90371*

than 95%. Synergistic extraction of lithium from seawater using a TTA-TOPO mixture has been reported by Harvianto et al. [123]. About 93% of the lithium can be recovered by TTA-TOPO. With acidic solutions, the lithium ion can be easily removed, but the removal efficiency decreases with increasing pH of acidic solutions. The type of acid does not affect the stripping efficiency. Similarly, by liquid-liquid extraction, 65% of lithium can be extracted from seawater, in the liquid-liquid extraction process, a magnesium ion is precipitated in advance. The recovery efficiency of lithium ions is negated by other metal ions in seawater [123].

### **5.4 Membrane process recovery of lithium from seawater**

In recent years a number of authors have studied lithium recovery using different types of membranes. The membrane process of lithium reduction is a fairly advanced process that is gaining the attention of various researchers around the world.

Polysulfone (PSf)-based mixed matrix nanofiber dispersed with particulate lithium ion sieves as a flow-through membrane Li+ absorber has developed by Park et al. A mixed matrix of electro-spinning nanofibers was prepared by thermal annealing, where lithium-ion sieves were activated by acid pickling as Li0.67H0.96Mn1.58O4 or MO. PSF based mixed matrix nanofiber effectively improved Li+ selectivity. At minimal trans-membrane pressure, the mixed matrix nanofiber membranes were very permeable to water. By supporting the dynamic adsorption capacity of Li+ mixed matrix nanofibers, the shorter adsorption–desorption cycle time (24 h) was successfully controlled by continuous streaming operations. In a small volume of acid solution, Li+ enrichment was successfully achieved by repeated desorption of Li+ [115]. Recovery of lithium from seawater using an inorganic adsorbent containing a polymer membrane reservoir system, reported Chung et al. To extract lithium from seawater, Chung et al. used three different membranes: a PSf nonwoven membrane, a PSF nonwoven composite membrane and a Kimtex® composite membrane.

The proposed system has the advantage of direct application in the seawater eliminates the use of a pressurized flow system [124]. The proposed system can have a direct application in seawater using a pressure flow system. In addition, lithium extraction from seawater using an inorganic adsorbent containing a polymer membrane has been reported by Umeno et al. Lithium recovery from seawater desalination retentate using composite poly(acrylonitrile) nanofibers with H1.6Mn1.6O4 (HMO) lithium ion sieves was reported by Park et al. [110]. To obtain nanofibers, HMO/PAN dope solutions in N,N-dimethylformamide (DMF) with different HMO loads were used, and nanofibers were obtained by electrospinning. For efficient lithium extraction from seawater desalination retentate the material may be a potential membrane (Park et al.) [110]. The use of poly(vinyl chloride) (PVC) membrane adsorbent spinel-type manganese oxide by solvent exchange reported by Umeno et al. Poly(vinyl chloride) was dissolved in DMF solution, then lithium manganese oxide (spinel type) was mixed with DMF to obtain a suspension. The cured PVC film was prepared by applying a suspension to a thin film and immersed in water. To extract lithium obtained as a membrane type adsorbent the membrane was treated with HCl solution. Lithium extraction has been reported to be highly dependent on the method of preparation [109]. Hoshino reported on the recovery of lithium by dialysis and electrodialysis of seawater [111–113]. Selective extraction of lithium from seawater under laboratory conditions was investigated by electrodialysis using an ionic liquid (PP13-TFSI) impregnated with a membrane. The lithium recovery process was developed using

*Thermodynamics and Energy Engineering*

bution ratio is 4 × 104

25.7 mg L<sup>−</sup><sup>1</sup>

trates containing up to 1 g L<sup>−</sup><sup>1</sup>

a pilot plant with a capacity of 3 m3

HMnO from seawater was achieved [102]. A study using ISMA-1 sorbents to extract

exhibit a high capacity for lithium cations of about 20 mg/m. (4) Lithium concen-

A two stage scheme for obtaining Li2CO3 from seawater using this information of

presented [66]. ISMA-1 sorbents provide higher chemical stability, but manganese oxide degradation associated with ion exchange remains the most serious drawback for their large-scale application in the lithium reduction process. A Japanese researcher developed a composite material by introducing a fine powder k-MnO2 with spinel structure into polyvinyl chloride to improve the kinetic properties of manganese oxide sorbents [121]. Sorbents ISM and ISM-1, synthesized in Russia, are also a composite material obtained using a polymer binder [66, 119]. In Korea, it has also been reported to recover lithium from seawater using an ion exchange type of manganese oxide adsorbent. To recover dissolved lithium in seawater a highly efficient ion exchange adsorbent was prepared according to their method. A highly efficient ion exchange type adsorbate was synthesized as a result of the solid state reaction of Li2CO3 and MgCO3. The ion sieve is formed after treatment of seawater with adsorbate, which is reduced by acid treatment. The lithium-ion sieve was produced by 3 cycles of 0.5 m HCl treatment with 24 h/cycle stringing, which shows

lithium absorption from artificial seawater [98]. Extraction of lithium

from seawater by manganese oxide ion-sieve reported by Liu et al. The most promising method of industrial application was considered to be the extraction of lithium from seawater by adsorption using manganese oxide-ion sieves [104]. The sorption properties of HMnO in seawater and wastewater have been studied by Park et al. [105]. Lithium recovery from lake Urmia by the MnO2 ion sieve, where more than 90% lithium recovery can be achieved, was reported by Zandevakili et al. [122]. Wajima et al. studied the adsorption behavior of lithium from seawater using the adsorbent manganese oxide [106]. In studies using a pseudo-second-order kinetic model, a higher adsorption Kinetics of lithium cations in seawater was observed [106]. Reduction of lithium from seawater using manganese oxide adsorbent

synthesized from Li1.6Mn1.6O4 precursor studied by Chitrakar et al. Manganese oxide adsorbent LiMnO2 was synthesized from H1.6Mn1.6O4 at 400°C by hydrothermal and reflux method. H1.6Mn1.6O4 was synthesized from precursor Li1.6Mn1.6O4. The suf-

**5.3 Liquid-liquid extraction method of recovery of lithium from seawater**

Scientists reported that liquid-liquid lithium extraction from seawater and liquid-liquid extraction are considered a potential process for extracting lithium from seawater. The use of liquid-liquid extraction to extract lithium from seawater is very limited, but the separation, purification and extraction of lithium by liquidliquid extraction have been considered by several authors [81]. On the basis of the reference liquid-liquid extraction of lithium from seawater discussed below. Scientists have used several extractants, such as primary alcohol C3-C5 and aliphatic alcohol C6-C8, to extract lithium from seawater, but the most effective and promising is Isobutanol. Japanese scientists have developed the most interesting method of extraction and in fact the most modern technology [107, 115]. In these methods, lithium is first extracted with cyclohexane and trioctyloxyphosphine, then the lithium reacts with hydrochloric acid and potassium phosphate, followed by lithium precipitation. The product obtained by this method has a purity of more

ficiently effective adsorbent can absorb lithium up to 40 mg g<sup>−</sup><sup>1</sup>

. (2) Sorbents are easily regenerated by nitric acid. (3) They

of lithium can be achieved under optimal conditions.

of seawater per hour has been developed and

cation distri-

from seawater [48].

lithium from seawater shows the following information: (1) The Li+

**200**

a membrane process [112, 113]. Lithium extraction from seawater was selectively achieved by dialysis using a lithium ion superconducting membrane. For appropriate industrial lithium mass production applications, the dialysis process can be energy efficient and easily scalable [111]. Recovery of lithium by membrane desalination followed by crystallization was reported by Quist-Jensen et al. [114]. Extraction of lithium chloride and comparison of membrane crystallization in direct contact, vacuum and osmotic configuration were carried out. In their environment, the necessary supersaturation for crystallization was achieved for the simultaneous production of pure water and lithium by vacuum-membrane distillation [114].
