Lithium ion recovery from brine using granulated polyacrylamide–MnO2 ion-sieve

doi:10.1016/j.cej.2015.05.075

Chemical Engineering Journal

Volume 279, 1 November 2015, Pages 659-666

https://doi.org/10.1016/j.cej.2015.05.075 Get rights and content

Highlights

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PAM is taken as the binder material, and the granulation does not affect Li⁺ uptake capacities and rate.
•
The granulated ion-sieve has a high stability.
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The maximum Li⁺ concentration in the eluant is 13.74 times higher than that in the feed solution.
•
A mathematical model was built to calculate the film and pore diffusion coefficients.

Abstract

The granulated polyacrylamide (PAM)–MnO₂ ion-sieve with 0.3–0.7 mm diameter was prepared using the inverse suspension polymerization method, where the precursor was the Li₄Mn₅O₁₂ ultrafine powder synthesized in our laboratory, the binder was acrylamide, the cross-linker was N,N′-methylenebisacrylamide (MBA), and the initiator was ammonium persulfate (APS). And then Li⁺ in the granulated material was exchanged with H⁺ in a 0.5 M HCl solution to obtain PAM–MnO₂ ion-sieve for Li⁺ adsorption. The adsorption equilibrium isotherms of Li⁺ on the granulated PAM–MnO₂ ion-sieve were measured at 293, 298, 303, and 318 K, respectively. The Langmuir model was used to fit the experimental data, and the model parameters were estimated with the nonlinear regression method. The uptake curves of Li⁺ adsorption were measured. The film mass-transfer coefficient (k_f) and Li⁺ pore diffusivity (D_p) in the granulated PAM–MnO₂ ion-sieve were estimated using a mathematical model to fit the experimental data. Furthermore, the Li⁺ adsorption–desorption behaviors in the granulated PAM–MnO₂ ion-sieve packed column were investigated for three kinds of feedstock, namely brine, LiCl solution with and without impurities of Na⁺, K⁺, Ca²⁺, and Mg²⁺, respectively, and the regenerability of the granulated PAM–MnO₂ ion-sieve for the multicyclic Li⁺ adsorption from brine and desorption was assessed.

Introduction

Lithium and its derivatives have attracted great interest with the rapidly increasing demand in diverse applications, such as lithium-ion batteries, glass, catalysts, and pharmaceuticals [1], [2], [3], [4], [5]. As known, brines in some areas of the world contain a large amount of Li⁺ [6], [7], comprising 66% of the world’s total lithium resource [8], [9]. Therefore, it is more significant to recover Li⁺ from brines using a cost-effective and environment-friendly method, for example, the adsorption process [10].

MnO₂ ion-sieves are the potential adsorbent materials for Li⁺ recovery from brines because of low toxicity, low cost, and high Li⁺ selectivity [11], [12]. A series of MnO₂ ion-sieves have been synthesized from lithium manganese oxides with different Li/Mn molar ratios, namely LiMn₂O₄, Li₄Mn₅O₁₂, and Li_1.6Mn_1.6O₄ [13], [14], [15], [16], [17], [18]. However, The adsorbent materials with the powder form cannot be used directly in salt lakes because of the physical loss during postadsorption retrieval [10], [19], [20]. The granulation technology for the adsorbent powders is urgently needed to provide the granulated MnO₂ ion-sieve with high mechanical stability and high water permeability for the large-scale applications.

Lots of researchers have tried to immobilize the MnO₂ ion-sieve powder into spheres, foams, membranes, and fibers [13], [19], [20], [21], [22], [23], [24], [25] using binders, such as polyvinylchloride (PVC), polysulfone (PSf), polyurethane (PU), polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), silica, agar, and chitosan, respectively. However, it is found that the Li⁺ adsorption capacity of the granulated MnO₂ ion-sieve is decreased significantly when compared with the MnO₂ ion-sieve powder, either owing to powder leakage or blocked in the forming materials [10], [21], [24]. The granulation method still needs to be improved in order to obtain a new type of composite MnO₂ ion-sieve with a high Li⁺ adsorption capacity, a fast adsorption rate, and a stable structure.

The Li⁺ adsorption/desorption properties of MnO₂ ion-sieves have been investigated by many research groups. Chitrakar et al. [17], [26] studied the adsorption kinetics and isotherm properties by batch experiments. Wang et al. [27] studied the effect of pH value on Li⁺ uptake performance, and found the Li⁺ adsorption capacity was strongly dependent on the pH value in the solution. They suggested that the Li⁺ adsorption performance by MnO₂ ion-sieve should be studied in the buffer solution. Xiao et al. [21] investigated Li⁺ adsorption properties and selectivity by both batch and column experiments. However, a more systematic study is still needed to better understand the Li⁺ adsorption/desorption properties in the granulated MnO₂ ion-sieve packed column.

Polyacrylamide (PAM) is widely used in the water purification field because it is an inexpensive, hydrophilic, and highly water-absorbent material [28], [29], [30]. These properties of PAM indicate that it is a promising binding material because it will not severely affect the adsorption capacity of the powder. The objective of this work is to prepare the granulated MnO₂ ion-sieve using PAM as the binding material and test its Li⁺ adsorption properties. The isothermal and kinetic curves of Li⁺ adsorption on the granulated PAM–MnO₂ ion-sieve are measured by batch experiments at different temperatures. And then, the Langmuir isotherm model is used to fit the adsorption isotherm data, a mathematical model is developed to fit the kinetic data and calculate the mass-transfer coefficients. The Li⁺ adsorption properties of the granulated PAM–MnO₂ ion-sieve in the absence and presence of Na⁺, K⁺, Ca²⁺, and Mg²⁺ are investigated by adsorption breakthrough and desorption experiments using a column, and the stability of the granulated material is tested by 30-cyclic adsorption–desorption experiments for Li⁺ recovery from brine.

Section snippets

Theoretical

The Langmuir adsorption model [27], [31] is used to describe the Li⁺ adsorption equilibrium isotherms on the granulated PAM–MnO₂ ion-sieve at the various temperatures. This model assumes that a molecule can be adsorbed in one adsorption site, and the adsorbent has a uniform adsorption surface [32], [33], and it is expressed as: $C_{e} / Q_{e} = C_{e} / Q_{m} + 1 / (K_{L} \cdot Q_{m})$ where Q_m is the theoretical maximum monolayer adsorption capacity (mmol/g), K_L is the Langmuir empirical constant (L/mmol), C_e is the equilibrium

Reagents

Acrylamide (AM, >98.5%) and N,N′-methylenebisacrylamide (MBA, >98.0%) are purchased from Sinopharm Chemical Reagent Co., Ltd (China). Ammonium persulfate (APS, >98.0%), hydrochloric acid (HCl, RHM 36–38%), and Cyclohexane (C₆H₁₂, >99.5%) are purchased from Shanghai Lingfeng Chemical Reagent Co., Ltd (China). Lithium chloride (LiCl, ⩾97.0%) from Sinopharm Chemical Reagent Co., Ltd (China), Sodium chloride (NaCl, ⩾99.5%), Potassium chloride (KCl, ⩾99.5%), Calcium chloride (CaCl₂, ⩾96.0%),

Characterization of the granulated PAM–MnO₂ ion-sieve

Fig. 1 shows the IR spectra for PAM–MnO₂ ion-sieve precursor (before immersion in a 0.5 M HCl solution) and PAM–MnO₂ ion-sieve (after immersion in a 0.5 M HCl solution). The characteristic peak at 3417 cm⁻¹ represents the free –NH₂ vibration of the amide group. The peaks at 2924 and 2852 cm⁻¹ are due to the –CH₂ antisymmetry and symmetry stretching vibration in the long alkyl chain, respectively [38]. The peak at 1657 and 1458 cm⁻¹ are associated with the antisymmetry and symmetry stretching

Conclusion

The batch experimental results demonstrate that the granulation process of PAM–MnO₂ ion-sieves does not affect the Li⁺ adsorption capacity and adsorption rate of the MnO₂ powder contained in the granulated materials. The maximum Li⁺ equilibrium adsorption capacity is up to 2.68 mmol/g at 303 K, and the adsorption equilibrium isotherms can be described by the Langmuir model with an acceptable accuracy. The film mass-transfer coefficient (k_f) and pore diffusivity (D_p) are estimated in the range

Acknowledgments

The research was supported by NSFC (U1407120), National 863 Program (2012AA061601) and the Fundamental Research Funds for the Central Universities.

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Lithium ion recovery from brine using granulated polyacrylamide–MnO2 ion-sieve

Highlights

Abstract

Introduction

Section snippets

Theoretical

Reagents

Characterization of the granulated PAM–MnO2 ion-sieve

Conclusion

Acknowledgments

Resour. Policy

Appl. Energy

J. Chem. Thermodyn.

Fusion Eng. Des.

Ore Geol. Rev.

Chem. Eng. J.

Hydrometallurgy

Chem. Eng. J.

J. Membr. Sci.

Microporous Mesoporous Mater.

Chem. Eng. J.

Chem. Eng. J.

Colloids Surf. A

Powder Technol.

Eur. Polym. J.

Hydrometallurgy

J. Hazard. Mater.

J. Environ. Sci.

Chem. Eng. Sci.

Adv. Powder Technol.

J. Colloid Interface Sci.

Mater. Sci. Eng. B

Lithium ion recovery from brine using granulated polyacrylamide–MnO₂ ion-sieve

Characterization of the granulated PAM–MnO₂ ion-sieve