Full length articlePreparation of magnetic resin microspheres M-P(MMA-DVB-GMA) and the adsorption property to heavy metal ions
Introduction
Heavy metal ions (HMIs) in wastewater pose a serious threat to human health and natural environment because of the high toxicity, non-biodegradability and bioaccumulation characteristics [1]. HMIs like lead (Pd), cadmium (Cd), copper (Cu) and chrome (Cr), come from chemical manufacturing, battery manufacturing industries, metallurgical, leather tanning and mining [2]. At present, obvious chemical and physical methods have been developed to remove HMIs from wastewater. Comparatively, chemical methods e.g. chemical precipitation and electrochemical reduction are effective in removing high concentration of HMIs from wastewater, but could cause secondary pollution due to the use of chemical reagents [3]. Physical methods such as membrane separation, adsorption and ion exchange are feasible to remove low concentration of HMIs from wastewater, and environmental-friendly and easy to handle [4]. Obvious adsorbents including active carbon, carbon nanotube and resins have been developed [5,6]. Among them, resins show great advantages due to its high specific surface area, mechanical strength, adsorption capacity, easy regeneration and low cost [7]. Above all, ion-exchange resins give the best effect on the treatment of heavy metal waste water [8].
Conventional sulfonic acid ion exchange resin exhibits high activity to remove HMIs, but the adsorption selectivity on the resin is low, and furthermore, the removal of HMIs is easily disturbed by the coexisting ions. Recent literatures reported that novel chelating resins functionalized with OH, NH2, COOH and SH groups showed an improved adsorption selectivity for Hg(II), Pb(II) and Cu(II) [9,10]. Methyl methacrylate (MMA) was often selected as monomer for preparation of polymers because alkaline hydrolysis of the methyl ester in MMA easily produced COOH on the surface of polymers [11,12]. Recently, the application of magnetic polymer adsorbents for the removal of HMIs has become a new topic of research since it combines the advantages from both components: magnetic particles and polymers. The magnetic particles make the rapid and facile separation of adsorbents possible in an external magnetic field. The high specific surface area and functional groups of polymers help to adsorb HMIs on resins [13]. For instance, a novel magnetic cation-exchange resin developed via suspension polymerization (methyl acrylate as monomer, diallyl itaconate and divinylbenzene as cross-linkers) and basic hydrolysis process, exhibited high adsorption capacities for Cu(II) and Ni(II) [14]. According to Kara et al., magnetic vinylphenyl boronic acid microspheres were prepared by copolymerizating of ethylene glycol dimethylacrylate with 4-vinyl phenyl boronic acid, showing great potential for Cr(VI) removal [15]. In another report, micron-sized monodisperse superparamagnetic polyglycidyl methacrylate particles with functional amino groups were prepared by the dispersion polymerization and subsequently chemical modification, and further direct precipitation of magnetite nanoparticles within the polymer particles [16]. In this study, glycidyl methacrylate (GMA) was selected as monomer because its epoxy groups can be easily converted into alcohol functional group by acidic hydrolysis. Therefore, the development of magnetic polymers with high concentration of functional groups such as COOH and OH via selecting proper monomers and technical process for selective adsorption of HMIs from wastewater is possible.
In present work, magnetic resin microspheres with carboxyl and hydroxyl groups were prepared by suspension polymerization combined with acidic and basic hydrolysis. The adsorption property to HMIs was investigated.
Section snippets
Materials
Methyl methacrylate (MMA, AR), divinylbenzene (DVB, 55%), glycidyl methacrylate (GMA, AR) and dibenzoyl peroxide (BPO, AR) were obtained from Shanghai Mclean Biochemical Technology Co. Ltd., China. FeCl3·6H2O, FeCl2·4H2O, polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP) were of analytical grade and purchased from Guangzhou Jinhua Da Chemical Reagent Co., Ltd. Oleic acid (OA), toluene and heptanes were of analytical grade and obtained from Chengdu Kelong Chemical Reagent Factory.
Preparation of magnetic resin microspheres
Characterization of the resin microsphere
The XRD pattern of the MPMDG2 is presented in Fig. 2(a), which is compared with that of pure Fe3O4 particles. Obvious diffraction peaks appear at 2θ = 30.390°, 35.640°, 43.251°, 57.250° and 62.831°, which correspond to the planes (220), (311), (400), (511) and (440), respectively, of the inverse spinel structure of Fe3O4 (JCPDS file no. 16–629) [18]. The magnetization curves of resin samples measured at RT are shown in Fig. 2(b). The loop areas for both resin samples (MPMDG1, MPMDG2) are
Conclusions
In this study, magnetic resin microspheres called MPMDG2 were prepared by suspension polymerization combined with basic and acidic hydrolysis. The adsorption property of resin to Cr(III), Cu(II), Cd(II) and Pb(II) ions was investigated. Structural and morphological analyses revealed that the resulting resin had higher specific surface area and mesoporous structure. The resin contained about 9.2 wt% Fe3O4, exhibiting a high magnetic response. The resin showed selective adsorption to Cr(III),
Declaration of competing interest
The authors declare no competing financial interest.
Acknowledgments
This work was supported by the National Natural Science Foundation of China (21566004), and the Scientific Research Foundation of Guangxi University (XGZ120081, XTZ140787, XJPZ160713).
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