Preparation of magnetic resin microspheres M-P(MMA-DVB-GMA) and the adsorption property to heavy metal ions

doi:10.1016/j.apsusc.2019.143708

Applied Surface Science

Volume 496, 1 December 2019, 143708

https://doi.org/10.1016/j.apsusc.2019.143708 Get rights and content

Highlights

•
Magnetic resin microspheres were prepared by suspension polymerization combined with basic and acidic hydrolysis.
•
Methyl methacrylate, divinylbenzene and glycidyl methacrylate were used as monomers.
•
The resin contained about 9.2 wt% Fe₃O₄ and exhibited a high magnetic response.
•
The resin exhibited selective adsorption to Cr(III) and Pb(II) and good reproducibility.

Abstract

Magnetic resin microspheres called MPMDG₂ were prepared by suspension polymerization combined with basic and acidic hydrolysis. The adsorption property of resin microspheres to heavy metal ions was investigated. Structural and morphological analysis revealed that the resin had high specific surface area and mesoporous structure. The resin contained about 9.2 wt% Fe₃O₄ and exhibited a high magnetic response. Adsorption experiments showed that the resin can selectively absorb Cr(III) and Pb(II) ions. The adsorption process was well described by a pseudo-second-order kinetic model, and the equilibrium adsorption data fitted the Langmuir isotherm model better than the Freundlich model. Ion exchange along with chemistry chelating was the most probable mechanisms for the adsorption of metal ions on the resin. The superior magnetic response, regeneration and selective adsorption property of the MPMDG₂ make it a good candidate as an adsorbent for removing Cr(III), Pb(II) and Cu(II) from wastewater.

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).

References (31)

A.I.A. Sherlala et al.
A review of the applications of organo-functionalized magnetic graphene oxide nanocomposites for heavy metal adsorption
Chemosphere
(2018)
M.A. Barakat
New trends in removing heavy metals from industrial wastewater
Arab. J. Chem.
(2011)
D. Kołodyńska et al.
Comparison of sorption and desorption studies of heavy metal ions from biochar and commercial active carbon
Chem. Eng. J.
(2017)
J. Xu et al.
A review of functionalized carbon nanotubes and graphene for heavy metal adsorption from water: preparation, application, and mechanism
Chemosphere
(2018)
M. Šćiban et al.
Adsorption of heavy metals from electroplating wastewater by wood saw dust
Bioresour. Technol.
(2007)
F.L. Fu et al.
Removal of heavy metal ions from wastewaters: a review
J. Environ. Manag.
(2011)
B. Pan et al.
Development of polymeric and polymer-based hybrid adsorbents for pollutants removal from waters
Chem. Eng. J.
(2009)
L.Y. Wang et al.
Study on adsorption mechanism of Pb(II) and cu(II) in aqueous solution using PS-EDTA resin
Chem. Eng. J.
(2010)
Y. Zhang et al.
Construction of wettability gradient surface on copper substrateby controlled hydrolysis of poly(methyl methacrylate–butylacrylate) films
Appl. Surf. Sci.
(2014)
H. Bagheri et al.
Preparation and characterization of magnetic nanocomposite of Schiff base/silica/magnetite as a preconcentration phase for the trace determination of heavy metal ions in water, food and biological samples using atomic absorption spectrometry
Talanta
(2012)

Q. Li et al.

Synthesis and characterization of a novel magnetic cation exchange resin and its application for efficient removal of Cu²⁺ and Ni²⁺ from aqueous solutions

J. Clean. Prod.

(2017)

A. Kara et al.

Magnetic vinylphenylboronic acid microparticles for Cr (VI) adsorption: kinetic, isotherm and thermodynamic studies

J. Hazard. Mater.

(2015)

M. Davarpanah et al.

Preparation and characterization of anion exchange resin decorated with magnetite nanoparticles for removal of p-toluic acid from aqueous solution

J. Magn. Magn. Mater.

(2015)

Z. Li et al.

Magnetite nanoparticles with high heating efficiencies for application in the hyperthermia of cancer

Mater. Sci. Eng., C

(2010)

A. Javaid et al.

Removal of heavy metals by adsorption on Pleurotus ostreatus

Biomass Bioenergy

(2011)

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Full length articlePreparation of magnetic resin microspheres M-P(MMA-DVB-GMA) and the adsorption property to heavy metal ions

Highlights

Abstract

Introduction

Section snippets

Materials

Preparation of magnetic resin microspheres

Characterization of the resin microsphere

Conclusions

Declaration of competing interest

Acknowledgments

Chemosphere

Arab. J. Chem.

Chem. Eng. J.

Chemosphere

Bioresour. Technol.

J. Environ. Manag.

Chem. Eng. J.

Chem. Eng. J.

Appl. Surf. Sci.

Talanta

J. Clean. Prod.

J. Hazard. Mater.

J. Magn. Magn. Mater.

Mater. Sci. Eng., C

Biomass Bioenergy

Full length article
Preparation of magnetic resin microspheres M-P(MMA-DVB-GMA) and the adsorption property to heavy metal ions