Adsorption of chromium (VI) from aqueous solutions by cellulose modified with β-CD and quaternary ammonium groups

doi:10.1016/j.jhazmat.2011.01.025

Journal of Hazardous Materials

Volume 187, Issues 1–3, 15 March 2011, Pages 303-310

https://doi.org/10.1016/j.jhazmat.2011.01.025 Get rights and content

Abstract

Cellulose powder was grafted with the vinyl monomer glycidyl methacrylate using ceric ammonium nitrate as initiator and was further derived with β-CD and quaternary ammonium groups to build Cell-g-GMA-β-CDN⁺ adsorbent. Epoxy cellulose was made up of Cell-g-GMA and Cell-hydro-g-GMA, and was found to contain 3.71 mmol g⁻¹ epoxy groups. The adsorption process of the modified cellulose was described by the Langmuir model of adsorption well, and the maximum adsorption capacity of chromium (VI) reached 61.05 mg g⁻¹. The adsorption–desorption tests of β-CDN⁺-type cellulose derivatives exhibited that the reproducibility of the adsorbent was well and the adsorbent could be reused five times at least.

Introduction

Although chromium (VI) compounds are extensively used in electroplating, anodizing operations in the surface finishing industry, corrosion control, oxidation, leather industry and various other industrial applications, they are known as a poisonous substance [1], [2], [3], [4]. A long list of methods has been available for the removal of chromium (VI) such as chemical precipitation, ion exchanger, membrane separation, solvent extraction, and adsorption. Especially the adsorption is considered as one of the most popular techniques [5].

CDs are cyclic oligosaccharides built from six to eight (α = 6, β = 7, γ = 8) d-glucose units and are formed during the enzymatic degradation of starch and related compounds. CDs have gained prominence in recent years because of their cavity, which is hydrophobic in nature, capable of binding aromatic and other small organic molecules, and therefore provide ideal binding sites. CDs are widely used in basic research and industrial processes for the microencapsulation of unstable or volatile substance.

Recently, modified cellulose as a kind of cheaper and more effective sorbents has been investigated. Cellulose is not only renewable, biodegradable, and inexpensive, but also has many primary active hydroxyls which are easy to trigger many reactions, such as free radical reaction, esterification, halogenation, oxidation, and etherification [6]. Various kinds of cellulose derivatives are synthesized by these reactions. Usually, a kind of modified cellulose is made up of carrier, grafting chain, and adsorption function groups. According to references [7], [8], the effective adsorption function groups such as quaternary ammonium groups and ethylenediamine groups, were used for the treatment of chromium (VI) compounds from aqueous solutions.

In this study, chromium (VI) adsorption behavior on a novel modified cellulose containing β-cyclodextrin and quaternary ammonium groups as adsorption function groups in the aqueous solution was investigated (Scheme 1). The reproducibility of β-CDN⁺ type modified cellulose derivatives was also studied. The new absorbent which contains β-cyclodextrin and quaternary ammonium groups, was expected to deal with the solution mixed of heavy metal ions and organic contaminants.

Section snippets

Materials and reagents

Regenerated cellulose powder was used as the form of cellulose. Ceric ammonium nitrate (CAN), trimethylammonium (>33%), epichlorohydrin used in the tests were purchased from Sinopharm Chemical Reagent Co., Ltd. Glycidyl methacrylate (>99%, GMA) was obtained from Shangqiu Shengyuan Industrial Assistant Co., Ltd. and further treated by reduced pressure distillation method. β-Cyclodextrin (>98%, β-CD) was purchased from Shanghai Jianglai Biotechnology Co., Ltd. Potassium dichromate (K₂Cr₂O₇) was

Determination of the content in adsorbent

In this study, as shown in Eq. (1), the epoxy group content of the epoxy cellulose was calculated to contain 3.71 mmol g⁻¹ by the HCl–dioxane titration method. The content of quaternary ammonium groups was calculated to contain 3.93 mmol g⁻¹ by the sodium sulfite method. And the N⁺ content of adsorbent was determined by the AgNO₃ solution titration method. The Cl⁻ content of adsorbent was calculated to contain 1.16 mmol g⁻¹.

FTIR characterization

The FTIR spectra of the cellulose, epoxy cellulose, quaternary ammonium

Conclusions

A new type of adsorbent, Cell-g-GMA-β-CDN⁺, was synthesized, characterized and applied to uptake chromium (VI) in water samples. Batch adsorption experiments were performed to evaluate the efficiency of Cell-g-GMA-β-CDN⁺ towards Cr (VI) ions, and the effects of adsorption conditions on adsorptive performance were investigated. The adsorption process fit the assumptions of the Langmuir isotherm and the pseudo-second-order kinetics model, which was determined by the values of correlation

Acknowledgement

The authors are grateful for the financial support of the Foundation of Science and Technology Cooperation of Henan Province in China (No. 084300510056).

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Adsorption of chromium (VI) from aqueous solutions by cellulose modified with β-CD and quaternary ammonium groups

Abstract

Introduction

Section snippets

Materials and reagents

Determination of the content in adsorbent

FTIR characterization

Conclusions

Acknowledgement

J. Hazard. Mater.

Chem. Eng. J.

Bioresour. Technol.

Carbohydr. Polym.

Sep. Purif. Technol.

Water Res.

Colloid Surf. A

React. Funct. Polym.

Radiat. Phys. Chem.

Carbohydr. Res.

Fuel

J. Hazard. Mater.

Water Res.

Colloid Surf. A