Adsorption of Cu(II), Cd(II), and Pb(II) from aqueous single metal solutions by sugarcane bagasse and mercerized sugarcane bagasse chemically modified with succinic anhydride

doi:10.1016/j.carbpol.2008.05.023

Carbohydrate Polymers

Volume 74, Issue 4, 21 November 2008, Pages 922-929

https://doi.org/10.1016/j.carbpol.2008.05.023 Get rights and content

Abstract

This work describes the preparation of new chelating material from mercerized sugarcane bagasse. The first part treats the chemical modification of non-mercerized sugarcane bagasse (SCB) and twice-mercerized sugarcane bagasse (MMSCB) with succinic anhydride. Mass percent gains (mpg) and degrees of succinylation (DS) of succinylated non- and twice-mercerized sugarcane bagasse 1 (SCB 1 and MMSCB 1) were calculated. MMSCB 1 exhibited an increase in mpg and DS of 49.2% and 0.9 mmol/g in relation to SCB 1. SCB 2 and MMSCB 2 were obtained by treatment of MMSCB 1 and SCB 1 with bicarbonate solution to release the carboxylate functions and characterized by FTIR. The second part evaluates and compares the adsorption capacity of SCB 2 and MMSCB 2 for Cu²⁺, Cd²⁺ and Pb²⁺ ions in an aqueous single metal solution. Adsorption isotherms were developed using Langmuir model. MMSCB 2 exhibited an increase in Q_max for Cd²⁺ (43.6 mg/g) and Pb²⁺ (83.3 mg/g) in relation to SCB 2.

Introduction

Heavy metal ions are known to be toxic and carcinogenic to living organisms (Clement et al., 1995, MacCarthy et al., 1995). Their presence in the aquatic environment has been of great concern because of their toxicity and non biodegradable nature. Some metal ions are cumulative poisons, capable of being assimilated and stored in the tissues of organisms, causing noticeable adverse physiological effects (Gupta & Ali, 2000).

The removal of toxic metal ions from water is a very difficult task due to the high cost of treatment methods (Weng & Huang, 1994). There are various methods for the removal of toxic metal ions from aqueous solutions: reverse osmosis, ion exchange, precipitation, electrodialysis, adsorption, etc. Among these methods, adsorption is by far the most versatile and widely used for the removal of different pollutants (Gupta & Ali, 2004).

Brazil is the world leading producer of sugarcane for both the alcohol and the sugar industries. These industries produce a large amount of sugarcane bagasse. According to the last official survey from CONAB, an agency from the Brazilian Ministry of Agriculture, the national production of sugarcane in 2007/2008 was 527 million tons, the largest of all times. On average, 280 kg of sugarcane bagasse containing 50% moisture are produced by ton of sugarcane. In those industries, bagasse is burned in order to produce energy for sugar mills, but the leftovers are still significant (Karnitz Júnior et al., 2007). The remaining bagasse still continues to be a menace to the environment and a suitable utilization of this residue is an important target to be pursued (Sun, Sun, Zhao, & Sun, 2004). Sugarcane bagasse is constituted mainly of cellulose (40–50%), polyoses (25–30%), and lignin (20–25%) (Caraschi, Campana, & Curvelo, 1996).

Hassan and El-Wakil (2003) have reported the use of amidoximated bagasse (Am-B) for adsorption of some heavy metal ions such as Cu(II), Hg(II), Ni(II), Cr(III), and Pb(II) from aqueous solutions. Adsorption studies were performed at different pHs, contact times, metal ion concentration, and temperatures. The maximum milligrams of metal ions adsorbed per gram of AM-B were 672, 156, 137, and 47 for Hg²⁺, Cr³⁺, Cu²⁺, and Ni²⁺, respectively.

Nada and Hassan (2006) have recently reported the chemical modification of bagasse fibers with the aim to prepare lignocellulosic materials for removal of heavy metal ions from wastewater. Different reactions were used to modify bagasse fibers and to produce the following materials: oxy-bagasse, succinylated bagasse, and carboxymethylated bagasse. Adsorption studies were performed to evaluate the ability of these cation exchangers to remove heavy metal ions. The maximum milligrams of metal ions adsorbed per gram of oxy-bagasse, succinylated bagasse, and carboxymethylated bagasse were 233, 88, 394, and 200; 170, 113, 321, and 88; 392, 460, 504, and 465, for Cu²⁺, Ni²⁺, Cr³⁺, and Fe³⁺, respectively.

Karnitz Júnior et al. (2007) have recently reported the use of sugarcane bagasse modified with succinic anhydride (MSB 2) for removal of Cu(II), Cd(II) and Pb(II) from aqueous solutions. The authors have reported that the hydroxyl and phenolic groups in sugarcane bagasse could be easily converted to carboxylic groups by using succinic anhydride. Adsorption studies to determine the maximum adsorption capacity (Q_max) of MSB 2 towards each heavy metal were developed. The results were analyzed by Langmuir and Freundlich models. MSB 2 exhibited a maximum adsorption capacity of 114 mg/g for Cu²⁺, 196 mg/g for Cd²⁺ and 189 mg/g for Pb²⁺ according to Langmuir model.

Gurgel, Karnitz Júnior, Gil, and Gil (2008) reported the use of modified non- and mercerized cellulose with succinic anhydride for removal of Cu(II), Cd(II) and Pb(II) from aqueous solutions. The authors reported the effect of mercerization in the increase of the fibers specific surface area and in their reactivity. The mercerization makes the hydroxyl groups of the cellulose macromolecules more accessible and decreases the cellulose crystallinity index by 7%. Modified mercerized cellulose exhibited an increase in the mass percent gain and in the concentration of carboxylic functions in relation to modified non-mercerized cellulose by 68% and 2.8 mmol/g, respectively. Adsorption studies to determine the maximum adsorption capacity (Q_max) of modified celluloses for metals ions were developed. The results were analyzed by Langmuir model. Modified mercerized cellulose exhibited an increase in the adsorption maximum capacity of 30.4 mg/g for Cu²⁺, 86.0 mg/g for Cd²⁺ and 205.9 mg/g for Pb²⁺ in relation to modified non-mercerized cellulose.

This work describes the preparation and evaluation of two materials from sugarcane bagasse to adsorb heavy metal ions in aqueous solutions. The first material was prepared by modification of sugarcane bagasse with succinic anhydride (SCB) and the second was prepared by mercerization of sugarcane bagasse with an aqueous NaOH solution (20 wt%) followed by reaction with succinic anhydride (MMSCB). The adsorption studies of Cu²⁺, Cd²⁺ and Pb²⁺ from aqueous single metal ion solutions by SCB and MMSCB were developed at different times, pHs, and metal ion concentration.

Section snippets

Materials

Sugarcane bagasse, a waste material of sugar-alcohol industry, was collected from an alcohol factory at Ouro Preto, Brazil. Succinic Anhydride and Pyridine were purchased from VETEC (Brazil). CuSO₄·5H₂O, Pb(NO₃)₂, CdCl₂·2.5H₂O were purchased from SYNTH (Brazil). Pyridine was refluxed with NaOH overnight and distilled.

Sugarcane bagasse preparation

Integral sugarcane bagasse was first dried under sunlight. The fibers were manually broken into small pieces and subsequently dried at 90 °C in an oven for 24 h. Sugarcane bagasse

X-ray diffraction and FTIR analysis for SCB, MSCB and MMSCB

The treatment of lignocellulosic materials such as sisal, cotton linters and sugarcane bagasse with aqueous NaOH solution and the removal of lignin and polyoses together with the rearrangement of chain crystal packing from cellulose I in cellulose II have been reported by Ass, Ciacco, and Frollini (2006) and López et al. (2000), regarding position shifts and peak intensities in diffractrogram and FTIR spectra. Reactions such as the inclusion of alkali and water in cellulose and the splitting

Conclusions

The two alkaline treatments of sugarcane bagasse removed large amount of lignin and polyoses and also the amorphous cellulose fraction, converted cellulose I into cellulose II, decreased the crystallinity index and increased the separation of the cellulose chains. These modifications provided a higher degree of succinylation proven by higher mass percent gain and concentration of carboxylic functions exhibited by modified mercerized sugarcane bagasse MMSCB 1. MMSCB 2 exhibited higher adsorption

Acknowledgements

The authors thank the financial support from the following Brazilian Government Agencies: Fundação de Amparo à Pesquisa do Estado de Minas Gerais – FAPEMIG, Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – CAPES. The authors are also grateful at Universidade Federal de Ouro Preto – UFOP.

References (23)

B.A.P. Ass et al.
Cellulose acetates from linters and sisal: Correlation between synthesis conditions in DMAc/LiCl and product properties
Bioresource Technology
(2006)
V.K. Gupta et al.
Utilisation of bagasse fly ash (a sugar industry waste) for the removal of copper and zinc from wastewater
Separation and Purification Technology
(2000)
V.K. Gupta et al.
Removal of lead and chromium from wastewater using bagasse fly ash – A sugar industry waste
Journal Colloid Interface Science
(2004)
L.V.A. Gurgel et al.
Adsorption of Cu(II), Cd(II), and Pb(II) from aqueous single metal solutions by cellulose and mercerized cellulose chemically modified with succinic anhydride
Bioresource Technology
(2008)
Y.S. Ho et al.
Regression analysis for the sorption isotherms of basic dyes on sugarcane dust
Bioresource Technology
(2005)
S.Y. Oh et al.
Crystalline structure analysis of cellulose treated with sodium hydroxide and carbon dioxide by means of X-ray diffraction and FTIR spectroscopy
Carbohydrate Research
(2005)
M. Schwanninger et al.
Effects of short-time vibratory ball milling on the shape of FT-IR spectra of wood and cellulose
Vibrational Spectroscopy
(2004)
J.X. Sun et al.
Isolation and characterization of cellulose from sugarcane bagasse
Polymer Degradation and Stability
(2004)
J.C. Caraschi et al.
Preparação e caracterização de polpas para dissolução obtidas a partir de bagaço de cana-de-açúcar
Polímeros: Ciência e Tecnologia
(1996)
R.E. Clement et al.
Environmental analysis
Analytical Chemistry
(1995)

D. Fengel

Characterization of cellulose by deconvoluting the OH valency range in FTIR spectra

Holzforschung

(1992)

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Adsorption of Cu(II), Cd(II), and Pb(II) from aqueous single metal solutions by sugarcane bagasse and mercerized sugarcane bagasse chemically modified with succinic anhydride

Abstract

Introduction

Section snippets

Materials

Sugarcane bagasse preparation

X-ray diffraction and FTIR analysis for SCB, MSCB and MMSCB

Conclusions

Acknowledgements

Bioresource Technology

Separation and Purification Technology

Journal Colloid Interface Science

Bioresource Technology

Bioresource Technology

Carbohydrate Research

Vibrational Spectroscopy

Polymer Degradation and Stability

Preparação e caracterização de polpas para dissolução obtidas a partir de bagaço de cana-de-açúcar

Polímeros: Ciência e Tecnologia

Environmental analysis

Analytical Chemistry

Characterization of cellulose by deconvoluting the OH valency range in FTIR spectra

Holzforschung