Simultaneous removal of Cr(VI) and Amido black 10B (AB10B) from aqueous solutions using quaternized chitosan coated bentonite

doi:10.1016/j.ijbiomac.2016.07.085

International Journal of Biological Macromolecules

Volume 92, November 2016, Pages 694-701

https://doi.org/10.1016/j.ijbiomac.2016.07.085 Get rights and content

Highlights

•
Quaternized chitosan coated bentonite was prepared and characterized.
•
Simultaneous removal of Cr(VI) and Amido Black 10B (AB10B) was investigated.
•
The pseudo-second-order model described the adsorption kinetic behavior of Cr(VI) and AB10B.
•
This adsorbent showed higher adsorption capacities for Cr(VI) and AB10B.
•
The antagonism effect existed between Cr(VI) and AB10B in binary systems.

Abstract

In this study, simultaneous removal of Cr(VI) and Amido Black 10B (AB10B) using quaternized chitosan coated bentonite was investigated by a batch method. The factors affecting adsorption process such as pH, adsorbent dosage, contact time and initial concentration and the interaction of two components in binary solutions have been studied. The results showed that the antagonism effect existed between Cr(VI) and AB10B in binary systems. The equilibrium time for Cr(VI) adsorption was less than the one for AB10B adsorption. The maximum adsorption capacities of the modified bentonite, according to the Langmuir isotherm model were 847.5 mg/g for AB10B and 66.6 mg/g for Cr(VI) at 298 K. The experimental results demonstrated that both Cr(VI) and AB10B were well described by the pseudo-second-order model. Thermodynamic study depicted that the adsorption of Cr(VI) and AB10B onto the modified bentonite was both spontaneous. The adsorption for Cr(VI) was exothermic while the one for AB10B was endoth- ermic in nature.

Introduction

Dyes are among the most commonly used pollutants which appear in various industries including dyestuff, textile, leather, and paper. A large number of dyes are azo compounds that are linked by an azo bridge. It was important to remove these dyes from water based on an environmental point of view because these dyes can be highly toxic to aquatic systems even at very low concentrations. Heavy metals are another hazardous pollutant commonly found in the effluents from several industries such as electronics assembly and fabrication, battery manu- facturing, paper and pulp industries, metal fabrication, and mining activities. Adsorption is considered as an economical method for improving water quality and can be used to remove different types of pollutants, especially dyes and heavy metals. At present, much attention has been paid to investigate the removal of dyes or heavy metals from single-component solutions [1], [2], [3], [4], [5]. Various adsorbents have been developed and applied, and they include activated carbons, natural and synthetic polymers, clays, zeolites, biomasses, agricultural and industrial by-products [6], [7], [8], [9], [10], [11], [12], [13]. However, heavy metals and dyes often existed together in the practical industrial effluents. A limited emphasis has been given to the study of multi-component systems. For example, R. Tovar-Gómez et al. reported the synergic adsorption in the simultaneous removal of acid blue 25 and heavy metals (Zn²⁺, Ni²⁺ and Cd²⁺) using a Ca(PO₃)₂-modified carbon [14]. N.P. Jović-Jovičić et al. investigated the simultaneous adsorption of Pb²⁺ and reactive dye-RB5 on the modified bentonites with hexadecyltrimethylammonium (HDTMA⁺) and quaternary alkyl ammonium cations (QAACs) [15]. Visa et al. studied the simultaneous removal of methylene blue and Cu²⁺, Ni²⁺ and Cd²⁺ in multi-component systems using fly ash modified with NaOH [16].

Bentonite is a clay mineral consisting of two tetrahedral sheets with Si in the cationic sites sandwiching an octahedral Al sheet. The partial substitution of Al³⁺ for the tetrahedral Si⁴⁺ and Mg²⁺ makes the layers negatively charged. Bentonite almost has no adsorption for anionic pollutants due to its negatively charged sheets. Therefore, bentonite, as an adsorbent, was often modified to broaden the application scope. Bentonite may be neutralized by exchangeable cations such as Ni, Co, Zn [17], cationic surfactants [15], and polymers [18], [19]. However, some cationic substances are difficult to degrade in nature and may be toxic to humans and the environment. Therefore, the use of natural cationic substances such as chitosan has generated increasing interest [20], [21]. However, chitosan has several disadvantages including easy agglomeration, poor mech- anical strength, and its solubility in dilute acids, thus the broad application of chitosan was limited to some degree.

Quaternized chitosan is a cationic polymer which is the quaternized derivative of chitosan. It contains multiple cationic charges and has good solubility in water. Based on its properties of biodegradability, biocompatibility, antimicrobial effects, good film formation, and high positive charge, quaternized chitosan has been applied in the preparation of composite films [22], [23], adsorbent material [24], and nanocomposites [25], [26]. In our previous work, it was found that quatenized chitosan/bentonite composite showed a potential for the removal of anionic pollutants [27]. In addition, Wang et al. [28] demonstrated that modification of montmorillonite with quater- nized chitosan could enhance the antimicrobial activity of montmorillonite in a weak acidic or weak basic medium.

In the present study, the modification of bentnoite was achieved by coating quaternized chitosan on bentonite. As heavy metal ion (target pollutant), Cr(VI), a highly toxic pollutant causing liver damage, pulmonary congestions and severe diarrhea, usually exist in many dyeing effluents discharged from leather tanning and dyestuff industries [29]. Chromium exists in the environment in the trivalent state or in the hexavalent state such as Cr (VI) anions: HCrO₄⁻, CrO₄²⁻and Cr₂O₇²⁻. Amido Black 10B (AB10B) was chosen as an azo dye molecule because it has been established that this dye has very high toxicity, and can damages the respiratory system of humans and also causes skin and eye irritations [30]. Moreover, since AB10B can be considered a typical anionic dye and Cr(VI) usually coexists in dyeing effluents, AB10B and Cr(VI) have been selected as target pollutants. The objective of this study is to coat quaternized chitosan on bentonite in order to increase or strengthen the interactions between the anionic pollutants (heavy metal and dye) and positively charged quaternized chitosan. The characterization of the composite material was investigated using FTIR and XRD techniques. The adsorption evaluation of Cr(VI) and Amido Black 10B was done by a batch method. Major adsorption factors including pH, adsorbent dosage, contact time, and initial pollutants’ concentrations as well as the interaction between Cr(VI) and Amido Black 10B were determined. In order to study the simultaneous removal of Cr(VI) and Amido Black 10B (synergetic or antagonistic), the isotherm and kinetic experiments in single and binary solutions (i.e., dye–metal ion) were also carried out.

Section snippets

Materials

Chitosan [weight-average molecular weight (MW) = 100,000 Da, degree of deacetylation (dd) = 90%] was purchased from the Sinopharm Group Chemical Reagent Limited Company (China) and used in the synthesis of quaternized chitosan. Quaternized chitosan, N-2-hydroxy- propyl trimethyl ammonium chloride chitosan was prepared according to our previous literature [27]. Bentonite powder with a particle size of 200-mesh was acquired from the chemical factory of Shentai, Xinyang, Henan, China. Amido black 10B

Characterization of quaternized chitosan coated bentonite

The XRD patterns of the composites with various quaternized chitosan/bentonite mass ratio were shown in Fig. 1. The XRD pattern of bentonite presented a typical reflection of mon- tmorillonite (d₀₀₁) at 6.56°. It is obvious that the d₀₀₁ diffraction peak in the quaternized chitosan coated bentonite with this ratio being 0.5 was shift to a lower angle, suggesting that the interlayer spacing of bentonite was expanded due to the intercalation of crosslinked quaternized chitosan into the interlayer

Conclusion

In this study, the quaternized chitosan coated bentonite was used for the simultaneous adsorption of Cr(VI) and AB10B from binary solution. The antagonism adsorption was observed between AB10B and Cr(VI) in binary solution. Equilibrium isotherm, kinetic and thermodynamic studies were also investigated. Both Cr(VI) and AB10B agreed well to Langmuir for both single and binary systems. The adsorption capacity (mg/g) of the modified bentonite was greater significantly for AB10B than the one for

References (35)

Z.C. Wu et al.
J. Biol. Macromol.
(2015)
Y.Hua G.Wang et al.
Appl. Clay Sci.
(2016)
M. Ji et al.
Appl. Clay Sci.
(2015)
S.C. Santos et al.
J. Environ. Chem. Eng.
(2016)
K. Chinoune et al.
Appl. Clay. Sci.
(2016)
W.W. Ngah et al.
Bioresour. Technol.
(2008)
D. Sud et al.
Bioresour. Technol.
(2008)
M.P. Elizalde-González et al.
Int. J. Chem. Eng.
(2008)
L.S. Chan et al.
Desalination
(2008)
I.A. Aguayo-Villarreal et al.
Chem. Eng. J.
(2011)

M. Ghaedi et al.

Fresenius Environ. Bull.

(2011)

S. Khodadoust et al.

Spectrochim. Acta A: Mol. Biomol. Sp.

(2014)

S. Khodadoust

Spectrochim. Acta A: Mol. Biomol. Sp.

(2014)

R. Tovar-Gómez et al.

J. Hazard Mater.

(2012)

N.P. Jović-Jovičić et al.

J. Contam. Hydrol.

(2013)

M. Visa et al.

Appl. Surf. Sci.

(2010)

E. Eren et al.

Dyes Pigm.

(2008)

Cited by (30)

Applications and perspectives of quaternized cellulose, chitin and chitosan: A review
2023, International Journal of Biological Macromolecules
Recently, increasing attention has been paid to natural polysaccharides for their low cost, biocompatibility and biodegradability. Quaternization is a modification method to improve the solubility and antibacterial ability of natural polysaccharides. Water-soluble derivatives of cellulose, chitin and chitosan offer the prospect of diverse applications in a wide range of fields, such as antibacterial products, drug delivery, wound healing, sewage treatment and ion exchange membranes. By combining the inherent properties of cellulose, chitin and chitosan with the inherent properties of the quaternary ammonium groups, new products with multiple functions and properties can be obtained. In this review, we summarized the research progress in the applications of quaternized cellulose, chitin and chitosan in recent five years. Moreover, ubiquitous challenges and personal perspectives on the further development of this promising field are also discussed.
Functionalized bentonite for removal of Pb(II) and As(V) from surface water: Predicting capability and mechanism using artificial neural network
2023, Journal of Water Process Engineering
An efficient material is required to develop effective removal systems with high flexibility and low cost for capturing toxic ions. In this study, a synthesized lanthanum oxide-modified bentonite (B-La) adsorbent was used for the adsorption of As(V) and Pb(II). The prepared material, B-La, shows a feather shape surface with a 25 nm average particle size and was also confirmed by SEM and TEM. Texture and chemical composition confirmed by XRD and FTIR. From the XPS investigation, the underlying mechanism for Pb(II) and As(V) removal was investigated, and the production of B-La-As(V) and B-La-Pb(II) inner-sphere complexation was shown to be the dominating pathway. As per the pH effect studies, it was observed that B-La efficiently adsorbed Pb(II) and As(V) over a pH range of 6.0. Pb(II) adsorption was not substantially impacted by ionic strength or coexisting ions; however, As(V) adsorption was influenced by phosphate and fluoride, showing that B-La has a strong affinity towards Pb(II) and As(V). A pseudo-second-order model could well fit Pb(II) and As(V) adsorption, and Langmuir equilibrium adsorption describes Pb(II) and As(V) adsorption. The adsorption capacity was 147.05 mg of Pb(II)/g and 156.26 mg of As(V)/g, reflected at the dosage of 0.2 g/L at 25 °C, pH 6.0. Using the response surface methodology, the optimum values for process parameters, such as initial concentration, temperature, pH, and time, for both Pb(II) and As(V) removal are identified. Desorption studies were also performed to confirm the presented B-La adsorbents' environmental suitability. The Pb(II) and As(V) were completely desorbed with 0.2 M HNO₃ and 0.2 M NaOH; after washing with water, it is ready to reuse in the next cycle and can be reused in several cycles of Pb(II) and As(V) adsorption operations. The identified data-driven quadratic model strongly correlated with the experimental values. Machine-learning techniques like artificial neural networks (ANN) and adaptive neuro-fuzzy inference systems (ANFIS), based on results ANN predicted model shows high correlation R² value for both metal ions. All the findings indicated that porous B-La was a promising material for Pb(II) and As(V) removal.
A novel adsorbent of bentonite modified chitosan-microcrystalline cellulose aerogel prepared by bidirectional regeneration strategy for Pb(II) removal
2021, Journal of Environmental Chemical Engineering
Citation Excerpt :
It could be clearly found from the pattern of BT that there was a characteristic peak at 6.42° (d001), which was the standard reflection of montmorillonite. For the XRD pattern of BT-CS-MCCA, the similar characteristic peak at 5.99° appeared after the addition of MCC and CS, indicating that the interlayer space of BT was enhanced owing to the insertion of CS and MCC into the sandwiched layer of BT [27]. In the XRD pattern of CS-MCCA, there were two main characteristic peaks at 10.97° and 20.73°, which could be attributed to the hydrated crystalline structure of CS [28] and crystallographic planes of MCC [29], respectively.
Traditional chitosan aerogel (CSA) could be used to chelate heavy metal ions due to its large specific surface area, high porosity and rich amino groups. However, the CSA was rarely applied in practical application because of its easy hydrolysis, low mechanical strength and slow adsorption rate. In this study, we developed a novel method for increasing the anti-hydrolytic ability and mechanical strength of CSA by bidirectional regeneration of chitosan and microcrystalline cellulose to synthesize chitosan-microcrystalline cellulose aerogel (CS-MCCA). In addition, bentonite (BT) was introduced in the regeneration process to enhance the adsorption rate of CSA, and an efficient adsorbent of bentonite-chitosan-microcrystalline cellulose aerogel (BT-CS-MCCA) for Pb(II) removal was developed, and the maximum adsorption amount and adsorption equilibrium time of Pb(II) on BT-CS-MCCA were 256.24 mg g⁻¹ and 60 min, respectively. Additionally, it was found that with the increase of Na⁺ or K⁺ concentration in the solution from 0 mol L⁻¹ to 0.1 mol L⁻¹, the adsorption capacity of BT-CS-MCCA was enhanced, because the Ca²⁺ in BT was substituted by Na⁺ or K⁺, and then the ion-exchange ability of BT-CS-MCCA was improved. Moreover, the preparation method of BT-CS-MCCA possessed merits of simple operation, low cost and hypotoxicity. Thus, the BT-CS-MCCA had a broad potential application for the purification of Pb(II) in wastewater, and the bidirectional regeneration strategy might offer a brand-new path for the utilization of biomass resources.
Nitrate removal by quaternized mesoporous silica gel in ternary anion solutions: Flow-through column experiments and artificial neural network modeling
2021, Journal of Water Process Engineering
The aim of this study was to examine nitrate removal by quaternized silica gel (q-SG) in ternary solutions of nitrate, phosphate, and sulfate under flow-through column conditions. q-SG was synthesized by grafting dimethyloctyl[3-(trimethoxysilyl)propyl] ammonium chloride on silica gel. Fixed-bed column experimental conditions (N = 15) were designed using central composite design to examine dynamic removal behaviors of competing anions in columns containing q-SG. During the experiments, influent solution containing ternary anions of nitrate, phosphate, and sulfate was injected into flow-through columns. In the effluent, the ternary anions along with chloride were monitored to obtain competitive breakthrough curves. Column experiments demonstrated the dynamic and competitive removal behaviors of anions during adsorption and leaching in the columns. Artificial neural network (ANN) model was developed based on the column experimental data to predict the removal rates of anions in the column experiments. In the model development, influent concentrations of nitrate, phosphate, and sulfate were selected as three variables in the input layer, whereas removal rates of nitrate, phosphate, and sulfate were chosen as three variables in the output layer. The developed ANN model with topology 3:8:9:3 (three input variables, eight neurons in the first hidden layer, nine neurons in the second hidden layer, and three output variables) could simultaneously predict the removal rates of anions in column experiments.
Sorption kinetics of an eco-friendly and sustainable Cr (VI) ion scavenger in a batch reactor
2021, Journal of Environmental Chemical Engineering
Citation Excerpt :
The rough surface and small size of CMNPs might have provided enhanced surface area which supported the biosorption of Cr (VI) from liquid phase [81,94]. Chitosan coating rendered surface of nanoparticles porous and uneven morphologically [39,61]. The EDX analysis was performed to confirm the presence of elements which contributed a major role in the synthesis of CMNPs.
In the present work, Cr (VI) was successfully biosorbed and reduced to less toxic Cr (III) by using chitosan coated MnO₂ nanoparticles synthesized through green route using curcumin and Citrus limetta peel extract. X-ray photoelectron spectroscopic analysis of chromium loaded nanoparticles confirmed that most of the Cr (VI) ions were reduced to Cr (III). Scanning electron and transmission electron microscopic images showed that these nanoparticles were spherical in shape, crystalline in nature, ranged from 14 to 24 nm in size. The Fourier-transform infrared spectroscopy analysis indicated hydroxyl, carboxyl and amino groups on its surface. The dynamic light scattering showed a size distribution of nanoparticles as 299.50 ± 25.32 nm. High Brunauer- Emmett-Teller specific surface area (76.19 m²/g) of these nanoparticles provided more active sites for binding of chromium ions. Energy dispersive X-ray and ultimate analysis indicated the presence of Mn, O, C, H, and N. These elements were the major components of these nanoparticles and confirmed the presence of chitosan on nanoparticle surface. The lower value of pH_zpc (3.17) proved the suitability of acidic pH values for conducting biosorption experiments. The values of dimensionless numbers and diffusivity coefficients indicated that biosorption was controlled by film and pore diffusion. Pseudo-second order (R² = 0.99) and Freundlich isotherm (R² = 0.99) showed a better goodness of fit over other kinetic and isotherm models. The thermodynamic study showed that biosorption was exothermic and spontaneous. But, the enthalpy is endothermic and the reaction is entropy driven. Results showed that these nanoparticles have high Cr (VI) uptake capacity (92.19 mg/g) and can be reused over several cycles of adsorption–desorption.
Highly efficient and selective removal of anionic dyes from aqueous solution by using a protonated metal-organic framework
2021, Journal of Alloys and Compounds
Citation Excerpt :
Then, the pH effect on the removal efficiency was investigated. AB was chosen as a model anionic dye, which is a toxic and primary pollutant of water resources [49,50]. In Fig. 4, the removal efficiency for AB was studied in the pH range of 3.5–10.5.
Hydrothermal reaction of Zn(NO₃)₂·6H₂O with a flexible bipyridyl ligand, (pyridin-4-yl)methyl 3-(2-(4-((pyridin-4-yl)methoxy)phenyl)diazenyl)benzoate (L) and 1,3-benzenedicarboxylic acid (1,3-H₂BDC) gave rise to a novel metal-organic framework (MOF), {[Zn (1,3-BDC)L]∙H₂O}_n. The as-synthesized MOF has been characterized by Fourier transformed infrared (FT-IR), powder X-ray diffraction, single-crystal X-ray diffraction and scanning electron microscopy (SEM). By introduction of the ligand L containing ester, diazene and ether groups, a large number of oxygen and nitrogen sites that can be readily protonated in acidic conditions were successfully decorated on the surfaces of the predesigned MOF. The as-prepared protonated Zn-MOF with abundant positive charges (−NNH⁺−, –OH⁺−, –COOH⁺−) was applied as an adsorbent to remove anionic dyes from aqueous solutions. Such an adsorbent exhibited ultrahigh uptake capacities for different sized anionic dyes of Amido Black 10 B (AB, 2402.82 mg g⁻¹), Methyl Orange (MO, 744.02 mg g⁻¹), Orange ΙΙ (OII, 522.83 mg g⁻¹) and Direct Red 80 (DR, 1496.34 mg g⁻¹). The anionic dyes uptakes of the adsorbent are obviously higher than that of most reported adsorbents. Moreover, the adsorbent showed excellent selectivity in the adsorption of anionic dyes. The adsorption process followed the pseudo-second-order kinetics. The equilibrium adsorption isotherm data were well fitted by Langmuir and Sips models. FT-IR, zeta potential analysis and SEM investigation revealed that the interactions between the protonated Zn-MOF and the anionic dyes are mainly dominated by electrostatic interaction and surface adsorption. This work may provide a new perspective for the development of functional materials on the removal of contaminants from water environment.

View all citing articles on Scopus

View full text

Simultaneous removal of Cr(VI) and Amido black 10B (AB10B) from aqueous solutions using quaternized chitosan coated bentonite

Highlights

Abstract

Introduction

Section snippets

Materials

Characterization of quaternized chitosan coated bentonite

Conclusion

J. Biol. Macromol.

Appl. Clay Sci.

Appl. Clay Sci.

J. Environ. Chem. Eng.

Appl. Clay. Sci.

Bioresour. Technol.

Bioresour. Technol.

Int. J. Chem. Eng.

Desalination

Chem. Eng. J.

Fresenius Environ. Bull.

Spectrochim. Acta A: Mol. Biomol. Sp.

Spectrochim. Acta A: Mol. Biomol. Sp.

J. Hazard Mater.

J. Contam. Hydrol.

Appl. Surf. Sci.

Dyes Pigm.