Efficient Removal of Acidic Dye Using Low-Cost Biocomposite Beads

Subscriber access provided by OAKLAND UNIV

Article

Efficient removal of acidic dye using a low-cost biocomposite beads Ay#egül Ü. Metin, Hakan Çiftçi, and Erol Alver Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/ie400480s • Publication Date (Web): 05 Jul 2013 Downloaded from http://pubs.acs.org on July 17, 2013

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

Industrial & Engineering Chemistry Research is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Industrial & Engineering Chemistry Research

OH

OH O

OH O O

O

NH2

OH

NH3+

OH

O OH

n chitosan chains

O -

+

O

NH3

OH

O-

OOH

O

O +

zeolite particles

O P

OH O

NH3+

OH

P O O-

O-

OH

O

O

NH3+

O

P

O

OH O

OH

NH3+

O

O NH3+

OH

+ P3O10-5 O

Tripolyphosphate solution (TPP)

O

O

OH

O O O

O O

O NH3+ OH

Cl

O

O

NH3+

O

NH3+

OH

Epichlorohydrin (ECH)

O O O O P O P- O P OO-

OH O OH

NH3

O OH

O-

OH O

O +

NH3

OH

NH3+

OH

O

O O

O O

O

O

+O

O

O NH3+

O

O

OH

NH3+

OH

NH3+

O

crosslinked chitosan chains

crosslinked chitosan/zeolite biocomposite bead

Figure 1. Schematic presentation of the preparation of the chitosan/zeolite biocomposite beads

The objective of this study is to prepare and characterize chitosan/zeolite biocomposite beads and utilize them as adsorbent for removal of anionic dye. The chitosan/zeolite beads were prepared by mixing different masses of zeolite with chitosan solution to increase both the mechanical and functional properties of chitosan, making it more suitable material for engineering applications, such as the treatment of wastewater. For the preparation of the chitosan/zeolite biocomposite beads, two modification procedures were performed. Firstly, for ionic crosslinking, zeolite dispersed chitosan solution was dropped slowly into sodium tripolyphosphate (TPP) solution and then for chemical crosslinking, epichlorohydrin (ECH) modification was performed. After synthesis, the chitosan/zeolite biocomposite beads washed several times with deionized water and used as adsorbent for removal of anionic dye, AB194. The obtained results indicate that chitosan/zeolite biocomposite beads as an adsorbent is promising for dye removal from wastewater. ACS Paragon Plus Environment


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 33

Efficient removal of acidic dye using a low-cost biocomposite beads Ayşegül Ü. Metin †, Hakan Çiftçi ‡, Erol Alver *, § †Department of Chemistry, Faculty of Arts and Sciences, Kırıkkale University, 71450 Yahşihan, Kırıkkale, Turkey ‡Department of Chemistry and Chemical Processing Technologies, Kırıkkale Vocational High School, Kırıkkale University, 71450 Yahşihan, Kırıkkale, Turkey *§

Department of Chemical Engineering, Faculty of Engineering, Hitit University, 19030, Çorum,

Turkey KEYWORDS: chitosan, zeolite, biocomposite, bead, acidic dye ABSTRACT: The objective of this study is to prepare and characterize chitosan/zeolite biocomposite beads and utilize them as adsorbent for removal of anionic dye, Acid Black 194 (AB194). Characterization studies of biocomposite beads were carried out by using FTIR, TGA and SEM-EDX. The ability of chitosan/zeolite biocomposite beads as an adsorbent for the removal AB194 from an aqueous solution has been investigated under various experimental conditions. Maximum adsorption capacity of biocomposite beads was calculated as 2140 mg/g. The increase in temperature resulted in a higher AB194 loading per unit weight of biocomposite beads. As an additional factor affecting the adsorption behavior of AB194, the effect of ionic strength was investigated and the adsorption capacity of biocomposite beads significantly decreased. Four isotherm models were employed to elucidate the adsorption process. The most appropriate model for the equilibrium process was the Freundlich. The kinetic studies indicated that the adsorption of AB194 followed the pseudo-second-order kinetic. Thermodynamic calculations showed that the adsorption of reactive dye was a spontaneous and endothermic process. The obtained results indicate that chitosan/zeolite biocomposite beads as an adsorbent is promising for dye removal from wastewater.

ACS Paragon Plus Environment

1

Page 3 of 33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


INTRODUCTION Industrial wastewaters are an important environmental problem worldwide, and many investigations have been made examining how to rehabilitate them. Dyes are significant environmental pollutants because they are visible at low concentrations in water.1-3 Dyes are mostly toxic and even carcinogenic, which constitutes a serious danger to human and aquatic life.4-7 The highly colored wastewaters may significantly affect photosynthetic activity of aquatic plants by blocking sunlight penetration into the water and result in the destruction of aquatic life such as hindering the growth of microbes, creating micro toxicity to fish and other organisms.8-10 Dyes can be classified as anionic (direct, acid and reactive dyes), cationic (basic dyes) and nonionic (disperse dyes).11 Acidic dyes are used in many industries, such as textile, paper, food processing, cosmetics, plastics, printing, leather, pharmaceutical and dye manufacturing.12,13 These dyes are classified as azo, anthraquinone, triphenylmethane, azine, xanthene, nitro and nitroso.13 Acid Black 194 is one of the most popular dyes in leathers and wools, polyamides, silks and wool blended fabric dyeing, direct printing in wool, silk fabric fiber and nylon nonwoven microfabric dyeing.14 A number of processes, such as adsorption, coagulation, flocculation, chemical degradation and biological treatment, membrane filtration, and electrochemical techniques have been tested for the removal of dyes from textile wastewater.15-18 Among these processes, adsorption is known to be a simple, low-cost and effective method,19,20 produces low level residue and is suitable for adsorbent recycling and reuse.21 Various types of adsorbents have been used to remove dyes, such as alumina, silica, chitosan, peat, activated carbon, zeolite, bentonite, activated clay fly ash, wood, coal, kaolin and palm oil ash.8,13,22,23 Natural zeolites are highly porous hydrated alumina silicate materials with three dimensional crystal structures.24 There are more than 40 natural zeolites identified in the world.1,7 Natural zeolites have been used widely for the removal of heavy metal ions and dyes from wastewater because they have a high ion-exchange capacity and relatively high specific surface areas as well as being relatively inexpensive and plentiful in the world.1,7 However, the adsorption of anionic dyes using natural zeolite is not suitable due to both the surface of the zeolite and the dye molecules having negative charges.7,23,25 Chitosan, (poly (β1-4)-2-amino-2-deoxy-D-glucopyranose) is synthesized through the deacetylation of chitin and it is the second most abundant polymer in nature after cellulose.26 Chitosan can be extracted from crustacean shells such as prawns, crabs, fungi and insects.26,27 Chitosan is an extremely attractive adsorbent due to its biocompatibility, biodegradability, hydrophilicity, non-toxicity and antibacterial properties. Also, it is economical and in abundance.28-30 Chitosan is crosslinked with various cross-linkers, such as glutaraldehyde (GLA), ethylene glycol diglycidyl ether (EGDE) and epichlorohydrin (ECH) chemically and also with tripolyphosphate (TPP) as ionic due to it being soluble in an acidic medium.16,19 Crosslinked chitosan can be used as an adsorbent to remove heavy metals, proteins and dyes because of its amine (–NH2) and hydroxyl (–OH) groups.26 Chitosan effectively removes anionic dyes because its amino groups are protonated at acidic pH.1,26 Although cross-linked chitosan beads have greater mechanical strength, they have the disadvantage of low specific gravity and the structure is too soft.31,32 Therefore, researchers aim to find a solution that will improve the stability of chitosan beads. It has been reported that the physical and functional properties of chitosan can be enhanced when chitosan is used in conjunction with other powders, such as clays and activated carbon.31,32 In various studies,


2


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 33

chitosan composites have been prepared with different materials, such as bentonite, montmorillonite, activated carbon, activated clay, zeolite, silica, alumina, MgO and perlite.26,33,34 The aim of the present study is to evaluate the ability of chitosan/zeolite biocomposite beads to remove the acidic dye. Firstly chitosan/zeolite biocomposite beads were prepared by crosslinking tripolyphosphate and epichlorohydrin, respectively. The chitosan/zeolite biocomposite beads were characterized by scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The effects of various adsorption conditions, such as temperature, salt concentration, and initial pH value of the dye solution, have been studied. Langmuir, Freundlich, DubininRadushkevich, and Redlich–Peterson isotherm models were examined in terms of their appropriateness for the experimental data obtained. Pseudo first-order, second-order, and intraparticle diffusion kinetic models were used to evaluate the mechanism of adsorption. Thermodynamic parameters, such as ∆Go, ∆Ho, and ∆So were calculated. EXPERIMENTAL SECTION Materials Chitosan (deacetylation degree: ≥75%) and epichlorohydrin were obtained from Sigma Aldrich (St. Louis, USA) and zeolite (minerals of Heulandite type, average particle size 0.99). According to the results of the study, the most suitable isotherm models for AB194 adsorption on chitosan/zeolite biocomposite beads were determined in the order of Freundlich > Redlich– Peterson > Langmuir > Dubinin-Radushkevich. Effect of temperature and determination of thermodynamic parameters Temperature is an important parameter affecting the adsorption process. When the temperature increases in the adsorption medium, it is known that the rate of diffusion of the adsorbate molecules across the external boundary layer and in the internal pores of adsorbent increase owing to the reduced viscosity of solution.57,58 In addition, changing the temperature will alter the equilibrium capacity of the adsorbent for a particular adsorbate.58 Therefore, temperature studies give valuable information about enthalpy and entropy changes of the adsorption process.57


23

Page 25 of 33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Fig.12. Effect of temperature on the adsorption of AB194 (pH: 3.0, initial dye concentration: 500 mg/L, adsorbent dosage: 5 g wet bead/L). Fig.12 presents the effect of temperature on the adsorption of AB194 onto chitosan/zeolite biocomposite. The adsorption studies were performed under desired conditions at 8, 22 (ambient temperature), 30, 40, 50 and 60 oC and calculated thermodynamic parameters. As seen, the equilibrium adsorption capacity was evidently affected by temperature. The amount of AB194 adsorbed increased from 561 to 1015 mg/g at 500 mg/L initial dye concentration when the temperature was increased from 8 to 50 oC and remained constant after 50 oC. This approximately 50% increase in AB194 adsorption with increasing temperature showed that adsorption process has been affected by temperature rise and that the adsorption of AB194 on biocomposite beads was of an endothermic nature. In addition, it was thought that this rise may be caused by different parameters during the adsorption process. With a rise in temperature, hydrophobic interactions between alkyl groups of chitosan and dye molecules can be increased, and the mobility of molecules increases generally; thus facilitating the formation of a surface monolayer.57 The thermodynamic parameters of process, such as enthalpy change (∆Ho), entropy change (∆So) and Gibbs free energy change (∆Go) of dye adsorption on chitosan/zeolite biocomposite can be calculated by using the following equations:59 ∆Go = –RT ln K ∆Go = ∆Ho – T∆So

(14) (15)


24


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 26 of 33

Combining the above two equations, we get: ln K = –∆Ho/RT + ∆So/R

(16)

where R is universal gas constant (8.314 J/mol K), K is the equilibrium constant, T is the temperature (K). The values of ∆Ho and ∆So were calculated from slope and intercept of Van’t Hoff plot of ln K versus T-1 as presented in Fig.13. ∆Ho and ∆So values were determined as 10.494 kJ/mol and 89.201 J/mol K, respectively, while the ∆Go values were -14.515, -15.761, -16.473, -17.363, 18.253, -19.143 kJ/mol at 281, 295, 303, 313, 323 and 333 K respectively.

Fig.13. Plot of ln K versus T-1: estimation of thermodynamic parameters for the adsorption of AB194 onto chitosan/zeolite biocomposites (pH: 3.0, initial dye concentration: 500 mg/L, adsorbent dosage: 5 g wet bead/L). The adsorption process can be classified as physical adsorption and chemisorption by the magnitude of the enthalpy change. It is accepted that if the magnitude of free enthalpy change is less than 84 kJ/mol, the adsorption is physical. However, chemisorption occurs in the range from 84 to 420 kJ/mol.60 The positive value of ∆Ho showed that AB194 adsorption was endothermic and the magnitude of ∆Ho implies that the nature of adsorption was also physical in nature, involving weak interactions such as electrostatic or hydrophobic interactions.


25

Page 27 of 33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


The positive value of ∆So (89.201 J/mol/K) suggests increased randomness at the solid-solution interface during the adsorption process. Also, a positive entropy value represented a degree of freedom of the adsorbed species.61 The negative values of (-14.515, -15.761, -16.473, -17.363, -18.253, -19.143 kJ/mol) ∆Go indicate the spontaneous nature of adsorption at 281, 295, 303, 313, 323 and 333 K, respectively. Generally, the ∆Go value is in the range of 0 to −20 kJ/mol and -80 to −400 kJ/mol for physical and chemical adsorptions, respectively (Liu et al., 2010). The values of ∆Go of the adsorption process altered from -14.515 to -19.143 kJ/mol when the temperature increased from 281 to 333 K, it can be deduced that the adsorption of AB194 on chitosan/zeolite biocomposite is controlled by physisorption.57 CONCLUSIONS The chitosan/zeolite beads were prepared by mixing different masses of zeolite with chitosan solution to increase both the mechanical and functional properties of chitosan, making it more suitable material for engineering applications, such as the treatment of wastewater. The adsorption study showed that chitosan/zeolite biocomposite beads could be effectively used to remove anionic dyes (AB194 was used as a model in this study). The adsorption is dependent on various parameters, such as pH, initial dye concentration, competitive ions and temperature. It has been observed that the adsorption capacity increases when initial dye concentration or temperature increase. Maximum adsorption capacity of biocomposites beads was calculated as 2140 mg/g. According to the adsorption results obtained at room temperature, the relative standard deviation (RSD) was calculated as 4.4% (n=5). The results of thermodynamic parameters imply that the adsorption process is spontaneous and physical because of the negative value of ∆Go and the value of enthalpy change being less than 84 kJ/mol, respectively. The positive value of ∆So suggests increased randomness at the solid-solution interface during the adsorption process. The results of this study indicate that the chitosan/zeolite biocomposite beads can be successfully used as an adsorbent for removal of contaminates such as dye or heavy metal from hazardous aqueous solutions. In addition, biopolymers are environmentally friendly materials and their biocomposites with clay is easy to prepare and has low-cost. AUTHOR INFORMATION *

Corresponding author: E-mail address: [email protected]

Tel: +90 364 227 45 33; Fax: +90 364 219 19 38 / 219 19 44

REFERENCES


26


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 28 of 33

(1) Qiu, M.; Qian, C.; Xu, J.; Wu, J.; Wang, G. Studies on the adsorption of dyes into clinoptilolite. Desalination 2009, 243, 286–292. (2) Gòmez, V.; Larrechi, M. S.; Callao, M. P. Kinetic and adsorption study of acid dye removal using activated carbon. Chemosphere 2007, 69, 1151–1158. (3) Chiou, M-S.; Chuang, G-S. Competitive adsorption of dye Metanil Yellow and RB15 in acid solutions on chemically cross-linked chitosan beads. Chemosphere 2006, 62, 731–740. (4) Wong, Y. C.; Szeto, Y. S.; Cheung, W. H.; McKay, G. Equilibrium studies for acid dye adsorption onto chitosan. Langmuir 2003, 19, 7888–7894. (5) Zhu, H-Y.; Jiang, R.; Xiao, L. Adsorption of an anionic azo dye by chitosan/kaolin/γFe2O3 composites. Appl. Clay Sci. 2010, 48, 522–526. (6) Piccin, J. S.; Dotto, G. L.; Vieira, M. L. G.; Pinto, L. A. A. Kinetics and mechanism of the Food Dye FD&C Red 40 adsorption onto chitosan. J. Chem. Eng. Data 2011, 56, 3759–3765. (7) Crini, G. Non-conventional low-cost adsorbents for dye removal: a review. Bioresour. Technol. 2006, 97, 1061–1085. (8) Fu, F.; Gao, Z.; Gao, L.; Li, D. Effective Adsorption of Anionic Dye, Alizarin Red S, from Aqueous Solutions on Activated Clay Modified by Iron Oxide. Ind. Eng. Chem. Res. 2011, 50, 9712–9717. (9) He, Chun; Xijun Hu. Anionic Dye Adsorption on Chemically Modified Ordered Mesoporous Carbons. Ind. Eng. Chem. Res. 2011, 50, 14070–14083. (10) Roy, A.; Chakraborty, S.; Kundu, S. P.; Adhikari, B.;Majumder, S. B. Adsorption of anionic-azo dye from aqueous solution by lignocellulose-biomass jute fibre: Equilibrium, kinetics and thermodynamics study. Ind. Eng. Chem. Res. 2012, 51,12095–12106 (11) Mall, I. D.; Srivastava, V. C.; Agarwal, N. K. Removal of Orange-G and Methyl Violet dyes by adsorption onto bagasse fly ash—kinetic study and equilibrium isotherm analyses. Dyes Pigments 2006, 69, 210–223. (12) Anbia, M.; Salehi, S. Removal of acid dyes from aqueous media by adsorption onto amino-functionalized nanoporous silica SBA-3. Dyes Pigments 2012, 94, 1–9. (13) Gupta, V. K.; Suhas. Application of low-cost adsorbents for dye removal – a review. J. Environ. Manage. 2009, 90. 2313–2342. (14) Sebastiano, R.; Contiello, N.; Senatore, S.; Righetti, P.G.; Citterio, A. Analysis of commercial Acid Black 194 and related dyes by micellar electrokinetic chromatography. Dyes Pigments 2012, 94, 258–265. (15) Hamzeh, Y.; Ashori, A.; Azadeh, E.; Hamzeh, A. A.; Ashori, A.; Azadeh, E.; Abdulkhani, A. Removal of Acid Orange 7 and Remazol Black 5 reactive dyes from aqueous solutions using a novel biosorbent. Mater. Sci. Eng. C 2012, 32, 1394–1400. (16) Chen, C-Y.; Chang, J-C.; Chen, A-H. Competitive biosorption of azo dyes from aqueous solution on the templated crosslinked-chitosan nanoparticles. J. Hazar. Mater. 2011, 185, 430– 441. (17) Kittinaovarat, S.; Kansomwan, P.; Jiratumnukul, N. Chitosan/modified montmorillonite beads and adsorption Reactive Red 120. Appl. Clay Sci. 2010, 48, 87–91. (18) Gibbs, G.; Tobin, J. M.; Guibal, E. Influence of Chitosan preprotonation on Reactive Black 5 Sorption Isotherms and Kinetics. Ind. Eng. Chem. Res. 2004, 43, 1–11. (19) Tirtom, V. N.; Dinçer, A.; Becerik, S.; Aydemir, T.; Comparative adsorption of Ni(II) and Cd (II) ions on epichlorohydrin crosslinked chitosan-clay composite beads in aqueous solution. Chem. Eng. J. 2012, 197, 379–386.


27

Page 29 of 33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(20) Dotto, G. L.; Pinto, L. A. A. Adsorption of food dyes Acid Blue 9 and Food Yellow 3 onto chitosan: Stirring rate effect in kinetics and mechanism. J. Hazar. Mater. 2011, 187, 164– 170. (21) Rosa, S.; Laranjeira, C. M. M.; Riela, H. G.; Fávere, V. T. Cross-linked quaternary chitosan as an adsorbent for the removal of the reactive dye from aqueous solutions. J. Hazar. Mater. 2008, 155, 253–260. (22) Piccin, J. S.; Dotto, G. L.; Vieira, M. L. G.; Pinto, L. A. A. Kinetics and mechanism of Tartrazine adsorption onto chitin and chitosan. Ind. Eng. Chem. Res. 2012, 51, 6862−6868. (23) Armagan, B.; Turan, M.; Celik, M.; Equilibrium studies on the adsorption of reactive azo dyes into zeolite. Desalination 2004, 170, 33–39. (24) Alver, E.; Metin, A.U. Anionic dye removal from aqueous solutions using modified zeolite: Adsorption kinetics and isotherm studies. Chem. Eng. J. 2012, 200-202, 59–67. (25) Karadag, D.; Turan, M.; Akgul, E.; Tok, S.; Faki, A. Adsorption equilibrium and kinetics of Reactive Black 5 and Reactive Red 239 in aqueous solution onto surfactant-modified zeolite. J. Chem. Eng. Data 2007, 52, 1615–1620. (26) Ngah, W. S. W.; Teong, L. C.; Wong, C. S.; Hanafiah, M. A. K. M. Preparation and Characterization of chitosan–zeolite composites. J. Appl. Polym. Sci. 2012, 125, 241–2425. (27) Ngah, W. W. S.; Isa, I. M. Comparision study of Cooper Ion adsorption on chitosan, dowex A-1 and Zerolit 225. J. Appl. Polym. Sci. 1998, 67, 1067–1070. (28) Dragan, E. S.; Dinu, M. V.; Timpu, D.; Preparation and characterization of novel composites on chitosan and clinoptilolite with enhanced adsorption properties for Cu2+. Bioresour. Technol. 2010, 101, 812–817. (29) Jothiramalingam, R.; Lo, S-L.; Phanthi, L-A. Chitosan-Type Bioadditive-Modified Electronic Industry Waste Sludge for Heavy Metal Stabilization with Assistance of Microwave Heating. Ind. Eng. Chem. Res. 2010, 49, 2557–2561 2557. (30) Chang, M-Y.; Juang, R-S. Adsorption of tannic acid, humic acid, and dyes from water using the composite of chitosan and activated clay. J. Colloid Interf. Sci. 2004, 278, 18–25. (31) Dincer, A., Becerik, S., Aydemir, T., Immobilization of tyrosinase on chitosan–clay composite beads. Int. J. Biol. Macromol. 2011, 50, 815–820. (32) An, J-H.; Dultz, S. Adsorption of tannic acid on chitosan-montmorillonite as a function of pH and surface charge properties. Appl. Clay Sci. 2007, 36, 256–264. (33) Futalana, C. M.; Kan, C-C.; Dalida, M. L.; Hsien, K-J.; Pascua, C.; Wan, M-W. Comparative and competitive adsorption of copper, lead, and nickel using chitosan immobilized on bentonite. Carbohydr. Polym. 2011, 83, 528–536. (34) Ngah, W. W. S.; Teong, L. C.; Hanafiah, M. A. K. M. Adsorption of dyes and heavy metal ions by chitosan composites: A review. Carbohydr. Polym. 2011, 83, 1446–1456. (35) Lagergren, S. About the theory of so-called adsorption of soluble substances. Kungliga Svenska Vetenskapsakademiens Handlingar 1898, 24, 1–6. (36) Ho, Y. S.; McKay, G.; Pseudo-second-order model for sorption processes. Process Biochem. 1999, 34, 451–465. (37) Khaled, A.; Nemr, A. E.; El-Sikaily, A.; Abdelwahab, O. Removal of Direct N Blue- 106 from artificial textile dye effluent using activated carbon from orange peel: adsorption isotherm and kinetic studies. J. Hazard. Mater. 2009, 165, 100–110. (38) Nesic, A. R; Velikovic, S. J; Antonovic, D. G. Characterization of chitosan/montmorillonite membranes as adsorbents for Benzactiv Orange V-3R dye. J. Hazard. Mater. 2012, 209-210, 256–263.


28


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 30 of 33

(39) Karge, H. G. Characterization by IR spectroscopy, in: Verified Syntheses of Zeolitic Materials, Elsevier: Amsterdam, 2001, (40) Toor, M.; Jin, B., Adsorption characteristics, isotherm, kinetics, and diffusion of modified natural bentonite for removing diazo dye. Chem. Eng. J. 2012, 187, 79–88. (41) Wong, Y. C.; Szeto, Y. S.; Cheung, W. H.; Mckay, G. Adsorption of acid dyes on chitosan-equilibrium isotherm analyses. Process Biochem. 2004, 39, 693–702. (42) Kumar, P. S.; Ramalingam, S., Senthamarai, C.; Niranjanaa, M.; Vijayalakshmi, P.; Sivanesan, S. Adsorption of dye from aqueous solution by cashew nut shell: Studies on equilibrium isotherm, kinetics and thermodynamics of interactions. Desalination 2010, 261, 52– 60. (43) Vimonses, V.; Lei, S.; Jin, B.; Chow, C. W. K.; Saint, C.; Adsorption of Congo Red by three Australian kaolins. Appl. Clay Sci. 2009, 43, 465–472. (44) Nepradit, S.; Thiravetyan, P.; Towprayoon, S. Adsorption of three azo reactive dyes by metal hydroxide sludge: effect of temperature, pH and electrolytes. J. Colloid Interf. Sci. 2004, 270, 255–261. (45) Baocheng, Q. U.; Jiti, Z.; Xuemin, X.; Chunli, Z.; Hongxia, Z.; Xiaobai, Z. Adsorption behaviour of azo dye C.I. Acid Red 14 in aqueous solution on surface soils. J. Environ. Sci. 2008, 20, 704–709. (46) Nandi, B. K.; Goswami, A.; Purkait, M. K. Adsorption characteristics of Brilliant Green Dye on kaolin. J. Hazard. Mater. 2009, 161, 387–395. (47) Han, X.; Wang, W.; Ma, X. Adsorption characteristics of Methylene Blue onto low cost biomass material lotus leaf. Chem. Eng. J. 2011, 171, 1–8. (48) Bilgili, M. S. Adsorption of 4-chlorophenol from aqueous solutions by xad-4 resin: Isotherm, kinetic, and thermodynamic analysis. J. Hazard. Mater. B 2006, 137, 157–164. (49) Mahmoud, D. K.; Salleha, M. A. M.; Karim, W. A. W. A.; Idris, A.; Abidin, Z. Z.; Batch adsorption of basic dye using acid treated kenaf fibre char: Equilibrium, kinetic and thermodynamic studies. Chem. Eng. J. 2012, 181– 182, 449– 457. (50) Gupta, S.; Babu, B. V. Utilization of waste product (tamarind seeds) for the removal of Cr(VI) from aqueous solutions: Equilibrium, kinetics, and regeneration studies. J. Environ. Manage. 2009, 90, 3013–3022. (51) Rahchamani, J.; Mousavi, H. Z.; Behzad, M. Adsorption of Methyl Violet from aqueous solution by polyacrylamide as an adsorbent: Isotherm and kinetic studies. Desalination 2011, 267, 256–260. (52) Greluk, M.; Hubicki, Z. Kinetics, isotherm and thermodynamic studies of Reactive Black 5 removal by acid acrylic resins. Chem.Eng. J. 2010, 162, 919–926. (53) Yousef, R. I.; El-Eswed, B.; Al-Muhtaseb, A. H.; Adsorption characteristics of natural zeolites as solid adsorbents for phenol removal from aqueous solutions: Kinetics, mechanism and thermodynamics studies. Chem. Eng. J. 2011, 171, 1143–1149. (54) Abdullah, M. A.; Chiang, L.; Nadeem, M. Comparative evaluation of adsorption kinetics and isotherms of a natural product removal by Amberlite polymeric adsorbents. Chem. Eng. J. 2009, 146, 370–376. (55) Mane, V. S.; Mall, I. D.; Srivastava, V.C. Kinetic and equilibrium isotherm studies for the adsorptive removal of Brilliant Green dye from aqueous solution by rice husk ash. J. Environ. Manage. 2007, 84, 390–400.


29

Page 31 of 33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(56) Gupta, S.; Babu, B. V. Removal of toxic metal Cr(VI) from aqueous solutions using sawdust as adsorbent: Equilibrium, kinetics and regeneration studies. Chem. Eng. J. 2009, 150, 352–365. (57) Almeida, C. A. P.; Debacher, N. A.; Downs, A. J.; Cottet, L.; Mello, C. A. D. Removal of methylene blue from colored effluents by adsorption on montmorillonite clay. J. Colloid Interf. Sci. 2009, 332, 46–53. (58) Doğan, M.; Alkan, M.; Türkyılmaz, A.; Özdemir, Y. Kinetics and mechamism of removal of methylene blue by adsorption onto perlite. J. Hazar. Mater. 2004, B109, 141–148. (59) Wang, L.; Zhang, J.; Zhao, R.; Li, C.; Li, Y.; Zhang, C. L. Adsorption of basic dyes on activated carbon prepared from Polygonum orientale Linn: equilibrium, kinetic and thermodynamic studies. Desalination 2010, 254, 68–74. (60) Errais, E.; Duplay, J.; Darragi, F.; M'Rabet, I.; Aubert, A.; Huber, F.; Morvan, G. Efficient anionic dye adsorption on natural untreated clay: Kinetic study and thermodynamic parameters, Desalination 2011, 275, 74–81. (61) Raymon C.; Chemistry, McGraw-Hill, Boston. 1998.


30


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 32 of 33

Figure Captions: Fig.1. Schematic presentation of the preparation of the chitosan/zeolite biocomposite beads Fig.2. FTIR spectra of crosslinked chitosan (a) and crosslinked chitosan/zeolite biocomposite with amount of zeolite of 1% (b) Fig.3. TG curves of chitosan and chitosan zeolite biocomposites. The zeolite content in biocomposite 2.0% (a), 4.0% (b) Fig.4A. SEM images of chitosan beads (I, II) SEM images and EDX spectra of chitosan/zeolite biocomposite beads (III, IV and V) Fig. 4B. Inverted microscope images of chitosan/zeolite biocomposites (I) and AB194 loaded chitosan/zeolite biocomposite beads (II); SEM image of AB194 adsorbed chitosan/zeolite biocomposites (III) Fig.5. Effect of initial solution pH on AB194 adsorption (initial AB194 concentration: 1000 mg/L adsorbent dosage: 5 g wet bead/L, adsorption time: 4 h, temperature: 22oC). Fig.6. AB194 adsorption on chitosan/zeolite biocomposite beads as a function of zeolite content loaded in the chitosan/zeolite biocomposite (pH: 3.0, initial AB194 concentration: 1000 mg/L, adsorbent dosage: 5 g wet bead/L, adsorption time: 4 h, temperature: 22oC). Fig.7. Effect of ionic strength on AB194 adsorption (pH: 3.0, initial AB194 concentration: 1000 mg/L, adsorbent dosage: 5 g wet bead/L, adsorption time: 4 h, temperature: 22oC). Fig.8. Effect of adsorbent dosage on the adsorption of AB194 (pH: 3.0, initial dye concentration: 2000 mg/L, temperature: 22oC, contact time: 4h). Fig.9. Effect of initial dye concentration on the adsorption of AB194 (pH: 3.0, adsorbent dosage: 5 g wet bead/L, temperature: 22oC). Fig.10. Pseudo-second order kinetic equation for adsorption of AB194 on zeolite/chitosan biocomposite at 22oC. Fig.11. Intra particle diffusion model for adsorption of AB194 on zeolite/chitosan biocomposite at 22oC. Fig.12. Effect of temperature on the adsorption of AB194 (pH: 3.0, initial dye concentration: 500 mg/L, adsorbent dosage: 5 g wet bead/L). Fig.13. Plot of ln K versus T-1: estimation of thermodynamic parameters for the adsorption of AB194 onto chitosan/zeolite biocomposites (pH: 3.0, initial dye concentration: 500 mg/L, adsorbent dosage: 5 g wet bead/L). Scheme 1. Schematic presentation of the possible interactions between dye molecules and biocomposite


31

Page 33 of 33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Table Captions

Table 1. Calculated kinetic parameters for pseudo first-order, second-order and Weber Morris intra-particle diffusion models for the adsorption of AB194 using chitosan/zeolite biocomposite as an adsorbent ( T: 22 oC, adsorbent dosage: 5 g/L). Table 2. Isotherm constants and regression coefficient of determination at different temperatures for various adsorption isotherms for the adsorption of AB194 onto chitosan/zeolite biocomposite beads (pH: 3.0, adsorbent dosage: 5 g/L, initial dye concentration: 500-4000 mg/L).


32

Efficient Removal of Acidic Dye Using Low-Cost Biocomposite Beads

Recommend Documents