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Preparation and application of grafted Holarrhena antidycentrica fiber as cation exchanger for adsorption of dye from aqueous solution
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JECE 580 1–9 Journal of Environmental Chemical Engineering xxx (2015) xxx–xxx
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Preparation and application of grafted Holarrhena antidycentrica fiber as cation exchanger for adsorption of dye from aqueous solution
3 Q1
Balbir Singh Kaith a, * , Jitender Dhiman a , Jaspreet Kaur Bhatia b
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a b
Department of Chemistry, B.R. Ambedkar National Institute of Technology, Jalandhar, Punjab 144011, India Department of Chemistry, Lyallpur Khalsa College, Jalandhar, Punjab 144001, India
A R T I C L E I N F O
A B S T R A C T
Article history: Received 14 August 2014 Received in revised form 23 February 2015 Accepted 3 March 2015
Present investigation deals with the removal of methylene blue from waste water using Holarrhena antidycentrica cellulose based cation-exchanger. Initially hydroxyethylmethacrylate was graft copolymerized onto H. antidycentrica cellulose and was converted into cation exchanger through phosphorylation. On optimization of different reaction parameters maximum graft yield obtained was 632.0%. Characterization of the synthesized samples was done by FTIR, SEM–EDX and XRD techniques. Thermal stability of samples was investigated through TGA/DTA/DTG techniques. Dye removal study was done in terms of contact time, initial concentration of dye and dose of cation exchanger. Ion-exchanger was found to be highly efficient for removal of methylene blue with maximum removal of 85%. The results showed that ion exchanger could be employed as effective and low cost ecofriendly material for removal of dyes and color from aqueous solution. ã 2015 Published by Elsevier Ltd.
Keywords: Cation exchanger Methylene blue Dye removal Graft copolymerization Thermal stability
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Introduction
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Mankind has used dyes for thousands of years. Synthetic dyes are extensively used in different fields like paper industries, food industries, leather industries, agriculture research, ground water tracing and many more. There are more than 100,000 commercial dyes used for different applications having estimated production of 7 105–1 106 t year1 [1]. Extensive application of synthetic dyes can cause considerable environmental pollution and are dangerous to the health of living organisms due to their toxic, mutagenic, allergic and carcinogenic nature. High volumetric discharge of these toxic products makes it necessary to develop various technologies for the effective removal of dyes from wastewater. Different technologies and processes like biological treatments [2], chemical and electrochemical techniques [3], membrane processes [4], advanced oxidation processes [5], and adsorption procedures [6–8] are widely used for removing dyes from industrial waste. Each method has own set of advantages and disadvantages when used for different applications. Removal of contaminants by adsorption using sorbents is one of the most popular methods
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Abbreviations: HaC, Holarrhena antidycentrica cellulose fiber; HaC-g-poly (HEMA), Holarrhena antidycentrica cellulose graft poly(HEMA); HaC-g-poly (HEMA)-IE, Holarrhena antidycentrica cellulose graft poly(HEMA)ion exchanger. * Corresponding author. Tel.: +91 1812690301x2201, 2205; fax: +91 812690320. E-mail address: [email protected] (B.S. Kaith).
as this method shows high removal efficiency as well as offers potentially economical and ecological way for water decontamination [9]. Adsorption is a well-known equilibrium separation process in which adsorbents used may be of mineral, organic or biological origin. Silica beads [10], activated carbons [11,12], clays [13], agricultural wastes [14] and polymeric materials [15] are well developed for removal of dyes from water. Recently, there is renewed research interest in development of cheaper and effective adsorbents based on natural polymers to replace costly materials and processes. Natural polymers, particularly, polysaccharides represent promising candidates as adsorbents due to their particular structure, chemical stability and high reactivity as well as selectivity towards aromatic compounds owing to presence of reactive functional groups like hydroxyl, amino and carboxyl in polymer chains, fast adsorption kinetics and appealing diffusion properties. Moreover, polysaccharides are preferred due to their abundance availability, renewability and biodegradability. Different polysaccharides such as chitin, starch, cyclodextrin and their derivatives have been studied as adsorbents for dye removal from waste water [16–18]. Adsorption capacities of natural polymers can be enhanced by different chemical modifications out of which graft copolymerization of different functional groups onto polymer backbone is promising one. Grafted cellulosic fibers have good selectivity, favorable physicochemical stability, adjustable functionality, enhanced surface area porosity and structural diversity. Moreover, graft copolymerization increases the density of adsorption sites
http://dx.doi.org/10.1016/j.jece.2015.03.001 2213-3437/ ã 2015 Published by Elsevier Ltd.
Please cite this article in press as: B.S. Kaith, et al., Preparation and application of grafted Holarrhena antidycentrica fiber as cation exchanger for adsorption of dye from aqueous solution, J. Environ. Chem. Eng. (2015), http://dx.doi.org/10.1016/j.jece.2015.03.001
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Fig. 1. Structure of methylene blue. 52
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and thereby sorption selectivity for the target metal and dyes. Graft copolymerization of carboxyl, hydroxyl, ammine and sulphur compounds has been reported on different natural backbones [19–23]. Methylene blue (MB) is a heterocyclic aromatic organic compound (Fig. 1). It has been used widely in different fields of biology and chemistry. MB is one of the highly used dyes in printing industries as stabilizer and as indicator in chemical analysis. Present investigation deals with development of novel cationexchanger by graft copolymerization and phosphorylation of Holarrhena antidycentrica cellulose (HaC) fiber for removal of methylene blue from aqueous solution. Graft copolymer of cellulosic fiber was developed using hydroxyethylmethacrylate as monomer through free radical polymerization. Graft copolymer and cation exchanger was characterized by FTIR, SEM–EDX and XRD studies. Thermal stability was investigated by TGA/DTA/DTG. Utility of cation- exchange was studied for removal of methylene blue from aqueous solution.
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Experimental
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Material and methods
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Holarrhena antidycentrica (Ha) fiber was collected from the hilly region of district Kangra, Himachal Pradesh, India. Fiber was purified through soxhlet extraction in acetone for 72 h. Hydroxyethyl methacrylate (HEMA, SD Fine Chemicals) was purified by vacuum distillation at 0.5 mm of Hg at 85 C. Ferrous ammonium sulphate (FAS) was purchased from SD Fine Chemicals and recrystallized from hot water. Potassium persulphate (KPS, SD Fine Chemicals) was used as received. Phosphorous oxychloride and methylene chloride used were of analytical grade. Methylene blue was supplied by E-Merk Chemicals.
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Extraction of cellulose from the H. antidycentrica fiber
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H. antidycentrica fiber was defatted by refluxing in acetone for 72 h. Fiber was crushed and digested with sodium chloride maintaining fiber to liquid ratio of 1:1.50 for 4 h at 65 C. pH of solution was lowered to 4.0 by adding acetic acid. Fiber was repeatedly washed with water to ensure removal of lignin and water soluble organic components. The resulting fiber was treated with 5% sodium bisulphite solution. Finally, washing was done with water and dried in oven at low temperature (45 C) to ensure the moisture content of 5–10% (Eq. (2)) [24].
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Graft copolymerization
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The Holarrhena antidycentrica cellulose fiber (HaC) was activated by immersing 0.5 g of fiber in 100 mL of distilled water for 24 h. A definite molar ratio of initiator FAS-KPS was added and reaction was carried out at definite temperature for specific period of time. Homo-polymer was removed by extraction with DMF. Graft copolymer was dried at 50 C to get constant weight. Percentage graft yield (Pg) was calculated as per the method reported elsewhere (Eq. (3)) [25].
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Synthesis of ion exchanger [HaC-g-poly(HEMA)-IE]
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Ion exchanger was prepared by phosphorylation of HaC-g-poly (HEMA) with phosphooxy chloride in pyridine. The reaction was performed by refluxing reaction mixture at 115 C for 2 h. Product obtained was repeatedly washed with water, 0.1 N HCl and methanol to remove traces of pyridine and was dried in hot air oven. The exchanger was converted into H+ form by treating with 1 mole HNO3 for 24 h with occasional shaking and intermittently replacing the supernatant solution with fresh acid. The excess of the acid was removed after several washing with DMW. The particle size of the range (125 mm) was obtained by sieving (Eq. (3)) [26].
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Ion exchange capacity of cation exchanger Ion exchange capacity of HaC-g-poly(HEMA)-PO42-2 H+ was determined with respect to different alkali and alkaline earth metal ions. Glass column having an internal diameter (i.d.) 1 cm was fitted with glass wool support at the bottom. The bed length was approximately of 1.50 cm. 1.0 g of ion-exchanger was equilibrated with 1.0 mol dm3 solution of different alkali and alkaline earth metal chlorides. Flow rate was maintained at 0.5 mL min1 and effluent was titrated against standard 0.1 mol dm3 NaOH solution using phenolphthalein indicator [27].
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Characterization
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FTIR spectra were recorded with Agilent Carry 630 Fourier transform infrared (FTIR) spectrometer with resolution 8 cm1 with sample scans 32 using KBr pellets. SEM–EDX studied of HaC, graft copolymer and cation-exchanger was carried out using FEI Quanta 200 microscope for morphological and elemental analysis of the samples. TGA, DTA and DTG studies were carried-out in the temperature range of 50 –700 C at a heating rate of 10 C min1 on TG/DTA 6300, SII EXSTAR 6000. Crystalline studies of the samples were performed on X-ray diffraction instrument (Bruker D8, USA) under ambient conditions using Cu-Ka (1.5418 Å).
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Dye adsorption studies of cation exchanger
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Adsorption studies were carried-out using 50 mL of methylene blue solution maintained at a constant temperature to study the effect of initial concentration of dye, contact time and dose of the cation exchanger. Experiments were performed at concentrations of 2, 4, 6, 8 and 10 mg L1 of dye using 100–600 mg of cation exchanger at 7.0 pH and 25 C temperature to attain equilibrium. The extent of adsorption was determined at different time intervals during adsorption process. Each experiment was repeated three times. Dye concentration was determined by UV spectrophotometer at lmax 664 cm1. The calibration curve was plotted in order to calibrate the instrument to find-out the concentration of unknown samples. Percentage of dye removal was calculated using the Eq. (1) [28]: ðC 0 C eq Þ (1) 100 %Dye removal ¼ C eq
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103 104 105 106 107 108 109 110 111 112
114 115 116 117 118 119 120 121 122
125 126 127 128 129 130 131 132 133
136 137 138 139 140 141 142 143 144 145
Q2 146 147
where C0 and Ceq are the initial and equilibrium concentration of dye in mg L1.
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Results and discussion
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Graft copolymerization
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Reaction parameters were found to play a significant role to achieve the maximum graft yield. Maximum grafting was achieved by optimizing different reaction conditions such as reaction
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temperature, time, initiator concentration, monomer concentration and pH. Optimum conditions obtained for maximum graft
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copolymerization and further conversion into cation exchanger can be represented by the Eqs. (2) and (3):
196 197
(2)
(3)
158 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173 174 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 194 195
percentage (632.0%) were: 60 min (reaction time), 60 C (reaction temperature), 1:1.25 (initiator ratio), 50 mL (solvent amount), 7 (pH of medium) and 8.24 104 mol L1 (monomer concentration) (Table 1). Initially with increase in reaction parameters like reaction temperature, reaction time and pH of medium Pg was found to increase up to critical limit. Initial increase in Pg was attributed to more extensive generation of free radical sites which is due to greater interaction of OH and SO42 radicals with backbone as well as monomer. Increase in temperature enhanced the activation energy as well as swelling extent of fiber in solvent which led to the easy diffusion of monomer from solution phase to active site of fiber. After optimum reaction conditions decrease in Pg was observed due to predominance of homopolymerization over graft copolymerization. Acidic and basic conditions of medium also decline graft yield due to premature termination of graft chains and deactivation of primary free radicals like OH and SO42 [29]. Amount of different reaction components like initiators, monomer and solvent play significant role towards extent of graft copolymerization. Initially Pg was found to increase with increase in molar ratio of KPS:FAS, up to critical ratio (1:1.25) which was tend to decreased with increase in molar ratio. Interaction of FAS and KPS generated Fe3+ along with generation of SO4 ions, that increased the graft yield. However, increase in Fe3+ ion concentration attacked growing graft copolymer chain and terminated the reaction with reduction of Fe3+ ions to Fe2+ and resulted in decreased Pg. In diluted solution concentration of free radical per unit volume decreased which slow down the interaction of free radicals with backbone and monomer moiety. Initial increase in monomer concentration led to the accumulation of monomer free radicals in a close proximity to the backbone and gave rise to high graft yield. However, at higher monomer concentration, the primary radicals attacked the monomer instead of reacting with the backbone and thus initiated homo-polymerization reaction which resulted in low Pg [30]. Grafting of poly(2-hydroxy ethylmethacrylate) chains took place over the backbone on the —OH and —CH2 groups which are the active sites for chemical modifications. Mechanism for graft
Ion-exchange capacity
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Table 2 showed ion-exchange capacity of cation-exchanger for alkali and alkaline earth metal ions. The maximum ion-exchange capacity was found to be 1.50 mmol g1 for K+ ions and 1.46 for Na+ ions. The affinity sequence for alkali metal ions was K+ > Na+ > Li+, whereas, alkaline earth metals showed affinity sequence Sr2+ > Ca2 + > Mg2+. Ion-exchange capacity order is in accordance with size of hydrated radii of exchanging ions. Ions with smaller hydrated ionic radii can easily enter the pores of ion-exchanger which results in greater ion-exchange capacity [31].
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Fourier transform-infrared (FT-IR)
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FTIR spectra of HaC, HaC-g-poly(HEMA) and phosphate cationexchanger are shown in Fig. 2. HaC fiber showed a broad peak at 3319.4 cm1 due to the presence of free —OH, at 2928.9 and 1024.5 cm1 due to C—H and C—O stretching, respectively (Fig. 2a). HaC-g-poly(HEMA) exhibited additional peak at 1704.4 cm1 due to presence of C¼O which confirmed the grafting of HEMA onto fiber. Grafted fiber also showed decrease in the intensity of peak due to free —OH (3363.2 cm1) it revealed involvement of —OH in graft copolymerization (Fig. 2b). FTIR spectra of phosphate ionexchanger exhibited peak at 1143.2 cm1 due to presence of P¼O (Fig. 2c). Intensity of free —OH decreased to large extent which showed that phosphorylation involved —OH of graft copolymer [32,33]. However, after the adsorption of MB dye on cation exchanger additional peaks were observed at 829.3 cm1 due to C— H bending vibrations in heterocycle and 1635.6 cm1 due to ¼N+ ammonium band; bending vibrations of OH groups included in a hydrogen bond [34–36].
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SEM and energy-dispersive X-ray (EDX) studies
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EDX analysis confirmed the successful grafting of HEMA onto HaC fiber. HaC fiber showed presence of carbon and oxygen in atomic percentage of 52.97 and 47.03% as fiber is lignocellulosic
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Table 1 Optimized reaction conditions of MHa-g-poly(HEMA).
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Sr. no.
Initiator ratio (mol: mol)
Monomer (HEMA) 104 (mol L1)
Reaction temperature ( C)
Reaction time (min)
Solvent (mL)
pH of reaction medium
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
(1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (0.25:1) (0.5:1) (0.75:1) (1:1) (1.25:1) (1.50:1) (1.250:1) (1.250:1) (1.250:1) (1.250:1) (1.250:1) (1.250:1) (1.250:1) (1.250:1) (1.250:1) (1.250:1)
6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 2.47 3.71 4.95 6.18 7.42 6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 2.06 4.12 6.18 8.24 10.3
60 60 60 60 60 30 40 50 60 70 80 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60
60 90 120 150 180 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150
50 50 50 50 50 50 50 50 50 50 50 20 30 40 50 60 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50
7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 2.0 4.0 6.0 8.0 10.0 7.0 7.0 7.0 7.0 7.0
% Grafting
Mean ( SD) ( SE) 210.6 252.2 284.5 335.6 134.9 48.0 284.0 309.8 335.6 196.3 57.7 267.0 404.2 418.7 426.1 407.6 243.5 270.1 337.2 344.7 489.0 373.7 102.6 362.0 403.7 368.6 73.5 47.3 94.4 398.3 632.0 592.1
1.3578 2.4668 1.496 2.4635 3.3457 2.7548 3.5487 4.8752 3.5679 3.2367 4.5237 5.3789 5.4735 4.2367 3.4521 4.5243 3.1764 1.4658 2.489 3.9863 2.5765 4.2869 3.5619 2.1376 2.5619 2.6891 3.2879 2.5315 3.2167 2.9402 1.8431 1.5648
0.784855 1.425896 0.86474 1.423988 1.933931 1.59237 2.051272 2.818035 2.06237 1.870925 2.614855 3.109191 3.163873 2.44896 1.995434 2.615202 1.836069 0.847283 1.438728 2.30422 1.489306 2.477977 2.058902 1.235607 1.480867 1.554393 1.90052 1.463295 1.859364 1.699538 1.065376 0.904509
Number of replications: 3; initial weight of each sample: 0.5 g. 230
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material containing carbon backbone (Fig. 3a). SEM images of fiber revealed continuous morphology with homogeneous surface. EDX of HaC-g-poly(HEMA) with 58.45% carbon content showed that carbon content has been increased on graft copolymerization. Moreover, increase in heterogeneity was revealed by rough surface shown in SEM image (Fig. 3b). It confirmed the incorporation of poly(HEMA) chains onto HaC backbone. SEM of cation-exchanger observed high degree of heterogeneity as compare to graft copolymer and EDX analysis indicated presence of phosphorous along with carbon and oxygen. It revealed the presence of PO43 group in the cation-exchanger (Fig. 3c).
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X-ray diffraction
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Fig. 4 exhibited XRD patterns of HaC fiber, graft copolymer and cation-exchanger. XRD pattern of HaC fiber showed sharp peak at 22 with 796 counts (Fig. 4a). % Crystallinity of fiber has been found to be 50.1%. On the other hand XRD pattern of graft copolymer (Fig. 4b) and phosphate cation-exchanger (Fig. 4c) showed broad peak at 18.2 and 19.5 on 2u scale with 658 and 554 counts, having
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Table 2 Ion-exchange capacity of various exchanging ions on phosphate cation-exchanger. Exchanging ions +
Li Na+ K+ Mg2+ Ca2+ Sr2+
pH 6.70 6.70 6.80 6.50 6.50 6.30
Ionic radii Hydrated ionic radii Ion-exchange capacity (Å) (Å) (mmol g1) 0.68 0.97 1.33 0.78 1.06 1.27
3.40 2.76 2.32 7.00 6.30 –
1.06 1.46 1.50 1.04 1.14 1.18
% crystallinity of 35.04 and 31.96%, respectively. It indicated the amorphous nature of graft copolymer and phosphate cation exchanger. Incorporation of monomer moiety and phosphate group impaired natural crystallinity of fiber and enhanced the amorphous nature of fiber. Low crystallinity of graft copolymer and ion exchanger indicated poor order of crystal lattice in fiber. This decrease in crystallinity was due mis-orientation of fiber axis in crystal lattice of graft copolymer and cation-exchanger.
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Thermal studies
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TGA of ungrafted fiber, grafted fiber and ion-exchanger was studied as a function of percentage weight loss with temperature. Dehydration, glycogen formation and depolymerization are the different processes involved during degradation of HaC-fiber. HaC showed two stages of thermal degradation in the temperature range of 227.9–339.7 C with 58.2% weight loss and in the range of 339.7–495.9 C with 30.6% weight loss (Sup Fig. 1). The first stage corresponds to loss of weight by dehydration and volatilization process whereas weight loss in later stage is due to loss by depolymerization. Hac-g-poly(HEMA) showed degradation in temperature range of 213.2–305.3 C with 58.1% weight loss and 305.2–423.1 C with 128.8% weight loss (Sup Fig. 2). It has been observed that IDT and FDT of grafted fiber were lower than that of unmodified fiber. Lower IDT of grafted fiber indicated early decomposition of grafted poly(HEMA) chains. Thermal analysis was done by taking decomposition temperature at every 20% weight loss (Table 3). It has been further observed that temperature difference of ungrafted fiber up to 40% and 60% weight loss were 47.9 and 22 , respectively. After 60% weight loss this difference has been increased to 70 which indicated the formation
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Fig. 2. FT-IR spectra of (a) HaC (Holarrhena antidysenterica cellulose), (b) HAC-g-poly(HEMA), (c) phosphate ion-exchanger of graft copolymer.
277 278 279 280 281 282 283 284 285 286 287
of glycogen. In case of grafted fiber, temperature difference up to 40% weight loss was less (10 ) whereas after 40% weight loss temperature difference for every 20% weight loss has been found to be very high, beyond 40% temperature difference lie between 50 and 80 C. These observations indicated that fiber on grafting attained stability towards increasing temperature. DTA studies have been found to support the TGA data. In case of backbone the exothermic peaks were found at 310.4 C and 445.6 C with 25.8 and 20.6 mV energy release, respectively. Whereas, the exothermic peaks observed with grafted sample were found at 280.3 C and 410.5 C with energy release of 16.7 and 32.5 mV,
5
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respectively. In case of backbone DTG studies showed the rate of weight loss 0.287 and 0.100 mg min1 at temperatures 300.4 C and 445.6 C, respectively. However, the grafted sample showed rate of weight loss 0.316, 0.427 and 0.142 mg min1 at temperatures 223.1, 269.8 and 399.2 C, respectively [37,38]. TGA studies of phosphorylated ion-exchanger revealed two stage decomposition in temperature range of 274.4–340.5 C with 49.4% weight loss and 340.5–627.3 C with weight loss of 30.5% Q4 (Sup Fig. 3). Ion exchanger showed high IDT and FDT as compared to unmodified and grafted fiber. Moreover, temperature difference for every 20% weight loss indicated slow decomposition up to 40%
Fig. 3. a–a1 to c–c1: SEM–EDX of (a–a1) HaC-fiber, (b–b1) HaC-g-poly(HEMA), (c–c1) phosphate cation-exchanger.
Please cite this article in press as: B.S. Kaith, et al., Preparation and application of grafted Holarrhena antidycentrica fiber as cation exchanger for adsorption of dye from aqueous solution, J. Environ. Chem. Eng. (2015), http://dx.doi.org/10.1016/j.jece.2015.03.001
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Fig. 4. XRD pattern of (a) HaC-fiber, (b) HaC-g-poly(HEMA), (c) cation-exchanger. 299 300 301 302 303 304 305 306 307 308 309 310
and after 60% weight loss. However, temperature difference between 40 and 60% weight loss was found to be less which indicated region of depolymerization. In case of DTA of cation exchanger the exothermic peaks were found at 335.3 C and 490.1 C with 28.9 and 14.4 mV energy release, respectively [39,40]. DTG studies also indicated this region as region of fast decomposition (0.518 mg min1 at 308 C) whereas at the low temperature the rate of degradation was found to be less i.e., 0.190 mg min1 at 246.6 C. It showed that incorporation of PO43 group enhanced thermal stability of fiber. Higher thermal stability of ion-exchanger was further supported by higher residue percentage (12%) after final decomposition temperature [41–43].
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Dye adsorption studies
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Cation exchanger synthesized was found to remove effectively the methylene blue from aqueous solution and 85% of dye removal was observed. The dye sorption could be due to the electrostatic interaction between PO32 group of HaC-g-poly(HEMA)-PO322H+ and MB = N+(CH3)2 groups of MB (Eq. (4)). Further it could be explained on the basis of cation-cation exchange with the effective removal of MB = N+(CH3)2 from the aqueous medium and release of H+ ions (Eq. (5)). Mechanism of the dye sorption is presented by the Eqs. (4) and (5) [44–48].
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Cation exchange takes place through the exchange of MB = N+(CH3)2 with H+ ions resulting in the removal of dye from the aqueous solution and release of H+ ions. The effectiveness of cation-exchanger as adsorbent for MB has been studied as a function of contact time. When dye comes in contact with adsorbent its diffusion on adsorbent and ultimately adsorption on adsorbent is a time dependent process. The concentration of MB was found to decrease with the increase in contact time. With time, adsorption takes place in three phases. Initial phase showed sharp slope of adsorption curve from 0–30 min (Fig. 5a). Second phase showed slow uptake of dye on adsorbent which ultimately led to final phase of approximately constant adsorption. Initial uptake involved diffusion of dye on adsorbent which is a fast process. The phase of fast uptake of dye also contributed to presence of large number of vacant reactive sites. After initial phase of adsorption availability of reactive site decreased and resulted in slow adsorption. This phase of slow adsorption attributed to intraparticle diffusion which is a slow process. Finally, diffusion occurred through small pores of adsorbent led to equilibrium between adsorbate and adsorbent. Thus, saturation of different reaction sites of cation-exchanger resulted in constant slope of curve. Saturation was attained within 75 min (2 mg L1), 105 min (4 mg L1), 180 min (6 mg L1), 240 min (8 mg L1) and 255 min (10 mg L1). At 4 mg L1 rate of dye removal increased from 65 to 85% of maximum adsorption within 105 min [49–52].
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Effect of initial concentration of dye Initial concentration of dye is one of the important parameter which effect rate of adsorption of dye on adsorbent. The effect of initial concentration of MB was studied at different concentrations of 2, 4, 6, 8 and 10 mg L1 with fixed amount of cation-exchanger (500 mg/50 mL of MB) and contact time 255 min. Fig. 5b depicted that rate of dye removal increased from 75 to 85% with initial increase in dye concentration from 2 to 4 mg L1. Further increase in dye concentration from 4 to 10 mg L1 decreased the rate of dye removal from 85 to 71%. Initially with the increase in dye concentration rate of adsorption increased due to increase in electrostatic interaction of dye with adsorbent. However, further
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350 351 352 353 354 355 356 357 358 359 360
(4)
þ þ HaC g polyðHEMAÞPO2 4 2H þ MB 2 þ ! HaC g polyðHEMAÞPO4 2MB þ 2Hþ
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(5)
Effect of the time on removal of dye The removal of dye through cation exchanger takes place by two processes i.e., cation exchange (Eq. (5)) and adsorption (Eq. (4)).
increase in dye concentration resulted in decreased electrostatic interactions between the adsorbent and dye. This was due to predominance of electrostatic repulsions over electrostatic attractions at higher dye concentration. Thus, cation–cation repulsion became dominate over cation–anion attraction thereby resulting in lesser removal of dye from waste water at concentration beyond 4 mg L1. Thus, the available active sites of adsorbent for the removal of dye molecules became limiting factor and at low
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Table 3 Results of HaC, HaC-g-poly(HEMA) and cation exchanger from TGA/DTA/DTG. Sample code
TGA IDT ( C)
FDT ( C)
DT at every 20% weight loss Residue (%) (%) 20
40
HaC fiber
227.9
627.3
250.1
298.0 320.1
HaC-g-poly (HEMA)
213.2
423.1
230.2 240.1
290.0 365.2 39
Cation-exchange resin
274.4
495.5
275
355.5 530.1
320
60
DTA
DTG
Exothermic peaks at different temperature, ( C) (mV)
Rate of weight loss (mg min1) at different temp ( C)
310.4 (25.8) 445.6 (20.6) 280.3 (16.7) 410.5 (32.5)
0.287 (300.4) 0.100 (445.6) 0.316 (223.1) 0.427 (269.8) 0.142 (399.2) 0.190 (246.6) 0.518 (308.0)
80 390.0
0.5
12
335.3 (28.9) 490.1 (14.4)
IDT: initial decomposition temperature; FDT: final decomposition temperature; DT: decomposition temperature.
Fig. 5. Effect of (a) contact time, (b) initial concentration of dye, (c) dose of cation exchanger on % dye removal.
369 370 371 372 373 374 375 376 377 Q5 378 379 380 381 382
concentration molecules of dye had more chances to interact with adsorbent which could enhance the rate of adsorption [53,54]. Effect of adsorbent dose The effect of cation exchanger dose on dye adsorption was studied by varying the amount of adsorbent from 100 to 600 mg/ 50 mL of dye solution while keeping other parameters like initial concentration of dye (4 mg L1) and contact time constant (Fig. 5c). The percentage of dye removal was found to increase with the increase in adsorbent dose from 100 to 500 mg/50 mL of MB dye solution. Further increase in adsorbent dose decreased the rate of dye removal. As adsorbent dose increased from 100–500 mg/50 mL of dye solution availability of reaction sites increased which enhanced the percentage of adsorption of dye from 47.5 to 85%, respectively. Afterward decreased rate of adsorption attributed to
aggregation of adsorption sites which decreased the surface area of adsorbent available to dye and increased the diffusion path length. As a result increase in dose of cation exchanger above equilibrium amount declined the rate of removal of dye. Moreover, time required to reach equilibrium also increased with increase in dose of adsorbent [55–57].
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Conclusion
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Virgin HaC fiber cellulose was converted into HaC-g-poly (HEMA) graft copolymer and graft yield obtained was 632%. Phosphorylation of grafted cellulose yielded cation exchanger with high thermal stability. FTIR and SEM–EDX studies confirmed the formation of cation exchanger. XRD data revealed decrease in % crystallinity on graft copolymerization and phosphorylation due to
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disturbance in crystal lattice on incorporation of poly(HEMA) chains and phosphate groups. Synthesized cation exchanger was found to be an effective adsorbent for removal of dye from aqueous medium. Adsorption of dye on cation exchanger was found to increase with increase in contact time, initial concentration of dye and dose of cation exchanger. Equilibrium was achieved after 105 min at concentration of 4 mg L1 and cation exchanger dose of 500 mg. Thus, synthesized cation exchanger was found to be an efficient and cost effective adsorbent for removal of methylene blue from waste water.
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Acknowledgements
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Authors are highly grateful to DST-FIST New Delhi for providing financial assistance in procuring the FTIR and UV–vis spectrophotometer which were used for the analysis of the samples.
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Appendix A. Supplementary data
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Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.jece.2015.03.001.
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References
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Contents lists available at ScienceDirect
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1 2
Preparation and application of grafted Holarrhena antidycentrica fiber as cation exchanger for adsorption of dye from aqueous solution
3 Q1
Balbir Singh Kaith a, * , Jitender Dhiman a , Jaspreet Kaur Bhatia b
4 5
a b
Department of Chemistry, B.R. Ambedkar National Institute of Technology, Jalandhar, Punjab 144011, India Department of Chemistry, Lyallpur Khalsa College, Jalandhar, Punjab 144001, India
A R T I C L E I N F O
A B S T R A C T
Article history: Received 14 August 2014 Received in revised form 23 February 2015 Accepted 3 March 2015
Present investigation deals with the removal of methylene blue from waste water using Holarrhena antidycentrica cellulose based cation-exchanger. Initially hydroxyethylmethacrylate was graft copolymerized onto H. antidycentrica cellulose and was converted into cation exchanger through phosphorylation. On optimization of different reaction parameters maximum graft yield obtained was 632.0%. Characterization of the synthesized samples was done by FTIR, SEM–EDX and XRD techniques. Thermal stability of samples was investigated through TGA/DTA/DTG techniques. Dye removal study was done in terms of contact time, initial concentration of dye and dose of cation exchanger. Ion-exchanger was found to be highly efficient for removal of methylene blue with maximum removal of 85%. The results showed that ion exchanger could be employed as effective and low cost ecofriendly material for removal of dyes and color from aqueous solution. ã 2015 Published by Elsevier Ltd.
Keywords: Cation exchanger Methylene blue Dye removal Graft copolymerization Thermal stability
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Introduction
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Mankind has used dyes for thousands of years. Synthetic dyes are extensively used in different fields like paper industries, food industries, leather industries, agriculture research, ground water tracing and many more. There are more than 100,000 commercial dyes used for different applications having estimated production of 7 105–1 106 t year1 [1]. Extensive application of synthetic dyes can cause considerable environmental pollution and are dangerous to the health of living organisms due to their toxic, mutagenic, allergic and carcinogenic nature. High volumetric discharge of these toxic products makes it necessary to develop various technologies for the effective removal of dyes from wastewater. Different technologies and processes like biological treatments [2], chemical and electrochemical techniques [3], membrane processes [4], advanced oxidation processes [5], and adsorption procedures [6–8] are widely used for removing dyes from industrial waste. Each method has own set of advantages and disadvantages when used for different applications. Removal of contaminants by adsorption using sorbents is one of the most popular methods
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Abbreviations: HaC, Holarrhena antidycentrica cellulose fiber; HaC-g-poly (HEMA), Holarrhena antidycentrica cellulose graft poly(HEMA); HaC-g-poly (HEMA)-IE, Holarrhena antidycentrica cellulose graft poly(HEMA)ion exchanger. * Corresponding author. Tel.: +91 1812690301x2201, 2205; fax: +91 812690320. E-mail address: [email protected] (B.S. Kaith).
as this method shows high removal efficiency as well as offers potentially economical and ecological way for water decontamination [9]. Adsorption is a well-known equilibrium separation process in which adsorbents used may be of mineral, organic or biological origin. Silica beads [10], activated carbons [11,12], clays [13], agricultural wastes [14] and polymeric materials [15] are well developed for removal of dyes from water. Recently, there is renewed research interest in development of cheaper and effective adsorbents based on natural polymers to replace costly materials and processes. Natural polymers, particularly, polysaccharides represent promising candidates as adsorbents due to their particular structure, chemical stability and high reactivity as well as selectivity towards aromatic compounds owing to presence of reactive functional groups like hydroxyl, amino and carboxyl in polymer chains, fast adsorption kinetics and appealing diffusion properties. Moreover, polysaccharides are preferred due to their abundance availability, renewability and biodegradability. Different polysaccharides such as chitin, starch, cyclodextrin and their derivatives have been studied as adsorbents for dye removal from waste water [16–18]. Adsorption capacities of natural polymers can be enhanced by different chemical modifications out of which graft copolymerization of different functional groups onto polymer backbone is promising one. Grafted cellulosic fibers have good selectivity, favorable physicochemical stability, adjustable functionality, enhanced surface area porosity and structural diversity. Moreover, graft copolymerization increases the density of adsorption sites
http://dx.doi.org/10.1016/j.jece.2015.03.001 2213-3437/ ã 2015 Published by Elsevier Ltd.
Please cite this article in press as: B.S. Kaith, et al., Preparation and application of grafted Holarrhena antidycentrica fiber as cation exchanger for adsorption of dye from aqueous solution, J. Environ. Chem. Eng. (2015), http://dx.doi.org/10.1016/j.jece.2015.03.001
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Fig. 1. Structure of methylene blue. 52
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and thereby sorption selectivity for the target metal and dyes. Graft copolymerization of carboxyl, hydroxyl, ammine and sulphur compounds has been reported on different natural backbones [19–23]. Methylene blue (MB) is a heterocyclic aromatic organic compound (Fig. 1). It has been used widely in different fields of biology and chemistry. MB is one of the highly used dyes in printing industries as stabilizer and as indicator in chemical analysis. Present investigation deals with development of novel cationexchanger by graft copolymerization and phosphorylation of Holarrhena antidycentrica cellulose (HaC) fiber for removal of methylene blue from aqueous solution. Graft copolymer of cellulosic fiber was developed using hydroxyethylmethacrylate as monomer through free radical polymerization. Graft copolymer and cation exchanger was characterized by FTIR, SEM–EDX and XRD studies. Thermal stability was investigated by TGA/DTA/DTG. Utility of cation- exchange was studied for removal of methylene blue from aqueous solution.
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Experimental
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Material and methods
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Holarrhena antidycentrica (Ha) fiber was collected from the hilly region of district Kangra, Himachal Pradesh, India. Fiber was purified through soxhlet extraction in acetone for 72 h. Hydroxyethyl methacrylate (HEMA, SD Fine Chemicals) was purified by vacuum distillation at 0.5 mm of Hg at 85 C. Ferrous ammonium sulphate (FAS) was purchased from SD Fine Chemicals and recrystallized from hot water. Potassium persulphate (KPS, SD Fine Chemicals) was used as received. Phosphorous oxychloride and methylene chloride used were of analytical grade. Methylene blue was supplied by E-Merk Chemicals.
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Extraction of cellulose from the H. antidycentrica fiber
83
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H. antidycentrica fiber was defatted by refluxing in acetone for 72 h. Fiber was crushed and digested with sodium chloride maintaining fiber to liquid ratio of 1:1.50 for 4 h at 65 C. pH of solution was lowered to 4.0 by adding acetic acid. Fiber was repeatedly washed with water to ensure removal of lignin and water soluble organic components. The resulting fiber was treated with 5% sodium bisulphite solution. Finally, washing was done with water and dried in oven at low temperature (45 C) to ensure the moisture content of 5–10% (Eq. (2)) [24].
92
Graft copolymerization
93
The Holarrhena antidycentrica cellulose fiber (HaC) was activated by immersing 0.5 g of fiber in 100 mL of distilled water for 24 h. A definite molar ratio of initiator FAS-KPS was added and reaction was carried out at definite temperature for specific period of time. Homo-polymer was removed by extraction with DMF. Graft copolymer was dried at 50 C to get constant weight. Percentage graft yield (Pg) was calculated as per the method reported elsewhere (Eq. (3)) [25].
84 85 86 87 88 89 90
94 95 96 97 98 99 100
Synthesis of ion exchanger [HaC-g-poly(HEMA)-IE]
101
Ion exchanger was prepared by phosphorylation of HaC-g-poly (HEMA) with phosphooxy chloride in pyridine. The reaction was performed by refluxing reaction mixture at 115 C for 2 h. Product obtained was repeatedly washed with water, 0.1 N HCl and methanol to remove traces of pyridine and was dried in hot air oven. The exchanger was converted into H+ form by treating with 1 mole HNO3 for 24 h with occasional shaking and intermittently replacing the supernatant solution with fresh acid. The excess of the acid was removed after several washing with DMW. The particle size of the range (125 mm) was obtained by sieving (Eq. (3)) [26].
102
Ion exchange capacity of cation exchanger Ion exchange capacity of HaC-g-poly(HEMA)-PO42-2 H+ was determined with respect to different alkali and alkaline earth metal ions. Glass column having an internal diameter (i.d.) 1 cm was fitted with glass wool support at the bottom. The bed length was approximately of 1.50 cm. 1.0 g of ion-exchanger was equilibrated with 1.0 mol dm3 solution of different alkali and alkaline earth metal chlorides. Flow rate was maintained at 0.5 mL min1 and effluent was titrated against standard 0.1 mol dm3 NaOH solution using phenolphthalein indicator [27].
113
Characterization
123
FTIR spectra were recorded with Agilent Carry 630 Fourier transform infrared (FTIR) spectrometer with resolution 8 cm1 with sample scans 32 using KBr pellets. SEM–EDX studied of HaC, graft copolymer and cation-exchanger was carried out using FEI Quanta 200 microscope for morphological and elemental analysis of the samples. TGA, DTA and DTG studies were carried-out in the temperature range of 50 –700 C at a heating rate of 10 C min1 on TG/DTA 6300, SII EXSTAR 6000. Crystalline studies of the samples were performed on X-ray diffraction instrument (Bruker D8, USA) under ambient conditions using Cu-Ka (1.5418 Å).
124
Dye adsorption studies of cation exchanger
134
Adsorption studies were carried-out using 50 mL of methylene blue solution maintained at a constant temperature to study the effect of initial concentration of dye, contact time and dose of the cation exchanger. Experiments were performed at concentrations of 2, 4, 6, 8 and 10 mg L1 of dye using 100–600 mg of cation exchanger at 7.0 pH and 25 C temperature to attain equilibrium. The extent of adsorption was determined at different time intervals during adsorption process. Each experiment was repeated three times. Dye concentration was determined by UV spectrophotometer at lmax 664 cm1. The calibration curve was plotted in order to calibrate the instrument to find-out the concentration of unknown samples. Percentage of dye removal was calculated using the Eq. (1) [28]: ðC 0 C eq Þ (1) 100 %Dye removal ¼ C eq
135
103 104 105 106 107 108 109 110 111 112
114 115 116 117 118 119 120 121 122
125 126 127 128 129 130 131 132 133
136 137 138 139 140 141 142 143 144 145
Q2 146 147
where C0 and Ceq are the initial and equilibrium concentration of dye in mg L1.
149 148 150
Results and discussion
151
Graft copolymerization
152
Reaction parameters were found to play a significant role to achieve the maximum graft yield. Maximum grafting was achieved by optimizing different reaction conditions such as reaction
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temperature, time, initiator concentration, monomer concentration and pH. Optimum conditions obtained for maximum graft
3
copolymerization and further conversion into cation exchanger can be represented by the Eqs. (2) and (3):
196 197
(2)
(3)
158 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173 174 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 194 195
percentage (632.0%) were: 60 min (reaction time), 60 C (reaction temperature), 1:1.25 (initiator ratio), 50 mL (solvent amount), 7 (pH of medium) and 8.24 104 mol L1 (monomer concentration) (Table 1). Initially with increase in reaction parameters like reaction temperature, reaction time and pH of medium Pg was found to increase up to critical limit. Initial increase in Pg was attributed to more extensive generation of free radical sites which is due to greater interaction of OH and SO42 radicals with backbone as well as monomer. Increase in temperature enhanced the activation energy as well as swelling extent of fiber in solvent which led to the easy diffusion of monomer from solution phase to active site of fiber. After optimum reaction conditions decrease in Pg was observed due to predominance of homopolymerization over graft copolymerization. Acidic and basic conditions of medium also decline graft yield due to premature termination of graft chains and deactivation of primary free radicals like OH and SO42 [29]. Amount of different reaction components like initiators, monomer and solvent play significant role towards extent of graft copolymerization. Initially Pg was found to increase with increase in molar ratio of KPS:FAS, up to critical ratio (1:1.25) which was tend to decreased with increase in molar ratio. Interaction of FAS and KPS generated Fe3+ along with generation of SO4 ions, that increased the graft yield. However, increase in Fe3+ ion concentration attacked growing graft copolymer chain and terminated the reaction with reduction of Fe3+ ions to Fe2+ and resulted in decreased Pg. In diluted solution concentration of free radical per unit volume decreased which slow down the interaction of free radicals with backbone and monomer moiety. Initial increase in monomer concentration led to the accumulation of monomer free radicals in a close proximity to the backbone and gave rise to high graft yield. However, at higher monomer concentration, the primary radicals attacked the monomer instead of reacting with the backbone and thus initiated homo-polymerization reaction which resulted in low Pg [30]. Grafting of poly(2-hydroxy ethylmethacrylate) chains took place over the backbone on the —OH and —CH2 groups which are the active sites for chemical modifications. Mechanism for graft
Ion-exchange capacity
198
Table 2 showed ion-exchange capacity of cation-exchanger for alkali and alkaline earth metal ions. The maximum ion-exchange capacity was found to be 1.50 mmol g1 for K+ ions and 1.46 for Na+ ions. The affinity sequence for alkali metal ions was K+ > Na+ > Li+, whereas, alkaline earth metals showed affinity sequence Sr2+ > Ca2 + > Mg2+. Ion-exchange capacity order is in accordance with size of hydrated radii of exchanging ions. Ions with smaller hydrated ionic radii can easily enter the pores of ion-exchanger which results in greater ion-exchange capacity [31].
199
Fourier transform-infrared (FT-IR)
208
FTIR spectra of HaC, HaC-g-poly(HEMA) and phosphate cationexchanger are shown in Fig. 2. HaC fiber showed a broad peak at 3319.4 cm1 due to the presence of free —OH, at 2928.9 and 1024.5 cm1 due to C—H and C—O stretching, respectively (Fig. 2a). HaC-g-poly(HEMA) exhibited additional peak at 1704.4 cm1 due to presence of C¼O which confirmed the grafting of HEMA onto fiber. Grafted fiber also showed decrease in the intensity of peak due to free —OH (3363.2 cm1) it revealed involvement of —OH in graft copolymerization (Fig. 2b). FTIR spectra of phosphate ionexchanger exhibited peak at 1143.2 cm1 due to presence of P¼O (Fig. 2c). Intensity of free —OH decreased to large extent which showed that phosphorylation involved —OH of graft copolymer [32,33]. However, after the adsorption of MB dye on cation exchanger additional peaks were observed at 829.3 cm1 due to C— H bending vibrations in heterocycle and 1635.6 cm1 due to ¼N+ ammonium band; bending vibrations of OH groups included in a hydrogen bond [34–36].
209
SEM and energy-dispersive X-ray (EDX) studies
226
EDX analysis confirmed the successful grafting of HEMA onto HaC fiber. HaC fiber showed presence of carbon and oxygen in atomic percentage of 52.97 and 47.03% as fiber is lignocellulosic
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205 206 207
210 211 212 213 214 215 216 217 218 219 220 221 222 223 224 225
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Table 1 Optimized reaction conditions of MHa-g-poly(HEMA).
Q8
Sr. no.
Initiator ratio (mol: mol)
Monomer (HEMA) 104 (mol L1)
Reaction temperature ( C)
Reaction time (min)
Solvent (mL)
pH of reaction medium
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
(1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (1:1) (0.25:1) (0.5:1) (0.75:1) (1:1) (1.25:1) (1.50:1) (1.250:1) (1.250:1) (1.250:1) (1.250:1) (1.250:1) (1.250:1) (1.250:1) (1.250:1) (1.250:1) (1.250:1)
6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 2.47 3.71 4.95 6.18 7.42 6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 2.06 4.12 6.18 8.24 10.3
60 60 60 60 60 30 40 50 60 70 80 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60
60 90 120 150 180 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150
50 50 50 50 50 50 50 50 50 50 50 20 30 40 50 60 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50
7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 2.0 4.0 6.0 8.0 10.0 7.0 7.0 7.0 7.0 7.0
% Grafting
Mean ( SD) ( SE) 210.6 252.2 284.5 335.6 134.9 48.0 284.0 309.8 335.6 196.3 57.7 267.0 404.2 418.7 426.1 407.6 243.5 270.1 337.2 344.7 489.0 373.7 102.6 362.0 403.7 368.6 73.5 47.3 94.4 398.3 632.0 592.1
1.3578 2.4668 1.496 2.4635 3.3457 2.7548 3.5487 4.8752 3.5679 3.2367 4.5237 5.3789 5.4735 4.2367 3.4521 4.5243 3.1764 1.4658 2.489 3.9863 2.5765 4.2869 3.5619 2.1376 2.5619 2.6891 3.2879 2.5315 3.2167 2.9402 1.8431 1.5648
0.784855 1.425896 0.86474 1.423988 1.933931 1.59237 2.051272 2.818035 2.06237 1.870925 2.614855 3.109191 3.163873 2.44896 1.995434 2.615202 1.836069 0.847283 1.438728 2.30422 1.489306 2.477977 2.058902 1.235607 1.480867 1.554393 1.90052 1.463295 1.859364 1.699538 1.065376 0.904509
Number of replications: 3; initial weight of each sample: 0.5 g. 230
240
material containing carbon backbone (Fig. 3a). SEM images of fiber revealed continuous morphology with homogeneous surface. EDX of HaC-g-poly(HEMA) with 58.45% carbon content showed that carbon content has been increased on graft copolymerization. Moreover, increase in heterogeneity was revealed by rough surface shown in SEM image (Fig. 3b). It confirmed the incorporation of poly(HEMA) chains onto HaC backbone. SEM of cation-exchanger observed high degree of heterogeneity as compare to graft copolymer and EDX analysis indicated presence of phosphorous along with carbon and oxygen. It revealed the presence of PO43 group in the cation-exchanger (Fig. 3c).
241
X-ray diffraction
242
Fig. 4 exhibited XRD patterns of HaC fiber, graft copolymer and cation-exchanger. XRD pattern of HaC fiber showed sharp peak at 22 with 796 counts (Fig. 4a). % Crystallinity of fiber has been found to be 50.1%. On the other hand XRD pattern of graft copolymer (Fig. 4b) and phosphate cation-exchanger (Fig. 4c) showed broad peak at 18.2 and 19.5 on 2u scale with 658 and 554 counts, having
231 232 233 234 235 236 237 238 239
243 244 245 246 247
Table 2 Ion-exchange capacity of various exchanging ions on phosphate cation-exchanger. Exchanging ions +
Li Na+ K+ Mg2+ Ca2+ Sr2+
pH 6.70 6.70 6.80 6.50 6.50 6.30
Ionic radii Hydrated ionic radii Ion-exchange capacity (Å) (Å) (mmol g1) 0.68 0.97 1.33 0.78 1.06 1.27
3.40 2.76 2.32 7.00 6.30 –
1.06 1.46 1.50 1.04 1.14 1.18
% crystallinity of 35.04 and 31.96%, respectively. It indicated the amorphous nature of graft copolymer and phosphate cation exchanger. Incorporation of monomer moiety and phosphate group impaired natural crystallinity of fiber and enhanced the amorphous nature of fiber. Low crystallinity of graft copolymer and ion exchanger indicated poor order of crystal lattice in fiber. This decrease in crystallinity was due mis-orientation of fiber axis in crystal lattice of graft copolymer and cation-exchanger.
248
Thermal studies
256
TGA of ungrafted fiber, grafted fiber and ion-exchanger was studied as a function of percentage weight loss with temperature. Dehydration, glycogen formation and depolymerization are the different processes involved during degradation of HaC-fiber. HaC showed two stages of thermal degradation in the temperature range of 227.9–339.7 C with 58.2% weight loss and in the range of 339.7–495.9 C with 30.6% weight loss (Sup Fig. 1). The first stage corresponds to loss of weight by dehydration and volatilization process whereas weight loss in later stage is due to loss by depolymerization. Hac-g-poly(HEMA) showed degradation in temperature range of 213.2–305.3 C with 58.1% weight loss and 305.2–423.1 C with 128.8% weight loss (Sup Fig. 2). It has been observed that IDT and FDT of grafted fiber were lower than that of unmodified fiber. Lower IDT of grafted fiber indicated early decomposition of grafted poly(HEMA) chains. Thermal analysis was done by taking decomposition temperature at every 20% weight loss (Table 3). It has been further observed that temperature difference of ungrafted fiber up to 40% and 60% weight loss were 47.9 and 22 , respectively. After 60% weight loss this difference has been increased to 70 which indicated the formation
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258 259 260
Q3 261 262 263 264 265 266 267 268 269 270 271 272 273 274 275 276
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Fig. 2. FT-IR spectra of (a) HaC (Holarrhena antidysenterica cellulose), (b) HAC-g-poly(HEMA), (c) phosphate ion-exchanger of graft copolymer.
277 278 279 280 281 282 283 284 285 286 287
of glycogen. In case of grafted fiber, temperature difference up to 40% weight loss was less (10 ) whereas after 40% weight loss temperature difference for every 20% weight loss has been found to be very high, beyond 40% temperature difference lie between 50 and 80 C. These observations indicated that fiber on grafting attained stability towards increasing temperature. DTA studies have been found to support the TGA data. In case of backbone the exothermic peaks were found at 310.4 C and 445.6 C with 25.8 and 20.6 mV energy release, respectively. Whereas, the exothermic peaks observed with grafted sample were found at 280.3 C and 410.5 C with energy release of 16.7 and 32.5 mV,
5
Q7
respectively. In case of backbone DTG studies showed the rate of weight loss 0.287 and 0.100 mg min1 at temperatures 300.4 C and 445.6 C, respectively. However, the grafted sample showed rate of weight loss 0.316, 0.427 and 0.142 mg min1 at temperatures 223.1, 269.8 and 399.2 C, respectively [37,38]. TGA studies of phosphorylated ion-exchanger revealed two stage decomposition in temperature range of 274.4–340.5 C with 49.4% weight loss and 340.5–627.3 C with weight loss of 30.5% Q4 (Sup Fig. 3). Ion exchanger showed high IDT and FDT as compared to unmodified and grafted fiber. Moreover, temperature difference for every 20% weight loss indicated slow decomposition up to 40%
Fig. 3. a–a1 to c–c1: SEM–EDX of (a–a1) HaC-fiber, (b–b1) HaC-g-poly(HEMA), (c–c1) phosphate cation-exchanger.
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Fig. 4. XRD pattern of (a) HaC-fiber, (b) HaC-g-poly(HEMA), (c) cation-exchanger. 299 300 301 302 303 304 305 306 307 308 309 310
and after 60% weight loss. However, temperature difference between 40 and 60% weight loss was found to be less which indicated region of depolymerization. In case of DTA of cation exchanger the exothermic peaks were found at 335.3 C and 490.1 C with 28.9 and 14.4 mV energy release, respectively [39,40]. DTG studies also indicated this region as region of fast decomposition (0.518 mg min1 at 308 C) whereas at the low temperature the rate of degradation was found to be less i.e., 0.190 mg min1 at 246.6 C. It showed that incorporation of PO43 group enhanced thermal stability of fiber. Higher thermal stability of ion-exchanger was further supported by higher residue percentage (12%) after final decomposition temperature [41–43].
311
Dye adsorption studies
312
Cation exchanger synthesized was found to remove effectively the methylene blue from aqueous solution and 85% of dye removal was observed. The dye sorption could be due to the electrostatic interaction between PO32 group of HaC-g-poly(HEMA)-PO322H+ and MB = N+(CH3)2 groups of MB (Eq. (4)). Further it could be explained on the basis of cation-cation exchange with the effective removal of MB = N+(CH3)2 from the aqueous medium and release of H+ ions (Eq. (5)). Mechanism of the dye sorption is presented by the Eqs. (4) and (5) [44–48].
313 314 315 316 317 318 319 320
Cation exchange takes place through the exchange of MB = N+(CH3)2 with H+ ions resulting in the removal of dye from the aqueous solution and release of H+ ions. The effectiveness of cation-exchanger as adsorbent for MB has been studied as a function of contact time. When dye comes in contact with adsorbent its diffusion on adsorbent and ultimately adsorption on adsorbent is a time dependent process. The concentration of MB was found to decrease with the increase in contact time. With time, adsorption takes place in three phases. Initial phase showed sharp slope of adsorption curve from 0–30 min (Fig. 5a). Second phase showed slow uptake of dye on adsorbent which ultimately led to final phase of approximately constant adsorption. Initial uptake involved diffusion of dye on adsorbent which is a fast process. The phase of fast uptake of dye also contributed to presence of large number of vacant reactive sites. After initial phase of adsorption availability of reactive site decreased and resulted in slow adsorption. This phase of slow adsorption attributed to intraparticle diffusion which is a slow process. Finally, diffusion occurred through small pores of adsorbent led to equilibrium between adsorbate and adsorbent. Thus, saturation of different reaction sites of cation-exchanger resulted in constant slope of curve. Saturation was attained within 75 min (2 mg L1), 105 min (4 mg L1), 180 min (6 mg L1), 240 min (8 mg L1) and 255 min (10 mg L1). At 4 mg L1 rate of dye removal increased from 65 to 85% of maximum adsorption within 105 min [49–52].
324
Effect of initial concentration of dye Initial concentration of dye is one of the important parameter which effect rate of adsorption of dye on adsorbent. The effect of initial concentration of MB was studied at different concentrations of 2, 4, 6, 8 and 10 mg L1 with fixed amount of cation-exchanger (500 mg/50 mL of MB) and contact time 255 min. Fig. 5b depicted that rate of dye removal increased from 75 to 85% with initial increase in dye concentration from 2 to 4 mg L1. Further increase in dye concentration from 4 to 10 mg L1 decreased the rate of dye removal from 85 to 71%. Initially with the increase in dye concentration rate of adsorption increased due to increase in electrostatic interaction of dye with adsorbent. However, further
349
325 326 327 328 329 330 331 332 333 334 335 336 337 338 339 340 341 342 343 344 345 346 347 348
350 351 352 353 354 355 356 357 358 359 360
(4)
þ þ HaC g polyðHEMAÞPO2 4 2H þ MB 2 þ ! HaC g polyðHEMAÞPO4 2MB þ 2Hþ
321 322 323
(5)
Effect of the time on removal of dye The removal of dye through cation exchanger takes place by two processes i.e., cation exchange (Eq. (5)) and adsorption (Eq. (4)).
increase in dye concentration resulted in decreased electrostatic interactions between the adsorbent and dye. This was due to predominance of electrostatic repulsions over electrostatic attractions at higher dye concentration. Thus, cation–cation repulsion became dominate over cation–anion attraction thereby resulting in lesser removal of dye from waste water at concentration beyond 4 mg L1. Thus, the available active sites of adsorbent for the removal of dye molecules became limiting factor and at low
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Table 3 Results of HaC, HaC-g-poly(HEMA) and cation exchanger from TGA/DTA/DTG. Sample code
TGA IDT ( C)
FDT ( C)
DT at every 20% weight loss Residue (%) (%) 20
40
HaC fiber
227.9
627.3
250.1
298.0 320.1
HaC-g-poly (HEMA)
213.2
423.1
230.2 240.1
290.0 365.2 39
Cation-exchange resin
274.4
495.5
275
355.5 530.1
320
60
DTA
DTG
Exothermic peaks at different temperature, ( C) (mV)
Rate of weight loss (mg min1) at different temp ( C)
310.4 (25.8) 445.6 (20.6) 280.3 (16.7) 410.5 (32.5)
0.287 (300.4) 0.100 (445.6) 0.316 (223.1) 0.427 (269.8) 0.142 (399.2) 0.190 (246.6) 0.518 (308.0)
80 390.0
0.5
12
335.3 (28.9) 490.1 (14.4)
IDT: initial decomposition temperature; FDT: final decomposition temperature; DT: decomposition temperature.
Fig. 5. Effect of (a) contact time, (b) initial concentration of dye, (c) dose of cation exchanger on % dye removal.
369 370 371 372 373 374 375 376 377 Q5 378 379 380 381 382
concentration molecules of dye had more chances to interact with adsorbent which could enhance the rate of adsorption [53,54]. Effect of adsorbent dose The effect of cation exchanger dose on dye adsorption was studied by varying the amount of adsorbent from 100 to 600 mg/ 50 mL of dye solution while keeping other parameters like initial concentration of dye (4 mg L1) and contact time constant (Fig. 5c). The percentage of dye removal was found to increase with the increase in adsorbent dose from 100 to 500 mg/50 mL of MB dye solution. Further increase in adsorbent dose decreased the rate of dye removal. As adsorbent dose increased from 100–500 mg/50 mL of dye solution availability of reaction sites increased which enhanced the percentage of adsorption of dye from 47.5 to 85%, respectively. Afterward decreased rate of adsorption attributed to
aggregation of adsorption sites which decreased the surface area of adsorbent available to dye and increased the diffusion path length. As a result increase in dose of cation exchanger above equilibrium amount declined the rate of removal of dye. Moreover, time required to reach equilibrium also increased with increase in dose of adsorbent [55–57].
383
Conclusion
389
Virgin HaC fiber cellulose was converted into HaC-g-poly (HEMA) graft copolymer and graft yield obtained was 632%. Phosphorylation of grafted cellulose yielded cation exchanger with high thermal stability. FTIR and SEM–EDX studies confirmed the formation of cation exchanger. XRD data revealed decrease in % crystallinity on graft copolymerization and phosphorylation due to
390
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disturbance in crystal lattice on incorporation of poly(HEMA) chains and phosphate groups. Synthesized cation exchanger was found to be an effective adsorbent for removal of dye from aqueous medium. Adsorption of dye on cation exchanger was found to increase with increase in contact time, initial concentration of dye and dose of cation exchanger. Equilibrium was achieved after 105 min at concentration of 4 mg L1 and cation exchanger dose of 500 mg. Thus, synthesized cation exchanger was found to be an efficient and cost effective adsorbent for removal of methylene blue from waste water.
406
Acknowledgements
407 Q6 409
Authors are highly grateful to DST-FIST New Delhi for providing financial assistance in procuring the FTIR and UV–vis spectrophotometer which were used for the analysis of the samples.
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Appendix A. Supplementary data
411 412
Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.jece.2015.03.001.
413
References
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