Application of chitosan and its derivatives in Cu(II) ion removal from water used in textile wet processing

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<ul><li><p> Research Journal</p><p> online version of this article can be found at:</p><p> DOI: 10.1177/0040517514523176 2014 84: 1539 originally published online 21 February 2014Textile Research JournalDP Chattopadhyay and MS Inamdar</p><p>processingApplication of chitosan and its derivatives in Cu(II) ion removal from water used in textile wet</p><p>Published by:</p><p></p><p> can be found at:Textile Research JournalAdditional services and information for </p><p> Alerts: </p><p> </p><p> </p><p> </p><p> </p><p> What is This? </p><p>- Feb 21, 2014OnlineFirst Version of Record </p><p>- Jul 10, 2014Version of Record &gt;&gt; </p><p> at UTSA Libraries on October 6, 2014trj.sagepub.comDownloaded from at UTSA Libraries on October 6, 2014trj.sagepub.comDownloaded from </p><p></p></li><li><p>Original article</p><p>Application of chitosan and its derivativesin Cu(II) ion removal from water usedin textile wet processing</p><p>DP Chattopadhyay and MS Inamdar</p><p>Abstract</p><p>The applicability of chitosan, trimethyl chitosan chloride and nano-chitosan for removal of Cu(II) ions from water used in</p><p>textile wet processing was studied. The liquor before and after treatment was analyzed iodometrically to find the</p><p>presence of Cu(II) ions, and Fourier transform infrared spectroscopy was employed for the characterization of</p><p>the chitosanCu(II) complex. The study included the effect of molecular weight of chitosan, particle size of chitosan</p><p>and the degree of quaternization of trimethyl chitosan chloride, pH of the medium, etc., on the sorption of Cu(II) ions.</p><p>The influence of the molecular weight of chitosan was found to be an important criterion on the rate of sorption of</p><p>Cu(II) ions. Reduction in the particle size of chitosan enhanced both the rate and amount of scavenging of metal ions.</p><p>Keywords</p><p>chitosan, chelation behavior, copper ions, nano-chitosan, trimethyl chitosan chloride</p><p>A plentiful supply of good-quality water is indispens-able for the textile wet processing industry. Water is notonly a vehicle to carry or fix the chemicals and dyes, butit is the medium for processing.1 The water employedfor various wet processing operations is nowadays lar-gely obtained from underground sources, which isaccompanied with various heavy metal ions. Therecycled water from effluent discharge also contributesto these impurities due to the inefficiency of conven-tional effluent treatment plants to remove such tracesof metal ions. The presence of these ions, even at theppm level, can have detrimental effects on processessuch as enzymatic desizing, hydrogen peroxide stabilityand its bleaching action, shade of dyes, etc.2,3</p><p>Among various metal ions, the Cu(II) ion has gainedattention due to both its beneficial and adverse effects.Use of copper compounds such as copper sulfate incertain dyeings, direct dyeing in particular, has foundto improve the fastness to washing and light. However,the presence of copper in water can seriously affect theperformance of various unit operations of textile pro-cessing, such as desizing, scouring, bleaching, dyeing,etc. Hence, it is advisable to avoid copper/brass fittings,especially in bleaching plants. Copper is found to beadsorbed by enzyme molecules to form complexes</p><p>and inactivate the enzymatic action. Copper exhibits acatalytic action on hydrogen peroxide decomposition.The presence of copper is reported to cause instabilityin peroxide bleaching baths and to damage the cottonduring bleaching. Copper is readily absorbed on wooland therefore causes damage during peroxide bleach-ing. The presence of copper ions causes a deleteriouseffect on the shades of various dyes used for cellulose,nylon and protein fibers; nevertheless, it enhances thewash and light fastness properties.2,4 The deleteriouseffect of Cu(II) ions observed on hydrogen peroxidebleaching of scoured cotton fabric and various directand reactive dyeing of cotton is presented in Table 1and Figure 1. Copper content in the textile and alliedindustries effluent was found to be approximately77mg/L5 as against the World Health Organization</p><p>Department of Textile Chemistry, The Faculty of Technology &amp;</p><p>Engineering, The M S University of Baroda, Vadodara, India</p><p>Corresponding author:</p><p>DP Chattopadhyay, Department of Textile Chemistry, The Faculty of</p><p>Technology &amp; Engineering, The M S University of Baroda, Vadodara,</p><p>India 390001.</p><p>Email:</p><p>Textile Research Journal</p><p>2014, Vol. 84(14) 15391548</p><p>! The Author(s) 2014</p><p>Reprints and permissions:</p><p></p><p>DOI: 10.1177/0040517514523176</p><p></p><p> at UTSA Libraries on October 6, 2014trj.sagepub.comDownloaded from </p><p></p></li><li><p>(WHO) norms 0.05mg/L.5 Traces of copper (545mg/L) in underground water and about 110 mg/kg of soil inand around Surat (India) have been detected.6</p><p>The adverse effect of such metal ions can be con-trolled either by using chelating agents such as ethylenediamine tetra acetic acid (EDTA), diethylene triaminepenta acetic acid (DTPA), nitrilo triacetic acid (NTA),etc.7 or metal ions can be chemically precipitated orcoagulated as salts or reduced to metallic form. Theycan be separated out from the liquid phase by filtration,settling, centrifuging or electro deposition.1,8,9 Variousnatural products, such as wood bark and clay,10</p><p>rice hull, cotton fibers, bamboo pulp, peanut skin,etc., and chitosan have been found to remove metalcations from streams.1114 The detrimental effects onthe environment still persist when water is treatedthrough the first route due to the existence of metalions in discharged water, while metal ions are removedfrom discharged water by the second route, which issafer.</p><p>Chitosan is a natural-based product derived fromalkaline deacetylation of a biopolymer, chitin. It isthe second most abundant biopolymer after cellulose.The amount of presence of primary amino groups pre-sent on the chitosan molecule is characterized by thedegree of deacetylation (DAC).15 The applicationpotential of chitosan and its derivatives for the recoveryof valuable metals or the treatment of contaminatedeffluents is well documented.16,17 Our earlier report18</p><p>has shown the scavenging property of chitosan for cal-cium ions. Karthikeyan et al.19 studied the dynamicsand equilibrium sorption of Zn(II) onto chitosan.They observed that a maximum of six minutes wererequired for complete sorption of Zn ions by chitosanobeying the Freundlich and Langmuir isotherms.Nomanbhay and Palanisamy20 used chitosan-coatedoil palm shell charcoal successfully for the adsorptionof chromium ions from water. Bioconversion of highly</p><p>CuSO4 content </p><p>in dye bath,</p><p>mg/L</p><p>C.I. Direct </p><p>Red 81</p><p>C.I. Direct </p><p>Yellow 44</p><p>C.I. Re.Red </p><p>152</p><p>C.I. Re.Blue </p><p>25</p><p>Control</p><p>50</p><p>100</p><p>200</p><p>Figure 1. Effect of Cu(II) ions in a dye bath on the shades of direct and reactive dyeing on cotton fabric.</p><p>Table 1. Effect Cu(II) ions on hydrogen peroxide bleaching of</p><p>cotton fabric</p><p>CuSO4 content in</p><p>bleach bath, mg/L</p><p>Whiteness</p><p>index</p><p>Yellowness</p><p>index</p><p>Brightness</p><p>index</p><p>Control 88.40 1.33 78.08</p><p>100 85.98 4.29 73.02</p><p>200 85.06 4.69 71.17</p><p>500 84.14 5.58 69.32</p><p>Scoured sample: W.I. 78.07, Y.I. 17.02 and B.I. 56.91.</p><p>1540 Textile Research Journal 84(14)</p><p> at UTSA Libraries on October 6, 2014trj.sagepub.comDownloaded from </p><p></p></li><li><p>toxic Cr(VI) into Cr(III) was also observed, which isessential in human nutrition, especially in glucosemetabolism. Chang and Chen21 isolated Au(III) ionsfrom water on chitosan-coated Fe3O4 nanoparticles.They found that the gold ions could be quickly andefficiently adsorbed. Guibal et al.22 synthesized thioureaderivative of chitosan for platinum and mercury recov-ery owing to the chelating affinity of sulfur ligands.Abdel-Mohdy et al.23 introduced diethyl amino ethylmethacrylate (DEAEMA) groups onto the chitosanbackbone through radiation grafting and studied thechelation property of grafted derivative on copper,zinc and cobalt ions. They reported that the extent ofmetal ions uptake by the chitosanDEAEMA deriva-tive was preferentially higher for copper ions, followedby zinc and cobalt ions. The present investigation wasaimed at understanding the chelation property of chit-osan and its derivatives towards Cu(II) ions. Chitosanof different molecular weight, nano-chitosan of varyingparticle size and trimethyl chitosan derivative of differ-ent degrees of quaternization were taken for the study.The test sample before and after treatment was ana-lyzed iodometrically for knowing the presence ofCu(II) ions and Fourier transform infrared (FTIR)spectroscopy was employed for the characterization ofthe chitosanCu(II) complex.</p><p>Materials and methods</p><p>Materials</p><p>One hundred percent cotton fabric (warp and weft 40 s,ends/inch 142, picks/inch 72 and g/m2 125), at ready fordyeing stage, was procured from Mafatlal IndustriesLtd, Nadiad, Gujarat State, India. Chitosan of differentmolecular weights was obtained from MarineChemicals, Kerala State, India (CHT-MC) andMahtani Chitosan Pvt Ltd, Gujarat State, India(CHT). A low molecular weight chitosan (CHT-D)</p><p>was synthesized from CHT by depolymerization withnitrous acid as described earlier.24 The specifications ofdifferent grades of chitosan are given in Table 2.Various direct and reactive dyes namely, C.I. DirectRed 81, C.I. Direct Yellow 44, C.I. Reactive Red 152and C.I. Reactive Blue 25 were kindly supplied byColourtex Industries Ltd, Gujarat State, India. Theanionic detergent (Ezee, Godrej, India) employed wasof commercial grade.</p><p>Other reagents, such as acetic acid, acetone, methylalcohol, methyl iodide, EDTA, sodium thiosulfate,potassium iodide, sodium iodide, sodium hydroxide,soda ash, sodium sulfate, copper sulfate, N-methyl-2-pyrrolidone (NMP), etc., used were of analytical grade.</p><p>Synthesis of trimethyl chitosan chloride</p><p>Trimethyl chitosan chloride (TMCHT) was synthesizedas follows: purified chitosan (CHT) (1 g) was treatedwith the required amount methyl iodide (5 and 15 gfor two different levels of degree of quaternization) inthe presence of sodium iodide 2.4 g and sodium hydrox-ide (2 g) dispersed in NMP(40mL) in a stainless steelreaction vessel at 50C for 24 h. Trimethyl chitosaniodide was recovered from using acetone then subjectedto ion exchange by treatment with sodium chloride(10%, 50mL) for 1 h. TMCHT was then recoveredfrom acetone with repeated washings and oven driedat 55C.</p><p>Synthesis of nano-chitosan dispersions</p><p>The method for synthesis of nano-chitosan dispersionswas followed as discussed elsewhere.18 The preparednano-chitosan (CHTN) from the starting materialCHT was stored in refrigerator. The particle size andsize distribution of the chitosan were analyzed using aparticle size analyzer (Zetasizer Nano ZS90, MalvernInstruments Ltd, UK).</p><p>Table 2. Chitosan derivatives employed for chelation study</p><p>Sample code Chemical name</p><p>Properties</p><p>DAC, % Molecular weight Particle size, nm DQ, %</p><p>CHT-MC Chitosan 89.03 654,127 </p><p>CHT Chitosan 90 135,839 4014 </p><p>CHT-D Chitosan 90 38,733 </p><p>CHTN1 Nano-chitosan 408.73 </p><p>CHTN2 Nano-chitosan 534.2 </p><p>TMCHT1 Trimethyl chitosan chloride 13.41</p><p>TMCHT2 Trimethyl chitosan chloride 50.92</p><p>DAC: degree of deacetylation; DQ: degree of quaternization.</p><p>Chattopadhyay and Inamdar 1541</p><p> at UTSA Libraries on October 6, 2014trj.sagepub.comDownloaded from </p><p></p></li><li><p>Hydrogen peroxide bleaching</p><p>of cotton fabric</p><p>Scoured cotton fabric was treated with solution con-taining hydrogen peroxide (30%, 10 g/L), soda ash(10 g/L), sodium silicate (10 g/L) and detergent (1 g/L)at about 85C for 60 minutes. The material-to-liquorratio was maintained at 1:30. After bleaching was over,the fabric was washed at 80C for 20 minutes and thenrinsed.</p><p>Dyeing with direct dyes</p><p>The cotton fabric was dyed with direct dye (1% o.w.m.)in the presence of Glaubers salt (20% o.w.m.) and sodaash (5% o.w.m.) at temperature 90C for 60 minutes.The material-to-liquor ratio was maintained at 1:40.The dyed sample was then rinsed with cold waterthree times, air dried and hot pressed. The dyedsamples were evaluated for color strength in terms ofK/S values on a computer color matching system(Spectroscan 5100A, Premier Colorscan, India).</p><p>Fourier transform infrared analysis</p><p>FTIR spectra of CHT and TMCHT derivatives weretaken on a Thermo Nicolet iS10 Smart ITR spectro-photometer (Thermo Fisher Scientific, USA) in thewavenumber between 4000 and 500 cm1.</p><p>Treatment of Cu(II) ions containingwater with chitosan derivatives</p><p>The required quantity of chitosan or chitosan deriva-tive (e.g. 1 g/L) was treated with copper sulfate solutioncorresponding to a Cu(II) ions concentration of394.32mg/L in the presence of acetic acid (0.7mL/Lfor pH 5.5 and 1.5mL/L for pH 3.5) with occasionalstirring. After the prescribed reaction time is over, chit-osan was precipitated out by the addition of a fewdrops of sodium hydroxide (10%) solution. The solu-tion was then filtered, the filtrate was analyzed forCu(II) ions content iodometrically and the residuewas analyzed for FTIR spectroscopy.</p><p>Iodometric method for determinationof Cu(II) ions</p><p>One hundred milliliters of aliquot (sample solution) wastaken in a conical flask and mixed with 10mL of 10%liquor ammonia to obtain a dark blue color. The solu-tion was then neutralized with acetic acid; a slightexcess acid was added, followed by 2 g of potassiumiodide. The flask was placed in the dark for about15minutes for complete liberation of free iodine and</p><p>then titrated against 0.1N sodium thiosulfate usingstarch as the indicator. Ammonium thiocyanate (2 gin 10mL water) was then added and titration contin-ued. The amount of Cu(II) present in the given solutionwas calculated using the following equation:24</p><p>CuII ions content; mg=L A 6:36 1000V</p><p>where A is the amount (mL) of 0.1N Na2S2O3 takenin the burette and V is the volume (mL) of aliquottaken for titration (100 mL).</p><p>Chelation efficiency in terms of sorption of Cu(II)</p><p>ions by chitosan (mg/g) I0 IFM</p><p>Chelation efficiency in terms of copper ions removal</p><p>from water (mg/L) I0 IF</p><p>where I0 is the initial concentration (mg/L) of Cu(II)ions and IF is the concentration (mg/L) of Cu(II) ions intreated water. M is the mass (g) of chitosan.</p><p>Results and discussion</p><p>Characterization and mechanism of chelationof copper (II) ions on chitosan</p><p>The important ligands on chitosan macro...</p></li></ul>