Removal of Cu(II) from Water by Adsorption on Chicken Eggshell

Transcription

1 Inrnaional Journal of Enginring & Tchnology IJET-IJENS Vol:3 No: 4 Rmoval of u(ii) from War by Adsorpion on hickn Eggshll Nurul Aimi bini Rohaizar*, Norhafizah bini Abd. Hadi*, Wong h Sin* Absrac Th us of chickn ggshll as adsorbn for h rmoval of coppr (II) from war was invsigad in h prsn sudy. Th ffcs of diffrn paramrs such as ph of h soluion, agiaion ra and conac im on h adsorpion procss wr sudid. Th opimum condiions for u(ii) adsorpion by chickn ggshll wr found o b a ph 7 wih h agiaion ra of 35 rpm. Euilibrium daa wr analyzd by Langmuir and Frundlich isohrm modls and h daa wr fid wll o Frundlich isohrm modl. Th adsorpion kinics daa wr valuad by h psudo-firs-ordr and psudo-scond-ordr modls. Th daa wr wll corrlad wih h psudo-scond-ordr kinic modl, which indicad ha chmisorpion procsss could b h ra-limiing sp in h adsorpion procss. Th rsuls show ha chickn ggshll has h ponial o b usd as biosorbn for adsorpion of coppr (II) from war. Indx Trm oppr, chickn ggshll, adsorpion isohrm, kinic modl I. INTRODUTION THE rlas of oxic subsancs in h waswar from indusrial aciviis such as mining, mal procssing, pharmacuicals, psicids, organic chmicals, rubbr and plasics, c. may caus srious ffcs on h nvironmn and human halh. I is bcaus h oxic subsancs hav a ndncy o accumula in h soil, sa war, frsh war and sdimns du o hir high disprsion from whr hy nr ino h food chain []. oppr is on of h oxic havy mals dischargd ino h nvironmn du o indusrial opraions, anhropognic aciviis and naural sourc of coppr xposur []. In ordr o hav a polluion-fr nvironmn, h oxic havy mals should b rmovd from waswar bfor is disposal. Rmoval of oxic havy mals from indusrial waswar has bn pracicd for svral dcads by h convnional physico-chmical rmoval mhods, such as chmical prcipiaion, lcroplaing, mmbran sparaion, vaporaion and rsin ionic xchang. Howvr, hs mhods ar usually ar found o b infficin and xpnsiv, spcially whn * Scion of hmical Enginring Tchnology, Malaysian Insiu of hmical and Bionginring Tchnology, Univrsii Kuala Lumpur, Vndor iy, Taboh Naning, 78 Alor Gajah, Mlaka, Malaysia. raing waswar wih low concnraion of havy mals [] [4]. Thrfor, alrnaiv mhod has bn ampd using low cos marials such as chickn ggshll o rmov havy mals by a simpl adsorpion procss. hickn ggshll can b usd o adsorb havy mal in waswar du o is calcium carbona conn which is rsponsibl for mal adsorpion [5]. This alrnaiv mhod will no produc chmical sludg, hnc no scondary polluion and i is mor fficin and asy o opra compard o ohr mhods []. Th objcivs of his projc ar o sudy h ffcs of diffrn opraing paramrs including ph, agiaion ra and conac im on h adsorpion fficincy of u(ii) from war by chickn ggshll. Bsids, h prsn sudy is also aimd o valua h uilibrium of adsorpion procss using Langmuir and Frundlich isohrms. Manwhil, h kinics of u(ii) adsorpion on chickn ggshll will also b analyzd using diffrn modls including h psudo-firs-ordr and psudo-scond-ordr kinic modls. II. MATERIALS AND METHODS A. Marials oppr sulfa (uso 4 ) was usd for h prparaion of sock sandard soluions of u(ii) in disilld war. For ph adjusmn hroughou h xprimn,. M hydrochloric acid (Hl) and/or. M sodium hydroxid (NaOH) wr usd as ncssary. All chmical usd in h prsn sudy wr of analyical grad from Mrck, Grmany. Aomic adsorpion spcromr (AAS Modl HGA 85, USA) was usd o masur h u(ii) concnraion. B. Prparaion of Adsorbn Th chickn ggshlls wr collcd from kichn was and washd by dionizd war for svral ims o rmov h dir paricls. Th ggshlls wr hn drid ovrnigh in h ovn a 4. Th drid ggshlls wr ground ino small paricls and sord in an airigh conainr for fuur us.. Effc of ph on u(ii) Adsorpion Th ffc of soluion ph on adsorpion of u(ii) was sudid by mixing.5 g of adsorbn wih ml of coppr soluion of 5 mg/l concnraion a diffrn ph valu (4 8) undr 3. Th ph was adjusd wih. M NaOH or. M Hl soluions and masurd by ph mr. Agiaion was mad a a consan sirring spd of 5 rpm for 8 minus. Th rmaining concnraion of u(ii) afr adsorpion was IJET-IJENS Fbruary 3 IJENS

2 Inrnaional Journal of Enginring & Tchnology IJET-IJENS Vol:3 No: 4 masurd using aomic adsorpion spcromr (AAS). D. Effc of Agiaion Ra on u(ii) Adsorpion Th ffc of agiaion ra on u(ii) adsorpion was invsigad by adding.5 g of adsorbn ino ml of coppr soluion of 5 mg/l concnraion a opimum ph drmind prviously. Th soluion was agiad using war bah shakr a diffrn sirring ras (5 35 rpm) undr consan mpraur of 3. Th rmaining concnraion of u(ii) afr adsorpion was masurd using AAS. E. Euilibrium Sudis of u(ii) Adsorpion A sris of soluions conaining diffrn iniial concnraions of u(ii) ions (in h rang of 5 35 mg/l) was prpard and mployd for h bach adsorpion sudis a 3 o chck h applicabiliy of h Langmuir and Frundlich adsorpion isohrms undr opimum condiions obaind prviously. Th rmaining concnraion of u(ii) afr adsorpion was masurd using AAS and h amoun of adsorpion a uilibrium, (mg/g) was calculad by: W V whr and (mg/l) ar h liuid-phas concnraion of coppr a iniial and uilibrium, rspcivly, V (L) is h volum of h soluion and W (g) is h mass of dry adsorbn usd. Th adsorpion fficincy of u(ii) can b calculad as: Adsorpion prcnag = () F. Kinics Sudis of u(ii) Adsorpion Th kinics sudis of u(ii) adsorpion wr carrid ou by bach adsorpion a opimum condiions valuad prviously. Th sampls wr akn a prs im inrvals up o 8 minus undr mpraur of 3. Th rmaining concnraion of u(ii) afr adsorpion was masurd using AAS and h amoun of adsorpion a im, (mg/g) was calculad by: W V whr (mg/l) is h liuid-phas concnraions of u(ii) soluions a any im,. III. RESULTS AND DISUSSION A. Effc of ph on u(ii) Adsorpion Soluion ph is on of h mos imporan paramrs conrolling adsorpion of havy mals from auous soluions bcaus waswar from various sourcs will hav diffrn ph valus. Thrfor, in his sudy h ffc of ph on rmoval of u(ii) was xamind in h ph rang of 4 8. Th () (3) concnraion of u(ii), h amoun of chickn ggshlls and conac im wr kp consan a 5 mg/l,.5 g and 8 minus, rspcivly. Fig. shows ha h adsorpion capaciis of u(ii) incrasd significanly as h ph incrasd from 4 7 and approachd a plaau a ph rang of 7 8. Th adsorpion capaciis rachd almos % a highr ph. A lowr ph, lil adsorpion could b ascribd o h hydrogn ions comping wih mal ions for adsorpion si [6]. Th ffc of ph can b xplaind by ion-xchang mchanism of adsorpion in which h imporan rol is playd by carbona groups on h chickn ggshlls ha hav caion-xchang propris. A lowr ph valus, coppr adsorpion was inhibid du o h compiion bwn hydrogn and coppr ions on h adsorpion sis, which rsrics h approach of mal caions. As h ph incrasd, h carbona groups in chickn ggshlls would b xposd, incrasing h ngaiv chargs on h adsorbn surfac, aracing h mal caions and allowing h adsorpion ono h adsorbn surfac [7]. B. Effc of Agiaion Ra on u(ii) Adsorpion Agiaion ra plays an imporan rol in h adsorpion procss and h ffc of agiaion spd on adsorpion capaciy of coppr has bn sudid by varying h agiaion spd from 5 35 rpm. Th coppr adsorpion prcnag a diffrn agiaion spds by chickn ggshlls is shown in Fig.. I has bn obsrvd ha h prcnag of coppr adsorpion incrasd wih incrasing agiaion spd du o h propr conac bwn h mal ions in soluion and h adsorbns binding sis ha promos ffciv ransfr of coppr ions o h adsorbns sis. Rsuls indicad ha h u(ii) adsorpion by chickn ggshlls rachd almos % a 35 rpm. A lowr spd, h adsorbn will accumula a boom and rsul in burial of various aciv sis undr h abov layrs of adsorbn [8].. Analysis of Adsorpion Isohrm Th uilibrium sudy is imporan for an adsorpion procss as i shows h capaciy of h adsorbn and h adsorpion isohrm is normally applid o dscrib h adsorpion mchanism for h inracion of caions on h adsorbn surfac. In h prsn sudy, xprimnal daa wr analyzd o xamin h adsorpion isohrm using Langmuir and Frundlich modls. Th Langmuir isohrm is applicabl o monolayr adsorba covrag on h adsorbn surfac [9], whras h Frundlich isohrm is an mpirical modl ha considrs hrognous adsorpion on h adsorbn surfac []. Th linarizd uaions for h Langmuir and Frundlich isohrms ar xprssd as (4) and (5), rspcivly: IJET-IJENS Fbruary 3 IJENS

3 Inrnaional Journal of Enginring & Tchnology IJET-IJENS Vol:3 No: 4 log b m m n logk F log (5) whr is h adsorba concnraion a uilibrium (mg/l), is h adsorpion capaciy a uilibrium (mg/g), b is h adsorpion uilibrium consan (L/mg) rlad o h apparn nrgy of adsorpion, m is h maximum adsorpion capaciy of absorbn (mg/g), n indicas h bond nrgis bwn mal ion and h adsorbn, and k F (L/g) is rlad o bond srngh []. Th linar plos of Langmuir and Frundlich uaions rprsning u(ii) adsorpion by h chickn ggshlls ar illusrad in Figs. 3 and 4. Th adsorpion consans of Langmuir and Frundlich uaions and hir corrlaion cofficins (R ) ar prsnd in Tabl I. Th valu of R is a masur of h goodnss-of-fi of xprimnal daa on h isohrm modls []. Rsuls showd ha h adsorpion procss by chickn ggshlls was br rprs nd by h Frundlich uaion compard o h Langmuir isohrm, whr h R valus wr found o b.988 and.736, rspcivly. This indicad ha h upak of coppr on chickn ggshlls was happnd hrough hrognous adsorpion. From Tabl I, h k F consan of Frundlich isohrm, which xprsss h slciv upak of coppr and affiniy of adsorbn was L/g, whras h /n valu was found o b Gnrally, h valu of /n ha is rlad o h disribuion of si bonding nrgis is ranging bwn..7 []. If /n is highr han, i indicas ha h surfac aras of adsorbn covrd by h mal ions incras, and h nrgis of adsorpion will dcras []. D. Analysis of Adsorpion Kinics Th kinic sudy of mal ion adsorpion is imporan o giv insigh ino h adsorpion ra, provid informaion on h conac im ruird for considrabl adsorpion o ak plac and also h facors affcing or conrolling h adsorpion ra. Th adsorpion of u(ii) by chickn ggshlls a diffrn conac im is shown in Fig. 5. Th adsorpion occurrd rapidly a h firs 5 minus and almos % adsorpion fficincy of u(ii) was aaind afr 6 minus. In ordr o invsiga h mchanism of u(ii) adsorpion by chickn ggshlls and h ponial ra-conrolling sps, wo of h mos commonly usd kinic modls, psudo-firsordr and psudo-scond-ordr kinic modls wr mployd o valua h adsorpion of u(ii). Th linar form of uaions for h psudo-firs-ordr and psudo-scond-ordr kinic modls can b rprsnd by (6) and (7), rspcivly. log k (6).33 log (4) (7) k whr is h adsorpion capaciy a im (mg/g), k is h firs-ordr racion ra consan (L/min) and k rprsns h scond-ordr racion ra consan (g/mg.min). Th plos of psudo-firs-ordr and psudo-scond-ordr modls ar illusrad in Figs. 6 and 7, rspcivly. A comparison of h racion ra consans and R valus simad from h psudo-firs-ordr and scond-ordr uaions is prsnd in Tabl II. From Tabl II, h R valu for h psudo-scond-ordr modl was highr han h psudo-firs-ordr modl. This showd ha h adsorpion of coppr on chickn ggshlls was wll-fid o h psudo-scond-ordr kinics modl compard o h firs-ordr modl. I can b concludd ha h psudo-scond-ordr kinics modl provids a good corrlaion for h adsorpion of u(ii) on chickn ggshlls and i also suggss ha h chmisorpion procss could b h ra-limiing sp in h adsorpion procss. Similar conclusion was also rpord for h adsorpion of havy mal ions by ohr adsorbns such as modifid groundnu husks, oil palm fibrs, was a lavs and r lavs was []. IV. ONLUSION Th rmoval of u(ii) from war by using chickn ggshlls has bn xprimnd undr svral condiions such as a diffrn ph, agiaion ra and conac im. Th opimum ph for coppr adsorpion was found a ph 7, whras h opimum agiaion ra was drmind a 35 rpm. From h analysis of adsorpion uilibrium, h corrlaion rgrssion cofficins showd ha h adsorpion procss was br dfind by Frundlich uaion. Rsuls also indicad ha adsorpion kinics of u(ii) adsorpion on chickn ggshlls followd h psudo-scond-ordr kinic modl whr h chmisorpion procss may b h ra-limiing sp in h adsorpion procss. This sudy shows ha chickn ggshlls hav high ponial o b usd as low-cos adsorbn for h rmoval of coppr from war. Sinc h mals upak by chickn ggshlls is highly dpndan on h numbr of aciv binding sis or funcional groups on h adsorbns, furhr rsarch can b ampd o nhanc h xising rsuls by modifying h chickn ggshll adsorbns using acids or bass. As a rsul of chmical modificaion, i is xpcd ha h numbr of aciv binding sis or funcional groups on h adsorbns migh b incrasd o improv h adsorpion capaciy of adsorbns. REFERENES [] S. Rahnakumar, R. Y. Shja, and T. Murugsan, Rmoval of coppr (II) from auous soluions using ak (Tcona grandis L.f) lavs, Inrnaional onfrnc on hmical Enginring and Tchnology, Augus 6-8, 9, Singapor IJET-IJENS Fbruary 3 IJENS

4 Adsorpion (%) Adsorpion (%) Inrnaional Journal of Enginring & Tchnology IJET-IJENS Vol:3 No: 43 [] E. S. Z. El-Ashoukhy, N. K. Amin, and O. Abdlwahab, Rmoval of lad(ii) and coppr(ii) from auous soluion using pomgrana pl as a nw adsorbn, Dsalinaion, vol. 3, pp. 6-73, 8. [3] A. Dabrowski, Z. Hubicki, P. Podkoscilny, and E. Robns, Slciv rmoval of h havy mal ions from wars and indusrial waswars by ion-xchang mhod, hmosphr, vol. 56, pp. 9-6, 4. [4] B. Volsky, and A. Lusch, Th influnc of film diffusion on cadmium biosorpion by marin biomass, Journal of Biochnology, vol. 43, pp. -, 995. [5] W. T. Tsai, J. M. Yang,.W. Lai, Y. H. hng,.. Lin, and. W. Yh, haracrizaion and adsorpion propris of ggshlls and ggshll mmbran, Biorsourc Tchnology, vol. 97, pp , 6. [6] A. Sad, Muhammad Ibal, and M. Wahd Akhar, Rmoval and rcovry of lad (II) from singl and mulimal (d, u, Ni, Zn) soluions by crop milling was (black gram husk), Journal of Hazardous Marials, vol. 7, pp , 5. [7] G. Kalyani, G. B. Rao, V. Saradhi, and P. Kumar, Euilibrium kinic sudis on biosorpion of zinc ono Gallus domsicus Shll Powdr, ARPN Journal of Enginring and Applid Scincs, vol. 4, pp , 9. [8] J. Anwar, Wahd-uz-Zaman, Umar Shafiu, Muhammad Salman, Amara Dar, and Shafiu Anwar, Rmoval of Pb(II) and d(ii) from war by adsorpion on pls of banana, Biorsours Tchnology, vol., pp ,. [9] O. O. Abdulrasa, and O. G. Basiru, Rmoval of coppr (II), iron (III) and lad (II) ions from mono-componn simulad was fflun by adsorpion on coconu husk, Acadmic Journals, vol. 4, pp ,. []. Arunlrar, W. Kawsomboon, A. Kumsopa, P. Pokhiiyook, and P. Panyawahanaki, Rmoval of lad from bary manufacuring waswar by gg shll, Songklanakarin Journal of Scinc and Tchnology, vol. 9, pp , 7. [] W. Kawsomboon, Rmoval of Lad from Bary Manufacuring Waswar by Egg Shll, Masr Thsis, Mahindol Univrsiy, Thailand, 6. [] M. Horsfall, and L. V. Jos, Kinic sudy of liuid phas adsorpiv rmoval of havy mal ions by almond r lavs was, African Journals Onlin, vol., pp , ph Fig.. Effc of ph on h adsorpion of u(ii) by chickn ggshlls Sirring ra (rpm) Fig.. Effc of sirring ra on h adsorpion of u(ii) by chickn ggshlls IJET-IJENS Fbruary 3 IJENS

5 Inrnaional Journal of Enginring & Tchnology IJET-IJENS Vol:3 No: c/ Adsorpion (%).5..5 y =.57x +.79 R = Euilibrium oncnraion of u(ii), c (mg/l) Fig. 3. Linar plo of Langmuir isohrm for h adsorpion of u(ii) by chickn ggshlls.5 log.5.5 y =.6473x +.43 R = log c Fig. 4. Linar plo of Frundlich isohrm for h adsorpion of u(ii) by chickn ggshlls onac im (min) Fig. 5. Effc of conac im on h adsorpion of u(ii) by chickn ggshlls IJET-IJENS Fbruary 3 IJENS

6 / (g.min/mg) log ( - ) Inrnaional Journal of Enginring & Tchnology IJET-IJENS Vol:3 No: y = -.98x R =.96 - Tim, (min) Fig. 6. Linar plo of psudo-firs-ordr kinic modl for h adsorp ion of u(ii) by chickn ggshlls y =.474x +.34 R = Tim, (min) Fig. 7. Linar plo of psudo-scond-ordr kinic modl for h adsorpion of u(ii) by chickn ggshlls T ABLE I ISOTHERM PARAMETERS FOR THE ADSORPTION OF U(II) BY HIKEN EGGSHELLS Langmuir isohrm Frundlich isohrm R m (mg/g) b (L/mg) R /n k F (mg/l) T ABLE II PARAMETERS OF KINETI MODELS FOR THE ADSORPTION OF U(II) BY HIKEN EGGSHELLS Psudo-firs-ordr modl Psudo-scond-ordr modl k (L/min) R k (g/mg.min) R IJET-IJENS Fbruary 3 IJENS