Al-Khriet Agricultural Waste Adsorbent, for Removal Lead and Cadmium Ion from Aqueous Solutions

Transcription

1 Al-Khwarizmi Enginring Journal Al-Khwarizmi Enginring Journal, Vol. 9, No., P.P (3) Al-Khri Agriculural Was Adsorbn, for Rmoval Lad and Ion from Auous Soluions Maha H. Al-Hassani Dparmn of hmical Enginring/ ollg of Enginring/ Univrsiy of Baghdad (Rcivd 5 Novmbr ; accpd 3 April 3) Absrac Th availabiliy of low- cos adsorbn namly Al-Khri ( a subsanc found in h lgs of Typha Domingnsis) as an agriculural was marial, for h rmoval of lad and cadmium from auous soluion was invsigad. In h bach ss xprimnal paramrs wr sudid, including adsorbn dosag bwn (.-) g, iniial mal ions concnraion bwn (5-) ppm (singl and binary) and conac im (/-6) h. Th rmoval prcnag of ach ion ono Al-Khri rachd uilibrium in abou 4 hours. Th highs adsorpion capaciy was for lad (96%) whil for cadmium i was (9%) wih 5 ppm ions concnraion, g dosag of adsorbn and ph 5.5. Adsorpion capaciy in h binary mixur wr rduc a abou 8% for lad and % for cadmium, which was aribud o compiiv adsorpion. Th adsorpion paramrs wr analyzd using boh h Frundlich and Langmuir. Al-Khri was bs fid by h Frundlich isohrm comparing wih Langmuir modl, and h ra consan was found o b.35 and.6 ((mg/g)(l/mg) /n ) for lad and cadmium rspcivly, whil h kinic of adsorpion obyd a scond ordr ra uaion and h ra consans wr found o b (.6) for lad and (.5) mg.g -.min - for cadmium. Kywords: Agriculural was adsorbn, Biosorpion, havy mal ions, isohrm kinic modl.. Inroducion Th rapid progrss in indusrial chnology and war rmnans in Ira causs an incras in h lvl of oxic ions dischargd ino h was war and hs mals ar harmful o h human and auaic livs. Many counris pay anion o his global issu and hy dvo concnrad ffors o solv his nvironmnal problm (Abdl-Ghani al., 9). Lad is on of h vry dangrous havy mals, which causs many dysfuncions in all human bings. In childrn, xcss amouns of his mal would probably lad o a dcras in hir IQ scor, and an impairmn of larning, haring, physical growh, h circulaing sysm, h rproduciv sysm, nrvous sysm spcially h brain, kidny funcions and som mnal disas such as dmnia, dprssion, madnss, as wll as problms in mabolism sysm.,.g., dficincy of viamin D, also incrasing lvl of his oxic mal may lad o dah (Okoy al.,, Okoro and Ejik, 7). Lad as (Pb + ) has a hug fficincy o h hio (-SH) and (PO 4 ) conaining nzyms and ohr dangrous molculs which in urn affcing h prmabiliy of kidny, livr and brain clls by inhibiing h synhsis of hams uni, lading o rardaion or brak down of hs organs funcion (Admoroi, 996). is anohr of havy mals wih a high oxiciy. Accumulaion of cadmium in h body rsuls in, diarrha, muscular cramps, nausa, ryhriis, problm in h vision, chronic pulmonary disas (PD), and cardio vascular disas (VD). Th world halh organizaion (WHO) gav h rcommndd sandards of drinking war which is.5mg d/l and. mg Pb/L (Munhr I. al.,). Whil in Ira in h rocar of Al-Eshaki bcaus of h ffc of Al- Somood company for sl indusry and powr plan in h souh of Baghdad, h lvl of oxic mals (d +,Pb + ) xcdd h allowd limi for xampl, h concnraion of cadmium ion was 8 mg/l and h concnraion of lad ion was

2 Maha H. Al-Hassani Al-Khwarizmi Enginring Journal, Vol. 9, No., P.P (3) mg/l which was mus highr han h prmissibl limis for drinking war. Many chnius such as ion xchang, prcipiaion, adsorpion, flocculaion, advanc oxidaion and mmbran procss hav bn usd for h rmoval of oxic mal ions (Shla al.,, Mohamad al.,). Th rason bhind our using h absorpion chniu is ha i is a vry conomical procss spcially whn using a locally availabl adsorbn (Saad Al-Jlil, ). Th ssnial bnfis of his absorpion procss for nvironmnal polluion ar: h low cos, simpl dsign asy opraion as wll as no ffc of oxic subsanc, whn comparing o ohr biological ramn procss (Yahia, 6, Hamd al., 9). This rsarch invsigad h possibiliis for using chap wasd marial, locally availabl in Ira namly Al-Khri which is found as a powdr in h lgs of Typha Domingsis as ponial adsorbn. Th Prsnc of his plan in indusrial was war indicas ha i rsiss h polluans. Th ffc of various paramrs including h adsorbn dosag iniial of mal ion concnraion (singl and binary) and conac im wr sudid ono Al-Khri powdr for rmoval lad and cadmium ion from auous soluion. By rviwing ohr liraur survys, i is obvious ha a fw of hm wr prformd on h conaminaion lvls of diffrn havy mals in h was war in Ira.. Marial and Mhods.. Marial Al-Khri was collcd from marshs in h souh of Ira. Firs i was washd wih dionizd war o rmov h suspndd paricl and hn drid in h air for wo days bfor drying in an ovn a for 4 hours, Finally Al-Khri powdr was sord in discaor... Exprimnal Work Diffrn concnraions of d +,Pb + auous soluion wr prpard from h sock of 5 mg/l soluion prpard by dissolving agn grad Pb(NO 3 ).H O and d(no 3 ) in dionizd war, h propris of hs compound wr shown in Tabl. Adsorpion was prformd in a bach xprimn. Th uilibrium isohrms wr drmind by mixing.5gm of Al-Khri wih 5 ml of d +,Pb + soluions in a conical flask a diffrn concnraion (5,,5 and ) mg/l. Flasks wr shakn in a shakr (yp B,Baun Karlkob) for 4 h a room mpraur. I was noicd ha h adsorbd mals ions of adsorbn sysm rachd o uilibrium afr 4 h. This phnomnon was clarly sn in a sris of xprimns of diffrn im inrvals which showd ha h adsorpion procss rachd uilibrium afr 4 h. Soluion and adsorbns wr sparad by filring hrough a filr papr. Th concnraion of h solu in soluion was drmind by using aomic absorpion spcrophoomric (yp Prkin-Elmr-5, USA). Th adsorbd amoun was calculad by h following uaion: V( ) = () w Whr (mg/g) is h amoun adsorbd a uilibrium, V (L) is h volum of soluion,, (mg/l) is h iniial and uilibrium concnraion, w (g) is h amoun of adsorbn. Th adsorpion kinic was analyzd by adding.5 g of Al-Khri o 5 ml of 5 mg/l of d +, Pb + soluions. Th sampls wr shakn and xamind a diffrn im inrvals. Th ffc of adsorbn dosag and iniial concnraion of h fd soluion wr also sudid by using diffrn amoun of adsorbn (.-) gm for iniial concnraion of (5-) mg/l (singl and binary). Th ph valu for cadmium and lad wr 5.5 bfor and afr mixing wih adsorbn..m of NaOH and Hl wr usd for ph adjusmn o fix h ph valu in all xprimns. Tabl, Physical Propris of Adsorba. Adsorba Lad Nira Nira Molcular wigh (g/mol) War solubiliy (g/ ml HO ) a Rsuls and Discussion Th rmoval fficincy was calculad by h uaion blow f Rmoval fficincy( R) = * () 7

3 Maha H. Al-Hassani Al-Khwarizmi Enginring Journal, Vol. 9, No., P.P (3) Whr and f ar h iniial and final ions concnraions, rspcivly. 3.. Effc of onac Tim As shown in Fig., h prcn rmoval of lad ion and cadmium ion by adsorpion ono Al-Khri incrass wih conac im and aain uilibrium in abou 4 h. Rmoval fficincy ual o (94.6%) and (85.9%) for lad and cadmium ion rspcivly a ph 5.5 and of 5 ppm ions concnraion and.5 gm of adsorbn in 4 h. Th rsul indicas ha h ra of sorpion of boh ions on Al-Khri was fas bcaus of a largs amoun of d +,Pb + aachd o h sorbns wihin h of adsorpion. Similar rsuls wr rpord by Mahvi al.,(7), Ajmal al.,(3) and Madhava al., (8). This bhavior suggss ha h iniial sag, sorpion aks plac rapidly on h xrnal surfac of h Al-khri followd by a slowr inrnal diffusion procss, which may b h ra drmin sp. Th rason bhind our sudying his par bcaus h uilibrium im is on of h paramrs for conomical was war ramn plan applicaion. Ths obsrvaion agr wll wih h invsigaion by Hamd al., (9). Lad was found o adsorb mor han cadmium, ha is du o is diffrn affiniis of wo ion for h raciv funcional groups locad on h surfac of Al- Khri powdr. Rmoval prcn% im(min) Lad 3.. Th Effc of Al-Khri Dos on Ions Adsorpion Th rlaion bwn Al-Khri dos and % rmoval fficincy of d + and Pb + ar shown in Figs. and 3. Th xprimns wr carrid ou a ph 5.5 and fixd d + and Pb + iniial concnraions for boh singl and binary of 5 ppm soluion on Al-Khri. As can b dpicd from hs figurs, whn Al-Khri dos incrasd, h upak of boh ion dcrasd and h prcn rmoval incrasd for boh singl and binary soluion du o h gra possibiliy of xchangabl sis or surfac ara. I is apparanc ha by incrasing h dosag from (.-) g, h prcn rmoval incrasd from (9% o 96%) for lad and from (83% o 9%) for cadmium as shown in Fig.. Figur 3. shows ha h adsorpion curv for wo solu oghr. In h binary soluion adsorpion prcn rmoval of Pb + and d + wr 88%, 79% wih g dosag and 5 ppm ion concnraion. This indicas ha h adsorpion capaciis of h adsorbn obsrvd in binary mixur bach xprimns wr lowr (abou 8% for Pb and % for d) han ha obsrvd in a singl solu, which was aribud o compiiv adsorpion. ompiiv adsorpion rsuls from h availabl adsorpion sis xising on h surfac of h adsorbn whn prsn in a muli-componn mal ion auous soluion. I was found ha h rmoval fficincy of Al-Khri for Pb + is grar han d +. I can b clarly sn from abl ha lad nira is lss solubl han cadmium nira which aribu o hir molcular wigh, duo o h fac ha h highr molcular wigh, h lowr solubiliy in a war is similar rnd was rpord by Riaz Qadr (). This bhavior migh b also aribud o h molcular siz. Lad ion has h smallr molcul han cadmium ion, hus i migh b visibl for on paricular por hold mor lad ions molculs han cadmium ions molculs. Th dcrasing rnd in adsorbd phas concnraion for cadmium ion is du o h lss availabiliy of sis on h Al-Khri bcaus of h compiiv ffc of lad ions. Fig.. Effc of Tim on h Rmoval Efficincy using Al-Khri as Adsorbn, Biomass Dosag.5 g, ph 5.5, 5 rpm, d +, Pd + oncnraion 5 ppm. 7

4 Maha H. Al-Hassani Al-Khwarizmi Enginring Journal, Vol. 9, No., P.P (3) 9 Rmoval prcn % Lad R% Lad Adsorbrn dosag ppm Fig.. Effc of Adsorbn Dosag on h Prcn Rmoval for Singl of d +, Pb + by Al-Khri, onac Tim 4 h, Iniial oncnraion for Boh Ion 5ppm. Fig. 4. Rmoval of d +, Pb + Ion using Diffrn oncnraion of Ions Adsorpion Kinic Modl Rmoval prcn % Adsorbrn dosag Lad Th psudo firs ordr modl (PFOM) (Augusin and Emmanual,) is givn by h following uaion ln( ) = ln k (3) Th psudo scond ordr modl (PSOM) (Augusin and Emmanual,) is givn by h following uaion = k + (4) Fig. 3. Effc of Adsorbn Dosag on Prcn Rmoval for Binary Sysm of d +, Pb +, using Iniial oncnraion for Each Ion 5 ppm Effc of Iniial d +, Pb + Ions oncnraion Figur 4 showd h rlaion bwn h prcn rmoval fficincy and h iniial ions concnraion of d + and Pb +, as h iniial ions concnraion incras h prcn rmoval dcrass. Tha is bcaus a highr concnraion, numbr of havy mals wr rlaivly highr in comparison wih h availabiliy of adsorbn sis. Ths obsrvaion agr wll wih h invsigaion rpord by Sulaymon al., (Sulaymon al.,). Whr is h amoun of ions adsorbd a uilibrium (mg.g - ), is h amoun ions adsorbd a im in ( mg.g - ), k (min - ) and k (g/(mg.min)) ar h ra consans of PFOM and PSOM rspcivly. Th PFOM and PSOM plos shown in Fig. 5 and 6. kand k for d +, Pb + as wll as corrlaion cofficin obaind ar prsnd in abl. I can b found ou ha h obaind corrlaion cofficin for PSOM wr grar han for PFOM. Ths suggs ha h adsorpion sysm is h scond ordr modl basd on assumpion ha h boh sorba (Pb,d) and Al-Khri ar involvd in a ra drmining sp, which may b a chmical sorpion rahr han diffusion. (Ho and Mckay, 998). 7

5 Maha H. Al-Hassani Al-Khwarizmi Enginring Journal, Vol. 9, No., P.P (3) ln( - ) im Fig. 5. PFOM Plos for d +, Pb +. Lad Frundlich and Langmuir (Ajay al., ) isohrms according o h following uaion: = n (9) Frundlich k b m = () Langmuir + b Euaions 9 and can b wrin in linar form as givn blow rspcivly ln = lnk f+ ln () n = + () b m m / im(min) Fig. 6. PSOM Plos for d +, Pb +. Lad Tabl, Th Ra onsan and orrlaion officin for Psudo Firs and Scond Ordr for Boh Ions. Kinic modl Paramrs Pb + d + PFOM k (min - ).6.99 (mg/g).5. R PSOM k (mg.g -. min - ) (mg/g) R Whr and ar h uilibrium concnraion of lad and cadmium in adsorbd and liuid phas in mg/g and mg/l, rspcivly, k and n ar h Frundlich consans which can f b calculad from h slop and inrcpd of h linar plo wih ln vs. ln. m and b ar Langmuir consans which can b calculad from h inrcp and slop of h linar plo / vs.. Th Frundlich and Langmuir isohrms ar shown graphically in Figs. 7 and 8. Th fid consan for wo modls ar abulad in abl (3). Tabl (3) indica h Frundlich modl provids h bs fi as judgd by is corrlaion cofficin for Pb + and d +. Th n valu of Frundlich modl bwn and, indicas good adsorpion fficincy (Trybal,98). This dmonsra ha h dvlopd adsorbn has good adsorpion fficincy for Pb +,d + rmoval. ln() Lad 3.5. Euilibrium Isohrms Th uilibrium isohrm display a nonlinar dpndnc on h uilibrium concnraion. Th obaind adsorpion daa wr analyzd using ln(c) Fig. 7. Adsorpion Isohrm of Pb,d a ph (5.5) by using Frundlich. 73

6 Maha H. Al-Hassani Al-Khwarizmi Enginring Journal, Vol. 9, No., P.P (3) / Lad gram dosag of adsorbn and ph 5.5, whil h mixd havy mal wr rducd a abou 8% for Pb and % for cadmium. In his sudy of kinic of adsorpion, h PSOM provids br corrlaion of sorpion daa han h PFOM, whil h adorpion uilibrium was br dscribd by Frunlich modl han Langmuir modl. Hnc h marial Al-Khri undr considraion would b usful conomical ramn of was war conaining lad and cadmium mal. 5. Rfrncs Fig. 8. Adsorpion Isohrm of Pb,d a ph (5.5) by using Langmuir. Tabl 3, Paramr of Isohrms for d,pb and orrlaion officin for Frundlich and Langmuir Isohrm R. Kinic modl Langmuir Frundlich Paramrs Pb + d + m (mg/g) b L/mg.7.8 R k 4. onclusion f mg g ( L mg ) n.35.6 n R Th invsigaion show ha Al-Khri a local naural agn which is ar abundan and low cos, hrfor can b usd as a bioadsorbn for rmoval Pb +, d + ions from auous soluions. I was nod ha rmoval procss incrasd wih conac im and aains sauraion in abou 4 h. Th rapid kinic of adsorpion procss has significan pracical imporanc nsuring fficincy and conomy. Also h adsorpion of Pb +, d + on Al-Khri was dpndn on iniial concnraion and dosag of adsorbn. Adsorpion capaciy for cadmium was lss han ha for lad, Th highs adsorpion capaciy was for lad (96%) and for cadmium (9%) wih 5 ppm ions concnraion, [] Abdul-Ghani N.T., A.K. Hgazy, G.A.El- haghaby,9. Typha domingnsis laf powdr for dconaminaion of Aluminum, iron,zinc and lad, Biosorpion kinics and uilibrium modling, In. J.Environ. Sci. Tch., 6(), [] Admoroi,.M.A., 996. Environmn chmisry and oxicology,polluion by havy mal. Foludx prss, 7-7. [3] Ajay Kumar Mna, hira Rajagopal, Kiran and GK Mishra.. Rmoval of havy mal ion from auous soluion using chmically (Na S) rad granular acivad carbon as an adsorbn, Journal of scinific and indusrial rsarch vol 69, pp [4] Ajmal,M.,Roa,R.A., Anwar,S., Ahmad,J., Alunad,R. 3.Adsorpion sudis on ric husk., rmoval and rcovry of d(ii) ion from was war, Biorsour.Tchnol., 86(), [5] Augusin E. Ofomaja, Emanul I.,. Adsorpion kinics of 4-nirophnol ono a cllulosic marial, mansonia wood saw dus and muli sag bach adsorpion procss opimizaion, carbohydra polymrs, 83,9-6. [6] Hamd B.H., J.M. Salman,A.L. Ahmad. 9. Adsorpion isohrm and kinic modling of,4-d psicid on acivad carbon drivd from da son, Journal of Hazardous marials, 63, -6. [7] Ho,Y.S. Mckay,G.A., 998. omparision of chmisorpion kinics modl applid o polluan rmoval or various sorbns. Transacions of h insiuion of chmical nginring, 76B, [8] Madhav M. Rao,G.P.handra Rao, K. Sshaiah, N.V. Ghoudary, M..Wang. 8. Acivad carbon from iba pnandra hulls, an agriculur was as an adsorbn in h 74

7 Maha H. Al-Hassani Al-Khwarizmi Enginring Journal, Vol. 9, No., P.P (3) rmoval of lad and zinc from auous soluion", was managmn, 8, [9] Mahvi,A.H., Nour,J,Qmani, G.A., Gholami,F., 7. Applicaion of plaanus orinalis lavs in rmoval of cadmium from auous soluion. World Appl. Sci. J., (3), [] Mohamad M. Ayad, Ahmd Abu El-Nasr, Jaroslav Sjskal,. Kinics and isohrm sudis of mhyln blu adsorpion ono polyanilin nanoubs bas / silica composi, J. Ind. Eng. hm. hp://dx.doi.org/.6/j.jic. [] Munhr I.Kandah, Fahmi A. Abu Al-Rub, Lucy Bawarish, Mira Bawarish, Hiba Al- Tamimi, Rm Khalil, and Raja'a Saad,. Adsorpion of ono Acivad and Non-Acivad da pis, world Acadmy of scinc, Enginring and Tchnology, 6. [] Okoro,I.A.,Ejik,E.N.,7.Sorpion modl of Pb(II) rmoval from auous soluion using common dibl frui was, Eur.J.Sci.Rs., 7(), [3] Okoy A.I., P.M.Ejikm, O.D.Onukwuli,. Lad rmoval from waswar using flud pumpkin sd shll acivad carbon Adsorpion modling and kinics, In.J.Environ.Sci.Tch., 7(4), [4] Riaz Qadr,. A sudy of h adsorpion of phnol by acivad carbon from auous soluion, Yurk.J.chm.,6, [5] Saad, A. Al-Jlil,, Rmoval of havy mals from indusrial waswar by adsorpion using local bnoni clay and roasd da pis in Saudi Arabia. Trnds in Applid scinc rsach 5(), [6] Shla T.,Y.Arhoba Nagaka,R. Viswanaha, S. Basavanna, T.G.Vnkasha,.Kinics and hrmodynamics sudis on h adsorpion of Zn(II), d(ii) and (HgII)from auous soluion using zinc oxid nanoparicls, Powdr Tchnology, 7,63-7. [7] Sulaymon, Abbas H., Shahlaa E. Ebrahim, Sama M. Abdullah,Tari J.Al-Musawi,. Rmoval of lad,cadmium and mrcury ion using biosorpion, dsalinaion and War Tramn, 4, [8] Yahia A.Alhamd, 6, Acivad carbon from das son by Znl acivaion, IKAV: Eng. Sci. vol.7 no.,

8 مھا ھادي مصطفى مجلة الخوارزمي الھندسیة المجلد 9 العدد صفحة (3) استخدام الخریط كماده مازه لازالھ ایونات الرصاص والكادمیوم من المحالیل الماي یھ مھا ھادي مصطفى الحسني قسم الھندسة الكیمیاویة/ كلیة الھندسة/ جامعة بغداد الخلاصة یھدف البحث الى استخدام النفایات الزراعیھ المتوفره محلیا وباقل كلفھ لازالة المركبات الثقیلھ كالرصاص والكادیمیوم من المحالیل الماي یھ كالخریط وھو ماده موجوده في سیقان نبات البردي كماده مازه. تم دراسة تا ثیر تركیز الماده المازه تركیز أیونات الرصاص والكادیمیوم بصوره منفرده وممزجھ معا وزمن الا متزاز عن النسبھ الموي یھ للا زالھ والكمیھ الممتزه. تم الحصول عاى نسبھ ازالھ للرصاص ٩٦% وللكادیمیوم ٩٠% عن الظروف التشغیلیھ درجھ حامضیھ ٥,٥ وكمیة الماده المازه ١ غم وتركیز الا یونات ٥٠ ملغم لكل لتر وزمن الا متزاز ٤ ساعھ وعند مزج الا یونات قلت نسبة الا متزاز بحوالي ٨% للرصاص و ١٢ % للكادیمیوم بسب ظاھرة التزاحم والتنافس على المراكز الفعالھ للخریط. تم استخدام معادلة لانكمایر وفریندلج بشكل ناجح, وكان استخدام معادلھ لانكمایر لتمثیل نتاي ج امتزاز كل من الا یونات بشكل افضل من معادلھ فریندلج حیث كان معدل ثابت لانكمایر ١,٣٠٥ و ٠,٦٢١ ملغم\ غم لكل من الرص اص والك ادیمیوم عل ى الت والي بینم ا حركی ة عملی ة الا متص اص تمثل ت بمعادل ھ م ن الدرج ھ الثانی ھ حی ث ك ان مع دل ثاب ت الا متص اص ٠,٠٦١ و ٠,٠١٢٥ ملغم\غم دقیقھ لكل من الرصاص والكادیمیوم على التوالي. 76