ࡱ> QSPUVWXYZ[\]^_`abcdefghb c `Lebjbj .&%6666%%%8:%\%K2.&D&"f&f&f&_/_/_/"J$J$J$J$J$J$JALhN$JB0[/_/B0B0$J66f&f&JP;P;P;B0:68f&f&"JP;B0"JP;P;\FhntGf&"& !ƛ%|6FH4J0KFO:O tGtG&OGT_/"/P;//_/_/_/$J$J:^_/_/_/KB0B0B0B0> >666666 UKLANJANJE IONA NIKLA I KROMA IZ VODENIH OTOPINA UPOTREBOM OTPADNOG LJEVAONI KOG PIJESKA REMOVAL OF NICKEL AND CHROMIUM IONS FROM AQUEOUS SOLUTIONS BY USE THE WASTE MOULD SAND Raenovi*, J. Malina*, A. `trkalj*, L. urkovi** * University of Zagreb, **University of Zagreb Faculty of Metallurgy Faculty of Mechanical Engineering Aleja narodnih heroja 3 and Naval Architecture 44 000 Sisak Ivana Lu ia 5 Croatia 10002 Zagreb Croatia SA}ETAK U ovom radu procijenjena je mogunost upotrebe otpadnog ljeva kog pijeska iz ljevaonica eli nog lijeva za uklanjanje iona nikla i kroma iz vodenih otopina. Vrlo je interesantno uklanjanje navedenih iona iz vodenih otopina zbog njihovog atetnog utjecaja na ljudsko zdravlje i druge sustave u okoliau. Odreen je kemijski i mineraloaki sastav otpadnog ljeva kog pijeska. Utjecaj koncentracije i vremena kontakta na izdvajanje metalnih iona praen je primjenom jednostavne  batch tehnike. Rezultati ukazuju da je otpadni ljevaoni ki pijesak potencijalni jeftini materijal za uklanjanje toksi nih iona nikla i kroma iz vodenih otopina. Klju ne rije i: otpadni ljevaoni ki pijesak, ioni kroma i nikla, uklanjanje ABSTRACT The objective of this work was to evaluate the ability of using waste mould sand from steel foundry for removing nickel and chromium ions from aqueous solutions. Because of the harmful effect of these ions on human health and other environmental systems, their removal from solution has become very interesting. Chemical and mineralogical composition of the waste mould sand was determined. Simple batch experiments were carried out to study the effect of the concentration and contact time on the uptake of the metal ions. The results suggest that the mould sand is potential low-cost material for removal the toxic nickel and chromium ions from aqueous solutions. Key words: waste mould sand, nickel and chromium ions, removal UVOD Kalupni materijal se sastoji od mjeaavine pijeska, veziva, vode i odgovarajuih aditiva. Pri velikoserijskoj proizvodnji koristi se obi no kru~na ili osvje~ena mjeaavina, gdje se dio izgorenih aditiva i gline kao i isparene vode nadomjeatava pri svakom ciklusu [1]. estice pijeska zauzimaju 70-95% ukupnog kalupnog materijala u mjeaavini. U ljevaonicama se naj eae koristi kvarcni pijesak, a u manjoj mjeri pijesci drugih vatrostalnih materijala. isti kvarcni pijesak iji je osnovni sastojak SiO2, u obliku kvarca, slu~i za pripremu svje~ih kalupnih mjeaavina. Kvalitetni kvarcni pijesci trebaju sadr~avati minimalno 97% SiO2 [2]. Sastav kvarcnog pijeska odreuje se na osnovu kemijske analize, pri emu je va~an sadr~aj onih sastojaka koji imaju utjecaj na tehnoloaka svojstva, a to su: SiO2, karbonati i alkalije, oksidi i sulfidi ~eljeza [3]. Tijekom zadnje dvije dekade u injen je napredak u proizvodnji kalupa i jezgri uporabom kemijskih veziva. Ovi postupci uvelike su doprinijeli poboljaanju kvalitete odljevaka i poveanju produktivnosti. Premda u tehnoloakom smislu predstavljaju napredak, kemijski vezane mjeaavine posebno su problemati ne s aspekta zaatite okoliaa, tako da se njihovoj primjeni, regeneraciji i deponiranju mora posvetiti posebna pa~nja. Veliki problem za ljevaonice je i pitanje odlaganja otpadnog pijeska koji sadr~i atetne tvari. Stoga se u razvoju pojavljuje novi kriterij ocjenjivanja postupaka s glediata o uvanja okoliaa. Za svaku ljevaonicu nadvladavanje problema otpadnih i opasnih materijala je postao jednako va~an kriterij kao i odr~avanje kvalitete i profita. Cilj je svakako, smanjiti koli inu otpadnih tvari i izvraiti njihovu regeneraciju. U posljednje vrijeme se sve eae upotrebljavaju otpadni produkti iz razli itih proizvodnih procesa, pa tako i otpadni ljevaoni ki pijesak, za uklanjanje teakih metala iz otpadnih voda [4]. U ovom radu pokazana je mogunost koriatenja otpadnog ljevaoni kog pijeska za uklanjanje iona nikla i kroma adsorpcijom iz vodenih otopina. EKSPERIMENT Kao adsorbens iona nikla i kroma iz vodenih otopina koristio se otpadni ljevaoni ki pijesak s odlagaliata ljevaonice Felis produkti d.o.o. Sisak. Kemijska analiza (sadr~aj SiO2, Al2O3, Fe, Ca, Mg, Mn, Ni, Cr i C) otpadnog ljevaoni kog pijeska provedena je spektrometrijskom metodom na atomskom apsorpcijskim spektrofotometru (AAS, AA-6800, Shimadzu), a sadr~aj SiO2 je odreen gravimetrijski. Fazni sastav uzorka odreen je metodom XRD na ureaju Philips, PW 1830. Adsorpcija je praena mjerenjem koncentracije nikla i kroma prije i nakon uspostavljanja ravnote~e na ispitanom adsorbensu tzv. "batch" postupkom. Otopine nikla i kroma pripravljene su otapanjem NiCl2"6H2O, odnosno K2Cr2O7 analiti ke istoe u deioniziranoj vodi. Po etne koncentracije otopina iznosile su od 50-500 mg/l. Ispitani uzorci adsorbensa to ne odvage (1g) preneseni su u tikvice i uravnote~eni tijekom 0,5; 1; 1,5; 2 i 3 sata sa 50 ml otopine nikla, odnosno 50 ml otopine kroma razli itih koncentracija. Za potpuniji kontakt adsorbensa i adsorbata koriatena je laboratorijska tresilica. Nakon uspostavljanja ravnote~nog stanja, otopina je filtriranjem odijeljena od ispitivanih uzoraka otpadnog ljevaoni kog pijeska. Sadr~aj nikla i kroma u vodenim otopinama odreen je spektrofotometrijskim mjerenjem apsorbancije kod 450 nm za nikal, odno: B d f h l n x L D  2 Z \ ` p ķķķķķķķķij~nbhzh=5CJaJh|*/ha5CJaJmHsHh|*/haCJaJmHsHhX%mHsHh|*/hamHsHhX%mH sH hzhamH sH haha5CJaJmH sH h|*/ha5CJaJ h=<5hq5mH sH h=<h=<5mH sH h=<h=5 h=5hXh=5$d f h v  L \ ^ ` p r fh$a$gd=gd=gd=\^\gda $h^ha$gda $ & Fa$gda$a$gda$a$gda$a$gd=dFeJep h Hqotz7Wɽɽ}n_nPhjFh|*/CJaJmH sH hjFhoPCJaJmH sH hjFhaCJaJmH sH hjFha5CJaJmH sH hj#CJaJmH sH h/CJaJmH sH hoPCJaJmH sH h=<CJaJmH sH haCJaJmH sH hhaCJaJmH sH hzha5CJaJmH sH  hoPh= h=5hoPh=5h=h F`"%%%%$a$gdx|$a$gd|*/gd=gda$a$gd=$bd8j~FHR"XZ^`p|Zh ɾзззЬŬŬŬœŇhvWhx|hohhMhIO hs{<H*hMhIOh_OFH* hIOh_OFhH hIOhp hIOh|*/hs{< hIOh^h^h|*/h^5 h|*/5h|*/h|*/5hj#h2h=h=CJaJmH sH 2h r (!*!!!"0"2"6""######$$$^$d$f$h$j$$$B%Z%%%%%%%%%2&H&v&&&&&&&&''' ' '''<'@'H'L'''踴hNh%bH*hj#hj#H*hj#h%bhvW h%bh%b h%bhNhIhN5 hIOhp hIOh|*/h#?hNhs{<hVIhhx|hn*?%%%H)+ZBXCCCDD E"E8E:ENE $$Ifa$gdx($a$gd2$a$gdx|$a$gdqM$a$gdN''*(\(^(z(|(((((( )D)F)H)*>*n*************+++++++",,,,N-P-x------.D.F...../͹űűť͙ͥͥͥ hCMhCMh=hvWh!hqMhVIhVIH*hDGhNH*hCMh*WhVIhNhn*h%bhn*hn*H*mHsHhn*mHsHh3hNmHsHhVImHsHhNmHsH9sno 540 nm za krom na ureaju Camspec M-107. Sva mjerenja su provedena pri sobnoj temperaturi od 20C kod konstantne pH vrijednosti otopina (6,65 za nikal i 6,00 za krom). REZULTATI I DISKUSIJA U tablici 1 su prikazani rezultati kemijskog sastava otpadnog ljevaoni kog pijeska. U ispitanom uzorku najviae je SiO2 (90,0%), Fe (6,8%), i Al2O3 (1,6%). Tablica 1. Kemijski sastav ljevaoni kog pijeska KOMPONENTA SASTAV, %SiO290,0Al2O31,6Fe6,8Ca0,55Mg0,08Mn0,04Ni0,004Cr0,01C0,98 Kvarc (-SiO2) je bio jedina faza koja je identificirana ispitivanjem mineraloakog sastava primjenom XRD metode (slika 1).  EMBED CorelPhotoPaint.Image.8  Slika 1. Difraktogram analiziranog uzorka ljevaoni kog pijeska Primjenom jednostavne  bach tehnike praen je utjecaj koncentracije i vremena kontakta na izdvajanje metalnih iona iz otopine. Ovisnost udjela izdvojenog nikla i kroma o vremenu za po etnu koncentraciju metala u otopini (c0=300mg/l) prikazana je na slici 2.  Slika 2. Ovisnost udjela izdvojenog nikla i kroma o vremenu za koncentraciju metala c0=300 mg/l u otopini pri temperaturi od 20C Iz slike je vidljivo da je vee izdvajanje nikla u odnosu na krom kod istih uvjeta ispitivanja. Takoer je vidljivo da se izdvajanje ispitanih metalnih iona odvija razli itom dinamikom. Uo ena su dva stadija procesa adsorpcije; prvi je relativno brz, a drugi sporiji. Ravnote~no stanje je uspostavljeno nakon 3 sata. Kapacitet adsorpcije qe (mg/g), povezuje masu metala adsorbiranog po jednom gramu otpadnog ljevaoni kog pijeska ukazujui na intenzitet adsorpcije. Izra unat je poznavanjem razlike po etne (c0) i ravnote~ne (ce) koncentracije (mg/l) metala u otopini, mase adsorbensa (g) i volumena otopine (l) prema izrazu: qe= (c0-ce)"V/m. Iz serije eksperimenata sa otopinama iona Ni+2 i Cr+6 razli itih po etnih koncentracija, izra unat je kapacitet adsorpcije otpadnog ljevaoni kog pijeska i prikazan na slici 3.  Slika 3. Ovisnost kapaciteta adsorpcije otpadnog ljevaoni kog pijeska o po etnoj koncentraciji iona nikla i kroma Iz slike je vidljivo da porastom po etnih koncentracija metalnih iona raste adsorpcijski kapacitet otpadnog ljevaoni kog pijeska. Takoer je vidljivo da je postignut vei kapacitet adsorpcije za ione nikla, u odnosu na isti za ione kroma. Maksimalni kapacitet adsorpcije (qe=2,5 mg/g) je postignut za c0(Ni2+)=400 mg/l. Iako su za kapacitete adsorpcije otpadnog ljevaoni kog pijeska prema ionima kroma dobivene ni~e vrijednosti, porast qe s porastom po etne koncentracije Cr+6 iona je pravilniji. Ove rezultate nadopunjuju ispitivanja ovisnosti efikasnosti uklanjanja Ni+2 i Cr+6 iona o po etnoj koncentraciji u otopini (slika 4). Efikasnost uklanjanja metalnih iona Ei (%) izra unata je prema izrazu Ei= (c0-ce)/c0. Za ispitano koncentracijsko podru je od 50-500 mg/l efikasnost uklanjanja iona nikla je od 18-11%, a kroma od 9,9-5,1%.  Slika 4. Ovisnost efikasnosti uklanjanja metalnih iona o po etnoj koncentraciji u otopini ZAKLJU AK Upotrebom otpadnog ljevaoni kog pijeska mogue je uklanjanje iona nikla i kroma iz vodenih otopina u podru ju ispitanih koncentracija (50-500 mg/l). Uklanjanje iona nikla i kroma postignuto je adsorpcijom na otpadnom ljevaoni kom pijesku jednostavnom  batch tehnikom nakon 3 sata. Vei adsorpcijski kapacitet otpadnog ljevaoni kog pijeska je postignut za ione nikla. Efikasnost uklanjanja iona nikla gotovo je dvostruko vea od iste za ione kroma, unutar ispitivanog koncentracijskog podru ja. Otpadni ljevaoni ki pijesak je potencijalni jeftini adsorbens za uklanjanje toksi nih iona nikla i kroma iz vodenih otopina. Zahvaljujemo ljevaonici Felis produkti d.o.o. na ustupljenim uzorcima otpadnog ljevaoni kog pijeska za provedena ispitivanja. ZAHVALA Ovaj rad izraen u okviru projekta 124-1241565-1524, financiran je sredstvima Ministarstva znanosti, obrazovanja i aporta Republike Hrvatske. LITERATURA [1] Granlund, J. M., Swenson, L.; Sand Reclamation=Sand Savings with Proper Planning, Modern Casting 92 (2002), (8), 29-31. [2] Brankovi, M.; Tehnologija liva kih kalupa, Tehnoloako-metaluraki fakultet Univerziteta Beogradu, Beograd, 1982., 3-177. [3] Piwonka, T. S. Agregate molding materials, AFS Transactions 96 (1988), 208-211. [4] Kurniawan, T. A., Chan, G. Y. S., Lo, W., Babel, S.; Comparisons of low-cost adsorbents for treating wastewaters laden with heavy metals, Science of Total Environment 366 (2006), 409-426.     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