TAP CH PHAT TRIEN KH&CN, TAP 10, SO 01 - 2007

S DNG VT LIU HP PH T NHIN X L KIM LOI NNG TRONG BN THI CNG NGHIP
L c Trung, Nguyn Ngc Linh, Nguyn Th Thanh Thy. Vin Mi Trng & Ti Nguyn, HQG- HCM 1. M U Khi thi b ty tin BTCN vo mi trng, KLN s d dng pht tn sang mi trng t, nc mt v nc ngm. y l mi nguy him tim tng i vi sc khe ca con ngi cng nh h sinh thi t nhin [1, 3, 4]. KLN thng tn ti trong bn di 5 dng: dng ion; dng lin kt cacbonate; dng lin kt trong hoc lp ph bn ngoi khi (ht) rn vi st oxyt v mangan oxyt; dng lin kt trong cc phc cht hu c; dng tr, bn, gi trong cu trc cc ht khong, khng b gii phng trong iu kin t nhin [5, 13]. Trong nhiu thp k, cc phng php cng ngh x l bn thi thng c p dng bao gm thiu t, n nh v ha rn, chn lp hay phn hy sinh hc. Tuy nhin nhng bin php ny u c im hn ch chung l kh khn trong vic kim sot thnh phn KLN trong sn phm sau x l mt cch an ton nht [5, 6, 7, 11]. gii quyt vn bc xc ny, gn y trn th gii c xu hng x l KLN bng nhng VLHP c ngun gc t nhin c gi thnh thp. KLN dng linh ng c th c hp thu v c nh cht trong cu trc ca nhng VLHP [5, 6, 7, 9, 10, 11, 14, 15]. Trong nghin cu ny, zeolite t nhin qua s ch dng aluminosilicate ngm nc v chitin th l v tm cua c trong b thi thy sn c s dng lm VLHP KLN. n thi im hin nay, vic x l KLN bng cc loi VLHP c ngun gc t nhin vn ang c nghin cu pht trin ti nhiu trung tm, phng th nghim trn th gii. Khoa Ha, i hc k thut Athen, Hy Lp s dng zeolite t nhin x l KLN c trong bn sau x l nc thi t hiu qu cao i vi Cd, Cr, Cu, Fe, Mn, Ni, Pb, Zn. Vin Nghin cu Mi trng ca Trng North Highland College v Vin UHI Millenium nghin cu x l KLN bng chitin th nh gi hiu qu x l i vi cc kim lai kim th v KLN. Kt qu nghin cu cho thy hiu qu x l ca chitin th vi KLN cao hn vi kim loi kim th [10, 16]. Zeolite t nhin l tinh th aluminosilicate ngm nc cha cc cation nhm I hoc II ca bng h thng tun hon cc nguyn t ha hc, cng thc tng qut: (Mn/2).Al2O3.xSiO2. yH2O (M: kim loi ha tr I hoc II; n: ha tr ca kim loi M; x: t l SiO2/Al2O3). V c thnh phn ion linh ng v cu trc tinh th xp t ong vi l rng chim ti 50% m zeolite c kh nng hp thu (by) v c nh KLN (trao i ion) c trong bn thi [8]. Chitin th l v tm cua c trong b thi ca ngnh cng nghip thy sn c cha khong 23,8% chitin tnh theo trng lng kh. Khng c v khng th phn hy sinh hc, chitin l mt polysaccharide tm thy nhiu nht trong t nhin gm cc phn t [poly - - (1,4) N acetyl D glucosamin]. Phn t chitin c nhiu nhm chc OH nn c thm nc cao, cu trc cao phn t linh ng v cha nhng nhm chitin hot tnh cao c kh nng bt gi v lin kt hydro vi ion KLN. Chnh v vy ngoi zeolite, x l KLN trong bn thi chitin th cng l mt trong nhng VLHP rt c tim nng v kha cnh mi trng cng nh tnh kinh t do gi thnh cnh tranh [10]. i vi s gia tng khi lng bn thi c cha KLN t hot ng sn xut cng nghip [1, 3] v s thi b ty tin chng vo cc h thng knh rch trong thnh ph, th vic s dng thnh cng nhng VLHP sn c v r x l s m ra nhiu trin vng v ng gp tch cc nhm ngn nga v gim thiu nhim, bo v mi trng. to c s cho vic xut quy trnh cng ngh, trc tin phi chng minh c mc , hiu qu x l KLN thc t ca zeolite c ngun gc t nhin ti Vit Nam i vi BTCN, sau cn phi xc nh nhng yu t k thut

Science & Technology Development, Vol 10, No.01 - 2007 quan trng c nh hng trc tip n hiu qu ca qu trnh x l, v cng chnh l mc tiu ca nghin cu ny. Bn cnh , kt qu nghin cu s b i vi chitin th cng s to tin cho nhng nghin cu tip theo tm ra nhng VLHP khc cng c kh nng x l tng t nhm mang li hiu qu kinh t cao hn trong thc tin v mang ngha to ln v mt mi trng. 2. VT LIU V PHNG PHP 2.1. Vt liu Bn ly t b cha bn sau x l nc thi tp trung ti KCN L Minh Xun v bn t knh Tn Ha L Gm c c tnh v thnh phn mt s KLN c trnh by trong bng 1, 2 v 3. Cng vi thnh phn tng thnh phn nhng KLN ny dng linh ng c xc nh c th dng exchangeable v carbonate. Bng 1. Thnh phn tng mt s KLN trong bn thi ca KCN L Minh Xun STT Cu Cd Pb Cr mg/kg bn kh 110 93 340 5.174 90% 7 m pH

Bng 2. Thnh phn tng mt s kim loi nng trong bn thi ca knh Tn Ha L Gm STT Cu Cd Pb Cr mg/kg bn kh 982,7 5,6 302,5 2.811,1 m pH

81%

6,8

Bng 3. Nng kim loi nng trong bn thi ca KCN L Minh Xun dng linh ng v carbonate. STT Cr Cd Pb Ex (mg/kg bn kh) 84,25 < 0,001 < 0,001 Car (mg/kg bn kh) 369,75 < 0,001 3,3 Tng Ex v Car (mg/kg bn kh) 454 3,3 Cc dng cn li (mg/kg bn kh) 4.270 93 336,7

Zeolite s dng cho ton b cc th nghim l sn phm s ch t khong thin nhin ca Trung tm Ha du i hc Bch Khoa Tp. H Ch Minh, c cng thc ha hc: Na2O. Al2O3. 2,1SiO2. yH2O. Chitin th l v cua c ly t b thi sau quy trnh ch bin tht cua ti Cng ty Ch bin Thy hi sn s 5, Hn Hi Nguyn, Qun 11, Thnh ph H Ch Minh. Thit b th nghim c tnh ton, thit k v ch to ph hp vi c tnh ca i tng bn thi (2)(Hnh 1).

TAP CH PHAT TRIEN KH&CN, TAP 10, SO 01 - 2007

Hnh 1. M hnh th nghim

2.2. Phng php th nghim 2.2.1. X l mu: Mu bn c ph bng HNO3 m c v l vi sng. Sau o cc ch tiu (tng hm lng) ca Cr, Cd, Pb, Cu trn my quang ph hp th nguyn t (AAS). Kt qu thu c trong cho thy rng thnh phn tng ca crom v ch trong bn thi l cao (so vi tiu chun x thi, 200mg/kg bn kh) v cn phi c x l (Bng 1). Ton b cc th nghim c tin hnh trn c s c mu i chng vi cc bc: Nghim thc th nghim: bn thi c x l bng zeolite v chitin th. Nghim thc i chng: bn thi khng c x l. 2.2.2.Phn tch mu: Nng crom v ch trong bn trc v sau hp ph bi zeolite v chitin th c xc trn my quang ph hp thu nguyn t AAS 200 Varian. Nng tng dng tn ti ca KLN xc nh theo phng php trnh by trong bng 4 [5, 7, 13]. Bng 4. Cc dng tn ti ca KLN trong bn v cch xc nh STT Dng tn ti Cch xc nh X l vi MgCl21M, trong thi gian 1h, pH = 7 (chnh bng NaHC O3), khuy lin tc nhit phng. Sau ly tm 30 pht vi tc 5000/ph, lc v xc nh nng bng my AAS. B cn li sau khi ly tm xc nh dng exchangeable c x l vi CH3COONa1M, trong thi gian 5h, pH = 5 (chnh pH bng axit axetic), khuy lin tc nhit phng, sau ly tm, lc v xc nh nng bng AAS. Ph mu bng hn hp m c HNO3 : HCl (3/1), trong thi gian 10h, sau un han lu 80oC trong 2h. Sau lc v xc nh nng bng my AAS.

ion (exchangeable)

Carbonate (unstable)

Tng

3. CC BC THC NGHIM 3.1. Xc nh kh nng x l crom trong bn thi (KCN L Minh Xun) ca zeolite

Science & Technology Development, Vol 10, No.01 - 2007 a. Th nghim 1: Trn zeolite vi bn thi trong m hnh trn vi t l trnh by trong Bng 5. b. Th nghim 2 : Trn c s kt qu ca th nghim 1 v hiu qu x l t c vi nhng t l zeolite khc nhau tin hnh kho st tip nh hng ca thi gian x l (trn) n hiu qu x l. Th nghim c tin hnh vi thi gian trn khc nhau t 15 n 120 pht. c. Th nghim 3: Tin hnh kho st nh hng ca m hn hp bn zeolite n hiu qu x l vi nhng gi tr thch hp v t l zeolite cng nh thi gian x l thu c t th nghim 1 v 2. Bng 5. T l trn zeolite vi bn Mu Z0 Z1 Z2 Z3 % bn (theo khi lng) 100 90 80 70 % zeolite (theo khi lng) 0 10 20 30

3.2. Xc nh kh nng x l KLN trong bn thi (knh Tn Ha L Gm) ca Chitin th S b xc nh kh nng x l KLN trong bn thi ca Chitin th. T l trn v kch thc chitin th (v cua) trong bng 6, thi gian trn l 180 pht. Bng 6. T l v kch thc ca chitin th (v cua) trn vo bn thi T l trn Mu K0 K1 K2 K3 K4 K5 % bn (theo khi lng) 100 90 90 90 90 90 % zeolite (theo khi lng) 0 10 10 10 10 10 Kch thc v cua (mm) 0 0,1 0,2 0,3 0,5 0,7

4. KT QU V THO LUN 4.1. nh hng ca t l trn zeolite n hiu qu x l crom Hiu qu x l crom ph thuc t l trn zeolite khc nhau c trnh by trong Bng 7. C th thy rng hiu qu x l crom dng exchangeable cao hn dng carbonate. Khi t l trn zeolite tng t 1020% th hiu qu x l crom dng exchangeable thay i khng ng k t 74,48% ln 75,67%. Khi t l trn zeolite tng ln n 40% th hiu qu x l crom dng carbonate ch t 63,29%, gi tr ny l thp so vi 86,65% dng exchangeable.

TAP CH PHAT TRIEN KH&CN, TAP 10, SO 01 - 2007 Khi t l zeolite t 1020% th tng % crom c x l thay i khng ng k t 60,02% ln 60,80%. T cc kt qu ny, r rng rng t l zeolite 10% l ph hp nht v do vy s c chn khi tin hnh cc th nghim tip theo.

Bng 7. Hiu qu x l Crom ph thuc t l zeolite Crom dng Exchangeable Hm lng (mg/kg bn kh) 84,25 21,50 20,50 12,00 11,25 % b hp thu 0 74,48 75,67 85,76 86,65 Crom dng Carbonate Hm lng (mg/kg bn kh) 369,75 160,00 157,50 137,75 135,75 % b hp thu 0 56,73 57,40 62,75 63,29

Mu

% zeolite (theo khi lng) 0 10 20 30 40

Z0 Z1 Z2 Z3 Z4

4.2. Anh hng thi gian x l (trn) ti hiu qu x l crom ca zeolite Phn trm crom c hp thu theo thi gian x l khc nhau c trnh by trong Bng 8. Kt qu thu c cho thy hiu qu x l tng cng vi vic tng thi gian trn. Hiu qu x l tng nhanh sau chm li v khng thay i nhiu sau khong 60 pht. Trn c s nhng kt qu ny thi gian trn s c chn l 60 pht khi tin hnh cc th nghim tip theo. Bng 8. Mi quan h gia thi gian v hiu qu x l crom Crom dng Exchangeable Mu T0 T1 T2 T3 T4 T5 Thi gian trn 0 15 30 60 90 120 Hm lng (mg/kg) 84,25 47,00 38,50 21,50 19,00 18,00 % b hp thu 0 44,21 54,30 74,48 77,45 78,64 Crom dng Carbonate Hm lng (mg/kg) 369,75 246,00 208,00 160,00 155,75 152,75 % b hp thu 0 33,47 43,75 56,73 57,88 58,69

4.3. Anh hng m ca bn ti hiu qu x l crom ca zeolite Sau khi tin hnh th nghim kho st nh hng ca thi gian trn n hiu qa x l, yu t c kho st tip theo l nh hng ca hm m hn hp bn zeolite n hiu qu x l crom. Kt qu th nghim c trnh by trong Bng 9. Kt qu ny cho thy hiu qu x l crom tng khi tng hm m ca hn hp. Vi hm m tng t 8285% hiu qu x l tng chm v khng ng k. Do vy c th nhn xt rng hm m ca hn hp khong 85% l ph hp nht thu c hiu qu x l cao nh mong mun.

Science & Technology Development, Vol 10, No.01 - 2007 Bng 9. Mi quan h gia m hn hp bn zeolite v hiu qu x l crom Crom dng Exchangeable Mu m (%) Hm lng (mg/kg) 46,25 26,96 25,12 21,50 20,10 19,73 % b hp thu 45,10 68,00 70,18 74,48 76,15 76,58 Crom dng Carbonate Hm lng (mg/kg) 257,75 189,95 181,74 160,00 153,55 147,55 % b hp thu 30,29 48,63 50,85 56,73 58,47 60,10

A0 A1 A2 A3 A4 A5

72 75 80 83,33 85 90

4.4. S b xc nh kh nng x l KLN (ch) trong bn ca chitin th Kt qu th nghim kho st s b kh nng x l ch trong bn thi ca chitin th c trnh by trong Bng 10. Kt qu cho thy rng chitin th c kh nng x l hiu qu KLN trong bn thi. Vi hm m l 81% v thi gian trn 180 pht, kch thc 0,3mm v t l trn 10% theo khi lng th hiu qu x l ch dng linh ng (exchangeable v carbonate) bi chitin th l cao nht: t 84,72%. Bng 10. Hiu qu x l ch trong bn thi bng chitin th STT Ch dng Exchangeable Ch dng Carbonate Hm lng (mg/kg) 1.074,23 184,44 163,90 140,96 257,41 313,95 % b hp thu 82,83 84,74 86,92 76,04 70,77 Ch dng tng Exchangeable v Carbonate Hm lng (mg/kg) 1.108,87 203,95 192,19 169,38 282,33 336,95 % b hp thu 81,61 82,67 84,72 74,54 69,61

Hm lng (mg/kg) K0 K1 K2 K3 K4 K5 36,64 19,51 28,29 28,92 24,92 23,00

% b hp thu 43,68 18,33 16,51 28,06 33,60

5.KT LUN Mt s kt lun rt ra c t nghin cu ny nh sau: 1. Zeolite c th x l hiu qu crom c trong bn thi t KCN. 2. Cc yu t nh t l s dng zeolite, thi gian x l v hm m u nh hng ng k n hiu qu x l.

TAP CH PHAT TRIEN KH&CN, TAP 10, SO 01 - 2007 3. Qu trnh x l nn c tin hnh vi t l s dng zeolite l 10% (theo khi lng bn kh), thi gian x l (trn) t nht l 60 pht v hm m hn hp bn zeolite l khong 85%. Khi hiu qu x l Crom c th t ti hn 61%. 4. Nghin cu bc u cho thy v cua c trong b thi ngnh thy sn (chitin th) cng l VLHP c tim nng x l KLN trong bn thi cng nghip. Vi hm m l 81% v thi gian trn 180 pht, kch thc v cua 0,3mm v t l trn l 10% theo khi lng th hiu qu x l ch dng linh ng t 84,72%. TI LIU THAM KHO [1]. Nguyn ng Anh Thi, Nghin cu phng n x l bn thi cha kim loi nng sinh ra t h thng x l nc thi ca cc c s xi m, Lun vn cao hc, Vin Mi trng v Ti nguyn, (2002). [2]. V B Minh, Hong Minh Nam, Qu trnh v thit b trong cng nghip ha hc & thc phm, tp 2, c hc vt liu ri, Nh xut bn i hc quc gia Tp. H Ch Minh., (2004). [3]. Phan Thu Nga, nh gi, nhn xt hin trng qun l mi trng khu cng nghip Tp. H Ch Minh v khu vc pha nam, Bo co chuyn nghin cu sinh, Vin Mi trng v Ti nguyn., (2004). [4]. L Trnh, Tp bi ging c hc mi trng, Chng trnh cao hc Cng ngh mi trng., (2004). [5]. Antonis, A.Z., Evagelos, K., Giovanis A. Z., Panagiotis, K., Apostolos, V., Ioanna H., Maria L., Compost produced from organic fraction of municipal solid waste, primary stabilized sewage sludge and natural zeolite, Journal of Hazardous Materials, Vol 77, pp. 149159., (2000). [6]. Nissena, L.R., Leppa, N.W., Edwardsb, R., Synthetic zeolites as amendments for sewage sludge based compost, Chemosphers, Vol 41, pp. 265-269., (2000). [7]. Zorpas A., Constantinides, T., Vlyssides, A.G., Haralambous, I., Loizidou, M, Heavy metal uptake by natural zeolite and metals partitioning in sewage sludge compost, Bioresource Technology, Vol 72, pp. 113119., (1999). [8]. Baerlocher, CH., Meier, W.M., Olson, D.H., Atlas Of Zeolite Framework Types, Elsevier, New York, (2001). [9]. Byrapa, K., Masahiro, Y., Handbook of Hydrothermal Technology A technology for Crystal Growth and Materials Processing, William Andrew, Norwich, New York, USA., (2001). [10]. H. K. AN, B. Y. Park, D. S. Kim, Crab shell for the removal of heavy metals from aqueous solution. Korea (2001). [11]. Leonard, A., Theo, M., Willwm, H., Van, R, Metal immobilization in soils using synthetic zeolite, Journal of Environmental, Vol 31, pp. 813-821., . (2001) [12]. Natalia, M., Xavier, Q., Andrs, A., Antonio, G., Snchez, A., Carles, A., Immobilization of heavy metals in polluted soils by addition of zeolitic meterial synthesized from coal fly ash., (2001). [13]. European commission DG ENV. E3, Heavy metals in waste, Cowi A/s, Denmark.,(2002). [14]. Ona Gyliene, Romualdas Rekertas, Mudis Slkauskas, Removal of free and complexed heavy metal ions by sorbents produced from fly (Musca domestic) larva shells. Lithuania (2002).

Science & Technology Development, Vol 10, No.01 - 2007 [15]. Frederick, A.M, Using Zeolites in Agriculture. [16]. Rae IB, Gibb SW, Removal of metals from aqueous solutions using natural chitinous materials, Water Sci Technol.