CHNG 1 : M U

Ngy nay vn mi trng ngy cng c th gii quan tm, khi nim cng nghip xanh, pht trin bn vng ang c chp nhn rng ri v tr thnh tiu ch quan trng i vi mi hot ng cng nghip. Ti Vit Nam trong nhng nm gn y, nn kinh t c bc pht trin vt bc, mang li i sng ngy cng tin nghi cho ngi dn. Nhng cng vi l s gia tng ca tnh trng nhim mi trng, i hi chng ta phi c nhn nhn ng n v u t xng tm cho cng tc qun l mi trng, qun l hot ng sn xut cng nghip v vn x l cht thi cng nghip, cng nh cht thi sinh hot. Nh nc, ngi dn v cc doanh nghip ang dn thay i t duy, hnh ng nhm kt hp hi ha ba mc tiu kinh t - x hi mi trng. Cng vi s pht trin ca nn cng nghip c nc, ngnh xi m pht trin nhanh chng c v cng ngh, s lng cc cng ty, sn lng v cht lng sn phm. Tuy nhin c mt thc t ng lo ngi l a s cc cng ty hot ng trong lnh vc xi m t ch trng n vn x l nhim, mc d cht thi t ngnh ny c xp vo cht thi nguy hi. Cc cht thi, nc thi thng c cc cng ty thi ra mi trng m khng qua x l, hoc x l cha t tiu chun x thi. iu ny c gii thch bi cc l do: x l nc thi nh hng ln n gi thnh sn phm v li nhun ( khong 10-15% gi thnh), nhng hn ch v kinh t, cng ngh v thiu s quan tm t pha ban lnh o. Ti cng ty TNHH Thng mi & Sn xut Thanh Lun, l mt cng ty sn xut kinh doanh cc sn phm trong ngnh xi m c uy tn ti thnh ph H Ch Minh, v ban lnh o cng ty cng lun ch trng vn x l nc thi trc khi x thi ra mi trng. Tuy nhin, do hn ch v cng ngh nn cht lng nc sau x l thng xuyn khng t tiu chun x thi, y l mt vn ln m cng ty rt lo ngi.

V nhng l do trn, m ti Nghin cu .. ti . c ngh thc hin.

CHNG 2 HIN TRNG 2.1 TNG QUAN NH MY Tn cng ty: Cng Ty TNHH SX & TM Thanh Lun. a ch: 930 C1, ng C, KCN Ct Li, P. Thnh M Li, Qun 2, TP.HCM. Giy php kinh doanh s: 072345. Ngy cp: 15/07/1999. Ni cp: S k Hoch v u T Tp. H Ch Minh. Lnh vc kinh doanh : M in v x l b mt kim loi. Gia cng cc sn phm c kh. Kinh doanh ha cht ngnh m. Phn tch dung dch m. Kim tra lp m. 2.2 CC DY CHUYN M ANG VN HNH M km t ng thng quay. M km t ng gi treo . M ng m v ng bng. M thic. M crm. M niken. M nha ABS.

2.3 H THNG THU GOM NC THI

2.3.1 dng thi Nc thi bao gm : Nc dng ty ra phi. Nc dng ty ra bn thnh phm t cc cng on. Nc ra sn phm sau m. Ha cht hng, nc ra thit b, dng c sn xut. Ha cht, nc thi t phng th nghim. c thu gom bng ng ng, h thng mng, rnh thu v a v hm thu gom. Hin ti, nc thi c phn ra thnh 3 dng tng i tch bit : Dng thi cyanua : bao gm nc thi ca cc quy trnh m cyanua nh m ng cyanua, m niken cyanua, m a lp ng - niken crom. Dng thi axit : cha cc ion kim loi nng, c ngun gc t qu trnh ra sau m, ra sau th ng ha, v ra sch sn phm trc khi lm kh ca cc quy trnh m km axit, m niken, ng , m nhav nc thi phng th nghim. Dng thi baz : c ngun gc t qu trnh ra phi s b, ty du, ty r v nc ra cc quy trnh m c pH > 7, ha cht hng c pH > 7. 2.3.2 Lu lng v tnh cht dng thi Bng 2.1 Lu lng v tnh cht dng thi Dng thi Cyanua Thng s Q = 3 ~ 6 m3/ngy. Qmax = 12 m3/ngy . pH = 10 ~ 13. [CN-] = 60 ~ 100 mg/l. Cu2+ = 200 ~ 450 mg/l. Ni2+ = 20 ~ 50 mg/l. Axit Q = 50 ~ 60 m3/ngy . Qmax = 100 m3/ngy.

pH = 3 ~ 7. Cu2+ = 50 ~ 70 ppm. Ni2+ = 20 ~ 50 ppm. Zn2+ = 140~ 170 ppm. Al3+ = 10 ~ 20 ppm. Fe tng = 500 ~ 800 ppm. Baz Q = 40 ~ 60 m3/ngy. Qmax = 80 m3/ngy. pH = 8 ~ 12.

2.4 H THNG X L NC THI

2.4.1. Quy trnh x l

Hnh 2.1 Quy trnh x l nc thi Thuyt minh : Nc thi t h thng sn xut c tch thnh ba dng thi v c a v ba hm cha ring bit : hm cha cyanua (3), hm cha baz (9), hm cha axit (10). Do th tch hm cha cyanua khng ln, khi mc nc thi trong hm y, chng c bm vo bn d tr (1). Nc thi t hm (3) v bn (1)

c bm vo bn phn ng (2). o pH trong bn bng cch ly mu ri o bng giy qu. Sau , ty theo gi tr ca pH ny, baz c a vo nng pH ln mc pH = 10. Javen c bm vo bn nhm oxi ha CN- thnh CO2 v N2. Th tch javen bm vo c xc nh thng qua thi gian bm ha cht. Trong bn phn ng c cnh khuy c kh. Sau 1h, cng nhn ly mu trong bn phn ng, lng, v kim tra bng mt thng. Nu nc sau x l c mu vng ca javen, qu trnh x l c xem l t hiu qu, nu nc cn mu xanh nht, javen c bm thm vo bn, tip tc khuy trn trong 30 pht. Sau , axit c bm vo trung ha nc thi v pH = 7. Kt thc giai on x l cyanua, nc thi c bm ln bn phn ng baz (5). Nc thi axit t hm thu (10) c bm ln bn phn ng (4) . Axit c bm vo iu chnh pH v pH = 4 nu cn thit. Phn st c bm vo kh Cr+6 thnh Cr3+ . Thi gian kh 10 pht. Sau kh, xt c bm vo n pH = 7.5 kt ta cc ion kim loi. Thi gian phn ng 5 pht . Bm PAA nhm keo t, tng kch thc ht ta. Sau , nc thi c bm sang b lng (6). Trong b phn ng c cnh khuy c kh, vn tc khuy c gi c nh. Nc thi baz t hm thu (9) c bm ln b phn ng (5), sau phn st c thm vo ng t huyn ph. Xt v axit thm vo iu chnh pH. PAA cng c thm vo keo t cc ht ta. Sau , nc c bm sang b lng (6) Nc trong b lng c khuy chm bng cnh khuy trong 5 pht. Sau yn. Sau 20 pht, nc thn trn b lng c dn sang cc b lc (7), phn nc cha cn y c dn sang hm cha bn (8). y cc b lc c lp ct mng v cc bao ti cha ct. Nc chy chm qua ng x ra cng. Ct ln cn c thay mi nh k. Bn trong hm cha bn (8) c p nh k bng my p bn (11). Nc sau nn bn c dn v hm cha nc thi baz (9). Bn sau nn a v sn phi bn (12), phi kh v ng bao.

2.4.3 Kim sot quy trnh Hin ti, dy chuyn x l cha c h thng kim sot quy trnh t ng. Mi m x l u c o pH u vo, u ra bng my o cm tay. Nng cc ion kim loi, cyanua sau x l c o nh k mi ngy. Thi gian s dng ha cht l lng ha cht tiu hao c ghi li trong s theo di sau mi m x l. 2.4.4 Cht lng nc sau x l a. Kt qu phn tch nc thi ( trch s liu thng k kt qu x l nc thi ca B phn x l nc thi, cng ty TNHH TM & SX Thanh Lun) Bng 2.1 Cht lng nc thi sau x l n v tnh : ppm Ngy QCVN 24/Ct B 14/02/2011 16/02/2011 18/02/2011 21/02/2011 22/02/2011 23/02/2011 24/02/2011 05/02/2011 01/03/2011 02/03/2011 05/03/2011 07/03/2011 09/03/2011 12/03/2011 14/03/2011 16/03/2011 18/03/2011 CN0.1 0.1 0.05 0.01 0.00 0.2 0.1 0.15 0.16 0.01 0.2 0.02 0.15 0.08 0.08 0.05 0.05 0.05 Cu 2 0,81 0,75 0,61 0,8 3,71 2,8 2,95 3,76 1,13 5,2 0,7 1,3 1,85 0,8 1,17 0,85 0,61 Cr(VI) 0.1 0,035 0,01 0,05 0,07 0,02 0,08 0,01 0,07 0,041 0,04 0,1 0,09 0,03 0,13 0,21 0,07 0,1 Ni 0.5 0,04 0,06 0,01 0,12 0,75 0,86 0,91 0,75 0,17 0,96 0,07 0,13 0,17 0,7 0,15 0,18 0,09 Zn 3 0,65 0,81 1,03 1,1 5,2 6,35 1,05 1,4 1,2 1,07 0,9 0,7 1,08 1,07 0,9 0,98 0,8 NH4+ 10 3,87 8,0 6,0 13,5 55,4 46,0 25,8 64,3 6,0 40,7 7,1 6,5 24,3 7,5 13,7 13,0 5,8 COD 100 pH 5,59 7,1 7,2 7,1 6,9 6,8 7,1 7,6 7,3 7,9 7,3 7,2 6,9 6,8 6,7 7,1 7,4 7,3

58,0

56,7

54,3

57,8

19/03/2011 21/03/2011 23/03/2011 24/03/2011 25/03/2011 28/03/2011 30/03/2011

0.1 0.12 0.00 0.08 0.05 0.07 0.01

3,7 4,5 0,5 0,7 0,65 1,75 1,71

0,75 0,61 0,81 0,15 0,13 0,044 0,026

5,21 0,27 0,2 0,08 0,06 0,94 0,26

6,0 1,1 0,57 0,96 1,2 1,48 0,13

56,0 0,0 27,1 16,5 14,3 60,2 51,5

96,0

7,6 7,1 6,9 6,8 6,7 7,2 7,0

b. Kt qu phn tch nc thi c lp Bng 2.2 - Kt qu phn tch cht lng nc sau x l Ngy QCVN 24/Ct B CN0.1 0.3 1.2 -45.54 20.45 11.28 4.57 26.83 54.25 92.56 85.67 0.51 0.76 6.68 7.88 8.05 Cu 2 1.81 5.54 0,65 5.8 13,7 12,8 11,50 13,76 24,23 15,21 10,7 10,3 8,85 10,8 11,17 5,85 4,61 Cr(VI) 0.1 0.05 5.21 0.15 0,02 0.25 0.05 0.00 0.25 0,12 0.21 0.15 0.19 0.00 0.02 0.01 0.00 0.04 Ni 0.5 1.12 9.61 0,01 0,12 0,75 0,86 0,91 0,75 34,17 25,96 35,07 15,13 7,19 10,8 4,56 5,17 0,09 Zn 3 9.6 6.54 1,03 1,1 5,2 6,35 1,05 1,4 15,20 17,07 40,91 10,75 5,78 8,67 12,78 7,98 0,8 NH4+ 10 19,9 38.5 16,0 13,5 55,4 46,0 25,8 64,3 96,0 40,7 77,1 66,5 74,3 87,5 93,7 93,0 58,8 COD 100 pH 5,59 8.5 7,8 8,1 6,9 6,8 8,7 7,9 8,3 6,9 7,8 7,9 8,9 8,8 7,7 7,1 6,4 7,3

11/04/2011

78,0

12/04/2011

66,7

14/04/2011

54,6

18/04/2011 19/04/2011

58,8

2.5. nh gi Khu vc sn xut :

Lng nc ra s dng nhiu. Nc ra chy trn sn ti khu vc sn xut, c bit ti khu vc m crm v niken. H thng thu gom nc thi : Nh my cha c s h thng thu gom nc thi. H thng thu gom nc thi c sa cha, nng cp nhiu ln, nhng cha t hiu qu. Theo kt qu kho st bc u, nng cyanua trong dng thi axit ln n 20 mg/l, nng Cr6+ trong dng thi baz 15 mg/l. Ngoi ra, c hin tng r r nc ra trong qu trnh m vo h thng thu gom nc ma. Axit v xt hng khng c tn dng dng cho cng on x l nc thi m x thng vo h thng thu gom, gy bin ng pH ln i vi nc thi trc x l. Cc ha cht hng khi pha, dung dch trong cc b m khi v sinh nh k c vo h thng thu gom m khng thng bo vi b phn x l nc thi. iu ny lm cho vic vn hnh h thng x l tr nn kh khn, cht lng nc sau x l bin ng nhiu. Nc ra cha crm cha c phn tch x l ring, m c c thu gom chung vo dng thi axit, gy tn km ha cht cho qu trnh kh crm. Tch ring dng thi axit, baz gy tn km xt kt ta cc ion kim loi trong dng thi axit. Ngoi ra, khng tn dng c kh nng ng t, hp ph ca kt ta kim loi i vi nh tng, cht hu c c trong dng thi baz. H thng x l nc thi : Vic vn hnh h thng da ch yu trn kinh nghim c nhn ca ngi thao tc. Cht lng nc x l trong mi m c nh gi bng yu t cm quan ( trong, mu ca nc sau lng) nn kh chnh xc v khng n nh. Cha c song chn rc. Rc thi gy nh hng khng tt n hot ng ca my bm v b lc.

Cha c thit b nh lng ha cht. nh lng ha cht s dng bng cch theo di thi gian bm ha cht vo b phn ng l khng chnh xc. Vic s dng ha cht cn ty tin, lng ph. Cha c thit b o pH ngay trong b phn ng, thit b o cm tay hot ng khng n nh. Keo PAA c bm vo b phn ng nhm keo t cc ht ta. Nhng sau cc ht ta ln b ph hy thy lc trong qu trnh bm sang b lng. B lc lm vic cha hiu qu, lng cn cn li sau lc nhiu, thng xuyn b tc ng dn nc ra. Nc sau x l nhiu bt. Lng ha cht tiu tn nhiu. Dng thi crm cha c tch ring, m x l chung vi dng thi axit, bng phn st FeSO4. Lng FeSO4 dng d nhiu so vi l thuyt nhm tng tc phn ng v hiu qu x l, nhng li gy tng lng bn thi, tng chi ph x l bn. Nhn chung, hiu qu x l nc cha cao. H thng x l thng xuyn gp s c. Cht lng nc sau x l thng xuyn vt ngng x thi cho php. Do , cn thit phi nghin cu phng php x l thay th phng php x l hin ti. Ngoi ra, cn thay i quy trnh nhm gim lng bn thi pht sinh v tn dng ha cht hng t qu trnh sn xut.

CHNG 3 M IN V VN PHT SINH NC THI

3.1 QUY TRNH M IN
3.1.1 Quy trnh m in Quy trnh m in c th tm tt nh sau :

Hnh 3.1 Quy trnh m in Gia cng c hc Nhm loi b ht g, oxyt, cht bn, ba via, khuyt tt th, v trn cnh v t c nhn bng cn thit theo yu cu cho b mt kim loi ngi ta thng p dng cc bin php sau : Phng php mi Phng php quay bng Xc Phun Ty du

Trn b mt chi tit cn m thng c cc loi du m hay thuc nh bng dnh vo. Mng du m gy hin tng bong lp kim loi m ng thi lm bn dung dch m Cc phng php ty du m: Ty du m trong dung mi hu c nhm lm sch cc loi du m, khong khng x phng ha c. Sau khi ty bng dung mi, trn b mt phi vn cn mt lp mng du m gy nh hng n bm kt ca kim loi m, do cn tin hnh ty ha hc hoc in ha. Ty du m ha hc trong dung dch kim v cht ty ra. Qu trnh x phng ha gip loi b cc loi du m c ngun gc ng thc vt. Loi cht bo khong vt khng x phng ha c ty bng x phng, hay cc cht hot ng b mt c bit. Cc ch phm tng hp ty du m c thng mi ha v c s dng rng ri. Ty du m in ha cho b mt rt sch, thi gian ty ngn, thng dng trong khu ty sch ln cui loi b mng du cn st li sau nhng ln ty trc . Dung dch ty in ha c thnh phn ging dung dch ty ha hc nhng vi nng long hn nhiu. C th dng dng in xoay chiu hay dng mt chiu u c. Phi c th l cc anot hoc catot. Ty g Ty g ha hc : thng s dng H2SO4 hoc HCl hoc hn hp ca chng. Trong qu trnh ty g, kim loi nn cng b tan theo, v thng xy ra hin tng gin hir. Ty g in ha : vt ty c th l anot hoc catot c ngm trong b. Mt dng thng dng ln hn 5A/dm2 . Hot ha b mt Hot ha b mt nhm lm mt i lp oxit cc mng hnh thnh trong qu trnh gia cng ti xng: nh bng, ty du m, ra, vn chuyn. Ngoi ra, khi hot ha, lp kim loi nn c ty nh, lm l cu trc gip cho lp m bm chc hn. Qu trnh hot

ha c tin hnh ngay trc khi a phi vo b m. C th hot ha in ha hoc hot ha ha hc. Vt bng thp trc khi m kn thng c hot ha in ha. Th ng ha tm thi Vt liu l thp, thp hp kim sau khi ty g nn c th ng nu cha m ngay, nhm trnh s xi ha. M bo v kim loi ngi ta dng cc lp m nh km, ng, niken, crm, thic, m ln kim loi cn bo v. M in tin hnh trong cc b m vi dng in mt chiu. Vt cn m l catot c ni vi cc m ca ngun in mt chiu. Kim loi dng m l anot v c ni vi cc dng. Qu trnh in cc xy ra nh sau: catot xy ra qu trnh kh ca kim loi cn m : [Me(H2O)X]z+ + Ze = Me + x H2O Me: kim loi to nn lp m ng thi catot cn c qu trnh ph kh hydro : 2H+ + 2e = H2

anot xy ra qu trnh ha tan in ha ( oxy ha) kim loi cn dng m: Me + xH2O = [Me(H2O)x]z+ + ze 4OH- = O2 + 2H2O + 4e Ra nc Trong qu trnh vn hnh, xng m cn rt nhiu nc ra sau mi cng on. Ra nhm trnh ha cht bm dnh trn phi t b ny sang b khc, nhm lm sch b mt phi tng gn kt ca lp m vi lp nn, nhm loi b ha cht ra khi sn

phm trc khi lm kh v ng gi. Tng lng nc thi t qu trnh ra l rt ln, thng thng cn 1 ~ 2 m3 cho mi m2 b mt phi. Ngi ta c gng tng hiu qu ca vic ra, ng thi tit kim nc n mc ti a, gim lng nc thi cn x l bng cch sng to ra nhiu phng php ra khc nhau : Ra nhng tnh Ra nhng c nc chy trn lin tc Ra ngc chiu Ra sc kh Ra phun Ra lin hp Ra ngng Ra siu m Ty theo yu cu v cht lng, nhm t hiu qu ra cao nht, hp l v gim chi ph m ta ra vi nc nng hay nc thng. Xng m s dng rt nhiu nc ra vt gia cng trong qu trnh sn xut, bnh thng cn n 2m3 cho 1m3 sn phm. V vy khi lng nc thi cn x l s rt ln, gy nhiu tn km. gim thiu lng nc cn x l cn phi hin i ha h thng ra, ng dng cc phng php tin tin lm sch nc thi dng li mt phn cho xng m, p dng cc h ra hp l c ch s kinh t - k thut cao, nc ra phi c cht lng cao v c phng tin kim tra, khng ch cht ch v phm cht v nh mc tiu th nc; ng thi phi nng cao tnh vn ha trong sn xut, tun th ng cc quy nh i vi h thng ra, Ra thu hi

Sau b m, thng c b ra thu hi dng li ha cht, gim lng ha cht tiu hao v gim nng nc thi. Nc ra thu hi c lc, v chm thm vo b m, hay pha dung dch m. Lm kh Lm kh sn phm sau khi m bng cch ly tm hoc thi kh nn, sy. Kim tra Kim tra s b bng mt thng, cc sn phm b li c a tr li khu m. Kim tra nh k bng my o, nhm iu chnh thng s k thut cho ton b quy trnh.

3.2 TNH CHT NC THI M IN V NH HNG CA CHNG N MI TRNG

3.2.1 Tnh cht ca nc thi m in Nc t xng m thi ra c thnh phn rt a dng, nng li thay i trong bin rt rng, pH cng bin ng lun t axit n trung tnh hoc kim. Tuy nhin nc thi t xng m thng c phn bit thnh 3 loi: nc thi kim axit, nc thi crom v nc thi cyanua. S d phi tch ring nc thi cyanua v khi gp nc thi axit hay nc thi crom (cng c ln axit) s sinh ra kh HCN rt c, lm nhim c xng m ln b phn x l nc tip theo . Vic tch ring nc thi crom l cn thit v Cr+6 l cht c, cn phi x l c bit. Hn na, nc thi crom c x l d dng v trit hn v vy khng nn pha long chng bng nc thi axit hay nc thi khc. Ngoi ra xng m cng c lc cn thi b cc dung dch c, hng. Trng hp ny khng nn thi chng ngay ra cng rnh m dng chng nh l mt ha cht cho trm x l nc thi ca xng hoc t chc thu hi nhng ha cht chnh trc khi thi b, nh vy va tn dng c vt t va d cho khu x l nc thi.

Trong nc thi crom ngoi Cr+6 cn c Fe2+, Cu2+, Ni2+, Zn2+, H2SO4, HCl, HNO3, tp cht c hc, nng cc tp cht thng dao ng trong vng 30 300 mg/l, pH t 7 n 1. Nc thi cyanua ngoi CN- t do cn c phc cyanua km, cadimi, ng, mui, mn, cht bng, cht hu c. Nng cyanua gm c dng t do v lin kt, dao ng t 5 n 300 mg/l, nng tng cc kim loi : 30 70 mg/l; pH >7 v cha mt t tp cht c hc. Nc thi kim axit cha cc loi axit nh H2SO4, HCl, HNO3, HF, kim nh NaOH, Na2CO3, cc kim loi Fe2+, Fe3+, Cu2+, Ni2+, Zn2+, Cd2+, v cc loi mui ca chng. pH dao ng t 1 n 8 10.Ngoi ra trong nc thi cn cha c du m, cht huyn ph, t ct, g st, Vy nc thi xng m gm loi thnh phn, cn nng li bin ng trong mt di kh rng. Do x l nc thi phi dng nhiu phng php khc nhau, ph hp vi tng loi nc thi v nng tp cht cha trong n. Ph bin nht l phng php dng ha cht, ri n phng php trao i ion, phng php chng ct, in thm tch, Chn phng php no l ty ch tiu kinh t - k thut cho php, iu kin mi trng a phng yu cu, nng nc thi, nc x l vi mc ch dng li cho sn xut ca xng hay thi ra mi trng, Chn phng php no cng phi m bo nc thi c nng cc cht nhim bng hay thp hn gii hn cho php trong QCVN 24:2009. 3.2.2 c tnh ca mt s cht c trong nc thi m in a. Cyanua Cyanua l mt cht ha hc rt c, phn ng nhanh, l cht ha hc c kh nng gy cht. Cyanide tn ti nhiu dng khc nhau, bao gm: Cyanua th kh , khng mu nh hydrogen cyanua (HCN), hay cyanogen chloride (CNCl)..

Cyanua th rn nh sodium cyanua (NaCN), hay potassium cyanua (KCN), Tip xc vi mt lng ln cyanua c th gy tn thng cho no v tim mch, nu tip xc liu lng thp c th gy nhng hu qu nh kh th, au tim, nn ma, au u, lm rng tuyn gip. Thng xuyn b nhim mt lng nh cyanua c th gy nn chng vim da, cc bnh v tuyn gip, mt s phi hp gia cc c bp. b. Crm Mc d crm tn ti nhiu trng thi khc nhau, ch c Cr3+ v Cr+6 gy nh hng ln n sinh vt v con ngi. ng xm nhp v o thi: Crm xm nhp vo c th theo 3 ng: h hp, tiu ha v qua da. Cr+6 c c th hp thu d dng hn Cr3+ nhng khi vo c th Cr+6 s chuyn thnh dng Cr3+. D xm nhp vo c th theo bt c ng no, crm cng c ha tan trong mu nng 0.001 mg/ml, sau c chuyn vo hng cu v s ha tan hng cu nhanh hn 10 ~ 20 ln. T hng cu, crm c chuyn vo cc t chc v ph tng. Crm gn vi Sidero filing albumin v c gi li phi, xng, thn, gan, phn cn li th c o thi qua phn v nc tiu. T cc c quan ph tng, crm li c ha tan dn vo mu, ri c o thi qua nc tiu t vi thng n vi nm. Do nng crm trong mu v nc tiu bin i nhiu v ko di. Tc ng n sc kho: Qua nghin cu ngi ta thy crm vi lng c vai tr tch cc sinh hc nh chuyn ha glucose, protein, cht bo ng vt hu nh. Du hiu ca thiu ht crm ngi gm c gim cn, c th khng th loi ng ra khi mu, thn kinh khng n nh. Tuy nhin vi hm lng cao crm lm gim protein, axit nucleic v c ch h thng men c bn.

Cr+6 c hn Cr3+. IARC xp Cr+6 vo nhm 1, Cr3+ vo nhm 3 i vi cc cht gy ung th. Ht th khng kh c nng crm (v d axit crmic hay crm trioxit) cao ( > 2 g/m3) gy kch thch mi lm chy nc mi, hen suyn d ng, ung th (khi tip xc vi crm c nng cao hn 100-1000 ln nng trong mi trng t nhin). Ngoi ra Cr+6 cn c tnh n mn, gy d ng, l lot khi tip xc vi da. c. Cac muoi cua ong : CuCl2 , CuSO4 , Cu(NO3)2 Co oc tnh gay kch thch nhe , gay d ng nhe. Hit phai bui cua ong se gay anh hng xau gan, tuy va lam ton thng te bao phoi. Cac muoi ong gay ra cac kch thch nga da va ket mac do b d ng. Oxit ong (I) con gay kch thch nga mat va ng ho hap tren. Nhng ngi tiep xuc thng xuyen vi cac hp chat cua ong thng b co hien tng mat mau cua da. Ngi uong phai ong sunfat se b oi ma, au da day, choang, thieu mau, vop be, co giat, hon me va co the chet. ong co the gay anh hng en than kinh, than, mot vai trng hp dan en gan to. d. Cac hp chat cua kem: ZnO, ZnSO4 , ZnCl2 Kem oxit, kem sunfat, kem clorua la chat t oc nhng khi ht phai khoi cua oxit kem th b mac benh goi la cam ong thau, neu ht phai cac loai khoi cua kem clorua se b b ton thng phoi. Cac muoi kem tan co v kim loai manh, lng nho muoi kem gay oi, ma, va nhieu hn se gay oi manh va gay xo. Ht phai khoi clorua kem lau ngay gay ra ton thng niem mac ho hap va gay ra chng xanh tai. Kem clorua co tnh an mon nen gay ra l loet ngon tay, ban tay, canh tay cho nhng ngi tiep xuc lau ngay. e. Cac hp chat niken: NiO, NiCl2 , NiSO4 .7 H2O , Ni(NO3)2 Cac hp chat cua niken c coi la chat gay nhiem oc he thong . Th mot lng ln 1 - 3mg/1kg oi vi cho cho thay niken gay ra roi loan tieu hoa, co giat, ngat th. Niken tm thay trong toc ngi tiep xuc lau ngay

vi cac hp chat cua niken. Hieu ng chung cho nhng ngi tiep xuc thng xuyen vi muoi niken la b nga. Viem da thng xay ra oi vi nhng ngi ma ken, ac biet de xay ra moi trng co o am va nhiet o cao.Thng tn trn c th thng xay ra tren ban tay va canh tay. Nikel cacbonyl gay kch thch phoi va gay ra ngat th. 3.2.3 nh hng n mi trng c cht i vi c v thc vt nc Tiu dit cc sinh vt ph du, gy bnh cho c v bin i cc tnh cht l ho ca nc, to ra s tch t sinh hc ng lo ngi theo chiu di chui thc n. Nhiu cng trnh nghin cu cho thy, vi nng ln, sinh vt c th b cht hoc thoi ha, vi nng nh c th gy ng c mn tnh hoc tch t sinh hc, nh hng n s sng ca sinh vt v lu v di. nh hng n ng ng dn nc, gy n mn, xm thc h thng cng rnh. nh hng n cht lng cy trng, vt nui, canh tc nng nghip, lm thoi ho t do s chy trn v thm ca nc thi.

CHNG 4 - CC PHNG PHP X L NC THI XI M

4.1 X L CYANUA
Nc thi cha cyanua thng c phn tch ring khi cc dng thi khc, nhm ngn cn s hnh thnh HCN trong nc thi cha qua x l. S phn tch dng thi cng ngn nga qu trnh to phc cyanide ca cc kim loi v gim thiu chi ph x l. 4.1.1 X l cyanua bng clo v cc hp cht clo Nguyn tc: oxy ha cyanua t do v phc ca n thnh hp cht t c hn: cyanat hoc nit v cacbonic. V d oxy ha bng natri hypoclorit, cc phn ng sau s xy ra:

NaCN + NaOCl = NaCNO + NaCl 2NaCNO + 3NaOCl + H2O = 2CO2 + N2 + 2NaOH + 3 NaCl NaCNO + H2O = NaHCO3 + NH3 Cc cht oxy ha thng dng trong cng nghip: clo kh hoc lng, hp cht clo ( vi clorua, cc hypoclorit), ozon, kali permanganat, st, sunfat, Ph bin nht l vi clorua v cc hypoclorit. iu kin tin hnh oxy ha cc cyanua ph thuc vo : loi cht oxy ha s dng, nng cyanua t do v phc cht, pH. Oxy ha cyanua bng clo v bng hp cht cha clo phi tin hnh trong phm vi pH t 8,5 10 (n 11 12, ty loi cht oxy ha). Khi phn ng xy ra lm cho pH tng nh v tc phn ng chm li (do th oxy ha gim i ). Nu pH<8,5 s sinh ra clo-xyan v HCN rt mnh, gy c hi. Nu pH>10 tc oxy ha chm nn tn nhiu cht oxy ha m sau li phi kh clo d. Ty pH mi trng v nng cht oxy ha m cyanua c th b oxy ha thnh xyanat hay thnh kh cabonic v nit. Trong mi trng axit cc cyanua b thy phn tc khc, nhng khi pH >12 chng hon ton khng b thy phn na. V vy phi khng ch pH lun trong phm vi trn. Liu lng cht oxy ha quyt nh mc sch ca nc sau x l, nhng liu lng ny khng c nh m ph thuc vo nng cyanua v dng tn ti ca chng trong nc thi, vo pH v bin ng pH trong qu trnh x l. Nng cyanua cng long cng tn nhiu cht oxy ha ( khng theo h s t lng ca phn ng), c nh vy mi oxy ha trit cyanua c. Cyanua t do, phc cht ng cyanua, km cyanua i hi thi gian x l 30 pht n 2 gi ty theo tnh cht nc thi v lng ha cht s dng. Thng thng, qu trnh x l c tin hnh trong hai giai on : Giai on u pH 10 trong thi gian 30 pht. Ngoi kim sot pH, ORP nn c hiu chun ti 325-400 milli-volt trong giai on u tin duy tr liu lng clo thch hp. Bc th hai i hi mt thi gian phn ng t 30 n 60 pht pH 8,5, ORP nn c kim sot mc 600 (in hnh)

n 800 mili-volts trong phn ng giai on th hai oxi ha hon ton cyanat v cc hp cht nit. Vn tc phn hy cc phc cyanua kim loi ph thuc vo hng s phn ly. Gi tr hng s phn ly ca mt s kim loi c m t trong bng 4.1 . Bng 4.1 - Nng [CN-] t do trong cc dung dch cha phc cyanua

Niken cyanua i hi thi gian x l ln n 12 gi vi lng ha cht gp hng chc ln so vi h s t lng trong phng trnh phn ng, do cc phn ng cnh tranh hnh thnh nn Ni2O3, c mu en v ngm nc mnh. ng hc ch khng phi nhit ng lc hc c th gii thch tc oxi ha chm ca phc niken cyanua, khi m hng s phn ly c gi tr tng ng phc ng cyanua, hp cht d b oxi ha hn. Phc st cyanua gn nh khng b phn hy bi clo. Cc phc cyanide c cha cadmium, ng v km c th d dng x l bng clo dng kh v cc hp cht hypoclorid. Phc cyanua ca cc kim loi khc : niken, st, coban, vng, bc i hi phng php x l khc.

4.1.2 Oxi ha bng Hydrogen Peroxide H2O2 c nhiu u im v mt cng ngh hn dng clo v chng khng sinh ra cc hp cht trung gian bay hi nhng gi thnh cao hn. Trong dung dch kim, hydrogen peroxide c hiu in th 0.878V, th hin tnh oxi ha cc mnh. Cyanua b oxi ha thnh cyanat, hydrogen peroxide phn hy thnh nc sau phn ng : CN + H2O2 CNO- + H2O pH 9.5 10.5

CNO + 2H2O NH3 + HCO32Vn tc oxi ha ph thuc nng cyanua, lng hydrogen peroxide dng tha, pH, nhit . Cc cht xc tc ng mt vai tr quan trng. Ion Cu2+ thng c s dng lm xc tc lm tng vn tc phn ng. Vic s dng Cu2+ to ra phc t din ng amoni, i hi phng php x l th cp kt ta ng. Cyanua khng b oxi ha thnh N2 v CO2, thay vo l NH3 hoc cc phc amoni v ion cacbonat. Qu trnh x l cyanua bng hydrogen peroxide thng tin hnh trong mi trng c tnh kim, pH cao lm gim tc phn ng. 4.1.2 Oxi ha bng ozon Ozon l mt trong nhng cht oxi ha mnh nht. Trong mi trng kim, vi th oxi ha kh ln n +1.24 V, n gip phn hy cyanua c dng t do v phc. Qu trnh oxi ha bng ozon thng c tin hnh trong hai bc, tng t qu trnh x l bng clo. Cyanua b oxi ha thnh cyanat : CN + O3 CNO + O2 Sau cyanat b phn hy thnh N2 v bicacbonat : 2 CNO- + 3O3 + H2O 2 HCO3- + N2 + 3O2 Thi gian lu cn thit cho qu trnh oxi ha hon ton cyanua , thng thng l 10 30 pht. Giai on 2 thng c vn tc phn ng thp hn giai on u. Phn ng thng tin hnh pH = 10 ~ 12 . Vn tc phn ng gn nh khng ph thuc pH v nhit .

Cc phc cyanua ca cadimi, ng, km, niken v bc c th d dng c x l vi ozon. ng v niken c s dng nh mt cht xc tc quan trng, gip tng nhanh vn tc phn ng phn hy cyanua ( giai on 1 ca qu trnh ), nhng li lm gim tc phn hy cyanat ( giai on 2 ca qu trnh ). Phc ca st, vng v coban rt n nh v ch b oxi ha mt phn, tr khi c thm vo mt cht xc tc thch hp. nh sng cc tm ( tia UV ), kt hp vi ozon c th tng cng qu trnh oxi ha cc phc. 4.1.3 Oxi ha bng tia cc tm ( UV ) Tia UV c tc dng y nhanh qu trnh phn ly phc cyanua kim loi thnh cyanua t do. Hydrogen peroxide v ozon, di tc ng ca tia UV bc sng 200 280 nanomet to ra ion OH* , tc nhn oxi ha mnh nht tng c bit n, c th phn hy trc tip tt c cc phc cyanua kim loi. Ngoi ra, oxi ha bng UV/ peroxide v UV/ozon khng to ra sn phm ph khng mong mun ( kh NH3 , phc amoni kim loi) . Oxi ha kt hp UV/TiO2 , UV/thuc th Fenton cng c nghin cu v p dng trong thc t. Phng trnh m t qu trnh to ion OH* : Hydrogen peroxide: H2O2 + || h 2 OH (14) H2O2 + OH H2O + O2H (15) H2O2 + OH H2O + OH + O2 (16) OH + OH H2O2 (17) O2H + O2H H2O2 + O2 (18) O2H + || OH H2O + O2 (19) Ozone: O3 +|| h O2 + O (20)

O + H2O 2OH (21) 4.1.4. Oxi ha bng thuc tm Oxi ha bng thuc tm mang li hiu qu lm sch cao, thit b phn ng n gin, d vn hnh. Thuc tm c th oxi ha trc tip phc cyanua, sn phm ca phn ng thng l N2 vo CO2 Nhng nhc im ca phng php ny l thuc tm kh t. Phng php ny thng ch ng dng trong phng th nghim, vi lng nc thi cn x l t. 4.1.5 S dng mui st Phc st cyanua thng c xem l khng c, t tan trong nc. Phng php gim c tnh ca cyanua bng mui st thng c p dng trong ngnh khai thc khong sn, x l cyanua pht tn ngoi mi trng. Fe+2 + 6CN- + O2 + H+ ===> Fe(CN)6 3- + H2O 4Fe+2 + 3Fe(CN)6 3- + O2 + H+ ===> Fe4[Fe(CN)6]3 + H2O 4.1.6 Phng php in ha Qu trnh ny c nghin cu lm sch nc thi khi cc tp cht tan nh cyanua, sunfocyanua, amin, cn, andehyt, hp cht nit, thuc nhum, azo, sunfua, mercaptan). Trong qu trnh oxi ha in ha cc cht trong nc thi phn r hon ton thnh CO2, NH3 v H2O hoc hnh thnh cc cht n gin hn v khng c. Cc cht ny c th tch bng cc phng php khc. Anot c th l cc vt liu khng tan bi in phn nh grafit, macnetit (Fe3O4), cc dioxit ch, magan v ruteni c bao ph ln titan. Catot c ch to t molipden, hp kim vonfam vi st hoc niken, t grafit, thp khng r v cc kim loi khc c ph bng molipden, vonfam hoc hp kim ca chng. Ngoi cc qu trnh chnh l oxi ha in ha v kh, ng thi cn xy ra cc qu trnh tuyn ni in, ng t in, in li. S oxi ha anot cc cyanua din ra theo phn ng:

CN- + 2OH 2e

CNO- + H2

Qu trnh oxi ha c th tip tc vi s to thnh nit : 2CNO- + 4OH- 6e CO2 + N2 + 2H2O

tng dn in ca nc thi v gim chi ph nng lng ngi ta cho thm NaCl vo nc. Nu nng CN- 1g/l th cho thm 20 ~ 30g/l NaCl. Trong qu trnh ny anot bng grafit cn catot bng thp. iu kin oxi ha ti u: mt dng in 3 ~ 4 A/dm3, khong cch gia cc in cc l 3 cm, vn tc nc 30 dm3/h, pH = 8 ~ 9. Hiu qu x l c th t 100%. S ph v cc cyanua din ra do oxi ha in ha trn anot v oxi ha bi clo, sinh ra trn anot do phn r NaCl. Qu trnh nh sau: 2Cl- - 2e Cl2 CNO- + 2Cl- + H2O 2CO2 + N2 + 6Cl- + H2O

CN- + Cl2 + OH2CNO- + 3Cl2 + 4OH-

4.1.7. Cc phng php x l khc c nghin cu Hp ph bng than hot tnh Phn hy cyanua bng Mono-Peroxy Sulfuric Acid hoc Caros Acid. Phn hy cyanua bng oxi khng kh. Phn hy cyanua bng aldehyde. Phn hy cyanua bng SO2. Phn hy cyanua bng thuc th Fenton. Phn hy cyanua bng vi sinh. 4.1.8 u nhc im ca cc phng php x l Bng 4.2 u nhc im ca cc phng php x l nc thi cha cyanua STT Phng php u im Nhc im

Oxi ha bng Clo v cc hp cht hypocloride

Chi ph thit b, chi ph vn hnh thp. Vn hnh n gin, d iu kin qu trnh.

Khng hiu qu khi x l cc phc cyanua ca niken, bc, vng.

Cn kim sot pH nghim ngt nhm duy tr tc phn ng v trnh to ra kh c. Cn x l clo d . Chi ph cao. To ra sn phm ph phc amoni.

2 Oxi ha bng hydrogen peroxide X l hiu qu cc phc cyanua ca hu ht cc kim loi. Vn hnh n gin, d iu kin qu trnh. 3 Oxi ha bng ozon X l hiu qu cc phc cyanua cc kim loi. -

Chi ph u t cao. i hi ngi vn hnh phi c kin thc v kinh nghim.

D sy ra s c pht tn kh ozon ra mi trng. Chi ph u t cao. Kt ta bm trn ng pht UV lm gim hiu qu qu trnh, i hi v sinh thit b thng xuyn.

Oxi ha bng UV/peroxide, UV/ozon

X l hiu qu cc phc cyanua ca cc kim loi. Thi gian phn ng nhanh.

Khng to ra sn phm ph.

Tia UV gy nguy him cho ngi vn hnh.

Oxi ha bng thuc tm

X l hiu qu tt c cc phc cyanua. Vn hnh n gin, khng c sn phm ph n gin, d p dng trong vic x l nc, t b nhim cyanua.

Chi ph cao.

S dng mui st

To ra bn thi nhiu. Chi ph cao. Khng loi tr hon ton cyanua. Tiu tn nhiu in nng, chi ph vn hnh cao. Thng sy ra hin tng st p, gim hiu qu x l. Cn x l clo d.

Phng php in ha

C th tn dng cc thit b c sn trong nh my.

Khng to ra sn phm ph -

4.2 X L CROM
4.2.1 X l Cr+6 bng phng php ha hc Tch Cr+6 ra khi nc thi bng phng php ha hc gm hai giai on : Kh Cr+6 v Cr3+ bng cht kh Kt ta Cr3+ ( v kim loi nng) di dng hidroxyt. Cht kh c th dng l natri sulfit, natri bisulfit, natri hidrosulfit, st (II) sulfat, kh CO2, phoi thp. V d

Dng bisulfit : Cr2O72- + 3HSO3-+ 5H+ = 2Cr3+ +3SO42- + 4H2O Dng sulfit : Cr2O72- + 3SO3- + 8H+ = 2Cr3+ +3SO42- + 4H2O Dng st (II) sulfat trong mi trng axit : H2Cr2O72- + 6FeSO4 + H2SO4 = Cr2(SO4)3 + 3 Fe2(SO4)2 + 7H2O Dng st (II) sulfat trong mi trng kim : Na2CrO4 + 4NaOH + 3FeSO4 + 4H2O = Cr(OH)3 + 3Fe(OH)3 + 3FeSO4 Dng cht kh c cha ion SO3- phi tin hnh trong mi trng axit c pH = 2.5 ~ 3.5 . Trong qu trnh phn ng, pH s tng ln, tc phn ng s chm li. Nu pH > 4, phn ng ngng hon ton. Nng Cr+6 trong nc thi c ngha rt quan trng. Khi nng Cr+6 thp qu, lng cht kh cn s dng v thi gian kh hiu qu s tng ln rt nhiu so vi khi nng Cr+6 cao. V d,trong mi trng pH = 4, kh Cr+6 bng FeSO4 t nng 50 mg/l xung 5 mg/l cn 1.5 ln FeSO4 so vi h s t lng trong thi gian 5 pht. Nhng kh t 5 mg/l xung 1 mg/l cn 4 ln FeSO4 so vi h s t lng trong thi gian 30 pht. 4.2.2 X l Cr+6 bng phng php in ha Phng php ny t hiu qu lm sch cao, c th p dng gim nng t 1000 xung 1 ppm. Khi in phn nc thi cha H2CrO7, iu kin ti u pH = 2, cn mt dng in 0,2-2 A/dm2. Phn ng kh din ra nh sau : Cr2O72- + 14H+ + 12e4.2.3 Cc phng php khc Trao i ion. 2Cr + 7H2O

 Kh crom bng kh SO2. Kh crom bng khong vt pirit st FeS2. X l crom bng bin php sinh hc. Hp ph crom bng bentonit. 4.2.5 u nhc im ca cc phng php STT Phng php 1 Dng phn st mi trng axid u im X l hiu qu nc thi cha crom Thi gian phn ng ngn. Thit b n gin, d vn hnh. Nhc im Lng bn thi ln. Tn km nhiu xt cho qu trnh kt ta. X l hiu qu nc thi cha crom Thit b n gin, d vn hnh. t tiu tn xt hn phng php dng phn st. 4 Phng php in ha C th thu hi crom. C th tn dng thit b c sn. X l hiu qu crom. D thu hi crom. Tn nhiu nng lng. i hi ngi vn hnh c kin thc v kinh nghim nht nh. Thng sy ra Kh thu hi crom 2 Dng phn st mi trng kim 3 Dng hp cht SO32Thi gian phn ng lu. Kh thu hi crom

(II) sulfat trong -

(II) sulfat trong -

hin tng st p 5 Trao i ion C th thu hi crom. Hiu qu lm sch cao. Cn pha long nc thi trc khi x l. Chi ph u t thit b, chi ph vn hnh cao. Du m, cn bn lm gim hiu qu . 6 Dng kh sulfurous SO2 Hiu qu lm sch cao. Chi ph vn hnh thp. D dng thu hi crom. Chi ph u t thit b cao. Kh vn hnh. Cn kim sot nghim ngt quy trnh, trnh pht tn kh c.

4.3 X L ION KIM LOI

4.3.1 Kt ta bng dung dch kim 4.3.2 Kt ta bng cacbonat 4.3.3 Kt ta bng sunfit 4.3.4 Hp th 4.3.5 Trao i ion 4.3.6 in ha 4.3.7 Trch ly 4.3.8 Cc phng php khc 4.3.8 u nhc im ca cc phng php