PHN M U

1- Thng tin chung v ti : Tn ti : p dng cc qu trnh oxi ha nng cao (AOPs) x l nc r rc qua x l sinh hc nh my x l G Ct, thc hin trn h pilot 15-20 m3/ngy. Ch nhim ti : GS. TSKH. Trn Mnh Tr C quan ch tr : Trung tm Cng ngh Ha hc v Mi trng (ECHEMTECH) Thi gian thc hin : bt u : 1/12/2006 ; kt thc : 1/04/2007 Kinh ph c duyt : 275.000.000 Kinh ph cp : 200.000.000 theo TB s 195/TB-SKHCN ngy 13/11/2006 2- Mc tiu : Xy dng cng ngh x l nc r rc hp l nhm nng cao cng sut, cht lng v gim chi ph vn hnh ca nh my x l nc r rc G Ct hin ti 3- Ni dung : (1) Kho st, phn tch, nh gi cht lng nc r rc qua x l sinh hc nh my x l G Ct. (2) Th nghim kim tra mt s qu trnh chnh s p dng trong quy m phng th nghim xc nh cng ngh x l. (3) Tnh ton, thit k, ch to cc thit b cng ngh cho h pilot cng sut 1020 m3/ngy. (4) Lp t h pilot 10-20 m3/ngy ti Cng trng G Ct.
1

(5) Vn hnh, o c cc thng s cng ngh, cng sut v cht lng nc x l. (6) nh gi chi ph vn hnh (ch yu l nng lng, ho cht) cho 1 m3 nc sau x l. (7) Kt lun v nh gi tnh kh thi ca cng ngh xut. 4- Sn phm ca ti : (1) H pilot cng sut 10-20 m3/ngy (2) Cng ngh x l nc r rc theo xut ca ECHEMTECH, bo m cht lng nc sau x l phi t cc mc sau: - pH - COD , mg/L - BOD, mg/L - SS, mg/L - Ntng s, mg/L - Ptng s, mg/L - Mu, Pt-Co (3) Bo co tng kt ca ti 5.5-9 100 50 100 60 6 50

- Coliform, MPN/100mL 10.000

CHNG I

TNG QUAN V TI NGHIN CU

1.1- Rc v cc cng trng x l rc thnh ph H Ch Minh V l mt thnh ph ln nn lng rc thi hng ngy ca thnh ph H Ch Minh cng rt ln, mi ngy c trn 7.000 tn rc cc loi thi ra, t rc sinh hot n rc thi cng nghip. Phn ln rc c tp trung v cc bi rc ngoi thnh x l, cho n nay ch yu vn bng phng php chn lp, tuy bit rng gii php ny khng lu di v cn c i vi qu t hn hp ca mt thnh ph ln. Thnh ph ang phn u gim dn t l chn lp t 98% hin nay xung cn 50% vo nm 2010 v cn 30% vo nm 2015. Tuy vy, mc tiu ny khng phi d dng t c nh mong mun nu khng c quyt tm cao. gii quyt vn nn rc ca thnh ph, trong nhng nm va qua thnh ph H Ch Minh trin khai xy dng 4 cng trng chn lp rc kh quy m sau y tip nhn rc hng ngy: - Bi chn lp G Ct (qun Bnh Tn) vi tng din tch cng trng 25 ha, cng sut thit k 3,6 triu tn, mi ngy c th tip nhn 2.000 tn theo thit k. Tuy nhin, do mt s cng trng chn lp rc khc b s c nn buc phi nng cng sut tip nhn hng ngy ln 3.000-3.500 tn, c bit c lc ln n gn 5.000 tn. lm cho tng lng rc tip nhn hin nay ln n 4,3 triu tn ! - Bi chn lp rc Phc Hip (huyn C Chi) vi tng din tch cng trng 43 ha, cng sut thit k 3 triu tn rc, mi ngy c th tip nhn 3.000 tn rc theo thit k (bi chn lp 1A). Tuy nhin, bi chn lp rc ny ang b s c, pha ng bc cng trng nn t b chui trt rt nghim trng. V vy, lng rc tip nhn hng ngy cn khong 1.100-1.200 tn. ng ch l cng trng x l rc Phc Hip (x Tam tn) c quy hoch m rng tr thnh khu x l lin

hp cht thi rn ln ca thnh ph vi din tch tng cng n 822 ha, thi gian hot ng d kin l 23 nm, hin nay vn trong qu trnh xy dng. - Bi chn lp rc a Phc (huyn Bnh Chnh) vi tng din tch cng trng 128ha, ang trin khai san lp mt bng d kin u nm 2007 s tip nhn rc, nhng cho n nay cng trng vn cha hon thnh cng tc xy dng. - Bi chn lp rc ng Thnh (huyn Hc Mn) vi din tch 70 ha, hot ng t nm 1991 n 2002, hin nay ng ca khng tip nhn rc, ch nhn x bn vi lng 900 tn/ngy. Khi lng rc tn ng khong 7,6 triu tn.

1.2- Nc r t cc cng trng chn lp rc thnh ph H Ch Minh cc cng trng chn lp rc trn a bn thnh ph H Ch Minh, nc r ra t cc bi chn lp rc v ang ni ln thnh vn ln, c ton x hi lo lng v quan tm hng ngy. Nguyn nhn mt mt v trong nc r rc ny cha nhiu mm bnh nguy him, cha nhiu cht nhim c hi, khi tch ng li s gy nguy c nhim ngun nc, t v khng kh quanh khu vc cng trng chn lp, nc r rc li c mi hi thi, c hi, lan to thng trc trong khng kh vi mt bn knh n vi cy s, nn dn c quanh nhng cng trng chn lp rc khng chu ni, nhiu ln yu cu chnh quyn tm gii php khc phc. Mt khc, v lng nc r rc thot ra hng ngy kh nhiu, (trung bnh c 10 tn rc chn lp trong 1 ngy m sinh ra 1 m3 nc r rc), v ma ma, lng nc r rc sinh ra cng nhiu hn, nu khng c gii php x l kp thi v hiu qu, nguy c nhim do nc r rc ph v b bao cc cng trnh h cha, trn vo khu dn c hoc ra ngun nc bn ngoi l khng trnh khi. Hin thnh ph tn ng khong 500.000 m3 nc r rc cha c x l trc ma ma nm nay. cng trng chn lp rc G Ct, hin nay lng nc r rc tn ng trong hai h cha khong 60.000 m3, mi ngy mi pht sinh thm. cng trng chn lp rc Phc Hip, hin tn ng khong trn 300.000 m3 v mi ngy pht sinh

thm khong 1.000 m3. Cng trng chn lp rc Phc Hip ang tr thnh mt ti cha nc rc khng l v tnh trng v b bao nh xy ra nm 2003 c th ti din. Ngay c cng trng chn lp rc ng Thnh tuy ng ca t nhiu nm nay nhng hin vn cn tn ng khong 50.000 m3 nc r rc cha c x l.

1.3- Nhng gii php x l nc r rc thnh ph H Ch Minh 1.3.1- Gii php x l nc r rc cng trng chn lp rc ng Thnh cng trng chn lp rc ng Thnh, ngay t u nhng nm 2000, rt nhiu n v tham gia nghin cu x l nc r rc nh Cng ty Quc Vit, Trung tm Cng ngh v qun l mi trng CENTEMA, Cng ty TNHH c Lm, Trung tm t vn cng ngh v mi trng CTA, Cng ty C phn nc v pht trin NUPHACO, Hi Ha hc Vit Nam. Cng ngh x l ch yu da vo phng php phn hy sinh hc nhng ni chung hot ng khng n nh, lun gp trc trc, thm ch nh Cng ty c Lm, cho n nay vn cha x thi c mt khi nc r rc no t yu cu (!). Tuy vy, hin nay h thng ny phi tip nhn thm nc r rc 700-700 m3/ngy ch t cng trng G Ct v x l tm thi h tr nh my x l nc G Ct trong thi gian b s c k thut. 1.3.2- Gii php x l nc r rc cng trng chn lp rc G Ct H thng x l nc r rc cng trng chn lp rc G Ct c xem l h thng x l nc r rc hon chnh v quy m nht hin nay TP H Ch Minh H thng x l do Cng ty Vemier (H Lan) thit k, u t thit b vi cng sut thit k 400 m3/ngy, vi cht lng nc sau khi x l phi t ct B theo TCVN 5945-1995, c Trung tm Cng ngh mi trng ECO xy dng. Cng trnh bt u tin hnh xy dng t nm 2003, a vo hot ng t nm 2003, nhng

nc x thi khng t yu cu so vi thit k nn thay i cng ngh, b sung thit b hon chnh. Cc giai on xy dng b sung thc hin ln lt nh sau: Giai on u (2003) : h thng x l c thit k ch da theo theo cng

ngh phn chia vt l trc tip ngun nc r rc thng qua hai cp lc : lc ct v lc tinh (micro v ultra) kt hp vi lc nano (hnh I-1):
Nc r rc th

Lc th qua ct

Lc tinh qua li lc : micro v ultra

Lc nano

Nc x l

Hnh I.1: S cng ngh x l nc r rc giai on u G Ct

Tuy nhin, thc t hot ng cho thy cng ngh ni trn khng ph hp vi i tng nc r rc cha nhiu tp cht l lng, nhiu cht nhim hu c phc tp nn cha mang li kt qu mong mun, cng sut nc sch sau khi ra h thng lc nano t rt thp tuy cht lng t tt. iu ny cho thy khng th x l trc tip nc r rc ch thng qua qu trnh phn chia vt l m khng c nhng qu trnh chun b trc . Giai on hai b sung (2004) : lp b sung b ln men k kh dung

cha 1000m3 trc khi vo h thng lc ni trn nhm x l phn hy cc cht hu c bng sinh hc (hnh I-2). Kt qu cng khng ci thin c cht lng v

s lng nc x l nh mong mun, c bit cha gii quyt c hm lng amoniac rt cao trong nc r rc.

Nc r rc th

Ln men k kh

Lng

Lc th qua ct

Lc tinh qua li lc : micro v ultra

Lc nano

Nc x l

Hnh I.2 S cng ngh x l nc r rc giai on hai G Ct

Giai on ba nng cp cht lng (2005) : xy dng thm b phn ng

sinh hc k kh vi dng chy ngc UASB do LeAF (H Lan) thit k x l trc tip nc u vo (x l bc 1), trong khi thit b ln men k kh xy dng giai on 2 c ci to li, b b phn np thu gom kh biogas, lp thm h thng sc kh bin thnh h thng x l sinh hc hiu kh bng bn hot tnh kt hp vi kh Nit trong 2 b tin v hu kh Nit, c b tr t trc v sau b lm thong hiu kh (x l bc 2). Sau , nc tip tc c a qua h thng x l hon thin (x l ho l) bng qu trnh keo t vi FeCl3, to bng bng

Polymer, lng, trung ha, lc ct. Sau 3 bc x l, nc thu c d kin s thi trc tip ra mi trng. Tuy vic a thm b sinh hc k kh UASB c hiu qu cao nhng cc cng on k tip hiu qu x l li thp, khng t ng nh thit k nn cht lng nc sau x l cui cng vn khng t, COD, BOD, TKN vn cn cao, ngoi ra vn cn mu v mi hi, nn phi cho tip tc vo h lc nano ca giai on thit k ban u x l tip. S cng ngh ca h thng x l nc r rc sau khi nng cp cui cng nh sau (hnh I-3):

Nc r rc th Phn hy sinh hc k kh trong h UASB X l tin kh Nit trong b anoxic

Phn hy sinh hc hiu kh trong b Aerotank

X l hu kh Nit trong b anoxic

Lng
Keo t bng FeCl3 v to bng bng polyme

Trung ha Lng

Lc th qua ct Lc tinh qua li lc (Micro v Ultra)

Thi ra mi trng

Lc nano

Thi ra mi trng

Hnh I.3- S cng ngh h thng x l nc r rc G Ct sau khi nng cp giai on 3

Khi vn hnh x l cc thnh phn nhim trong nc r rc theo s cng ngh m t trn y, kt qu v cht lng nc x l v hiu qu ca tng cng on trong dy chuyn cng ngh ghi nhn c trong thi gian thng 3/2006 v thng 7/2006 thu c nh sau (bng I-1):
Bng I.1- Cht lng nc x l qua tng thit b cng ngh
Thi im ly mu Thng 3/2006 Ch tiu, mg/L COD BOD N tng NNH3 NNO3 NNO2 Ptng SS pH Cm quang COD BOD N tng NNH3 NNO3 NNO2 Ptng SS pH Cm quang Sau UASB 5.424 2.280 2.376 2.436 4,3 0 17,5 1.440 8,26 c, en, 7.376 4.112 1.636 1.608 0 0 6,6 640 7,88 c, en, Sau tin kh Nit 2.712 840 989 954 51,8 596 21,3 1.660 8,53 c, en, 3.596 1.992 1.389 1.337 0 1,59 7,5 220 8,66 c, en, Sau b Aerotank 9.220 3.120 1.331 919,2 41,2 768 143,9 22.780 8,49 c, en, 7.986 1.544 1.625 1.336 0 0,62 99,2 6.860 8,62 c, en, V tr ly mu Sau hu Sau b kh Nit lng 8.678 3.560 1.334 937 23,5 613 135,8 31.740 8,53 c, en, 8.351 1.712 1.513 1.323 0 0 215 9.500 8,71 c, en, 2.712 788 975 937 33,5 460 46,1 1.100 8,59 c, en, 3.078 1.342 1.345 1.281 0 0 4,7 300 8,70 c, en, Sau x l hal 2.215 1.245 870 721 16,7 233,6 9,8 372 8,07 c, c mu 3.048 1.116 1.317 1.261 0 0 0 60 8,37 c, en, Sau lc ct 2.079 1.237 860 715 14,5 228,1 10,3 462 8,04 c, c mu 2.987 789,6 1.294 1.233 0 0,61 0 1.120 8,43 c, nu en Sau lc nano 350 308 480 470 7,3 91,7 11,7 37 7,59 Trong, musng 161 13,5 868,6 861 0 0,48 0 0 8,61 Trong, musng

u vo 16.814 9.200 2.427 2.887 6,2 0 19,8 700 7,6 c, en, 13.655 6.272 1.821 1.680 0 0 10,3 2.020 7,42 c, en,

Thng 7/2006

Ngun : S liu ca Cng ty Mi trng th TP HCM cung cp

Nh vy, nh my x l nc r rc G Ct t sau khi a vo vn hnh n nay gp phi nhng vn tn ti sau: V cng sut x l x thi: khng t cng sut x thi 400 m3/ngy,

ch t c khong 40 m3/ngy (tc ch t khong 10% thit k), thm ch t

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thng 11/2006 n nay ch t mc 16 m3/ngy (tc ch cn 4% cng sut thit k). V cht lng nc sau x l: khng n nh, COD v BOD giao ng

khng quy lut ch yu trong giai on x l bc 2 v x l ho l hon thin (phn nh du t m trong bng). Ngoi ra hm lng Nit trong nc thi cn cao hn rt nhiu so vi gii hn yu cu (khong 800 mg/L). Phn cm quang, nc x l cho n sau giai on x l hon thin vn cn mu sm, mi hi v cn c. Ch sau khi qua lc nano, nc trong, mu sng.

Nh phn tch, cho n nay trn a bn thnh ph H Ch Minh, vic x l nc r rc vn cn b tc, cng ngh x l da vo phn hy sinh hc l chnh, c kt hp thm khu x l keo t ha l hoc khu lc tinh v lc nano. Ni chung cha c mt cng ngh no c nh gi l thch hp, n nh v hiu qu [1,2,3,4].

1.4-

Nhng gii php x l nc r rc nc ngoi nc ngoi, vn x l nc r rc c cp nghin cu trong rt

nhiu cng trnh cng b trn cc tp ch hoc cc hi ngh khoa hc [5,6,7]. Cc cng trnh nghin cu x l nc r rc nc ngoi u t kt qu tt, cht lng nc sau x l t tt c cc yu cu x thi trc tip ra mi trng. Mt im chung nht ca tt c cc cng trnh ni trn nc ngoi trong thi gian 5 nm tr li y l ngoi vic da vo cc qu trnh phn hy sinh hc v x l ha l, tt c u da vo cc qu trnh phn hy ha hc, ch yu l cc qu trnh phn hy ha hc oxi ha nng cao (Advanced Oxidation Processes AOPs) nh ozon [ 8,9], Peroxon [5,9], Fenton [6,10].

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1.5- Nhng vn rt ra t nghin cu tng quan Nhng vn tn ti nu ra trong phn tng quan cho thy, s d vn x l nc r rc nc ta cha c gii quyt c bn chnh l do phn cng ngh ch da vo qu trnh phn hy sinh hc l chnh, cc qu trnh ny cha sc mnh phn hy nhng phn nhim hu c kh phn hy, bn vng v c hi trong nc r rc. Trong khi , cc cng ngh x l trin khai li cha cp nht c nhng qu trnh x l mi, hin i, in hnh l cng ngh x l da vo cc qu trnh oxi ha nng cao AOPs. Cc qu trnh Oxi ha nng cao AOPs ngy nay c xem l nn tng ca cng ngh x l nc v nc thi th k 21 [11,12,13]. Do , vic nghin cu p dng cc thnh tu khoa hc mi trong lnh vc mi trng xy dng cng ngh x l nc r rc cho cc cng trng chn lp rc TP H Ch Minh l cp bch v cn thit. Da trn kinh nghim p dng cc qu trnh oxi ha nng cao vo x l nc thi cha nhiu cht nhim hu c c hi, kh phn hy do Trung tm cng ngh ha hc v mi trng (ECHEMTECH) thc hin (nh cng trnh xy dng h thng x l nc thi sn xut thuc bo v thc vt nh my Thuc tr su Si Gn [14] hoc cng trnh x l nc thi sn xut bt giy ca nh my Giy Tn Mai [15]), Trung tm cng ngh ha hc v mi trng (ECHEMTECH) ng k ti vi ni dung : Nghin cu p dng cc qu trnh oxi ha nng cao (AOPs) x l nc r rc ( qua x l sinh hc) nh my x l G Ct trn h pilot 15-20 m3/ngy chnh l nhm tm kim mt gii php cng ngh mi p ng yu cu cp bch hin nay va ni trn.

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CHNG II NI DUNG NGHIN CU

2.1- Nghin cu nhn din nc r rc v nhng vn c tnh cht cha kho trong x l nc r rc 2.1.1- c tnh chung ca nc r rc Phn loi Nc r ra t cc bi chn lp rc khc nhau ni chung khng ging nhau, c tnh nc r rc thng khc nhau do c nhiu yu t nh hng nh thi gian chn lp rc (cn gi tui chn lp rc), cu trc bi chn lp rc, cch chn lp ln cht hay t do, khi rc dy hay mng, ngun gc rc, loi rc , phng thc qun l v khai thc bi rc. Rt nhiu qu trnh bin i sinh hc, ho hc v vt l xy ra xen k, ni tip nhau trong sut thi gian rc c tp trung v chn lp trong iu kin thiu hoc khng c khng kh, mi trng pH v nhit cao trong bi rc. Kt qu ca hng lot qu trnh bin i ny l to ra nhiu thnh phn hu c v v c gy nhim nhng cp khc nhau cng nh to ra nhiu hp cht c cu trc ho hc phc tp nhng cp khc nhau, chng c th d b phn hy sinh hc hoc kh hoc khng th b phn hy sinh hc. Tuy vy, c tnh chung ca tt c cc loi nc r rc bao gi cng c cc thnh phn quan trng sau y: (1) Thnh phn cc cht nhim hu c, c trng ti lng nhim theo COD v BOD5 rt cao. Trong thnh phn cht nhim hu c, bao gi cng cha hai phn : phn cht nhim hu c d b phn hy sinh hc v phn cht nhim hu c kh hoc khng th b phn hy sinh hc. cc bi rc thi gian chn lp khng lu (<1-2 nm), nc r rc c tr s COD rt cao (3.00060.000mg/L), ng thi t s BOD/COD cng cao (>0,6), tc trong nc r rc ny cha nhiu thnh phn hu c d b phn hy sinh hc. Ngc li cc bi rc thi gian chn lp lu (>10 nm) nc r rc c tr s COD tng i thp
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(100-500 mg/L), ng thi t s BOD/COD cng thp (<0,3), tc trong nc r rc ny cha nhiu thnh phn hu c kh (hoc khng) b phn hy sinh hc. Trong nc r rc nhng bi chn lp mt vi nm, thnh phn hu c c trng lng phn t thp, cc axit hu c bay hi (VFA) chim phn ln, trong khi , nc r rc t cc bi chn lp thi gian khong mi nm tr ln, thnh phn hu c c trng lng phn t cao li chin phn ch yu. in hnh nht ca thnh phn hu c kh phn hy trong nc r rc l axit fulvic, axit humic, c gi chung l cc cht humic (humic substances). Axit Fulvic v axit humic trong nc r rc ch yu do s phn hy sinh hc cc hp cht lipid, protein, cacbohydrat, lignin c trong xc thc vt v ng vt trong qu trnh chn lp rc. Chng l cc axit hu c cao phn t, c trng lng phn t rt cao, t 2.000 cho n 100.000-200.000, cu trc gm nhiu nhn thm ngng t cao, chung quanh nhn thm ngng t c nh cc nhm nh chc, ch yu l cc nhm cacboxyl (COOH), hydroxyl (-OH), cacbonyl (>C=O) lm cho phn t axit humic v fulvic c i lc cng ha (chelate) vi cc ion a ha tr nh Mg2+, Ca2+ v Fe2+.hoc mt s ion kim loi nng khc to thnh mt phc cht cu trc cng knh. Axit Fulvic c trng lng phn t thp hn trng lng phn t axit humic, ngc li, tnh axit ca axit fulvic cao hn ca axit humic. c tnh quan trng ca nht ca cc axit fulvic v humic l chng l nhng polyme mang mu (pigmented polymers), t mu vng m n nu en, lm cho nc r rc lun c mu nu sm, l thnh phn hu c kh x l nht trong nc r rc. C th thy r mang mu ca cc hp cht humic trn hnh v m t di y [18]

14

Hnh II.1- Tnh cht mang mu ca cc cht humic thay i theo trng lng phn t [18]

Tnh phc tp ca axit humic v axit fulvic c th thy qua m hnh cu trc phn t c trnh by bi mt s tc gi nh sau (hnh II.2 v II.3):

Hnh II.2- Cu trc ca phn t axit humic theo Stevenson [18]

Hnh II.3 Cu trc ca phn t axit Fulvic theo Buffle[18]

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Cng vi thi gian chn lp rc, phn hu c trong nc r rc gim dn, nhng t l thnh phn cc cht hu c khng b phn hy sinh hc li tng ln ng k. iu ny thy r trn s minh ho di y (hnh II-4):

Cht hu c khng b phn hu sinh hc Cht hu c b phn hu sinh hc

Hnh II.4 - Chiu hng bin i phn hu c trong nc r rc v t l phn hu c khng b phn hy sinh hc so vi phn b phn hy sinh hc theo thi gian chn lp rc (tui bi rc)

(2) Thnh phn cc cht nhim v c, ch yu l amoniac (NH3) nm di dng ion amoni (NH4+) trong nc r rc, thnh phn ny c to ra do s phn hy (thy phn v ln men) thnh phn protein xc ng vt hoc thc vt trong rc thi. c tnh quan trng ca thnh phn amoniac trong nc thi l chng c hm lng rt cao, n trn 2000 mg/L v li rt bn vng, khng b bin i theo thi gian, l thnh phn v c kh x l nht trong nc r rc. (3) Thnh phn cc cht c hi: vi trng, vi khun, mm bnh, virus cc loi v mt s kim loi nng.

c tnh ca nc r rc c phn chia thnh ba nhm khc nhau ph thuc vo thi gian ( tui) chn lp nh sau (bng II-1):

16

Bng II.1- c trng ca nc r rc cc bi chn lp vi thi gian khc nhau Loi Tui, nm pH COD, mg/l BOD/COD TOC/COD Cht hu c Mi (tr) <5 <6,5 >20.000 >0,3 0,3 Ch yu l 7090% VFA Trung bnh 5-10 7 3.000-15.000 0,1-0,3 20-30% VFA, 70-80% axit Humic v Fulvic 100 2.000 TKN 0,1 2 0,13-0,66 <2 1,0 <2 n nh (gi) >10 >7,5 <2.000 <0,1 0,4 Ch yu l axit Humicv axit Fulvic

Nit, mg/l TKN/COD Kim loi, g/l

Trong mt bi chn lp rc tr hay gi, qu trnh phn hy sinh hc u xy ra trong iu kin ym kh qua 3 giai an k tip nhau trong ton b khi rc b chn lp: giai on to axit (pha axit), giai on to mtan (pha mtan) v giai on trung gian (pha chuyn tip t pha axit sang pha mtan). Tu theo thi gian chn lp rc m u th ca tng giai on ni trn s thay i. Thi gian chn lp cng lu, tui ca bi rc cng gi, pha mtan s cng chim phn ch yu. Ngc li, tui bi rc chn lp cng tr, pha axit chim phn u th. C th cn c vo t s BOD/COD trong cc gii hn sau phn bit cc giai on xy ra trong bi rc chn lp : - Pha axit: - Pha chuyn tip : - Pha mtan : BOD/COD 0,4 0,4 > BOD/COD > 0,2 BOD/COD 0,2

17

2.1.2- c tnh nc r rc G Ct Qua kho st trong khong thi gian thng 3/2006 v thng 7/2006 ca Nh my x l nc rc G Ct cho thy thnh phn v tnh cht ca nc r rc Cng trng chn lp rc G Ct nm trong gii hn sau (bng II-2):
Bng II.2 Thnh phn v tnh cht ca nc r rc G Ct Thng s pH COD BOD BOD/COD TKN N-NH3 P tng SS Cm quang n v mg/L mg/L mg/L mg/L mg/L mg/L Thp 7,4 13.655 6.272 0,46 1.821 1.680 10,3 700 Cao 7,6 16.814 9.200 0,55 2.427 2.887 19,8 2.020 Trung bnh 7,5 15.234 7.735 0,50 2.124 2.283 15,05 1.360

c, nhiu cn, mu nu en n en, mi hi kh chu

Ngun : Cng ty mi trng th Thnh ph HCM

Nhng s liu trn y cho thy nc r rc Cng trng chn lp rc G Ct thuc loi chuyn sang tui trung bnh, c trng pH khng c tnh axit (pH~7); hm lng COD khng qu cao nh nc rc tui tr (>20.000 mg/L) v cng khng qu thp nh nc rc tui cao (<2.000 mg/L), m nm mc trung bnh (~15.000 mg/L); t s BOD/COD ~0,5, hm lng TKN cao (~2.000 mg/L), v t s TKN/COD nm gia 1,0 v 0,1 (~0,14). Vi nc r rc tui ny, trong thnh phn nhim hu c ngoi cc cht axit hu c bay hi cn cha mt phn ln (70-80%) l cc axit trng lng phn t ln (cao phn t) nh axit humic v axit fulvic nh m t trn. y l nhng
18

cht nhim hu c kh hoc khng th b phn hy sinh hc, do , vic x l nc rc G Ct t kt qu mong mun, khng th p dng cng ngh ch da vo cc qu trnh phn hy sinh hc. Ngoi ra, nh mi loi nc r rc, trong nc r rc G Ct cng cha cc cht c hi, cc mm bnh, vi trng, virus nguy him cho sc kho con ngi khi tip xc, khi xm nhp vo cc ngun nc mt, ao h, hoc vo cc mch nc ngm, nc ging trong khu vc quanh cc bi chn lp rc. Nc r rc tch ng trong cc h cha thng trc pht tn mi hi thi ra mi trng trong mt bn knh rt rng, lm nhim mi trng khng kh, nh hng rt xu n sc kho v sinh hot hng ngy ca ngi dn .

2.1.3- Vn c tnh cht cha kha trong x l nc r rc G Ct ni ring v nc r rc ni chung Nh kho st trn y, nc r rc l loi nc nhim ton din mc rt nng v rt khc bit so vi nc thi sinh hot hoc nc thi cng nghip thng thng. x l nc r rc t hiu qu mong mun, phi xc nh thnh phn nhim no cn phi tp trung tm gii php x l c bit mang tnh cht quyt nh hay cn gi mang tnh cht cha kho ha gii, thnh phn nhim no khng cn cc gii php x l c bit vn c th t yu cu mong mun. i vi nc r rc G Ct t cng trng chn lp rc G Ct, nhn din hai vn mang tnh cha kho cn phi gii quyt v mt cng ngh khi x l chng: 1- Vn x l cc cht nhim hu c c ti lng nhim cao, trong ngoi thnh phn hu c c kh nng phn hy sinh hc cn c bit phi x l thnh phn cc cht hu c kh hoc khng th phn hy bng vi sinh, ch yu l axit humic v axit fulvic. Gim ti lng

19

nhim hu c COD 12.000-16.000 mg/L, BOD 7.000-9.000 mg/L xung n gii hn yu cu COD ~ 100 mg/L, BOD ~ 50 mg/L, ngha l phi x l loi b >99% trong nc rc. 2- Vn x l cc cht nhim v c, ch yu l Nit di dng ion amoni c ti lng nhim cao khc thng so vi cc loi nc thi khc. Gim Ntng t 2.000-2.500 mg/L v N-NH3 t ~2.000 mg/L xung n gii hn yu cu Ntng ~ 30mg/L, N-NH3 ~10 mg/L ngha l phi x l loi b 98-99% trong nc rc. Nu c gii php cng ngh x l c hai vn nu trn, vic x l nhng phn nhim cn li trong nc r rc (Ptng s, SS, mu, mi, mm bnh) cng s c gii quyt theo, v do , vic x l ton b nc r rc G Ct xem nh gii quyt c mt cch c bn v trit .

2.2- Nghin cu gii php x l hm lng COD cao, c bit hm lng cc cht nhim hu c kh phn hy trong nc r rc G Ct 2.2.1- Gii php phn hy ha hc da vo cc qu trnh Oxi ha nng cao (Advanced Oxidation Processes AOPs) x l thnh phn nhim hu c kh hoc khng th b phn hy sinh hc, p dng phng php phn hy ho hc bng cc qu trnh Oxi ha nng cao (Advanced Oxidation Processes AOPs). y l phng php c hiu x l nhng thnh phn nhim hu c m cc phng php x l sinh hc khng th gii quyt ni v l s la chn ca ti ny. Phng php ny c xem nh thnh tu khoa hc mi trong lnh vc x l nc v nc thi trong gn hai thp k gn y ca th gii, c chng ti gii thiu trong sch Cc qu trnh oxi ha nng cao trong x l nc v nc thi C s khoa hc v ng dng, do Nh xut bn Khoa hc v K thut xut bn nm 2006[16].

20

Bn cht phng php l tin hnh phn hy cc thnh phn nhim hu c bn vng (khng th b phn hy sinh hc) da vo qu trnh oxi ha mnh hn bnh thng (tc qu trnh oxi ha nng cao- AOP), kh nng ph hy cc lin kt ha hc bn vng trong cc cht nhim. Qu trnh oxi ha nng cao da vo tc nhn oxi ha mnh l gc t do Hydroxyl (*OH), kh nng oxi ha cao cao hn tt c nhng tc nhn oxi ha thng s dng trong cng nghip ha hc nh Ozon, Clo hoc Hydrogen peroxit, ng thi khi phn ng vi cc cht nhim hu c, chng xy ra vi tc rt nhanh, hng nghn n hng t ln so vi cc tc nhn oxi ha thng thng. u th c bn ca gc t do hydroxyl *OH l: - Kh nng oxi ha ca gc t do Hydroxyl *OH cao gn 1,5 ln so vi Ozon, gn 1,6 ln so vi Hydrogen Peroxit, gp hn 2 ln so vi Clorin, nn c kh nng oxi ha hu nh tt c cc hp cht hu c, d l bn vng nht. - Nh kh nng oxi ha mnh ca gc t do hydroxyl *OH nn c kh nng ph hy nhng gc mang mu, lm sng mu nc x l km theo oxi ha ph hy nhng cht gy mi, lm mt mi nc rc. - Nh kh nng oxi ha mnh ca gc t do hydroxyl *OH nn c kh nng dit khun, kh trng trit k c virus, mnh gp i so vi clorin Mt iu ng lu l gc t do ny khng c sn nh cc tc nhn oxi ha thng thng m chng ch sinh ra ngay trong qu trnh x l (in situ) khi cho cc tc nhn ha hc tc dng vi nhau. Qu trnh oxi ha nng cao bng tc nhn oxi ha l gc t do *OH c s dng cho x l nc r rc G Ct l qu trnh PEROXON (Peroxone Process). Trng hp ny cho cc tc nhn Ozon O3 v Hydrogen Peroxit H2O2 tc dng trc tip vi nhau trong thit b, s to ra gc *OH ngay tc khc theo phn ng sau: H2O2 + 2O3 2*OH + 3O2 (II.1)

21

2.2.2- Gii php x l cc cht humic (axit humic v axit fulvic) bng qu trnh t hp keo t - to phc cht Fentony l gii php mi, t hp c 3 qu trnh: keo t, to phc cht, phn hy ha hc gn nh ng thi: (1) Qu trnh keo t v to phc cht PFS-Humic- Trong nhm cc hp cht nhim hu c kh hoc khng th phn hy sinh hc, ng ch nht l cc cht humic (axit humic v axit fulvic), l nhng hp cht nhim hu c c cha cc nhn thm a t bn vng v lin kt cng ha (chelate) vi cc kim loi nng dng phc cht nn va kh phn hy, va gy mu mnh nht. V vy, trong x l nc r rc, loi b nhm hp cht ny l ti cn thit v s lm gim ng k COD, gim dng k mu ca nc r rc, nhng li rt kh khn v nng n nht so vi x l cc thnh phn cn li. Khi nghin cu gii php cng ngh x l loi b cc hp cht ny, chng ti da vo tnh cht c th ca axit humic v axit fulvic. Axit Humic l nhng hp cht cao phn t c trng lng phn t >100.000, axit fulvic cng l nhng hp cht cao phn t nhng c trng lng thp hn, 2000-100.000. Trong mi trng kim, cc mui kim ha tr 1 ca axit humic (Natri Humat) tan tt trong nc, nhng trong mi trng axit, chng li kt ta di dng cc ht keo axit humic v khng tan trong nc. Trong khi , axit fulvic li tan tt trong c trong mi trng kim ln mi trng axit [18]. Khi s dng cc ho cht keo t thng thng Fe(III) dng monomer nh FeCl3 hoc Fe2(SO4)3 trong mi trng axit, chng ch c kh nng keo t phn ln axit humic nhng khng loi b c axit fulvic v trong iu kin , ch c axit humic kt ta v c tch ra nh Fe(OH)3 do phn ng thy phn FeCl3 hoc Fe2(SO4)3 trong mi trng axit. Trong khi , axit fulvic vn nm trong nc dng ho tan, lm cho nc vn cn mu sm v COD cao.

22

 loi b c axit humic v axit fulvic, chng ti s dng hp cht st (III) dng polymer l Polyferric sulfat (PFS) [Fe2(OH)n(SO4)3-(n-2)]x , trong n<2 v x>10. Trong mi trng axit (pH 4-5) s thy phn ca Fe(III) dng polyme (tc Polyferric sulfat) rt chm so vi s thy phn Fe(III) dng monome (tc FeCl3, Fe2(SO4)3), v vy khi PSF cha kp thy phn, gia cc nhm nh chc axit ca axit humic cng nh ca axit fulvic v PFS xy ra s to phc cht PFS v axit Humic-Fulvic dng kt ta khng tan. Phn ng to phc xy ra rt nhanh, v kt ta phc cht PFS-H/F axit cng lng xung rt nhanh [17]. Do , ch c s dng Polyferric sulfat mi c kh nng x l loi b ng thi c axit humic v axit fulvic nh c ch tch axit Humic v axit Fulvic bng PFS xy ra thng qua s to phc, trong khi vi FeCl3 ch c th tch c axit humic thng qua Fe(OH)3 do s thy phn FeCl3. (2) Qu trnh kiu nh Fenton (Fenton-like Process)- Trong qu trnh to phc gia PFS v axit humic, axit fulvic mi trng pH thp, phn phc cht khng tan tch ra, phn dung dch cn li bao gi cng c mt ion Fe(III) do phn ng thy phn ca Polyferric sulfat xy ra bn cnh phn ng to phc vi cc cht axit humic v axit fulvic. tn dng lng Fe(III) ni trn v nng cao hiu qu qu trnh x l, b sung mt lng nh Hydrogen Peroxit H2O2 thc hin qu trnh kiu nh FENTON (Fenton-like process). y cng l mt dng ca qu trnh oxi ha nng cao (AOPs)[16]. qu trnh Fenton chnh thng, s dng ion Fe(II) vi h Fe2+/H2O2, by gi xy ra phn ng to ra gc t do Hydroxyl *OH nh sau: Fe2+ + H2O2 Fe3+ + *OH + OH- (II.2)

trng hp s dng tc nhn Fe(III) tc dng vi H2O2 cng s to ra gc *OH kiu nh FENTON nhng theo hai bc nh sau: Fe3+ + H2O2 Fe2+ + H+ + *HO2 (II.3)

23

Vi Fe2+ va mi sinh ra ny, s tc dng vi H2O2 to ra gc t do *OH theo phn ng Fenton (II.2) ni trn. (3) Qu trnh x l kt hp gia keo t - to phc vi phn hy kiu nh Fenton gi tt l qu trnh t hp keo t - to phc Fenton c xem l qu trnh x l t hiu qu rt cao, chng nhng lm gim cht rn l lng (SS) nh qu trnh keo t, m cn lm gim rt ng k COD, trong loi b gn nh hon ton axit humic v axit fulvic, nh ko theo lm gim hn mu ca nc r rc.

2.3- Nghin cu gii php x l hm lng Ntng v N-NH3 cao trong nc r rc bng ba phng php kt hp Nu vic tm gii php cng ngh x l hm lng nhim hu c, c bit hm lng cc cht humic v cc cht kh phn hy sinh hc trong nc r rc cao kh, vic tm gii php x l hm lng cc cht nhim v c, ch yu l cc hp cht ca Nit nh N-NH3 cng kh khn hn nhiu. Nguyn nhn v hm lng NH3 trong nc r rc, d bi chn lp rc loi gi hay tr u rt cao, hng nghn mg/L, chng rt bn, khng b phn hy hoc t gii thot theo thi gian. V hm lng N-NH3 rt cao trong nc r rc, nn khi x l thc hin bng 3 gii php kt hp nh sau: 2.3.1- Gii php stripping mt phn(khng hon ton) Gii php ny thc hin qua 2 giai on: - Chuyn ion NH4+ thnh NH3 dng t do bng cch nng cao pH (pH 9-11) nh dung dch kim NaOH, phn ng xy ra nh sau: NH4+ + OHNH3 + H2O (II.4)

24

- Gii thot NH3 bng cch thi kh cng bc qua thp stripping (stripping tower). Phng php ny tch c hu ht lng NH3 to thnh ra khi nc rc, tuy nhin i hi lng khng kh sc vo rt ln (t l th tch khng kh / nc trong gii hn ~ 150-200/1), thi gian sc khng kh ko di, chi ph nng lng cao. Hn na, khi lng NH3 thot ra nhiu (trn 6 mg/m3), trc khi thi ra mi trng phi x l qua dung dch axt. V vy, tit kim chi ph nng lng, qu trnh stripping c thc hin trong thp ti ca thp lc sinh hc nh git khng c thi kh, v nh nc c dn tri qua b mt gi th c din tch ring ln nn h tr cho qu trnh bc hi NH3 c thun li. Mt phn NH3 (khong 30-40%) c gii thot c tc dng khng lm c ch qu trnh nitrat ha sinh hc tip sau. Phn N-NH3 cn li tip tc c x l bng phng php sinh hc. 2.3.2- Gii php sinh hcVic x l loi b thnh phn amoni bng gii php sinh hc c thc hin trong hai giai on : - Oxi ha NH3 thnh nitrat (nitrat ha) nh cc vi khun Nitrosomonas, Nitrobacter trong iu kin c oxi khng kh : NH4+ NH2OH NO2NO3(II.5)

Sau kh nitrat (denitrat ho) xy ra theo tng bc cho n nit N2

nh vi khun v nm Bacillus, Paracocus, Pseudomonas, Alcaligenes,... trong iu kin thiu oxi khng kh : NO3NO2NO N2O N2 (II.6)

Gii php sinh hc x l c cc hp cht Nit t kt qu. Tuy nhin, phng php sinh hc c rt nhiu yu t nh hng lm cho qu trnh kh kim sot t kt qu thun li mong mun. Cc yu t nh hng thng gp l thi

25

gain cn di v qu trnh xy ra chm, c bit chm nht v kh khn nht l giai on nitrat ha; vi khun qu trnh nitrat ha rt nhy vi pH v kim ca mi trng, cc vi khun li d b ng c vi kim loi nng c trong nc rc; s c mt NH3 nng cao lm c ch qu trnh nitrat ha; ng thi c s cnh tranh gia vi khun d dng phn hy cht hu c v vi khun nitrat ha, cc vi khun d dng pht trin rt nhanh c th n p khng cho vi khun nitrat ha pht trin nn rt kh kim sot, qu trnh ny thng gp hin tng hoc l xy ra hon ton, hoc l cm hon ton (all-or-none phenomenon hay on-or-off phenomenon). Hin tng cm ny tng xy ra nh my x l nc G Ct, c thy r qua cc s liu sau (bng II.3):
Bng II.3- Bin thin hm lng N-NH3 v Ntng qua cc thit b x l Nit G Ct Thi im 07/2006 Ch tiu, mg/L Ntng N-NH3 Sau UASB 1.636 1.606 Sau tin kh Nit 1.389 1.337 Sau b aerotank 1.625 1.323 Sau hu kh Nit 1.513 1.281

Ngun : Cng ty Mi trng th TP HCM

Do 2 gii php trn u c nhng nhc im nht nh, nn kh x l c NNH3 trit vi hiu qu n nh hm lng N- NH3 t hng ngn mg/L xung cn <10 mg/L, tc phi loi b n ~99% NH3 trong nc r rc. V vy, sau khi thc hin c hai gii php ni trn, i b phn Nit (~80%) c x l, phn nh cn li (<10%) s thc hin gii php ho hc khu cui cng. Vi gii php kt hp ny cho php x l trit hm lng Nit trong nc r rc G Ct. 2.3.3- Gii php ha hc Bn cht ca gii php ha hc l chuyn N-NH3 cn li thnh N2 trong thit b phn ng ha hc, c sc kh Ozon v c mt mui Brom (NaBr hoc

26

KBr) trong mi trng axit [19,20]. Phn ng xy ra nh sau: O3 + NaBr + H+ 3HOBr + 2NH3 HOBr + O2 + Na+ (II.7) (II.8)

N2 + 3Br- + 3H+ + 3H2O

Phn ng xy ra nhanh v trit , Nit dng kh c gii phng v thot ra t do ngoi mi trng. Gii php x l loi b NH3 ny bt buc phi c Ozon, ng thi phi s dng ha cht KBr hoc NaBr. Lng Br cho qu trnh xc nh bng phng trnh ha hc trn. Do trong gii php x l nhng thnh phn nhim hu c kh phn hy sinh hc p dng cc qu trnh oxi ha nng cao trong c s dng Ozon, nn gii php ny thc hin rt thun li. Hn na, v l phng php da trn cc phn ng ha hc nn xy ra nhanh, thit b khng i hi ln, cng knh, khng tn chi ph nng lng cung cp khng kh cho giai on nitrat ho, khng tn chi ph ngun Cacbon b sung cho giai on denitrat ha, qu trnh d iu khin, n nh. Vn quan trng trong qu trnh Ozone ho x l nc ni chung c cha Br l lu n nng HOBr trong nc, ch c hp cht ny mi cn ch v c th l tc nhn gy ung th. Tuy nhin, khi c NH3, do c phn ng mnh gia HOBr v NH3 nn ton b lng HOBr to ra u b NH3 bt gi phng ra N2. Do , chnh NH3 l tc nhn hn ch c tnh ca Br khi Ozone ho. Vn y l phi khng ch mt cch ch ng t l Br/N trong khong 0,4-0,6 v pH ~ 6 th d lng HOBr s ti thiu, di mc cho php trong nc thi.

27

CHNG III : KT QU V THO LUN

3.1- Th nghim kim tra cc qu trnh chnh trong phng th nghim xc nh cng ngh x l 3.1.1- Qu trnh keo t to phc Fenton Nc r rc th, sau khi x l phn hy sinh hc k kh trong b UASB h thng x l G Ct c ly lm mu nc th nghim trc tip cho qu trnh keo t to phc Fenton. K hiu MUASB Cht keo t Polyferric sulfat (PFS) do Vin Cng ngh Ha hc (Trung tm khoa hc t nhin v cng ngh Quc gia) nghin cu ch to v cung cp. Nng Fe(III) trong dung dch PFS ~12% (TL), pH < 2, t trng 1,4. Th nghim keo t bng PFS - Mi th nghim ly 1000 ml mu nc MUASB ni trn vo cc thy tinh, sau cho dung dch PFS vo tng cc sao cho c nhng nng khc nhau : mu M1 : 100 mg Fe3+/L mu M2 : 200 mg Fe3+/L mu M3 : 300 mgFe3+/L mu M4 : 400 mg Fe3+/L Dng my khuy khuy nhanh trong vng 5 pht, sau khuy chm thm 20 pht. Phn nc trong tch ra em phn tch tr s COD v nh gi hiu qu x l ca qu trnh bng % COD c x l loi b so vi tr s COD ca mu MUASB. Kt qu cho thy, lng PFS s dng cng nhiu, % COD c x l loi b cng cao, nhng vi lng PFS t 300-400 mg/L, mc c tng khng nhiu, t 53-55% (hnh III.1)

28

Hieu qua x ly, %COD

60 50 40 30 20 10 0 100 200 300 400

Lng chat keo tu, mg Fe(III)/L

Hnh III.1- Anh hng lng cht keo t n hiu qu x l COD (% so vi mu MUASB)

Th nghim phn hy kiu nh Fenton - Tin hnh keo t nh th nghim trc, nhng sau khi cho PSF vo v khuy nhanh vi nng PSF nh mu M3, tip tc cho thm H2O2 vo vi nng H2O2 thay i v khuy chm: mu M5 : 300 mg/L mu M6 : 400 mg/L mu M7 : 500 mg/L mu M8 : 600 mg/L

Tip tc khuy nh v sau 120 pht, tch phn nc lng trong ra. Phn nc trong tch ra em phn tch tr s COD v nh gi hiu qu x l ca qu trnh bng % COD c x l loi b so vi tr s COD ca mu MUASB do kt qu tng hp ca ton b qu trnh keo t Fenton. Kt qu cho thy nh trn hnh III.2 di y:

29

78 76 74 72 70 68 66 64 300 400 500 600

Hieu qua x ly,% COD

Ham lng H2O2, mg/L

Hnh III.2- Anh hng lng H2O2 n hiu qu x l COD (% so vi mu MUASB)

Kt qu trn cho thy, thc hin qu trnh oxi ha kiu nh Fenton, ch cn cho thm mt lng H2O2 khong 500 mg/L c th t hiu qu x l rt cao, n ~76% so vi ch thc hin qu trnh keo t n thun bng PFS ch t c ~53%. 3.1.2- Qu trnh PEROXON tip sau qu trnh keo t to phc Fenton Vi nc sau khi lng trong ca mu M7, trung ha chuyn pH ~8, ly 200 ml cho vo bnh phn ng khong 1000 ml v sc kh ozon. S dng my pht sinh ozon chy bng oxy cng nghip, cng sut 3 g/gi, lu lng oxi 5,0 L/pht. Cho thm H2O2 vo vi lng 300 mg/L, v sc kh Ozon trong thi gian khc nhau : - mu M9 : 5 pht - mu M10 : 10 pht - mu M11 : 20 pht - mu M12 : 30 pht Sau thi gian sc ozon, ly nc ra em phn tch tr s COD v nh gi hiu qu x l ca qu trnh bng % COD c x l loi b so vi tr s COD ca mu MUASB. Kt qu cho thy nh trn hnh III.3 di y:
30

120 Hieu qua x ly, %COD 100 80 60 40 20 0 5 10 20 30

Thi gian suc Ozon, phut

Hnh III.3- Anh hng thi gian phn ng n hiu qu x l COD (% so vi mu MUASB)

Kt qu tt nht t c vi thi gian sc ozon khong 30 pht, lng H2O2 s dng 300 mg/L. Kt qu trn cho thy, nu tip sau qu trnh keo t to phc Fenton, tin hnh thm qu trnh oxi ha nng cao Peroxon, ch cn thc hin phn ng vi ozon trong vng 30 pht c th t hiu qu x l cui cng cao hn na, loi b n ~97% so vi COD ca mu ban u MUASB. Tng hp cc kt qu thu c t cc th nghim tt nht nh sau (bngIII.1): Bng III.1- Hiu qu x l COD qua cc qu trnh khc nhau
Qu trnh x l Sau UASB Sau Keo t-To phc Sau keo t To phc - Fenton Sau keo t To phc Fenton - Peroxon COD, mg/L 3.060 1.425 733 76,8 Hiu qu x l, %COD 0 53,4 76,1 97,5

31

3.2- Xy dng cng ngh x l nc r rc G Ct Trn c s nhng th nghim s b trong phng th nghim, gip xc nh c cng ngh x l nc r rc t sau b x l sinh hc k kh UASB s phi qua cc giai on nh sau :

NC SAU B SINH HC K KH UASB

HON THIN X L SINH HC K KH TRONG THP LC SINH HC K KH V LC SINH HC NH GIT

T HP KEO T TO PHC - FENTON

LNG

CN BN

PHN HY HA HC OXI HA NNG CAO PEROXON

X L NIT pH CAO TRONG THP TI NH GIT TRN GA TH

X L NIT TRONG THP NITRAT HO

X L NIT TRONG THP DENITRAT HA

X L NIT TRONG THIT B SC OZON

NC R RC X L

Hnh III.4 . S khi cng ngh x l nc r rc G Ct do ECHEMTECH nghin cu v xy dng

32

3.3- Xy dng thit b pilot thc hin cc qu trnh chnh trong cng ngh x l nc r rc cng sut 15-20 m3/ngy 3.3.1- Thit b cho qu trnh keo t to phc FENTON X l ho l bng qu trnh t hp keo t- to phc Fenton c thc hin trong h thit b gm cc thnh phn sau: Thit b keo t to phc bng tc nhn Polyferric Sulfat (PFS)

[Fe2(OH)n(SO4)3-(n-2)]x c thit k vi dung tch 200 L, c trang b my khuy tc nhanh (>500 vng/pht) Thit b Fenton v kt bng bng polyme c thit k vi dung tch 500L,

c trang b my khuy tc chm (<50 vng/pht). Thit b lng tch bn keo t trong h thng chm ng nghing (49, 300

ng PVC). Modun h t hp keo t to phc Fenton lp t ti G Ct c trnh by nh di y (hnh III.5):

Hnh III.5- S modun h keo t tch hp keo t to phc Fenton lp t trong h pilot G Ct : P- Bm ly tm ; F- Lu lng k; 1- Thit b keo t- to phc c my khuy tc nhanh (>500v/pht); 2- Thit b Fenton kt bng c my khuy tc chm (<50 v/pht); 3- Thit b lng dng chm ng nghing

33

3.3.2- Thit b cho qu trnh PEROXON Thit b thc hin qu trnh x l ha hc oxi ha nng cao (AOPs) PEROXON bao gm cc thnh phn sau y : H my pht OZON, vi nng Ozon c th thay i bng cch thay i

lu lng dng Oxy i qua in cc ca my pht Ozon. H gm 3 cm my pht ozon, mi my c cng sut 25 g/gi. Reactor trong Ozon a vo v trn phn tn ng nht trong nc x l

nh h thng si bt lp trc tip trong reactor. Dung tch reactor 500 lt, thi gian tip xc 30-40 pht. Tc nhn H2O2 a vo b trn tnh trc khi vo reactor. Ozon d thot ra c a vo b x l tiu hy bng cht xc tc NiO/Al2O3 nhit thng. Modun h x l ha hc oxi ha nng cao AOPs bng Ozon v H2O2 (PEROXON) lp t ti G Ct c trnh by nh di y (hnh III.6):

Hnh III.6- S modun h x l ha hc PEROXON lp t trong h pilot G Ct F- Lu lng k; R- Reactor ha hc; O2- Bnh Oxi cao p; O3- My pht OZON; DeOz- B tiu hy Ozon d bng cht xc tc NiO/Al2O3 nhit thng

34

3.3.3- Thit b cho qu trnh x l NH3 pH cao Thit b thc hin vic gii thot NH3 pH cao c thc hin trong thp ti nh git kiu nh thp lc sinh hc nh git. Thp lc ti nh git c thit k vi kch thc nh sau: S 1000x1000mm, H 4000mm, trong thp np y gi th PLASDEX c b mt ring ~150 m2/m3. Tng b mt lm vic ca gi th ~600 m2. Gi th PLASDEX nm c nh v nc chy thnh mng trn b mt gi th. Khng kh c ht t nhin vo thp nh chuyn ng i lu ca khng kh.
TF

KHONG KH

KHONG KH

Hnh III.7- S modun thp lc sinh hc nh git lp t trong h pilot G Ct P- Bm ly tm ; F- Lu lng k; TF- Thp lc sinh hc nh git vi gi th PLASDEX

3.3.4- Thit b nitrat ho v denitrat ha Qu trnh nitrat ha c thc hin trong thp lc sinh hc thi kh vi gi th FLOCOR c b mt ring ~300m2/m3, trong iu kin cung cp khng kh v vi sinh pht trin dnh bm thnh mng trn gi th. Qu trnh denitrat ha cng c thc hin trong thp lc sinh hc thi kh vi gi th FLOCOR c b mt ring ~300m2/m3, nhng trong iu kin thiu khng kh v vi sinh pht trin dnh bm thnh mng trn gi th.

35

V vy, thit b cho qu trnh nitrat ha v denitrat ho ch khc nhau ch c thi kh hoc khng c thi kh v h. Vi sinh pht trin theo kiu dnh bm vo gi th c b mt ln, to thnh cc mng vi sinh v theo thi gian s ph kn ton b b mt gi th, v vy mt vi sinh trong thit b cao hn rt nhiu so vi mt vi sinh trong cc b bn hot tnh l lng, nh hiu qu x l cao, c th lm vic vi ti trng theo cht hu c ln (2-4 kg BOD5/m3.ngy; 5-10kg COD/m3.ngy), hoc vi ti trng amoniac cao (0,5-1,0 kg N-NH4/m3.ngy). u im ca thp lc sinh hc l va thc hin x l sinh hc, va tch sinh khi nh mt ct lc, v vy nc ra thp lc sinh hc khng cn lng, c th trc tip i vo cc thit b cng ngh tip sau. Cc qu trnh xy ra trong thp lc sinh hc c lng bn sinh khi t hn so vi trong b bn hot tnh t 1/5 1/10 ln, lng bn ny ly ra khi thp bng cch ra ngc.

Hnh III.8- S modun thp nitrat ha lp t trong h pilot G Ct P- Bm ly tm ; B- my thi kh; F- Lu lng k; BF- Thp lc sinh hc thi kh vi gi th FLOCOR (Trng hp Denitrat ha, trong h s khng c my thi kh)

36

3.3.5- Thit b x l NH3 bng Ozon c mt Bromua Thit b thc hin qu trnh x l NH3 bng phng php ha hc hon ton tng t nh thit b oxi ha nng cao (AOPs) PEROXON, bao gm cc thnh phn sau y : H my pht OZON, vi nng Ozon c th thay i bng cch thay i

lu lng dng Oxy i qua in cc ca my pht Ozon. H gm 1 my pht ozon c cng sut 25 g/gi. Reactor trong Ozon a vo v trn phn tn ng nht trong nc x l

nh h thng si bt lp trc tip trong reactor. Dung tch reactor 500 lt, thi gian tip xc 30-40 pht. Tc nhn dung dch KBr a vo b trn tnh trc khi vo reactor. Modun h x l ha hc N-NH3 bng Ozon v KBr lp t ti G Ct c trnh by nh di y (hnh III.9):

Hnh III.9- S modun h x l ha hc N-NH3 lp t trong h pilot G Ct F- Lu lng k; R- Reactor ha hc; O2- Bnh Oxi cao p; O3- My pht OZON;

3.3.6- Kt ni cc modun thit b thnh dy chuyn cng ngh

Cc modun thit b cng ngh m t trn y ghp c kt ni thnh mt dy chuyn cng ngh nh sau( hnh III.10):
37

Hnh III.10- S dy chuyn cng ngh h pilot x l nc r rc lp t G Ct I- Modun x l sinh hc k kh UASB ( c sn); II- Modun x l hon thin sinh hc k kh; III- Modun t hp x l KEO T- TO PHC- FENTON v lng bn keo t; IVModun x l ha hc oxi ha nng cao PEROXON; V- Modun x l Nit bng sinh hc v ha hc ; VI- Thit b lc ct (khng bt buc)

3.4- H pilot th nghim cng sut 15-20 m3/ngy lp t G CtBt u t thng 2/2007, sau khi ton b thit b cng ngh c thit k v ch to xong, tp kt v cng trng G Ct v tin hnh lp t theo tng modun trong dy chuyn cng ngh nghin cu (nh trnh by trn s khi hnh III.4 v hnh III.10) thnh mt h thng x l hon chnh, vi u vo l nc ly trc tip (khng pha long) t b x l sinh hc k kh UASB ca nh my x l G Ct, u ra l nc c x l, sn sng x thi. Bt u t cui thng 2/2007, ton h thng a vo vn hnh th nghim. Sau 1 tun vn hnh theo tng modun ring r, cc modun c lp ghp chy lin thng vi nhau trong vng 3 tun thch nghi v hiu chnh tnh ng b ca h thng. Vo thng 3/2007, h thng pilot c vn hnh ng b v hot ng lin tc nghin cu, kho st , hiu chnh cc thng s cng ngh v thu thp s liu thc nghim. Di y l hnh nh ca h thng pilot cng sut 15-20 m3/ngy lp t ti G Ct phc v cho ti nghin cu (hnh III.11)

38

Hnh III.11- Hnh nh h pilot thc t lp t v vn hnh ti Cng trng G Ct, cng sut 15-20 m3/ngy

39

3.5- Kt qu x l bng cng ngh p dng cc qu trnh Oxi ha nng cao (AOPs) do ECHEMTECH nghin cu, thc hin trn h pilot G Ct 15-20 m3/ngy 3.5.1- Cc thng s vn hnh - Nc u vo x l : trc tip t sau b sinh hc k kh UASB ca nh my G Ct. - Cng sut x l : 15-20 m3/ngy, c khng ch chnh xc nh cc lu lng k lp t trc khi vo tng thit b cng ngh. - Ti trng thy lc tnh cho 1 m2 gi th: * trong thp lc sinh hc thi kh : 0,1 m3/m2.ngy (trng hp nc khng tun hon li thp) v 0,3m3/m2.ngy (trng hp h s tun hon bng 3); * trong thp lc sinh hc nh git : 0,1 m3/m2.ngy (trng hp nc tun hon vi h s tun hon bng 3). - Ho cht s dng : * Axit H2SO4 loi cng nghip ( chnh mi trng pH theo yu cu) * Xt NaOH loi cng nghip ( chnh mi trng pH theo yu cu) * PolyFerric Sunfat (PFS) do Vin Cng ngh Ha hc (Vin Khoa hc v Cng ngh Vit Nam) nghin cu v cung cp theo yu cu th nghim ca ECHEMTECH * Hydrogen Peroxit H2O2 loi cng nghip * Kali Bromua KBr loi cng nghip * Polyme cationic (to bng) loi cng nghip - Cc chng vi sinh bao gm cc vi khun (bacteria) v nm mc (Fungi) do Phng Vi sinh ng dng thuc Vin sinh hc nhit i (Vin Khoa hc v Cng

40

ngh Vit Nam) nghin cu v cung cp theo yu cu th nghim ca ECHEMTECH nh sau: + Cc chng vi sinh hiu kh (dng bt), l mt hn hp ca vi khun Baccilus spp, Streptomycs spp, Nitrosomonas, Nitrobacter, trong chng vi sinh Nitrosomonas v Nitrobacter chim u th, vi mt t bo 109 CFU/g. + Cc chng vi sinh ym kh (dng lng), l hn hp ca vi khun Lactose Bacilus spp, v nm Aspergillus spp, Saccharomycs spp, vi mt t bo 109 CFU/ml. 3.5.2- Phng php phn tch Nh phn trc phn tch, trong x l nc r rc, hai vn mang tnh cht cha kho l lm sao gim c hm lng nhim hu c COD v hm lng nhim v c NH3. V vy, khi vn hnh, hai ch tiu nhim quan trng nht cn theo di iu khin qu trnh x l t kt qu mong mun l ch tiu COD v ch tiu N-NH3. Khi tin hnh th nghim cc ch cng ngh trn h pilot, giai on u c ly mu v tin hnh phn tch nhanh ti hin trng bng cc TEST KIT ca Nht, do Cng ty Kyoritsu Chemical-Check Lab., Corp. sn xut v cung cp, vi kt qu gn ng cho php nh gi s b hiu qu x l, trn c s s hiu chnh cc thng s cng ngh cho n khi t c kt qu x l tt v n nh, by gi s tin hnh phn tch chnh xc Phng th nghim theo phng php tiu chun APHA [21]. Cui cng, i vi mu x l ch cng ngh ti u cho kt qu tt nht, chuyn mu v Trung tm o to v Phn tch sc k TP H Ch Minh cho cc s liu chnh thc. 3.5.3- Kt qu 3.5.3.1- X l COD trong nc r rc S bin i COD qua cc modun thit b cng ngh nhn thy nh sau (bng III.2) di y:
41

Bng III.2- S bin i COD qua tng modun thit b cng ngh lp t ti G Ct Th t Modun thit b cng ngh COD, mg/L Hiu qu x l, %COD 1 2 3 4 5,6,7 Phn hy sinh hc k kh UASB Hon thin x l sinh hc k kh Keo tu - To phc - Fenton Phn hy ha hc AOP (Peroxon) X l Nit (3 cng on) 3.060 2809 858 159 80,0 0 8,2 72,0 94,8 97,4

Qua cc s liu ca bng III.2 cho thy, x l COD trong nc r rc qua x l sinh hc k kh trong b UASB, ba qu trnh quan trng c tnh cht quyt nh l x l (i) keo t to phc kt hp vi (ii) phn hy ha hc kiu nh Fenton v (iii) phn hy ha hc Peroxon. Vi ba qu trnh ny, c th t c mc x l rt cao, loi b c ~ 95% COD trong nc r rc. iu ny chng t nc r rc G Ct cha nhiu thnh phn nhim hu c khng th x l n thun bng phng php sinh hc, m ch c p dng cc phng php phn hy ha hc bng cc tc nhn oxi mnh hoc cc tc nhn c kh nng to phc cht vi cc cht humic (axit Fulvic v axit Humic) mi c kh nng x l c trit chng. S bin i COD ca nc r rc qua cc modun thc hin cc qu trnh x l khc nhau c minh ha trn hnh di y (hnh III.12):

42

3500 3000 2500 2000 COD,mg/L 1500 1000 500 0 I II III IV V

Hnh III.12 - Mc gim COD qua cc modun x l I- UASB; II- Modun x l hon thin sinh hc k kh; III- Modun x l Keo t- To phc- Fenton; IV- Modun x l ha hc oxi ha nng cao PEROXON; V- Modun x l nit

3.5.3.2- X l Nit trong nc r rc S bin i hm lng N-NH3 qua tng modun thit b cng ngh c trnh by trong bng III.3 di y:
Bng III.3- Mc x l N-NH3 qua tng modun thit b cng ngh Th t Modun thit b cng ngh Hm lng N-NH3, mg/L 1 2 UASB - Hon thin sinh hc k kh - Keo t to phc Fenton - Peroxon 3 4 5 X l gii thot NH3 pH cao X l NH3 bng nitrat ho v denitrat ho sinh hc X l NH3 bng Ozon c mt KBr 480 112,1 9,0 70,0 93,0 99,5 1591 986,6 % N-NH3 x l 0 38,0

43

Biu din s bin i hm lng N-NH3 qua tng modun thit b cng nghe bng th c th minh ho nh di y:
1600 1400 1200 1000 N-NH3, mg/L 800 600 400 200 0 I II III IV V

Hnh III.13- Mc gim hm lng N-NH3 qua cc modun thit b cng ngh I- UASB; II- Modun hon thin phn hy k kh+keo t-Fenton+Peroxon; III- Modun stripping; IV- Modun nitrat Denitrat ha; V- Modun x l bng Ozon v KBr.

Qua kt qu trn y, r rng phi p dng tng hp c 3 phng php mi c kh nng x l trit hm lng NH3 rt cao trong nc r rc. c bit, vic lp t h thng x l bng phng php ha hc cui cng c ngha nh mt by lc NH3 cn st li, cha x l ht hai khu x l trc, gip gi cho hm lng NH3 sau x l n nh.

3.5.3.3- Kt qu x l tng th giai on h thng hot ng n nh, cht lng nc ra t kt qu tt, ly mu nc u ra v gi i phn tch Trung tm o to v pht trin sc k TP HCM theo cc phng php tiu chun (COD: SMEWW 5220C-1995; Ntng: TCVN 5987-1995; N-NH3: TCVN 2662-1978). V COD, N-tng v N-NH3:
44

TT 1 2 3

M s mu 0704370 0704371 0704372

COD, mg/L 103 75 82

N-tng, mg/L 37 25 28

N-NH3, mg/L 7,3 10 17

V cc ch tiu c bn khc:

TT 01 02 03 04 05 06 07

Ch tiu COD BOD5 SS Tng Nit Tng Phospho Coliforms N-NH3

n v mg/L mg/L mg/L mg/L mg/L MPN/100mL mg/L

Phng php th SMEWW 5220C-1995 SMEWW 5210B-1995 SMEWW 2540D-1995 TCVN 5987-1995 SMEWW 4500-P-1995 SMEWW 9221B-1995 TCVN 2662-1978

Kt qu 82 36 19 28 1.1 3.6 17

Nhn xt Vi nhng s liu trn y cho thy cng ngh x l nc r rc theo cc gii php xut l hp l, hiu qu cao, cht lng nc sau x l t yu cu x thi trc tip ra mi trng, cng sut x l tng ng vi cng sut u vo.

45

3.5.4- Xc nh s b v cc chi ph ch yu cho vn hnh 3.5.4.1Chi ph ha cht (tnh cho 1 m3 nc x l):

Bng III.4- Chi ph ho cht cho 1m3 nc x l

TT 1 2 3 4

Tn ha cht Axit H2SO4 (98%) Xt NaOH, (vy) PolyFerric Sunfat (PFS), Dung dch 12% TL Hydrogen Peroxit H2O2 Dung dch 50% TL

nh mc 1 kg/m3 0,6 kg/m3 1,1 kg/m3 1,4 kg/m3

Gi n v, 3.000 /kg 8.500 /kg 6.500 /kg 9.000 /kg

Thnh tin, 3.000 5.100 7.150 12.600

5 6

Kali Bromua KBr Polyme cationic CNG

60 g/m3 5 g/m3

60.000 /kg 75.000 /kg

3.600 375 31.825

Ghi ch : Gi th trng ho cht, thng 4/2007

3.5.4.2- in nng cho 1m3 nc x l in nng phc v ch yu cho cc my bm, my thi kh, my pht sinh Ozon. in nng cho x l 1 m3 nc rc l 1,9 KWh, vi gi in trung bnh 968 / KWh, chi ph in nng cho 1m3 nc x l s bng 1.839 / m3 nc x l. Ghi ch: Trong phn ny, ch mi cp n chi ph v ha cht v nng lng, mang tnh cht nh hng s b cho vic xc nh hiu qu ca cng ngh x l. c th xy dng phng n trin khai c th, cn tnh ton y hn k c cc chi ph khu hao v chi ph bt thng khc.

46

Phn chi ph oxi cho cc my pht ozone, trong tnh ton cha ra v khi trin khai trong thc t s khng s dng oxi cao p, m s dng h thit b lm giu oxi trong khng kh bng Zeolite. Phn ny nm vo vn c nh (u t thit b v vt liu).

47

CHNG IV : KT LUN V NGH

Qua nghin cu th nghim thc t trn h pilot cng sut 15-20 m3/ngy x l nc r rc qua x l sinh hc Cng trng G Ct c th rt ra nhng kt lun sau: (1) x l thnh cng nc r rc, cn tp trung vo gii php x l 2 thnh phn c bn mang tnh cht cha kho quyt nh: * Thnh phn cc cht nhim hu c trong nc rc, c bit nhng cht hu c kh phn hy, nhng cht humic nh axit fulvic v axit humic. Nhng thnh phn ny c hm lng rt cao, phi x l trit , >99% mi c th t yu cu v tr s COD v BOD5 cho x thi trc tip. * Thnh phn cc cht nhim v c trong nc r rc, ch yu l amoniac NH3 di dng ion amoni NH4+ trong nc r rc. Nhng thnh phn ny cng c hm lng rt cao, phi x l trit , >99% mi c th t yu cu v tr s NNH3 v Ntng s cho x thi trc tip.

(2) i vi thnh phn cc cht hu c d b phn hy sinh hc, gii php x l sinh hc l thch hp v cn thit. Nhng i vi thnh phn cc cht nhim hu c khng th hoc kh b phn hy sinh hc, gii php x l ha hc bng cc qu trnh oxi ha nng cao (AOPs) l bt buc v khng th trnh khi. Ch c kt hp tt 2 gii php ni trn, mi c kh nng x l trit , trn 99% COD, BOD5 trong nc r rc.

(3) i vi thnh phn nhim v c, gii php x l trit trn 99% NH3 trong nc r rc ch c th t c bng cch kt hp nhiu phng php khc nhau (sinh hc v ha hc kt hp) v hm lng thnh phn nhim ny qu cao,

48

hot ng vi sinh vt kh kim sot v b c ch bi bn thn lng NH3 , lng cht nhim hu c v cc kim loi nng trong nc rc.

(4) Gii php cng ngh do ECHEMTECH nghin cu v xut qua vn hnh h thng pilot 15-20 m3/ngy x l nc r rc G Ct qua x l sinh hc k kh trong b UASB cho thy gii quyt c y 2 vn cha kho nu trn, kt qu t hiu qu cao, n nh v ph hp vi iu kin trong nc, trnh s dng nhng cng ngh t tin nhng hiu qu thp nh cng ngh lc nano p dng ti G Ct.

(5) Gii php cng ngh ny l c s c th xy dng cng ngh x l nc r rc cho cc cng trng chn lp rc khc trong thnh ph, tuy nhin trc khi bt tay vo gii quyt nhng trng hp c th, cn phi c s kho st v nghin cu thc t hiu chnh hoc b sung thm cc gii php cho ph hp.

(6) ngh S Khoa hc v Cng ngh, S Ti nguyn v Mi trng, Cng ty Mi trng th thnh ph xem xt cho trin khai gii php ca Trung tm Cng ngh Ha hc v Mi trng (ECHEMTECH) c th nghim thnh cng trn h pilot vo vic ci to h thng x l nc r rc G Ct t c cng sut v cht lng nh thit k ban u, gp phn h nhit cho tnh hnh cng thng v nc r rc ang tn ng G Ct vo ma ma ang ti.

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PH LC TI LIU THAM KHO

1- Cng trng x l rc G Ct TP H Ch Minh Nhiu vic cn lm ngay http://www.monre.gov.vn/ 28/6/2006 2- Cng ngh x l nc r rc : Bi hc t cng trng G Ct http://www.nea.gov.vn/ (11/5/2005) 3- Ni lo nc rc TP H Ch Minh http://moitruong.xaydung.gov.vn/ 4- Vn x l nc r rc TP H Ch Minh http://irv.moi.gov.vn/ 13/3/2007 5- F. Wang, Daniel W.Smith, and M. Gamal El-Din Application of Advanced Oxidation Methods for Landfill Leachate Treatment A review , J. Environ. Eng. Sci./Rev. gen. sci. env. 2(6), 413-427(2003) 6- R. Stegmann, K. U. Heyer, R. Cossu Leachate treatment- Proceedings Sardinia 2005, Tenth International Waste Management and Landfill SymposiumS. Margherita di Pula, Cagliari, Italy, 3-7 October (2005) 7- J. L. de Morais, P. P. Zamora Use of advanced oxidation processes to improve the biodegradability of mature landfill leachate J. of Hazardous Materials, Vol 123, Issues 1-3, 181-186 (2005) 8- A. Vilar, S.Gil,M.A. Aparicio, C. Kennes, M. C. Veiga Application of anaerobic and Ozonation processes in the landfill leachate treatment Water Practice & Technology, Vol 1, N 3(2006) 9- J.J. Wu, C.C. Wu, H.W. Ma, C.C. Chang- Treatment of landfill leachate by ozone-based advanced oxidation processes Chemosphere, Vol 54, N 7, 9971003 (2004) 10- I.W.C. Lau, P. Wang, H.H.P. Fanf Organic removal of anaerobically treated leachate by Fenton coagulation- J. Envi. Eng. Vol 127, Issues 7, 666-669(2001) 11- R. Munter- Advanced oxidation processes- Current status and prospects Proc. Estonian Acad. Sci. Chem., Vol 50, N 2, 59-80(2001) 12- H. Suty, C. de Traversay, M.Coste Applications of advanced oxidation processes: present & future- Proceeding of the 3nd Conference on oxidation technologies for waste and wastewater treatment, Goslaer, Germany, May 2003.

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13- Trn Mnh Tr Qu trnh oxi ha nng cao p dng vo x l nc v nc thi K yu Hi ngh Xc tc hp ph ton quc ln th 3- Hi xc tc v hp ph Vit Nam, Hu, thng 9/2005 14- Trn Mnh Tr v cc tc gi - Gii thng Hi thi sng to K thut-Cng ngh Ton quc (2001-2002) cho cng trnh Xy dng h thng x l nc thi sn xut thuc tr su Si Gn bng cng ngh cao tch hp 15- Trn Mnh Tr v cc tc gi- Gii thng Hi thi Sng to K thut- Cng ngh TP H Ch Minh (2005) cho cng trnh Xy dng h thng x l mu nc thi phn xng sn xut bt giy t g cy keo lai Cng ty Giy Tn Mai 16- Trn Mnh Tr, Trn Mnh Trung Cc qu trnh oxi ha nng cao trong x l nc v nc thi- C s khoa hc v ng dng Nh xut bn Khoa hc v K thut, 2006 17- W.P. Cheng, F.H. Chi- A study of coagulation mechanisms of polyferric sulfate reacting with humic acid using a fluorescence-quenching methodWater Res. Nov., Vol 36, N 18, 4583-91(2002) 18- Properties of Humic Substances http://www.ar.wroc.pl/ 19- M. Yang, K.Uesugi, H. Myoga Ammonia removal in bubble column by ozonation in the presence of Bromide Water Research, Vol 33, Issues 8, 19111917(1999) 20- W.R. Hang, J. Hoigne, H. Bader Improved ammonia oxidation by ozone in presence of bromide Water Research, Vol. 18, Issues 9, 1125-1128 (1984) 21- American Public Health Association (APHA) Standard methods for the examination of water and wastewater- American Public Health Association, Washington, D.C.(1992)

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