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Lun vn TI U HO QUY TRNH X L NC THI DT NHUM BNG H XC TC FENTON

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M U 1.1 L do chn ti Hin nay, nhiu nc trn th gii vic bo v mi trng tr thnh quc sch thng qua vic ban hnh cc lut bo v mi trng, huy ng nhiu nhn lc v ti lc bo v mi trng. nc ta, ang trong qu trnh cng nghip ho hin i ho t nc, nn kinh t Vit Nam khng ngng pht trin v t nhiu thnh tu, i sng ngi dn dn dn c ci thin. Song ngun ti nguyn thin nhin li ang dn cn kit, cht thi t sn xut cng nghip thi ra cng nhiulm cho cht lng mi trng xu i. Nu nh khng c mt gii php thch hp c tm ra th sc kho cng ng v h sinh thi b e do nghim trng. Sn xut cng nghip v th cng nghip tng trng s thi ra mi trng nhiu cht gy nhim.Trong , cng nghip dt nhum to ra lng ln cht thi c mc gy nhim cao. Nc thi sinh ra t dt nhum thng c nhit cao, pH ln, cha nhiu loi ha cht, thuc nhum kh phn hy, mu cao. Nu khng c x l tt, nc thi do dt nhum s gy nhim mi trng, c bit l nhim ngun nc mt, nc ngm. iu nh hng n i sng ca vi sinh vt nh ngn cn cc qu trnh quang hp, nh hng kh nng tch t sinh hc ca cc sinh vt trong nc lm gim tnh thm m mi trng. Hu ht cc nh my x nghip dt nhum nc ta c h thng x l nc thi tuy nhin nc thi u ra cha t QCVN 13:2008/BTNMT. Nguyn nhn do trong thnh phn cha mt s hp cht kh phn hu nn h qu x l khng trit , chi ph cao. Nhn thy tnh cp thit ca vic x l nc thi dt nhum t tiu chun, vi gi thnh hp l trc khi thi ra mi trng nn ti :TI U HO QUY TRNH X L NC THI DT NHUM BNG H XC TC FENTON c tin hnh. 1.2 Ni dung nghin cu

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Kho st cc yu t nh hng n hiu qu x l nc thi dt nhum bng phng php oxi ho nng cao: Fenton. Cc nhn t nh hng n qu trnh Fenton nh: ph, t l Fe2+/H2O2, thi gian 1.3 Mc ch: Qua vic kho st mu nc thi t to bng cht phn ng fenton tm ra cc thng s nhm t hiu qu x l cao nht. 1.4 i tng Cc mu nc thi t to cha thuc nhum hot tnh (pha t thuc nhum..) c s dng tm cc iu kin ti u qua hiu sut COD, hiu sut kh mu bng cht phn ng Fenton. Cc iu kin ti u c kim tra trn cc mu nc thi t to cha thuc nhum hot tnh khc, p dng cc thong s ti u trn cc mu nc thi cha thuc nhum hot tnh Xc nh COD ca cc mu nc thi trn trc v sau khi x l bng cht Fenton, tm ra hiu sut gim COD. 1.5 Phng php nghin cu 1.5.1 Phng php th nghim thc nghim ti thc hin nghin cu thc nghim t phng th nghim c dng c, thit b, ho cht cn thit.tin hnh th nghim lp li nhiu ln ly kt qu tin cy. 1.5.2 Phng php x l s liu Kt qu th nghim v kho st c nhp vo phn mm Design Expert 8.0.7.1 Trial, x l a ra bng biu, th, bn v tm kt qu nghin cu tin cy v ti u. 1.5.3 Phng php tng hp ti liu Cc ti liu lin quan ca nhm c thu thp t sch bo, internet, th vinc tng hp so snh, phn tch, nh gi.

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CHNG I: TNG QUAN 1.1 Vi nt s lc v ngnh cng ngh dt may Vit Nam. nc ta, ngnh cng nghip dt may ang chim mt vai tr v v tr quan trng trong nn kinh t. N khng ch tho mn nhu cu may mc ca x hi v y mnh xut khu, m cn gp phn gii quyt cng vic cho gn na triu ngi v gii quyt cc cng tc x hi, thc hin ng ch trng, ng li ca ng v Nh nc ta. Hn na c im ca ngnh dt may cn phi s dng nhiu lao ng, nn trc y thng phn b nhng khu dn c ng. Vit Nam, ngnh dt may phn b v pht trin trn ton vng lnh th, nhng tp trung vi mt cao cc thnh ph ln nh H Ni, H Ch Minh, Nng, Hu Ngnh dt may l mt trong nhng ngnh cng nghip c lch s pht trin lu nht nc ta, chnh v vy m trang thit b v cng ngh ca ngnh rt a dng. Bn cnh cc thit b cng ngh tin tin vn cn tn ti rt nhiu cc thit b lc hu, c c nhng thit b c sn xut t nhng nm 1930-1940. Do c im ca ngnh l khu nhum s dng lng ln v lng nc thi cha thuc nhum ln nn cng lm tng thm phn bc bch s nhim mi trng, nh hng n m quan v sc kho cng ng. 1.2. Vi nt s lc chung v cht thi ca ngnh dt may Cng nghip dt may gm rt nhiu qu trnh t sn xut x tng hp v sn xut vi ti bn l u c cc cht thi nh hng n mi trng. Cht thi khng ch dng rn, kh m cn dng dung dch. 1.2.1. Cht thi rn. Mi nm lng cht thi khong 300-500 ngn tn, bao gi cc loi: X than ca l hi Cc ph liu nh vi vn, bao b
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Cc loi ho cht, thuc nhum, thuc ty ra Cc loi ph liu ca ngnh c kh

1.2.2. Kh thi. Kh thi ca ngnh cng nghip dt may c pht thi t: Cc loi l hi nh l hi nhin liu l than, du FO, du diezen Kh thi trong cc cng on cng ngh thng cha cc loi bi bong, cc loi hi ho cht Cc mi cht lnh trong cc thit b lm lnh v iu ho trung tm s dng trong cc cng ngh ko si, dt, dy chuyn may 1.2.3. Nc thi. Theo s liu thng k ngnh dt may nc ta thi ra mi trng khong 20-30 triu m3 nc thi/nm. Trong c khong 10% tng lng nc thi qua x l, cn li u thi thng ra mi trng qua cc cng hay mng nc. Nc thi t dt nhum thng c nhit cao, pH ln, cha hn hp phc tp cc cht d tha (phm nhum, cht hot ng b mt, cht in li, cht to mi trng, men, cht i ho) di dng cc ion, cc kim loi nng v cc tp cht tch ra t x v c mu cao. Nhng, dng thi dt thay i t ngy ny qua ngy khc v thm ch thay i theo gi do bn cht ca m, ca qu trnh nhum, c th nh mc nhim ca nc thi dt nhum ph thuc rt ln vo loi v lng ho cht s dng, vo kt cu mt hng sn xut (ty trng, nhum, in hoa ) vo t l s dng si tng hp, vo loi hnh cng ngh sn xut (gin on, lin tc hay bn lin tc), vo c tnh my mc thit b s dng * Nhng nh hng ca nc thi nhum n lu vc tip nhn: - pH ca nc thi c gi tr 9-12 s nh hng nghim trng n s tn ti v pht trin ca cc loi thu sinh.

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- Tng lng cht rn l lng v ha tan u cao hn quy nh. Trong c nhiu cht c hi nh: thuc nhum kh phn gii, cc cht hot ng b mt, c bit l cc loi mui ha tan vi nng cao tiu dit cc laoij vi sinh vt. - Cc ion kim loi nng dng t do v dng phc cng gy nh hng rt bt li - Cc cht kh c trong nc thi lm gim ng k nng oxi ha tan trong nc. - Mu nc thi vi nng cao lm gim tnh thm m v ngn cn cc qu tr nh quang hp ca cc sinh vt trong nc. - Kh nng tch t sinh hc ca sinh vt trong nc l iu kh trnh. - Tim n c hi nc thi dt nhum nh hng n ngun nc ngm. 1.3. Cc thng s nh gi cht lng nc thi dt nhum 1.3.1 pH: Tr s pH cho bit nc thi c tnh axit, kim hay trung tnh. Qu trnh x l nc thi bng phng php sinh hc rt nhy cm vi s dao ng ca gi tr pH (cc vi sinh vt s b c ch hoc b cht khi c s thay i pH). V vy cn kim tra gi tr pH trong khong thch hp trc khi cho nc thi vo h thng x l. 1.3.2 Mu sc: Mu sc ca nc l do cc cht bn trong nc gy nn. Mu sc ca nc c th l do cc cht hu c v phn chit ca thc vt gi l mu thc. Ngoi ra l do cc cht v c l nhng ht rn c mu gy ra, gi l mu biu kin. 1.3.3 c: c ca nc do cc ht l lng, cc cht hu c phn hy hoc do gii thy sinh gy ra. c lm gim kh nng truyn nh sng trong nc, nh hng n kh nng quang hp ca cc vi sinh vt t dng trong nc. Nc cng bn, c cng cao. n v chun o c l s cn quang do 1 mg SiO2 ha tan trong 1 lit nc ct gy ra.
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1.3.4 Tng lng cht rn (TS): Tng lng cht rn l trng lng kh tnh bng mg ca phn cn li sau khi bay hi 1 lt mu nc trn ni cch thy ri sy kh 1030C cho ti khi trng lng khng i (n v: mg/l). 1.3.5 Cht rn huyn ph (SS): L cht rn dng l lng trong nc. Hm lng cht rn huyn ph SS l trng lng kh ca phn cht rn cn li trn giy lc si thy tinh khi lc 1 lt mu nc qua phu ri sy kh ( n v: mg/l ) 1.3.6 Cht rn ha tan (DS): Hm lng cht rn ha tan chnh l thng s ca tng lng cht rn v hm lng cht rn huyn ph (n v : mg/l ) DS = TS SS 1.3.7 Hm lng oxi ha tan ( DO - Dissolved oxigen): L lng oxi khng kh c th ha tan vo nc trong iu kin nhit thp, p sut xc nh. Ch s DO thp, c ngha l nc c nhiu cht hu c, nhu cu oxi ha tng nn tiu th nhiu oxi trong nc. Ch s DO cao, c ngha l nc c nhiu rong to tham gia vo qu trnh quang hp gii phng oxi. Ch s DO rt quan trng duy tr iu kin hiu kh v l c s xc nh nhu cu oxi ha sinh hc. 1.3.8 Nhu cu oxi ha sinh hc ( BOD - Biochemical oxigen Demand ) Ch tiu ny xc nh nhim ca nc thi hoc nc sng, h do cha cc cht dng tan, keo, khng tan kh lng. l lng oxi cn thit oxi ha cc cht hu c c trong nc thi bng vi sinh vt (ch yu l vi khun) hoi sinh, hiu kh.
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Quy trnh ny c tm tt nh sau: vi sinh vt Cht hu c + O2 CO2 + H2O Xc nh BOD c dng rng ri trong k thut mi trng : + Tnh gn ng lng oxi cn thit oxi ha cc cht hu c d phn hy c trong nc thi. + Lm c s tnh ton kch thc cc cng trnh x l. + Xc nh hiu sut x li ca mt s qu trnh. + nh gi cht lng nc sau khi x l c php thi vo cc ngun nc. Trong thc t, ngi ta khng th xc nh lng oxi cn thit phn hy hon ton cht hu c bng phng php sinh hc, m ch xc nh lng oxi cn thit trong 5 ngy u nhit 20oC trong bng ti ( trnh hin tng quang hp trong nc). Ch s ny c gi BOD5. BOD = DOu - DOsau 1.3.9 Nhu cu oxi ha hc (COD - Chemical oxigen Demand ): L lng oxi cn thit cho qu trnh oxi ha ton b cc cht hu c c trong mu nc thnh CO2 v H2O. Ch s COD c dng rng ri c trng ho hm lng cht hu c a nc thi v s nhim ca nc t nhin. xc nh COD ngi ta thng s dng mt cht oxi ha mnh trong mi trng axit. Cht oxi ha hay dng l kali bicromat (K2Cr2O7)
Ag2SO4

Cht hu c + K2Cr2O7 + H+

t0

CO2 + H2O + 2 Cr+3 + 2 K+

Vi lng bicromat d c chun bng dung dch mui mohr Fe(NH4)2(SO4)2


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Vi cht ch th l dung dch Ferroin: Cr2O7-2 + Fe+2 + H+ Cr+3 + Fe+3 + H2O Ch th chuyn t mu xanh lam sang nu . Ngoi ra cn c cc ch tiu: Tng cacbon hu c (TOC Total Organic Carbon) Nhu cu oxy l thuyt (ThOD Theoretical Oxygen Demand) Nhu cu oxy tng cng (TOD Total Oxygen Demand)

TOC ch c dng khi hm lng cc cht hu c rt nh trong nc.ThOD chnh l lng oxi cn thit oxi ha hon ton cc cht hu c c trong nc thnh CO2 v H2O.ThOD ch tnh c gi tr khi bit r cng thc ha hc ca cc cht hu c. V thnh phn ca nc thi rt phc tp nn khng th tnh c ThOD chnh xc, v vy ch c th tnh gn ng da vo gi tr COD. Cc thng s ny c ln nh sau: ThOD > COD > BODcui> BOD. 1.4. Thuc nhum: 1.4.1. Mt s c im ca cht mu hu c. - Cu trc ca phn t cht mu hu c Trong cc hp cht hu c thng gp hai loi lin kt c bn:lin kt n v lin kt i. Nu nh cc mi lin kt n v ni i trong mt hp cht hu c c xp thnh mt h thng "mt cch mt" th cc in t vng ngoi s linh ng hn. Nu nh hp cht hu c trong h thng mi lin kt ni i cch cng di th h thng in t vng ngoi cng linh ng, n cng d hp th cc tia sng c bc sng ln nn mu cng m. V d: C6H5-( CH= CH) - C6H5 (stiben)- khng mu C6H5-( CH= CH)3 - C6H5 (iphenyl hexatrien) - vng
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C6H5-( CH= CH)6 - C6H5 (ipheyl dodecahexaen) - da cam - nu Ngoi cc mch lin hp, cc nhm nguyn t khc m gia chng c cc lin kt khng bo ha cng quyt nh mu ca cht. Hp cht hu c c mu l do chng cha cc nhm mang mu trong phn t, nhng nhm mang mu quan trng hn c l: - CH = CH - nhm etylen - N = N- CH = N- N = O=C=O nhm azo nhm azo metyl nhm nitrozo nhm cacbonyl

Ngoi cc nhm mang mu cn thit, khi a thm vo phn t cc cht mang mu mt nhm nguyn t gi l "nhm tr mu" th mu ca hp cht s su hn v s c kh nng nhum mu cho mt s vt liu thch hp. Mt s nhm tr mu quan trng l: OH; -NH2; -N(CH3)2; -N(CH5)2 ... Theo thuyt in t, cho phn t hp cht hu c c mu su th phn t ca n phi c cu to phng m s tng tc ca cc in t khng b cn tr, bt k yu t no ph v yu cu ny cng lm nh hng n mu ca hp cht. C ch xut hin mu ca cht hu Khi cc bc x in t ngoi, kh kin hay hng ngoi tc ng vo cc phn t hu c s gy nn cc hiu ng: + S chuyn ng ca phn t ni chung, m c bn l chuyn ng quay ca n. + Vic tng nng lng dao ng ca cc phn ring bit ca phn t.

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+ Nng lng c dng chuyn cc electron t mc nng lng c bn sang mc nng lng cao hn. Trong phn t hu c gia cc nguyn t cacbon c 2 kiu lin kt c bn l lin kt v lin kt . Trong lin kt l lin kt bn hn, c to thnh do 2 obitan electron ca 2 nguyn t che ph nhau to thnh mt m my gm 2 electron tp trung dc theo ng thng ni lin 2 ht nhn ca 2 nguyn t gn nhau. Cn lin kt c hnh thnh do xen ph "bn" ca cc obitan electron p nm song song vi nhau. Khi hnh thnh nhng h thng trong cc electron c kh nng di chuyn kh t do t nguyn t khc. linh ng gia cc electron gia hai nguyn t cacbon cng ng i vi nhng cu trc c cc lin kt gia cacbon v nit, gia hai nguyn t ni..... S chuyn sang trng thi kch thch i i vi s phn b li mt electron gy ra s phn cc phn t. Do vy m hiu s cc mc nng lng gia trng thi c bn v trng thi kch thch gim xung. Nng lng cn kch thch tr nn b hn,to iu kin cho s hp th chn lc nhng lng t nng lng nh sng c nhng bc sng nm trong min ph ca nh sng kh kin. Kh nng phn cc tng mnh khi hai u ca h lin hp .....-CH=CH-CH=CH-..... c nhng nhm th lm cho cc electron di chuyn d dng. Nh vy tt c nhng bin i cu trc no m khng ph v cu to phng ca phn t v thc y s di chuyn h electron ca phn t, s phn cc ca phn t v s xut hin cch phn b c nh cc in tch m v dng th u lm cho phn t d dng chuyn sang trng thi kch thch di tc dng ca lng t nh sng kh kin, ngha l to iu kin cho s xut hin mu. Mt s tnh cht ca mu hu c: Mc d cu to ho hc khc nhau nhng cc cht mu hu c c hai tnh cht mu c bn + Tnh c mu c gy ra do cu to ho hc c trng. + Kh nng lin kt vi mt trong ca si do cc lc ho hc v vt l.
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1.4.2 Phn loi, c im ca thuc nhum Thuc nhum l tn ch chung nhng hp cht hu c c mu rt a dng v mu sc v chng loi, chng c kh nng nhum mu ngha l gn mu hay bt mu trc tip cho cc vt liu khc. Hin nay nc ta vn cha c cng ngh sn xut thuc nhum hu ht u phi nhp ngoi.Tuy nhin cng c mt vi c s nh trong nc sn xut cc loi bt mu v c, hu c t nguyn liu nhp ngoi. phn loi thuc nhum c hai cch: Theo cu to ho hc: Cn c nhng c im ging nhau trong cu to ho hc ca chng. Cch phn loi ny thng c s dng i vi cc nh sn xut nghin cu. S phn loi ny gip cho cc nh sn xut thuc nhum d dng nh hng phng php tng hp cc loi thuc nhum v gip cho con ngi s dng nm vng cc tnh cht ho hc ca thuc nhum. Phn loi da vo tnh cht v k thut s dng thuc nhum:

nhum in hoa cc sn phm dt, da, giy, vt liu cao phn t v cc vt liu khc. Theo cch phn lp ny th nhng thuc nhum tuy c xp cng mt lp theo phn lp ho hc c th nm cc lp khc nhau theo phn lp k thut. Ngi s dng thng dng cch phn loi ny. c th c phng n thch hp x l cc thuc nhum l ht sc quan trng. Di y l mt s tnh cht chung ca chng theo phn lp k thut c hai phn lp l: ho tan trong nc v khng ho tan trong nc. *Thuc nhum ho tan: + Thuc nhum trc tip: L nhng hp cht mu ho tan trong nc, c kh nng t bt mu vo mt s vt liu nh: cc x xenlulo, giy, t tm, da v x polyamit mt cc trc tip nh cc lc
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hp ph trong mi trng trung tnh hoc kim. Thuc nhum trc tip c gam mu t vng n en, mu tng i ti. Chng ho tan trong nc, nhit di 25 0C th kh ho tan hn. Lng thuc nhum trc tip ti a c th ho tan l 40g/l; thng ch t 20-25g/l. C cng thc toonhr qut l: Ar SO3Na. Khi ho tan vo nc thuc nhum phn ly nh sau: Ar SO3Na Ar SO3- + Na+

(Ar: l gc hu c mang mu ca thuc nhum) + Thuc nhum axit: C cng thc tng qut ging thuc nhum trc tip.cc laoij thuc nhum axit c c im chung l ho tan trong nc v chng bt mu vo vt liu trong mi trng axit, cn bn thn thuc nhum th c phn ng trung tnh. Loi thuc nhum ny c gam mu rt rng, mu thun sc v ti. Trong mi trng axit, chng lin kt vo vt liu bng lin kt ion theo phng trnh tng qut nh sau: Ar SO3Na + Ar1 NH3+Cl- = Ar SO3-H3N+ - Ar1 + NaCl Vi Ar : k hiu gc thuc nhum Ar1: k hiu cho vt liu in hoa + Thuc nhum hot tnh: L nhng hp cht mu m trong phn t chng c cha cc nhm nguyn t c th thc hin mi lin kt ho tr vi vt liu ni chung v x dt ni ring trong qu trnh nhum. Nh vy m chng c bn mu cao vi gia cng t, ma st v nhiu ch tiu khc na. Thuc nhum hot tnh c gam mu, mu ti v thun sc. Thuc nhum hot tnh c cng thc: S Ar T X S: l nhm to cho phn t thuc nhum c tnh tan Ar: l gc thuc nhum
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T: l gc mang nguyn t phn ng Cu ni gia S Ar v T X ca thuc nhum th ngi ta thng dng cc nhm: - NH -; - NH CH2 -; - SO2 N Trong iu kin nhum, khi tip xc vi vt liu thuc nhum hot tnh s tham gia ng thi vo hai phn ng: phn ng vi vt liu v phn ng thu phn. Thuc nhum b thu phn khng c kh nng lin kt ho hc vi vt liu na. Hu ht thuc nhum hot tnh ho tan tt trong mi trng nc v bt mu vo vt liu trong mi trng kim. + Thuc nhum baz cation: Thuc nhum baz l nhng hp cht mu c cu to khc nhau chng c gam mu, mu ti, thun sc v cng mu rt mnh. Song nhc im ca thuc nhum baz l cho mu km bn vi git v nh sng nn chng c dng nhum mt s sn phm dt t t xenlulo, nhum la t tm trang tr, dng nhum mt s sn phm dt t t xenlulo, nhum la t tm trang tr, dng nhum giy, lm mc in trong cng ngh in n, my tre, g ho tan tt trong nc. + Thuc nhum cation: C cu to ging thuc nhum baz nhng li bt mu mnh hn x PAN, c bn cao, d phi t ba mu c bn. Loi thuc nhum ny rt thch hp in hoa, nhum lin tc hoc nhum mt s ch phm t x PAN c yu cu x l hi trong quy trnh cng ngh nhum. Chng c gam mu t vng n en v ho tan tt trong nc. *Thuc nhum khng ho tan trong nc + Thuc nhum hon nguyn khng tan: L nhng hp cht mu dhuwux c khng ho tan trong nc, tuy c cu to ho hc v mu sc khc nhau nhng chng c chung mt tnh cht l tt c u cha nhm xeton phn t. Khi b kh dng khng tan s chuyn v dng lycaxit, n cha tan
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trong nc nhng tan trong kim v chuyn thnh dng lycbaz. Dng lycbaz do c i lc ln vi x v ho tan trong nc nn n hp th rt mnh vo x xenlulo, mt khc n d b thu phn v oxi ho v dng khng tan ban u + Thuc nhum hon nguyn tan: C cng thc tng qut l Ar CO SO3Na (Ar: gc thuc nhum). Dng ny l este sunfonat ca hp cht lycaxit ca thuc nhum hon nguyn khng tan, c mu n, ho tan tt trong nc. c tnh quan trng ca n l trong mi trng axit lin kt este b ph v gii phng ra hp cht laycoaxit. Nhng laycoaxit km bn, di tc dng ca cht oxi ho ca khng kh n chuyn v dng khng tan ban u. + Thuc nhum lu hunh: L nhng hp cht mu khng tan trong nc v mt s dung mi hu c, nhng trong dung dch kim ca natrisunfua th n b kh v dng laycobazo ho tan trong nc. + Thuc nhum phn tn: L nhng hp cht mu khng tan trong nc do khng cha cc nhm cho tnh tan nh SO3Na; -COONa. ho tan rt thp trong nc phi s dng dng huyn ph hay phn tn vi kch thc ht khong 0,2-2 m, 250C ho tan khong 0,2-8mg/l. Cn 800C ho tan ca chng cng ch t ti 50-350mg/l l ti a. Trong phn t c cha nhm amin dng t do hoc ankyl ho (- NH2; -NHR; NR2 ) c bit c cha cc nhm amin b th bng gc ankyl hydroxyl (- NH CH2 CH2 OH) nn nhng thuc nhum ny d dng phn tn trong nc hn. + Thuc nhum picmen: L nhng hp cht mu c cu to ho hc khc nhau c c im chung l khng tan trong nc do trong phn t cha cc nhm cho tnh tan ( - SO3H; - COOH) hoc
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ccnhm ny b chuyn v dng mui bari, canxi khng tan trong nc. Mt s picmen hu c tuy khng tan trong tan nhng ho tan trong mt s dung mi hu c c dng nhum du m, xng, sp. Chng khng c i lc vi x si v cc vt liu khc. picmen c th bm vo vt liu khi ngi ta dng mng cao phn t gn n vo vi. + Thuc nhum azo khng tan: L nhng hp cht c cha azo trong phn t nhng khng cha cc nhm cho tnh tan nh: - SO3Na; - COONa nn chng khng ho tan trong nc. Thuc nhum ny c mu ti, bn vi git, gi thnh thp, nhum v in n gin. 1.5. Cc ngun pht sinh, c tnh nc thi cng ngh dt nhum. Qua s nguyn l cng ngh dt nhum ta thy lng nc thi pht sinh trong cng ngh dt nhum t cc cng on: h, si, r h, nu ty, nhum v hon tt, trong lng nc thi pht sinh ln nht ch yu giai on git sau mi cng on. Pht thi t cng nghip dt di dng dng thi lng, ph thi vi t, x t cc qu trnh nhum, cht thi rn t cc qu trnh sy, cht thi nguy hi v kh thi. Dng thi lng cha nhiu hp cht khc nhau nh: thuc nhum v ho cht, cc cht lm u mu v cc cht phn tn, cc kim, cc mui, cc axit sau ch ra cc c tnh ca dng thi t cc hot ng trong sn xut ngnh dt.

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Hnh 1.5: S nguyn l cng ngh dt nhum hng si bng v cc ngun nc thi.
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Cng on

Cht nhim trong nc thi

c tnh ca nc thi

H si, gi h

Tinh bt, glucozo, carboxy

BOD cao (34-50% tng sn

Metyl xelulozo, polyvinyl lng BOD). alcol, nha, cht bo v sp. Nu, ty NaOH, cht sp v du m, kim cao, mu ti, BOD tro, soda, silicat natri v xo cao (30% tng BOD). si vn. Ty trng Hipoclorit, hp cht cha kim cao, chim 5% clo, NaOH, AOX, axit Lm bong NaOH, tp cht. BOD. kim cao, BOD thp (di 1% tng BOD). Nhum Cc loi thuc nhum, axitaxetic v cc mui kim loi. In mu rt cao, BOD kh cao (6% tng BOD), TS cao.

Cht mu, tinh bt, du, t mu cao, BOD cao v st, mui kim loi,axit du m. Kim nh, BOD thp, lng nh.

Hon thin

Vt tinh bt, m ng vt, mui.

Bng 1.5: Cc cht gy nhim v c tnh ca nc thi dt nhum

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Hm lng cc cht gy nhim trong tng loi hnh cng nghip, cc loi sn phm cng khng ging nhau, thnh phn nc thi rt a dng.Cc cht thi gy nh hng n ngun tip nhn. 1.6 Cc phng php x l thuc nhum hot tnh trong nc thi dt nhum Phng php vi sinh l phng php kinh t v sinh thi nht, l phng php c ngh n u tin trong x l nc thi. Nhng vi nhng c im ca nc thi dt nhum, nht l nc thi cha thuc nhum hot tnh th mt mnh phng php vi sinh khng th gii quyt c vn . Ngi ta ngh n vic phi tin hnh tin x l cc cht mu (thuc nhum) kh hoc khng phn gii sinh hc trong nc thi dt nhum bng phng php ha l, ha hc ri mi x l hon tt bng phng php vi sinh. i vi thuc nhum hot tnh, hin nay trn th gii v ti Vit Nam vn cha c mt phng php tin x l tht s hiu qu v kinh t v c tnh tan, bn v a dng v chng loi ca n. Phng php oxi ha, c bit l oxi ha pha lng, t ra c tim nng trong gii quyt vn ny. 1.6.1 Phng php ha l Cc phng php ha l n thun c c im chung l chuyn cht nhim (cht mu) t pha ny sang pha khc m khng lm bin i bn cht, cu trc cht mu. Do , trong x l cht mu th cc phng php ha l c nhc im chung l khng x l trit cht mu chuyn chng thnh cc cht khng gy nhim hoc cc cht d phn hy sinh hc hn. 1.6.1.1Phng php keo t Hin tng keo t l hin tng cc ht keo cng loi c th ht nhau to thnh nhng tp hp ht c kch thc v khi lng ln c th lng xung do trng lc trong mt thi gian ngn. Phng php keo t x l cht mu dt nhum l phng php tch loi cht mu gy nhim ra khi nc da trn hin tng keo t. V nguyn tc, do c phn tn ln, din tch b mt ring ln nn cc ht keo c xu hng ht nhau nh cc lc b mt. Song, do cc ht keo cng loi tch in cng
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du c trng bng th zeta () nn cc ht keo lun y nhau bi lc y tnh in, ngn chng ht nhau to ht ln hn v lng xung. Nh vy th cng ln h keo cng bn (kh kt ta), th cng nh ht keo cng d b keo t, trong trng hp l tng khi bng 0 th ht khng tch in v d dng ht nhau bi lc b mt to ht ln hn c th lng c. l c s ca phng php keo t.
Lp ion nghch

{[mFe(OH)3]nFe3n+3(n-x)Cl-}3x+3xClHt nhn

ht nhn lp hp th lp in tch tri du lp khuch tn


Th zeta, Th nhit ng o Lp ion nghch

HT KEO

Lp in kp X Lp ion quyt nh du hay lp hp ph

Hnh 1.6.12: S thay i th theo Hnh 1.6.1.1: Cu to ht keo khong cch t b mt ht keo

thc hin keo t h keo, c th s dng cc cch: - Ph tnh bn ca h keo do lc y tnh in bng cch thu hp lp in kp ti th = 0, iu ny c thc hin khi cho ht keo hp ph in tch tri du trung ha in tch ht keo. in tch tri du ny thng l cc ion kim loi a ha tr trong cc mui v c (cht keo t). - To iu kin cho ht keo va chm vi cc bng kt ta ca chnh cht keo t nh hin tng hp ph- bm dnh (hiu ng qut) - Dng nhng cht cao phn t - cht tr keo t - khu (hp ph) cc ht keo nh li vi nhau to ht c kch thc ln (bng cn) d lng. Cc cht keo t thng dng:

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- Phn nhm Al2(SO4)3.nH2O (n=1418), mui st Fe2(SO4)3.nH2O hoc FeCl3.nH2O (n=16) c coi l nhng cht keo t c in, trong phn nhm l cht keo t ph bin nht ti Vit Nam, trong khi mui st li l cht keo t ph bin cc nc cng nghip pht trin do khong pH keo t ti u rng hn (5 9), bng cn nng, bn hn v d lng st trong nc thp hn so vi dng phn nhm (pH keo t 5,5 7). Dng phn nhm hoc mui st lm cht keo t s xy ra phn ng thy phn to bng cn hydroxit tham gia hiu ng qut v ph tnh bn h keo: Al2(SO4)3 + 6H2O 2Al(OH)3 + 6H+ + 3SO42Fe2(SO4)3 + 6H2O 2Fe(OH)3 + 6H+ + 3SO42Tuy nhin do thi gian to hydroxit kim loi rt ngn (c micro giy) nn cc ion kim loi Al3+ v Fe3+ cha kp thc hin chc nng chnh l trung ha in tch ht keo. - Polime nhm (PAC): khi ha tan PAC to cc ht polime Al13 (thc cht l Al13O4(OH)247+) c in tch vt tri (7+) v kch thc ln gy keo t mnh, bng cn ln v thy phn chm nn tng tc dng c a chng ln cc ht keo cn x l. Cc cht tr keo t (hay cht to bng) gm: cht hiu chnh pH, dung dch axit silixic hot tnh, bt t st v polime (PAA- polyacrylamit). Cc cht hiu chnh pH c tc dng n nh pH tng hiu qu keo t. Axit silixic hot tnh, bt t st v polime c chung c im l mang in tch v ht cc ht keo nh mang in tch tri du vi n to bng cn ln. Cc yu t nh hng n qu trnh keo t gm c: pH, cc yu t hu c (to phc, hp ph) lm bn ht keo, khuy trn Phng php keo t c s dng rng ri trong x l nc thi dt nhum c cc thuc nhum phn tn v khng tan. y l phng php kh thi v mt kinh th tuy nhin n khng x l c tt c cc loi thuc nhum: thuc nhum axit, thuc nhum trc tip; thuc nhum hon nguyn keo t tt nhng khng kt lng d dng, bng cn cht lng thp; thuc nhum hot tnh rt kh x l bng cc tc nhn keo t thng thng v cn t c nghin cu. Bn cnh phng php keo t cng to ra mt lng bn thi ln v khng lm gim tng cht rn ha tan nn gy kh khn cho tun
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hon nc. 1.6.1.2Phng php hp ph Hp ph l s tch ly cht trn b mt phn cch pha. Cht c b mt trn xy ra s hp ph c gi l cht hp ph, cht c tch ly trn b mt l cht b hp ph. Da trn bn cht lc hp ph c th phn loi hp ph vt l v hp ph ha hc, trong , hp ph vt l gy ra bi lc Van der Waals cn hp ph ha hc gy ra bi lin kt ha hc. Do bn cht lc hp ph nn hp ph ha hc khng vt qua n lp phn t cn hp ph vt l c th c hin tng a lp (pha rn - kh). Hai loi hp ph ny khc nhau v nhit hp ph, tc hp ph, v ng ch l tnh c th, c ngha l hp ph vt l t ph thuc bn cht b mt trong khi xy ra hp ph ha hc nht thit cn c i lc gia b mt v cht b hp ph. V cc yu t nh hng n kh nng hp ph th ni chung cht c din tch b mt ring cng ln th kh nng hp ph cng cao. Tuy nhin, din tch b mt ring mi ni ln tim nng hp ph, n l iu kin cn nhng cha . s hp ph xy ra tt, nht l hp ph ha hc, th cn phi xt n yu t tng thch v kch c cht b hp ph v kch thc mao qun cht hp ph (vi vt liu xp), tng tc, lin kt gia cht hp ph v cht b hp ph. V d nh cc cht hp ph c xp ln, kch c mao qun nh, din tch b mt ring ln vn hp ph khng hiu qu i vi cc cht mu hu c cng knh. Cht phn cc d hp ph ln b mt phn cc, cht khng phn cc u tin hp ph ln b mt khng phn cc Hp ph c th biu din di dng mt cn bng: Cht b hp ph + b mt cht b hp ph lin kt vi b mt biu din lng cht b hp ph trn mt n v cht hp ph (khi lng, b mt) ngi ta dng i lng hp ph k hiu l a ( hoc ). i lng hp ph l mt hm ca nhit , nng hoc p sut: a = a(T,C) hoc a = a(T, P), khi c nh nhit trong phng trnh trn ta c ng hp ph ng nhit. m t s hp ph trng thi cn bng ngi ta thng dng cc phng trnh ng nhit hp ph, khi , i lng hp ph cn bng ph thuc vo nng cht b
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hp ph (pha lng) hay p sut ring phn ca cht b hp ph (pha kh) khi cn bng. C nhiu phng trnh ng nhit hp ph c thit lp cho hp ph trong nhng trng hp khc nhau (n lp, a lp, hp ph vt l, ha hc, hp ph trn b mt phn cch pha rn- lng, lng- kh), nhng i vi hp ph trn b mt phn cch pha rn- lng th quan trng nht l phng trnh hp ph ng nhit Langmuir v phng trnh hp ph ng nhit Freundlich: Phng trnh Langmuir:

Phng trnh Freundlich: a = kC1/n ,(n>1) Trong : a: i lng hp ph cn bng (g cht b hp ph/g cht hp ph). amax: i lng hp ph cc i (g cht b hp ph khi n che ph b mt cht hp ph). C: nng cht b hp ph trong dung dch (g/L, mol/L). k: hng s cn bng: hp ph gii hp. Cc cht hp ph s dng trong x l nc thi dt nhum: - Cacbon hot tnh: cht hp ph ph bin trong x l nc thi cha thuc nhum, c bit l hp ph thuc nhum giai on x l trit sau keo t. N khng c dng n l do gi thnh cao v hiu sut thp trong loi b cc phn t mu ln v i hi thi gian tip xc. Khi hp ph bo ha, than hot tnh c ti sinh, lng tn tht c 10 15%. - Cc cht hp ph v c khc: t st, than bn, silic oxit, mt s khong cng c dng lm cht hp ph thuc nhum kh hiu qu vi gi thnh r hn than hot tnh. - Cc cht hp ph do mt s cng ty v t chc ch to c kh nng hp ph tt cc
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ton b

thuc nhum tan, k c thuc nhum hot tnh. in hnh nh cht hp ph Acrasorb D, Macrosorb, Cucurbiturial. - Sinh khi: c s dng kh mu nc thi dt nhum bng c ch hp ph v trao i ion. Tuy nhin nu khng c x l ha hc th kh nng hp ph thuc nhum anion ca sinh khi rt thp. Chitin (polisacarit cu to ging xenllulo) v chitosan (chitin loi axetyl) c bit n nhiu nht v kh nng hp ph nhiu loi thuc nhum nh: thuc nhum phn tn, trc tip, axit, hon nguyn, lu ha v c thuc nhum hot tnh. Ngoi ra ngi ta cn dng xenlulo bin tnh v lignoxenlulo hp ph thuc nhum axit v thuc nhum cation. Cc vt liu thin nhin nh li ng, mt ca, thn cy ma, tru, cng c th nghim kh nng hp ph thuc nhum. Hp ph l phng php c ngh n nhiu trong x l thuc nhum hot tnh, tuy nhin nhc im ca phng php ny nm trong chnh bn cht ca n l chuyn cht mu t pha ny sang pha khc v i hi thi gian tip xc, to mt lng thi sau hp ph, khng x l trit cht nhim. 1.6.1.3 Phng php lc Cc k thut lc thng thng l qu trnh tch cht rn ra khi nc khi cho nc i qua vt liu lc c th gi cn v cho nc i qua. Cc k thut lc thng thng khng x l c cc tp cht tan ni chung v thuc nhum ni ring. Cc k thut lc mng, c th tch c thuc nhum tan ra khi nc thi dt nhum gm c vi lc, siu lc, thm thu ngc v in thm tch. im khc bit gia ba k thut trn l kch thc ht m chng c th lc c. Qu trnh vi lc c ng knh l mng t 0,110 m, siu lc c kch thc l mng trong khong 2 100nm, cn trong thm thu ngc l mng c kch thc t 0,5 2nm. Siu lc c th lc c cc phn t kch c nano, cng vi cc hiu ng hp ph, to mng th cp, siu lc cho php lc cc phn t. Trong phng php thm thu ngc, mng ch cho php nc i qua trong khi mui, axit v cc phn t hu c khng i qua do t vo dung dch nc thi cn x l mt p sut ln hn p sut thm thu ca dung dch . Trong cc k thut mng th k thut siu lc c th loi b cc cht tan vi khi lng phn t ln c
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1000100.000 g/mol. Tuy nhin n khng lc c cc loi thuc nhum tan v c phn t lng thp. Vic loi b cc loi thuc nhum ny c thc hin bng phng php lc nano v thm thu ngc. Lc nano c chng minh l c th tch thuc nhum hot tnh c khi lng phn t khong 400g/mol ra khi nc thi.[17] Tuy vi nhng u im trn nhng gi thnh ca mng, thit b lc cao v nng sut thp do thuc nhum lng xung lm bn mng. 1.6.2 Phng php sinh hc C s ca phng php sinh hc l s dng cc vi sinh vt phn hy cc hp cht hu c trong nc thi. Phng php sinh hc t hiu qu cao trong x l nc thi cha cc cht hu c d phn hy sinh hc vi pH, nhit , chng vi sinh thch hp v khng cha cc cht c lm c ch vi sinh. Tuy nhin nc thi xng nhum cha thuc nhum rt bn vi sinh hu nh khng b phn hy sinh hc. V vy x l nc thi dt nhum cn qua hai bc: tin x l cht hu c kh phn gii sinh hc chuyn chng thnh nhng cht c th phn hy sinh hc, tip theo l dng phng php vi sinh. X l sinh hc c th l x l vi sinh hiu kh hoc ym kh ty thuc vo s c mt hay khng c mt oxy. Qu trnh ym kh xy ra s kh cn qu trnh hiu kh xy ra s oxy ha cc cht hu c. Qu trnh ym kh c th chy vi ti lng hu c ln, loi b mt lng ln cc cht hu c ng thi to ra kh sinh hc, tiu tn t nng lng. Lng bn thi ca qu trnh ym kh rt thp. Tuy nhin, hiu qu kh mu ca qu trnh ny khng cao (i vi thuc nhum axit l 80 90%, thuc nhum trc tip l 81%). Ngc li, qu trnh hiu kh c hiu sut cao trn 85% nhng n li tiu tn nng lng cho sc kh v to lng bn thi ln.[17] C th s dng qu trnh vi sinh ym kh kh mu thuc nhum azo v cc thuc nhum tan khc to thnh amin tng ng. Song cc amin to ra c tnh c ln hn thuc nhum ban u tc l c mc nhim cao hn. Ngi ta c th s dng kt hp hai qu trnh trn: ym kh lm gim mu v x l hu c nng cao, tip theo l hiu kh oxy ha cc amin sinh ra bi cc qu trnh trc.
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Ngoi ra ngi ta c th kh mu thuc nhum bng vic s dng cc vi khun, nm, to v nm men. C ch ca qu trnh ny thng i t hp ph thuc nhum ln sinh khi t bo ri phn gii cht mu bng h enzim. 1.6.3 Phng php in ha Phng php ny c ng dng x l nc thi dt nhum. Phng php ny da trn c s qu trnh oxy ha/ kh xy ra trn cc in cc. anot, nc v cc ion clorua b oxy ha dn n s hnh thnh O2, O3, Cl2 v cc gc l tc nhn oxy ha cc cht hu c trong dung dch. Qu trnh kh in ha cc hp cht hu c nh thuc nhum, catot, kt hp vi phn ng oxy ha in ha v qu trnh tuyn ni, keo t in ha dn n hiu sut x l mu v khong ha cao. Phng php in ha vi in cc nhm hoc st l cng ngh x l hiu qu mu, COD, BOD, TOC, kim loi nng, cht rn l lng. Nghin cu cho thy hiu sut x l cc loi nc thi t xng nhum cha nhiu loi thuc nhum khc nhau c kh nng t ti 90%. y l phng php c chng minh hiu qu i vi vic x l mu, COD, BOD, TOC, kim loi nng, cht rn l lng ca nc thi dt nhum. Tuy nhin phng php in ha c gi thnh cao do tiu tn nng lng v kim loi lm in cc. 1.6.4 Phng php ha hc u im ni bt ca cc phng php ha hc so vi cc phng php ha l l bin i, phn hy cht nhim (cht mu) thnh cc cht d phn hy sinh hc hoc khng nhim ch khng phi chuyn chng t pha ny sang pha khc. So vi phng php vi sinh th tc x l cht thi bng phng php ha hc nhanh hn nhiu. 1.6.4.1Kh ha hc c ng dng trong trng hp nc thi cha cc cht d b kh. Phng php kh ha hc hiu qu vi cc thuc nhum azo nh phn gii lin kt azo to thnh cc amin thm khng mu c khn nng phn gii vi sinh hiu kh tt hn thuc nhum gc. Kh ha hc trn c s natri bohidrid, xc tc bisunfit p dng vi thuc nhum tan trong nc nh thuc nhum trc tip, axit, hot tnh cha cc nhm azo hoc cc nhm kh c v thuc nhum phc ng. Quy trnh ny c th kh mu trn 90%.
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1.6.4.2 Oxy ha ha hc a. Oxy ha bng cc tc nhn oxy ha thng thng Cc cht oxy ha thng thng nh clo, clodioxit, natri hipoclorit, kali permanganate, ozon, dicromat, hidropeoxit c th c dng oxy ha cc cht nhim ni chung v thuc nhum ni ring. Qu trnh oxy ha tiu tn mt lng ln tc nhn oxy ha, do , qu trnh oxy ha ha hc ch c s dng trong trng hp khi cht nhim khng th loi b bng cc phng php khc. Kh nng oxy ha c xc nh bi th oxy ha: Bng 1.3: Th oxy ha ca mt s cp oxy ha/ kh Cp oxy ha/kh Th oxy ha (V) O3/O22,07 OH/O22,8 Cl2/2Cl0,94 H2O2/H2O 0,68 KMnO4/Mn2+ 0,59

- Clo ha c nh gi cao v hiu qu x l mu nhng khi s dng nng cao kh mu s li d lng clo ln trong nc thi. N c th kh mu nhanh thuc nhum axit v thuc nhum hot tnh. Vi thuc nhum phn tn v thuc nhum trc tip th ngay nng clo cao cng khng thu c hiu qu ng k. Nhn chung, clo khng c a thch trong x l mu nc thi v sinh ra cc hp cht c clo gy ung th v c hi vi mi trng. - Ozon l cht oxi ha mnh v c th oxi ha thuc nhum trong nc thi m khng sinh ra cc hp cht hu c th cp c hi. pH< 5, ozon tn ti dng O3 v oxi ha chn lc ni i trong thuc nhum. pH> 8, ozon phn hy to gc t do OH phn ng khng chn lc vi cc cht hu c (theo c ch ca qu trnh oxi ha tin tin). Ozon c hiu qu nht trong loi b thuc nhum hot tnh. Nhc im ln nht ca phng php ny nm gi thnh cao v thi gian tn ti ca ozon ngn, chi ph cho thit b to ozon cao.
-

KMnO4, H2O2 l cht oxi ha c th oxi ha cha cao phn hy cc thuc

nhum. Hn na, chi ph ha cht nu s dng hai cht oxi ha ny l kh ln. b. Oxy ha tin tin (Advanced Oxidation Processes - AOPs)
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Cc qu trnh oxi ha tin tin da trn s to thnh cc gc t do hot ng nh OH, gc t do ny ng vai tr mt tc nhn oxi ha khng chn lc. Trong cc qu trnh ny, s khong ha hon ton thu c iu kin nhit p sut bnh thng. Cc qu trnh oxi ha tin tin phn bit nhau cch thc to ra gc t do. Gc t do c th c to ra bng nhiu cch: chiu tia UV, s phn ly ca H2O2 (c xc tc), O3 . Cc qu trnh quang ha Gc t do c to thnh di tc dng ca bc x t ngoi: - Quang ha khng xc tc: bc x t ngoi nng lng cao c hp th bi cc phn t, a phn t cht hp th ln trng thi kch thch. trng thi ny kh nng phn ng ca n l rt ln, n phn hy cho cc cht t c hn hoc khi mo phn ng dy chuyn phn hy cc cht hu c trong h. Phn ng to thnh gc OH : H2O H +OH - Qu trnh quang phn UV/ H2O2: s dng bc x t ngoi phn ly lin kt trong H2O2 to ra gc OH. C ch quang phn trong trng hp ny l s b gy lin kt O - O do hp th bc x t ngoi, hnh thnh hai gc OH: H2O2 2OH - Qu trnh xc tc quang ha: xc tc thng l cht bn dn nh TiO2 dng anatase. Cht bn dn hp th nng lng nh sng ph hp vi khong cch nng lng gia hai vng dn - khng dn to ra cp e- - l trng. TiO2 e- + h+ , h+ l l trng Cp e- - l trng ng vai tr h oxi ha kh trn b mt cht bn dn, thc hin phn ng oxi ha kh phn hy cc cht hu c. Thm vo OH cng c sinh ra trong qu trnh ny, do cht hu c khng ch b phn hy bi phn ng oxi ha kh m cn bi phn ng vi gc t do OH: TiO2(h+)H2Ohp TiO2 + 2OHhp + H+
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h h h

TiO2(h+) +OH-hp/bm TiO2 + OHhp TiO2(h+) + RXhp TiO2 + RX-hp Ozon ha Ozon ha c xem l mt trong nhng qu trnh oxi ha tin tin pH kim do cc cht hu c b oxi ha bi gc t do hot ng c to ra trong qu trnh phn hy ozon. Thc ra trong mi qu trnh ozon ha, cht hu c b oxi ha mt phn do phn ng ca cc gc t do, mt phn l s ozon ha trc tip cht hu c. Bi l, ozon l cht oxi ha mnh hn oxy, v v mt l thuyt , khng c hp cht hu c no khng b oxi ha bi ozon. Nhc im ln nht ca phng php ny l kh khn trong vic thu c ozon v s nhy cm pH ca qu trnh [Ullmann, 1995]. Hin nay, ozon ha c s dng cng on lm trng trong sn xut giy. Cc qu trnh ozon ha gm c: - Qu trnh UV/O3: qu trnh ozon ha c h tr bng vic chiu nh sng t ngoi tng hiu qu to OH hay to 2OH vi nng cao hn. H2O+O3 2OH + O2 - Qu trnh H2O2/O3: phn ng gia O3 v H2O2 tng s to thnh gc OH. Trong trng hp ny, ngoi gc OH cn c gc HO2 (to ra t H2O2). V vy phn ng oxi ha cht hu c t hiu qu cao hn. H2O2 + 2O3 2OH + 3O2 - Qu trnh H2O2/UV/O3: l s kt hp ca cc qu trnh UV/O3, H2O2/O3, UV/H2O2 thu c h bc 3. y l qu trnh hiu qu nht trong x l nc thi nhim nng v cho php gim TOC, khong ha hon ton cht nhim. C ch to gc t do c ch ra trong phn ng: H2O2 + 2O3 2OH + 3O2 Cc h Fenton (H2O2/Fe2+) v h kiu Fenton (H2O2/Fe3+): L cc h phn ng trong gc t do OH c to ra do s phn ly ca H2O2 xc tc bi Fe2+, Fe3+ :
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h h h

Fe2+ + H2O2 Fe3+ + OH- + OH H2O2 + OH HO2 + H2O Fe3+ + HO2 + H2O Fe2+ + O2+ H3O+ Gc OH sinh ra tn cng cc hp cht hu c: OH + RH R+ H2O R + Fe3+ R+ + Fe2+ pH thp s din ra phn ng ti to Fe2+ , khi Fe2+ ng vai tr xc tc tht s cho phn ng phn hy H2O2: Fe3+ + H2O2 H+ + FeOOH2+ FeOOH2+ HO2 + Fe2+ Ngoi ra cn c cc h trn c s h Fenton c s dng thm UV hoc oxalat tng cng phn ng oxi ha cc hp cht hu c, h quang Fenton ti to xc tc nh bc x t ngoi: Fe(OH)2+ Fe2+ + OH . Phn ng Fenton c pht hin t 1894 nhng cho n gn y mi c quan tm nh mt phng php kh hiu qu x l nhim cht hu c. H Fenton c kh nng x l thuc nhum tan (hot tnh, axit, trc tip), thuc nhum khng tan (hon nguyn, phn tn) ngay c khi nc thi c nng mu cao. S oxi ha cng lm gim COD ca nc thi ng thi tng kh nng phn hy sinh hc ca cc sn phm sau phn ng. So snh vi cc qu trnh oxi ha - kh x l thuc nhum nh in ha, ozon, hypclorit th Fenton t c hiu qu x l tt nht. Nhc im ca phng php ny l sn sinh lng bn thi ln t qu trnh keo t ca cht phn ng vi thuc nhum. Hn na, do h Fenton thc hin pH axit c 2,54 nn sau phn ng tn ha cht trung ha li nc thi x l. 1.6.4.3 Phng php oxy ha pha lng (WO) Oxi ha pha lng l qu trnh oxi ha bi cc gc t do xy ra khi mt dung dch cha cc cht hu c (hoc v c) c khuy trn tt vi kh oxy hoc tc nhn oxi ha khc nhit khong 150oC n 325oC. p sut 20 210 at c t vo h tng
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cng phn ng v kim sot s bay hi. Qu trnh oxi ha pha lng thch hp x l nc thi cha cht nhim nng cao nhng l long i vi cc phng php thiu t v bn vi s oxi ha ha hc thng thng hoc bn vi phn gii vi sinh. Phng php ny thu c kt qu x l tt nu nh cc iu kin nhit , p sut c ti u ha. Tuy nhin y l phng php c chi ph kh cao nu thc hin nhit , p sut cao (chi ph thit b, nng lng,). V vy, ty thuc vo yu cu x l m cn i gia mc oxi ha cn thit v chi ph x l. Oxi ha pha lng trc ti hn (Wet oxidation WO) c thc hin iu kin trc im ti hn ca nc (T < 375oC, P<22,1MPa). WO c th thc hin vi cht oxi ha l H2O2 (wet peroxide oxidation - WPO) hoc oxy khng kh (wet air oxidation WAO). Vic s dng oxi khng kh lm cht oxi ha lm cho chi ph ca phng php WAO thp hn nhiu so vi phng php WPO. Oxi ha pha lng siu ti hn (Supercritical wet oxidation - SCWO) c thc hin iu kin trn im ti hn ca nc (T < 375oC, P<22,1MPa). Phng php ny c chi ph v nng lng cao hn cc phng php WO. Phng php WO s dng xc tc nhm h nhit v p sut ca qu trnh oxi ha pha lng c gi l catalysis wet oxidation (CWO). Di y l bng so snh cc c im chnh ca 3 qu trnh oxi ha pha lng quan trng thy r c s khc nhau gia chng: Bng 1.4: c im chnh ca cc qu trnh oxi ha pha lng quan trng c im Nhit (C) p sut (bar)* Thi gian lu (pht) WO 200-325 20-210 10-90 SCWO 370-570 220-270 1-10 CWO 130-250 20-50 10-60

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Chuyn ha (%) Sn phm

80-99 CO2, H2O, N2, cc mui v axit hu c

99-99,999

90-98

CO2, H2O, N2

CO2, H2O, N2

*1bar = 101,3kPa ~ 1at T cc s liu trong bng trn ta thy: WO v SCWO c thc hin nhit v p sut rt cao dn n chi ph thit b v vn hnh cao. Vi vic s dng xc tc cho qu trnh WO, nhit , p sut v thi gian lu u gim ng k m vn thu c kt qu nh WO truyn thng. Qu trnh CWO mi c nghin cu cha nhiu, bng 1.5 tm lc mt s xc tc cho qu trnh ny. Bng 1.5: Xc tc cho qu trnh CWO Tc gi Xc tc ng/MCM-41 CuO-CeO2 PtxAg1xMnO2/CeO2

Tc nhn oxi ha

Cht nhim chnh

Wu et al., 2000 Hocvar et al., 2000 Hamoudi et al., 2000

Oxy Oxy Oxy

Phenol Phenol Phenol Cc hp cht cha nhm chc CHO Hp cht thm Cht hu c Xenlulo, ng Cht hu c Phenol

Hussain et al., 2001 Xiao et al., 2000 Batygina et al., 2000 Smith & Diehl, 1960 Weichgrebe & Vogelpohl, 1994 Fajerweg et al., 1997

K-Mn-Ce-O Cu2(OH)PO4 Ru Khng xc tc Khng xc tc Fe-ZSM-5

Oxy H 2 O2 Khng kh HClO3 v HIO3 H2O2 v Ozon H 2 O2

u im ca phng php oxi ha pha lng l n khng to ra nhng sn phm th cp gy c nh cc hp cht SOx, NOx, furan
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Phn ng oxi ha pha lng khng thng c s dng nh mt phng php c lp trong x l cc cht nhim bi l n thng khng oxi ha cht hu c n sn phm cui cng l CO2 v H2O m n thng c dng kt hp vi cc phng php khc. Trong s kt hp , oxi ha pha lng oxi ha khng hon ton cht nhim, chuyn n v dng d phn gii sinh hc hn a vo x l vi sinh. S kt hp ny va khc phc c kh khn ca phng php vi sinh trong x l cht nhim kh/ khng phn hy sinh hc, va gim chi ph x l. Khng ch c s dng nh mt phng php tin x l cc cht hu c c, bn m oxi ha pha lng cn c ng dng trong ti sinh than hot tnh m lm gim rt t hot tnh ca than. Trong mt s trng hp, phng php ny cn c dng x l cht nhim nng rt cao sau qu trnh lc mng. Nhng ng dng ca oxi ha pha lng u c mt im chung l oxi ha khng hon ton cht nhim bn, nng cao. Vi nhng u im v kh nng x l cc cht hu c bn hoc c, phng php CWAO c chng ti la chn nghin cu nh mt phng php tim nng trong x l nc thi cha nng cao cht hu c kh phn hy sinh hc ni chung v nc thi dt nhum cha thuc nhum hot tnh ni ring.

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